CN107407880B - Photosensitive resin composition - Google Patents
Photosensitive resin composition Download PDFInfo
- Publication number
- CN107407880B CN107407880B CN201680019911.6A CN201680019911A CN107407880B CN 107407880 B CN107407880 B CN 107407880B CN 201680019911 A CN201680019911 A CN 201680019911A CN 107407880 B CN107407880 B CN 107407880B
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- CN
- China
- Prior art keywords
- photosensitive resin
- compound
- resin composition
- ethylenically unsaturated
- composition according
- 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 abstract description 137
- 150000001875 compounds Chemical class 0.000 claims abstract description 122
- 229920005989 resin Polymers 0.000 claims abstract description 80
- 239000011347 resin Substances 0.000 claims abstract description 80
- 239000000758 substrate Substances 0.000 claims abstract description 65
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- 239000000126 substance Substances 0.000 claims abstract description 34
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 239000013043 chemical agent Substances 0.000 claims abstract description 7
- -1 acrylate compound Chemical class 0.000 claims description 82
- 238000000034 method Methods 0.000 claims description 48
- 238000011161 development Methods 0.000 claims description 37
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 29
- 125000002947 alkylene group Chemical group 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 24
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical group OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 238000011156 evaluation Methods 0.000 claims description 19
- 230000009477 glass transition Effects 0.000 claims description 18
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 16
- 239000004020 conductor Substances 0.000 claims description 16
- 238000010030 laminating Methods 0.000 claims description 16
- 238000007747 plating Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000003566 oxetanyl group Chemical group 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 75
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 36
- 239000000178 monomer Substances 0.000 description 24
- 229920001577 copolymer Polymers 0.000 description 15
- 230000035945 sensitivity Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 230000000740 bleeding effect Effects 0.000 description 12
- 239000011241 protective layer Substances 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 10
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 238000003475 lamination Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 125000003762 3,4-dimethoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000008365 aromatic ketones Chemical class 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 238000005422 blasting Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 2
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical class OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 2
- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2h-benzotriazole-5-carboxylic acid Chemical compound C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 description 2
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 235000005811 Viola adunca Nutrition 0.000 description 2
- 240000009038 Viola odorata Species 0.000 description 2
- 235000013487 Viola odorata Nutrition 0.000 description 2
- 235000002254 Viola papilionacea Nutrition 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000005529 alkyleneoxy group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000003884 phenylalkyl group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- XOHZHMUQBFJTNH-UHFFFAOYSA-N 1-methyl-2h-tetrazole-5-thione Chemical compound CN1N=NN=C1S XOHZHMUQBFJTNH-UHFFFAOYSA-N 0.000 description 1
- MHHJQVRGRPHIMR-UHFFFAOYSA-N 1-phenylprop-2-en-1-ol Chemical compound C=CC(O)C1=CC=CC=C1 MHHJQVRGRPHIMR-UHFFFAOYSA-N 0.000 description 1
- MACMNSLOLFMQKL-UHFFFAOYSA-N 1-sulfanyltriazole Chemical compound SN1C=CN=N1 MACMNSLOLFMQKL-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- NEBBLNDVSSWJLL-UHFFFAOYSA-N 2,3-bis(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCC(OC(=O)C(C)=C)COC(=O)C(C)=C NEBBLNDVSSWJLL-UHFFFAOYSA-N 0.000 description 1
- NSWNXQGJAPQOID-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-diphenyl-1h-imidazole Chemical class ClC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 NSWNXQGJAPQOID-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FXRQXYSJYZPGJZ-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethenylbenzene Chemical compound CC(C)(C)OC=CC1=CC=CC=C1 FXRQXYSJYZPGJZ-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- JQMPYPZEZKHJTJ-UHFFFAOYSA-N 2-[2,3-bis(fluoromethyl)phenyl]-2-[2-[2,3-bis(fluoromethyl)phenyl]-4,5-bis(3-methoxyphenyl)imidazol-2-yl]-4,5-bis(3-methoxyphenyl)imidazole Chemical compound FCC1=C(C=CC=C1CF)C1(N=C(C(=N1)C1=CC(=CC=C1)OC)C1=CC(=CC=C1)OC)C1(N=C(C(=N1)C1=CC(=CC=C1)OC)C1=CC(=CC=C1)OC)C1=C(C(=CC=C1)CF)CF JQMPYPZEZKHJTJ-UHFFFAOYSA-N 0.000 description 1
- XOLNSMTWLSOUQY-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]-1-(4-nonylphenoxy)ethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCCCCCCC1=CC=C(OC(O)COCCOCCOCCOCCOCCOCCOCCO)C=C1 XOLNSMTWLSOUQY-UHFFFAOYSA-N 0.000 description 1
- AIYITDGPHANYCA-UHFFFAOYSA-N 2-[4,5-bis(3-methoxyphenyl)-2-(2,3,4,5,6-pentafluorophenyl)imidazol-2-yl]-4,5-bis(3-methoxyphenyl)-2-(2,3,4,5,6-pentafluorophenyl)imidazole Chemical compound COC1=CC=CC(C=2C(=NC(N=2)(C=2C(=C(F)C(F)=C(F)C=2F)F)C2(N=C(C(=N2)C=2C=C(OC)C=CC=2)C=2C=C(OC)C=CC=2)C=2C(=C(F)C(F)=C(F)C=2F)F)C=2C=C(OC)C=CC=2)=C1 AIYITDGPHANYCA-UHFFFAOYSA-N 0.000 description 1
- WCQJWYPIPVYGHI-UHFFFAOYSA-N 2-[4-[3-(4-tert-butylphenyl)-5-[2-(4-tert-butylphenyl)ethenyl]-1,3-dihydropyrazol-2-yl]phenyl]-1,3-benzoxazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C=CC1=CC(C=2C=CC(=CC=2)C(C)(C)C)N(C=2C=CC(=CC=2)C=2OC3=CC=CC=C3N=2)N1 WCQJWYPIPVYGHI-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- QEARHKZQYSYPNS-UHFFFAOYSA-N 2-methylprop-2-enoic acid 1,3,5-triazinane-2,4,6-trione Chemical class CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.O=C1NC(=O)NC(=O)N1 QEARHKZQYSYPNS-UHFFFAOYSA-N 0.000 description 1
- TWKGRZHFOJJWGP-UHFFFAOYSA-N 2-phenyl-3-(4-propan-2-ylphenyl)-5-[2-(4-propan-2-ylphenyl)ethenyl]-1,3-dihydropyrazole Chemical compound C1=CC(C(C)C)=CC=C1C=CC1=CC(C=2C=CC(=CC=2)C(C)C)N(C=2C=CC=CC=2)N1 TWKGRZHFOJJWGP-UHFFFAOYSA-N 0.000 description 1
- FMFHUEMLVAIBFI-UHFFFAOYSA-N 2-phenylethenyl acetate Chemical compound CC(=O)OC=CC1=CC=CC=C1 FMFHUEMLVAIBFI-UHFFFAOYSA-N 0.000 description 1
- LZHCVNIARUXHAL-UHFFFAOYSA-N 2-tert-butyl-4-ethylphenol Chemical compound CCC1=CC=C(O)C(C(C)(C)C)=C1 LZHCVNIARUXHAL-UHFFFAOYSA-N 0.000 description 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- YCVSNZBGCXUYAK-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)-5-[2-(2,3-dimethoxyphenyl)ethenyl]-2-phenyl-1,3-dihydropyrazole Chemical compound COC1=CC=CC(C=CC=2NN(C(C=2)C=2C(=C(OC)C=CC=2)OC)C=2C=CC=CC=2)=C1OC YCVSNZBGCXUYAK-UHFFFAOYSA-N 0.000 description 1
- KCVVTXFNIHFLGX-UHFFFAOYSA-N 3-(2,4-dimethoxyphenyl)-5-[2-(2,4-dimethoxyphenyl)ethenyl]-2-phenyl-1,3-dihydropyrazole Chemical compound COC1=CC(OC)=CC=C1C=CC1=CC(C=2C(=CC(OC)=CC=2)OC)N(C=2C=CC=CC=2)N1 KCVVTXFNIHFLGX-UHFFFAOYSA-N 0.000 description 1
- XGIKBNXXNDSMQM-UHFFFAOYSA-N 3-(2,5-dimethoxyphenyl)-5-[2-(2,5-dimethoxyphenyl)ethenyl]-2-phenyl-1,3-dihydropyrazole Chemical compound COC1=CC=C(OC)C(C=CC=2NN(C(C=2)C=2C(=CC=C(OC)C=2)OC)C=2C=CC=CC=2)=C1 XGIKBNXXNDSMQM-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
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- 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
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
-
- 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
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
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- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- 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
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- 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
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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- 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
- G03F7/031—Organic compounds not covered by group G03F7/029
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- 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
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- 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
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- 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
- G03F7/20—Exposure; Apparatus therefor
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- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
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- General Physics & Mathematics (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
A photosensitive resin composition comprising an alkali-soluble polymer; a compound having an ethylenically unsaturated bond; and a photopolymerization initiator, wherein after a resist pattern obtained by forming a photosensitive resin layer made of the photosensitive resin composition on a substrate surface, exposing and developing the photosensitive resin layer is treated with a chemical agent for evaluating chemical resistance, the minimum line width of a cured resist line is 17 [ mu ] m or less.
Description
Technical Field
The present invention relates to a photosensitive resin composition and the like.
Background
Printed circuit boards have conventionally been manufactured by photolithography. In the photolithography method, first, a photosensitive resin composition layer stacked on a substrate is pattern-exposed. The exposed portion of the photosensitive resin composition is polymerized and cured (in the case of a negative type) or becomes soluble in a developer (in the case of a positive type). Next, the unexposed portion (negative type) or the exposed portion (positive type) is removed by a developer to form a resist pattern on the substrate. Further, etching or plating is performed to form a conductor pattern, and then the resist pattern is peeled off and removed from the substrate. Through these steps, a conductor pattern is formed on the substrate.
In the photolithography method, when the photosensitive resin composition is generally applied to a substrate, any of the following methods can be used: a method of coating a solution of a photosensitive resin composition on a substrate and drying the coated substrate; or a method of laminating a photosensitive resin laminate (hereinafter, also referred to as a "dry film resist") obtained by sequentially laminating a support, a layer formed of a photosensitive resin composition (hereinafter, also referred to as a "photosensitive resin layer"), and, if necessary, a protective layer on a substrate. The latter is mostly used in the manufacture of printed circuit boards.
With the recent miniaturization of wiring intervals of printed wiring boards, various characteristics have been required for dry film resists. For example, in order to improve the adhesion and resolution of a resist pattern and to make the resist pattern covering a through hole less likely to break in a stage up to before a development step, the following photosensitive resin composition has been proposed: which respectively contain a (meth) acrylate compound having a skeleton derived from dipentaerythritol as a compound having an ethylenically unsaturated bond and a pyrazoline compound as a photosensitizer (patent document 1).
In order to improve the adhesion and resolution of the resist pattern and to suppress the generation of residue at the bottom of the resist pattern in the developing step, the following photosensitive resin composition has also been proposed: it contains a (meth) acrylate compound having a dipentaerythritol-derived skeleton and a di (meth) acrylate compound having a bisphenol a-type skeleton and an alkylene oxide chain (patent document 2).
In or before a conductor pattern forming step of etching or plating a substrate on which a resist pattern is formed, the resist pattern and the substrate may be cleaned with a chemical agent such as a degreasing solution. In comparison before and after the contact with the chemical agent, it is required to suppress the change in the shape of the resist pattern.
However, the photosensitive resin compositions described in patent documents 1 and 2 still have room for improvement from the viewpoint of chemical resistance of the resist pattern and the like.
Further, various photosensitive resin compositions have been proposed for improving the characteristics of the resist layer (patent documents 3 to 6).
In patent document 3, the following photosensitive resin composition is studied from the viewpoint of the shape of the folded edge of the resist pattern, the resolution, and the residual film ratio: which comprises pentaerythritol polyalkoxytetramethacrylate as a compound having an ethylenically unsaturated bond.
In patent document 4, from the viewpoint of the shape of the folded edge of the resist pattern, resolution, adhesion, minimum development time, and bleeding property, the following combinations have been studied as monomers in the photosensitive resin composition: a combination of pentaerythritol tetra (meth) acrylate modified with ethylene oxide, di (meth) acrylate obtained by modifying bisphenol a with an alkylene oxide, and dipentaerythritol (meth) acrylate.
Patent documents 5 and 6 describe the following photosensitive resin compositions: which comprises an alkali-soluble polymer having a glass transition temperature exceeding 106 ℃.
However, in the production of printed wiring boards and the like, when the hardness of the cured resist layer is too high, the resist pattern may be broken by physical impact during development treatment or during transportation, and as a result, the yield of the wiring pattern may be deteriorated. Therefore, the cured resist layer is desired to have good flexibility in order to maintain adhesion to the substrate. Further, although the dry film resist may be wound up in a roll and stored, when the components of the dry film resist bleed out and adhere to the surface of the support film, stable wiring pattern production may be difficult.
However, the photosensitive resin compositions described in patent documents 3 to 6 have room for improvement in terms of improving the flexibility of the resist pattern to improve the adhesion and suppressing the bleeding of the constituent components of the dry film resist.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2012-048202
Patent document 2: international publication No. 2015/012272
Patent document 3: japanese patent laid-open publication No. 2013-156369
Patent document 4: japanese patent laid-open No. 2014-081440
Patent document 5: japanese patent laid-open publication No. 2013-117716
Patent document 6: japanese patent laid-open No. 2014-191318
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the background art described above, and an object of the present invention is to provide a photosensitive resin composition having excellent at least one of adhesion, resolution, and storage stability.
Means for solving the problems
The present inventors have found that the above problems can be solved by the following technical means.
A photosensitive resin composition comprising:
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated bond; and the combination of (a) and (b),
(C) a photopolymerization initiator,
after a resist pattern (resist pattern) obtained by forming a photosensitive resin layer made of the photosensitive resin composition on a substrate surface, exposing and developing the photosensitive resin layer is treated with a chemical agent for evaluating chemical resistance, the minimum line width of the cured resist line is 17 [ mu ] m or less.
The photosensitive resin composition according to [1], wherein the photosensitive resin layer is formed on the surface of the substrate, and the photosensitive resin layer is exposed with an exposure amount at which the maximum residual film number in the case of performing exposure using a Stouffer 41 stage exposure scale as a mask and then performing development becomes 15,
in the FT-IR measurement, the wave number before exposure was 810cm-1The peak height of (B) is represented by P, the reaction rate of an ethylenic double bond in the compound (B) having an ethylenic unsaturated bond after the exposure is represented by Q, and the value of P x Q/R when the film thickness of the photosensitive resin layer is represented by R is 0.21 or more.
According to [1]Or [ 2]]The photosensitive resin composition, wherein the alkali-soluble polymer (A) has a weight average Tg of glass transition temperatures TgtotalIs below 110 ℃.
The photosensitive resin composition according to any one of [1] to [3], wherein the weight average molecular weight of the compound (B) having an ethylenically unsaturated bond is 760 or more.
The photosensitive resin composition according to any one of [1] to [4], wherein the concentration of the methacryloyl group in the compound having an ethylenically unsaturated bond (B) is 0.20mol/100g or more.
The photosensitive resin composition according to any one of [1] to [5], wherein the concentration of the ethylene oxide unit in the compound (B) having an ethylenically unsaturated bond is 0.80mol/100g or more.
The photosensitive resin composition according to any one of [1] to [6], which comprises a hexaarylbisimidazole compound as the photopolymerization initiator (C).
A photosensitive resin composition comprising:
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated bond; and the combination of (a) and (b),
(C) a photopolymerization initiator,
the weight average Tg of the glass transition temperature Tg of the alkali-soluble polymer (A) istotalThe temperature of the mixture is below 110 ℃, and the mixture is,
and a (meth) acrylate compound having 3 or more ethylenically unsaturated bonds is contained as the (B) compound having an ethylenically unsaturated bond.
The photosensitive resin composition according to [8], which comprises a (meth) acrylate compound having 5 or more ethylenically unsaturated bonds and having an alkylene oxide chain as the compound (B) having an ethylenically unsaturated bond.
The photosensitive resin composition according to [8] or [9], wherein the alkali-soluble polymer (A) has an acid equivalent of 100 to 600 and a weight average molecular weight of 5000 to 500000, and has an aromatic group in a side chain thereof.
The photosensitive resin composition according to any one of [8] to [10], which comprises a (meth) acrylate compound having 5 or more ethylenically unsaturated bonds and having an ethylene oxide chain as the compound (B) having an ethylenically unsaturated bond.
The photosensitive resin composition according to any one of [8] to [11], which contains a (meth) acrylate compound having an ethylene oxide chain and a dipentaerythritol skeleton as the (B) compound having an ethylenically unsaturated bond.
The photosensitive resin composition according to any one of [8] to [12], further comprising a compound represented by the following general formula (II) as the compound having an ethylenically unsaturated bond (B),
{ formula (II), wherein R1And R2Each independently represents a hydrogen atom or a methyl group, A is C2H4B is C3H6，n1And n3Each independently is an integer of 1 to 39, and n1+n3Is an integer of 2 to 40, n2And n4Each independently is an integer of 0 to 29, and n2+n4An integer of 0 to 30, and the arrangement of the repeating units of- (A-O) -and- (B-O) -may be random or block, and in the case of blockIn this case, either one of- (A-O) -and- (B-O) -may be on the biphenyl side. }.
The photosensitive resin composition according to any one of [8] to [13], further comprising a compound represented by the following general formula (I) as the compound having an ethylenically unsaturated bond (B),
{ in formula (I), R3～R6Independently represents an alkyl group having 1 to 4 carbon atoms, X represents an alkylene group having 2 to 6 carbon atoms, and m1、m2、m3And m4Each independently is an integer of 0 to 40, m1+m2+m3+m41 to 40, and m1+m2+m3+m4When the number is 2 or more, X's may be the same as or different from each other }.
The photosensitive resin composition according to any one of [8] to [ 14 ], which contains a hexaarylbisimidazole compound as the (C) photopolymerization initiator.
The photosensitive resin composition according to any one of [8] to [15], which contains a pyrazoline compound as the photopolymerization initiator (C).
The photosensitive resin composition according to any one of [8] to [16], which is used for direct image-wise exposure.
According to [8]The photosensitive resin composition, wherein the alkali-soluble polymer (A) has a weight average Tg of glass transition temperatures TgtotalThe temperature of the mixture is below 105 ℃,
the photosensitive resin composition contains (B1) a compound having at least 3 methacryloyl groups as the (B) compound having an ethylenically unsaturated bond in an amount of more than 0 mass% and 16 mass% or less based on the total solid content of the photosensitive resin composition,
and 70% by mass or more of the compound (B) having an ethylenically unsaturated bond is a compound having a weight average molecular weight of 500 or more.
The photosensitive resin composition according to item [18], wherein the compound (b1) having at least 3 methacryloyl groups has a weight average molecular weight of 500 or more.
The photosensitive resin composition according to [18] or [19], which comprises (B2) a compound having a oxetane chain and 1 or 2 (meth) acryloyl groups as the (B) compound having an ethylenically unsaturated bond.
The photosensitive resin composition according to item [20], wherein the compound (b2) having a oxetane chain and 1 or 2 (meth) acryloyl groups has a weight average molecular weight of 500 or more.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a photosensitive resin composition having excellent at least one of adhesion, resolution and storage stability can be provided.
Detailed Description
Hereinafter, a mode for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be specifically described.
< photosensitive resin composition >
In the present embodiment, the photosensitive resin composition contains: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. The photosensitive resin composition may contain other components such as (D) additives, as required.
The first embodiment of the present invention is a photosensitive resin composition, which is designed as follows: a resist pattern obtained by forming a photosensitive resin layer made of a photosensitive resin composition on a substrate surface, exposing and developing the photosensitive resin layer is treated with a chemical agent for evaluating chemical resistance, and then the minimum line width of a cured resist line is 17 [ mu ] m or less. By using such a photosensitive resin composition, short-circuiting can be suppressed when a wiring pattern is formed by plating. Further, plating submergence (Japanese: めっき submersion り) can be suppressed, and a wiring pattern having excellent linearity can be obtained. That is, the photosensitive resin composition of the present invention is excellent in adhesion and/or resolution. The minimum line width of the cured resist line is preferably 16 μm or less, more preferably 15 μm or less, further preferably 12 μm or less, particularly preferably 10 μm or less, and most preferably 8 μm or less. The method and conditions for measuring the minimum line width of the cured resist line are described in the chemical resistance evaluation of examples.
The second embodiment of the present invention is a photosensitive resin composition, wherein (A) the weight average Tg of the glass transition temperature Tg of the alkali-soluble polymertotalA (meth) acrylate compound having not less than 110 ℃ and having 3 or more ethylenically unsaturated bonds as the (B) compound having an ethylenically unsaturated bond. By containing TgtotalThe (a) alkali-soluble polymer having a temperature of 110 ℃ or lower and the (meth) acrylate compound having 3 or more ethylenically unsaturated bonds can increase the reaction rate, and since the crosslinking density tends to increase and the unreacted (B) component does not easily remain, the photosensitive resin composition tends to provide a resist pattern having excellent at least one of adhesion, resolution and storage stability as a result.
When a photosensitive resin layer formed from the photosensitive resin composition of the present embodiment is formed on a substrate surface and the photosensitive resin layer is exposed with an exposure amount at which the maximum residual film number when the exposure is carried out with a schmitt 41 stage exposure scale as a mask and then development is carried out becomes 15 stages, the photosensitive resin layer preferably satisfies the relationship shown in the following formula.
P×Q/R≥0.21
{ wherein, in the FT-IR measurement of the photosensitive resin layer, P represents the wave number before exposure of 810cm-1Q represents the reaction rate of the ethylenic double bond in the compound having an ethylenic unsaturated bond (B) after exposure, and R represents the film thickness. }
The value represented by the formula P × Q/R described above is more preferably 0.22 or more, 0.23 or more, 0.24 or more, 0.25 or more, or 0.27 or more. The measurement method and conditions of the value represented by the formula P.times.Q/R are described in examples.
(A) Alkali soluble polymer
(A) The alkali-soluble polymer is a polymer that is soluble in an alkali substance. In the present embodiment, the photosensitive resin composition preferably has a carboxyl group from the viewpoint of alkali developability, and more preferably is a copolymer containing a carboxyl group-containing monomer as a copolymerization component.
In the present embodiment, the photosensitive resin composition preferably contains a copolymer having an aromatic group as the alkali-soluble polymer (a), and particularly preferably contains a copolymer having an aromatic group in a side chain, from the viewpoint of the high resolution and the shape of the folded edge of the resist pattern, and further from the viewpoint of the chemical resistance of the resist pattern. Examples of such aromatic groups include: substituted or unsubstituted phenyl, substituted or unsubstituted aralkyl.
The proportion of the aromatic group-containing copolymer in the component (a) is preferably 50% by mass or more, preferably 60% by mass or more, preferably 70% by mass or more, preferably 80% by mass or more, preferably 90% by mass or more, and may be 100% by mass.
From the viewpoint of the high resolution and the folded edge shape of the resist pattern, and further from the viewpoint of the chemical resistance of the resist pattern, the copolymerization ratio of the aromatic group-containing comonomer in the aromatic group-containing copolymer is preferably 20% by mass or more, preferably 30% by mass or more, preferably 40% by mass or more, preferably 50% by mass or more, preferably 60% by mass or more, preferably 70% by mass or more, and preferably 80% by mass or more. The upper limit of the copolymerization ratio is not particularly limited, but is preferably 95% by mass or less, more preferably 90% by mass or less, from the viewpoint of maintaining alkali solubility.
Examples of the aromatic group-containing comonomer include: a monomer having an aralkyl group, styrene, and a styrene derivative which can be polymerized (for example, methylstyrene, vinyltoluene, t-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene is preferable, and a monomer having an aralkyl group is more preferable.
Examples of the aralkyl group include: substituted or unsubstituted phenylalkyl (excluding benzyl), substituted or unsubstituted benzyl, etc., preferably substituted or unsubstituted benzyl.
Examples of the comonomer having a phenylalkyl group include: phenylethyl (meth) acrylate, and the like.
Examples of the comonomer having a benzyl group include: (meth) acrylates having a benzyl group such as benzyl (meth) acrylate, chlorobenzyl (meth) acrylate, and the like; vinyl monomers having a benzyl group, such as vinylbenzyl chloride, vinylbenzyl alcohol, and the like. Among them, benzyl (meth) acrylate is preferable.
The copolymer having an aromatic group (particularly preferably a benzyl group) in a side chain is preferably obtained by polymerizing a monomer having an aromatic group with at least 1 kind of the first monomer described later and/or at least 1 kind of the second monomer described later.
The alkali-soluble polymer (a) other than the copolymer having an aromatic group in a side chain is preferably obtained by polymerizing at least 1 kind of the first monomer described later, and more preferably obtained by copolymerizing at least 1 kind of the first monomer and at least 1 kind of the second monomer described later.
The first monomer is a monomer having a carboxyl group in a molecule. Examples of the first monomer include: (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid half ester, and the like. Of these, (meth) acrylic acid is preferred.
In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid, "(meth) acryloyl group" means acryloyl group or methacryloyl group, and "(meth) acrylate" means "acrylate" or "methacrylate".
The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all monomer components. From the viewpoint of exhibiting good developability, controlling the burring property, and the like, the copolymerization ratio is preferably 10 mass% or more. From the viewpoint of the high resolution and the shape of the folded edge of the resist pattern, and further from the viewpoint of the chemical resistance of the resist pattern, the copolymerization ratio is preferably 50% by mass or less, and among these, 30% by mass or less is more preferred, 25% by mass or less is further preferred, 22% by mass or less is particularly preferred, and 20% by mass or less is most preferred.
The second monomer is non-acidic and has at least 1 polymerizable unsaturated group in the molecule. Examples of the second monomer include: (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; vinyl alcohol esters such as vinyl acetate; and (meth) acrylonitrile, and the like. Among them, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-butyl (meth) acrylate are preferable.
In this embodiment, (a) the alkali-soluble polymer may be prepared by the following method: one or more of the monomers specified above are polymerized by a known polymerization method, preferably addition polymerization, more preferably radical polymerization.
From the viewpoint of chemical resistance, adhesion, high resolution, or the shape of the folded edge of the resist pattern, it is preferable to contain a monomer having an aralkyl group and/or styrene as a monomer, and for example, a copolymer formed of methacrylic acid, benzyl methacrylate, and styrene is preferable; copolymers formed from methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, and the like.
The glass transition temperature of the alkali-soluble polymer (A) obtained by the Fox equation (when the component (A) contains a plurality of copolymers, the glass transition temperature Tg of the entire mixture, that is, the weight average Tg of the glass transition temperature Tg, is determined from the viewpoint of chemical resistance, adhesion, high resolution, or the shape of the folded edge of the resist patterntotal) Preferably 110 ℃ or lower, more preferably 107 ℃ or lower, 105 ℃ or lower, 100 ℃ or lower, 95 ℃ or lower, 90 ℃ or lower, or 80 ℃ or lower. The lower limit of the glass transition temperature (Tg) of the alkali-soluble polymer (A) is not particularly limited, but is preferably 30 ℃ or higher from the viewpoint of controlling the meltabilityMore preferably 50 ℃ or higher, and still more preferably 60 ℃ or higher.
(A) The acid equivalent of the alkali-soluble polymer (when the component (a) includes a plurality of copolymers, the acid equivalent of the entire mixture) is preferably 100 or more from the viewpoint of the development resistance of the photosensitive resin layer, and the resolution and adhesion of the resist pattern, and is preferably 600 or less from the viewpoint of the development resistance and peeling property of the photosensitive resin layer. (A) The alkali-soluble polymer preferably has an acid equivalent of 200 to 500, more preferably 250 to 450.
(A) The weight average molecular weight of the alkali-soluble polymer (when component (a) includes a plurality of copolymers, the weight average molecular weight of the entire mixture) is preferably 5000 to 500000. (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5000 or more from the viewpoint of being able to uniformly maintain the thickness of the dry film resist and obtain resistance to a developer, and is preferably 500000 or less from the viewpoint of maintaining developability of the dry film resist, high resolution and a folded edge shape of the resist pattern, and further chemical resistance of the resist pattern. (A) The weight average molecular weight of the alkali-soluble polymer is more preferably 10000 to 200000, still more preferably 20000 to 130000, particularly preferably 30000 to 100000, and most preferably 40000 to 70000. (A) The dispersion degree of the alkali-soluble polymer is preferably 1.0 to 6.0.
In the present embodiment, the content of the alkali-soluble polymer (a) in the photosensitive resin composition is preferably within a range of 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 40 to 60% by mass, based on the total solid content of the photosensitive resin composition (hereinafter, the same applies to each component unless otherwise specified). (A) The content of the alkali-soluble polymer is preferably 10% by mass or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer, and is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less from the viewpoint of sufficiently exhibiting the performance as a resist material of a resist pattern formed by exposure, the viewpoint of high resolution and the shape of a folded edge of the resist pattern, and further the viewpoint of chemical resistance of the resist pattern.
(B) Compounds having ethylenic unsaturation
(B) The compound having an ethylenically unsaturated bond is a compound having polymerizability due to having an ethylenically unsaturated group in its structure.
The photosensitive resin composition of the present embodiment preferably contains a (meth) acrylate compound having 3 or more ethylenically unsaturated bonds as the (B) compound having an ethylenically unsaturated bond, from the viewpoint of chemical resistance, adhesion, high resolution, or the shape of the folded edge of the resist pattern. In this case, the ethylenically unsaturated bond is more preferably derived from a methacryloyl group.
The (meth) acrylate compound having 3 or more ethylenically unsaturated bonds is described later as, for example, a (meth) acrylate compound having an ethylene oxide chain and a dipentaerythritol skeleton, or (b1) a compound having at least 3 methacryloyl groups.
The photosensitive resin composition of the present embodiment preferably contains a (meth) acrylate compound having 5 or more ethylenically unsaturated bonds and having an alkylene oxide chain as the (B) compound having an ethylenically unsaturated bond, from the viewpoint of chemical resistance, adhesion, high resolution, or a folded edge shape of the resist pattern. At this time, the ethylenic unsaturated bond is more preferably derived from a methacryloyl group, and the alkylene oxide chain is more preferably an ethylene oxide chain.
The (meth) acrylate compound having 5 or more ethylenically unsaturated bonds and having an alkylene oxide chain is described later as a (meth) acrylate compound having an ethylene oxide chain and a dipentaerythritol skeleton, for example.
The concentration of the methacryloyl group in the compound having an ethylenically unsaturated bond (B) is preferably 0.20mol/100g or more, more preferably 0.30mol/100g or more, further preferably 0.35mol/100g or more, and particularly preferably 0.40mol/100g or more, from the viewpoint of chemical resistance, adhesion, high resolution, or the shape of the hems of the resist pattern. The upper limit of the concentration of methacryloyl group is not particularly limited as long as polymerizability and alkali developability are ensured, and may be, for example, 0.90mol/100g or less or 0.80mol/100g or less.
From the same viewpoint, the value of the concentration of methacryloyl group/(concentration of methacryloyl group + concentration of acryloyl group) in the compound having an ethylenically unsaturated bond (B) is preferably 0.50 or more, more preferably 0.60 or more, further preferably 0.80 or more, particularly preferably 0.90 or more, and most preferably 0.95 or more.
The concentration of the ethylene oxide unit in the compound having an ethylenically unsaturated bond (B) is preferably 0.80mol/100g or more, more preferably 0.90mol/100g or more, further preferably 1.00mol/100g or more, and particularly preferably 1.10mol/100g or more, from the viewpoint of chemical resistance, adhesion, high resolution, or the shape of the hems of the resist pattern. The upper limit of the concentration of the ethylene oxide unit is not limited as long as chemical resistance, adhesion, and resolution of the resist pattern can be ensured, and may be, for example, 1.60mol/100g or less, 1.50mol/100g or less, 1.45mol/100g or less, or 1.40mol/100g or less.
In the present embodiment, the photosensitive resin composition preferably contains a (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton as the (B) compound having an ethylenically unsaturated bond, from the viewpoint of chemical resistance, adhesion, high resolution, or a folded edge shape of the resist pattern. Examples of the alkylene oxide chain include: ethylene oxide chain, propylene oxide chain, butylene oxide chain, pentylene oxide chain, hexylene oxide chain, etc. When the photosensitive resin composition contains a plurality of alkylene oxide chains, they may be the same as or different from each other. From the above viewpoint, the alkylene oxide chain is more preferably an ethylene oxide chain, a propylene oxide chain, or a butylene oxide chain, still more preferably an ethylene oxide chain or a propylene oxide chain, and particularly preferably an ethylene oxide chain.
In the photosensitive resin composition, by using (a) an alkali-soluble polymer in combination with a (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, the balance among chemical resistance, adhesiveness, and resolution of a resist pattern tends to be maintained.
The (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton is an ester of a dipentaerythritol compound obtained by modifying at least 1 of a plurality of hydroxyl groups with an alkyleneoxy group and (meth) acrylic acid. 6 hydroxyl groups in the dipentaerythritol skeleton may be modified with an alkyleneoxy group. The number of ester bonds in an ester molecule may be 1 to 6, preferably 6.
Examples of the (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton include: a hexa (meth) acrylate obtained by adding an alkylene oxide to dipentaerythritol in an amount of 4 to 30 moles, 6 to 24 moles, or 10 to 14 moles on average.
Specifically, as the (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, a compound represented by the following general formula (III) is preferable from the viewpoint of chemical resistance, adhesion, high resolution, and a folded edge shape of a resist pattern,
{ wherein R represents a hydrogen atom or a methyl group, each independently represents a hydrogen atom or a methyl group, n is an integer of 0 to 30, and the total value of all n is 1 or more }.
In the general formula (III), it is preferable that the average value of all n is 4 or more, or each n is 1 or more. As R, methyl is preferred.
The content of the (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton in the photosensitive resin composition is preferably in the range of 1 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 7 to 30% by mass, from the viewpoint of chemical resistance of the resist pattern.
In the present embodiment, in order to suppress bleeding of the constituent components of the dry film resist and improve the storage stability, 70 mass% or more, preferably 80 mass% or more, more preferably 90 mass% or more, and further preferably 100 mass% of the compound having an ethylenically unsaturated bond in (B) the total amount of solid content of the compound having an ethylenically unsaturated bond is the compound having a weight average molecular weight of 500 or more. The weight average molecular weight of the compound (B) having an ethylenically unsaturated bond is preferably 760 or more, more preferably 800 or more, even more preferably 830 or more, and particularly preferably 900 or more, from the viewpoint of suppressing bleeding and chemical resistance of the resist pattern. (B) The weight average molecular weight of the compound having an ethylenically unsaturated bond can be measured by the method described in examples.
In order to improve the flexibility of the resist pattern, to improve the adhesion, and to suppress the bleeding of the components of the dry film resist, the photosensitive resin composition preferably contains (B1) a compound having at least 3 methacryloyl groups as (B) the compound having an ethylenically unsaturated bond.
(b1) The compound having at least 3 methacryloyl groups has a weight average molecular weight of preferably 500 or more, more preferably 700 or more, and further preferably 900 or more, from the viewpoint of suppressing bleeding.
With respect to (b1) the compound having at least 3 methacryloyl groups, the number of methacryloyl groups is preferably 4 or more, 5 or more, or 6 or more. The compound having at least 3 methacryloyl groups can have an alkylene oxide chain, such as an ethylene oxide chain, a propylene oxide chain, or a combination thereof.
Examples of the compound (b1) having at least 3 methacryloyl groups include: trimethacrylates such as ethoxylated glycerol trimethacrylate, ethoxylated isocyanuric acid trimethacrylate, pentaerythritol trimethacrylate, trimethylolpropane trimethacrylate (for example, trimethacrylate obtained by adding an average of 21 moles of ethylene oxide to trimethylolpropane or trimethacrylate obtained by adding an average of 30 moles of ethylene oxide to trimethylolpropane is preferable from the viewpoints of flexibility, adhesion, and bleeding inhibition); tetramethylacrylates such as ditrimethylolpropane tetramethylacrylate, pentaerythritol tetramethylacrylate, dipentaerythritol tetramethylacrylate, and the like; pentamethyl acrylates such as dipentaerythritol pentamethyl acrylate and the like; hexamethylacrylate, such as dipentaerythritol hexamethacrylate, and the like. Of these, tetramethylacrylate, pentamethylacrylate or hexamethylacrylate is preferable.
As the tetramethylacrylate, pentaerythritol tetramethylacrylate is preferable. The pentaerythritol tetramethacrylate may be a tetramethacrylate obtained by adding 1 to 40 moles in total of alkylene oxide to 4 terminals of pentaerythritol.
The tetramethylacrylate is more preferably a tetramethylacrylate compound represented by the following general formula (I),
{ formula (II) wherein R3～R6Independently represents an alkyl group having 1 to 4 carbon atoms, X represents an alkylene group having 2 to 6 carbon atoms, and m1、m2、m3And m4Each independently is an integer of 0 to 40, m1+m2+m3+m41 to 40, and m1+m2+m3+m4When the number is 2 or more, X's may be the same as or different from each other }.
While not wishing to be bound by theory, it is believed that: the tetramethylacrylate compound represented by the general formula (I) has a group R3～R6And has H2The tetraacrylate having a C ═ CH-CO-O-moiety can suppress the hydrolyzability in an alkaline solution as compared with the tetraacrylate having a C ═ CH-CO-O-moiety. From the viewpoint of improving the resolution of the resist pattern, in particular, the line shape, in particular, the fold shape of the line, and the adhesion of the resist layer, it is preferable to use a photosensitive resin composition containing a tetramethylacrylate compound represented by the general formula (I).
In the general formula (I), the group R3～R6At least 1 of (A) is preferably methyl, and more preferably a group R3～R6All are methyl groups.
In the resist pattern, X in the general formula (I) is preferably-CH from the viewpoint of obtaining a desired resolution, a folded edge shape and a residual film ratio2-CH2-。
Regarding the resist pattern, m in the general formula (I) is m from the viewpoint of obtaining a desired resolution, a folded edge shape and a residual film ratio1、m2、m3And m4Preferably, each of the above-mentioned groups is independently an integer of 1 to 20, more preferably an integer of 2 to 10. Further, in the general formula (I), m1+m2+m3+m4Preferably 1 to 36 or 4 to 36.
Examples of the compound represented by the general formula (I) include: pentaerythritol (poly) alkoxytetramethylacrylate, and the like. In addition, in the present specification, "pentaerythritol (poly) alkoxytetramethylacrylate" includes: in the above general formula (I), m1+m2+m3+m4"pentaerythritol alkoxytetramethylacrylate" and m ═ 11+m2+m3+m42 to 40 of pentaerythritol polyalkoxytetramethacrylate. Examples of the compound represented by the general formula (I) include: examples of the compounds include pentaerythritol (poly) alkoxytetramethylacrylate and the like described in Japanese patent application laid-open publication No. 2013-156369.
The hexamethylacrylate compound is preferably a hexamethylacrylate obtained by adding 1 to 24 moles of ethylene oxide in total to 6 terminals of dipentaerythritol, or a hexamethylacrylate obtained by adding 1 to 10 moles of epsilon-caprolactone in total to 6 terminals of dipentaerythritol.
The content of the compound having at least 3 methacryloyl groups (b1) is preferably more than 0 mass% and 16 mass% or less with respect to the total solid content of the photosensitive resin composition. When the content exceeds 0 mass%, the resolution tends to be improved, and when the content is 16 mass% or less, the flexibility of the cured resist layer tends to be improved and the peeling time tends to be shortened. The content is more preferably 2 mass% or more and 15 mass% or less, and still more preferably 4 mass% or more and 12 mass% or less.
The photosensitive resin composition preferably contains (B2) a compound having a oxetane chain and 1 or 2 (meth) acryloyl groups as (B) the compound having an ethylenically unsaturated bond.
(b2) The compound having an oxetane chain and 1 or 2 (meth) acryloyl groups has a molecular weight of preferably 500 or more, more preferably 700 or more, and further preferably 1000 or more, from the viewpoint of suppressing bleeding.
Examples of the compound (b2) having a butylene oxide chain and 1 or 2 (meth) acryloyl groups include: polytetramethylene glycol (meth) acrylate, polytetramethylene glycol di (meth) acrylate, and the like.
Specifically, the compound (b2) having a butylene oxide chain and 1 or 2 (meth) acryloyl groups is a compound having preferably 1 to 20, more preferably 4 to 15, and still more preferably 6 to 12 carbon atoms4H8O (meth) acrylate or di (meth) acrylate.
The content of the compound having a oxetane chain and 1 or 2 (meth) acryloyl groups (b2) is preferably more than 0 mass% and 20 mass% or less with respect to the total solid content of the photosensitive resin composition.
The photosensitive resin composition may contain (B3) a compound having an aromatic ring and an ethylenically unsaturated bond as (B) the compound having an ethylenically unsaturated bond.
(b3) The compound having an aromatic ring and an ethylenically unsaturated bond may further have an alkylene oxide chain. The aromatic ring is preferably introduced into the compound in the form of a divalent skeleton derived from bisphenol a, a divalent skeleton derived from naphthalene, a divalent aromatic group such as phenylene group or methylphenylene group. The alkylene oxide chain can be an ethylene oxide chain, a propylene oxide chain, or a combination thereof. The ethylenically unsaturated bond is preferably introduced into the compound in the form of a (meth) acryloyl group.
Specifically, a compound represented by the following general formula (II) can be used as (b3) the compound having an aromatic ring and an ethylenically unsaturated bond,
{ formula (II), wherein R1And R2Each independently represents a hydrogen atom or a methyl group, A is C2H4B is C3H6，n1And n3Each independently is an integer of 1 to 39, and n1+n3Is an integer of 2 to 40, n2And n4Are respectively independentGround is an integer of 0 to 29, and n2+n4The repeating units of- (A-O) -and- (B-O) -may be arranged randomly or in blocks, and in the case of blocks, either of- (A-O) -and- (B-O) -may be on the biphenyl side. }.
From the viewpoint of resolution and adhesion, for example, a dimethacrylate of polyethylene glycol obtained by adding ethylene oxide of 5 moles on average to each end of bisphenol a, a dimethacrylate of polyethylene glycol obtained by adding ethylene oxide of 2 moles on average to each end of bisphenol a, and a dimethacrylate of polyethylene glycol obtained by adding ethylene oxide of 1 mole on average to each end of bisphenol a are preferable.
As the compound having an aromatic ring, an alkylene oxide chain and an ethylenically unsaturated bond, a compound having a hetero atom and/or a substituent in the aromatic ring in the general formula (II) can be used.
Examples of the hetero atom include: halogen atom, and the like, and as the substituent, there may be mentioned: alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, aryl group having 6 to 18 carbon atoms, phenacyl group, amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkylmercapto group having 1 to 10 carbon atoms, aryl group, hydroxyl group, hydroxyalkyl group having 1 to 20 carbon atoms, carboxyl group, carboxyalkyl group having 1 to 10 carbon atoms in alkyl group, acyl group having 1 to 10 carbon atoms in alkyl group, alkoxy group having 1 to 20 carbon atoms, alkoxycarbonyl group having 1 to 20 carbon atoms, alkylcarbonyl group having 2 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, N-alkylcarbamoyl group having 2 to 10 carbon atoms or group containing a heterocycle, or aryl group substituted with these substituents. These substituents may form a condensed ring, or hydrogen atoms in these substituents may be substituted with hetero atoms such as halogen atoms. When the aromatic ring in the general formula (II) has a plurality of substituents, the plurality of substituents may be the same or different.
The content of the compound having an aromatic ring and an ethylenically unsaturated bond (b3) is preferably more than 0 mass% and 50 mass% or less with respect to the total solid content of the photosensitive resin composition. When the content exceeds 0 mass%, the resolution and the adhesion tend to be improved, and from the viewpoint of development time and edge fusion (edge fusion), 50 mass% or less is preferable.
The (meth) acrylate compounds having an alkylene oxide chain and a dipentaerythritol skeleton and the compounds (b1) to (b3) described above may be used independently or in combination. The photosensitive resin composition may contain, as the compound having an ethylenically unsaturated bond (B), not only a (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton and the compounds (B1) to (B3), but also other compounds.
Examples of other compounds include: acrylate compounds having at least 1 (meth) acryloyl group, (meth) acrylates having a urethane bond, compounds obtained by reacting an α, β -unsaturated carboxylic acid with a polyhydric alcohol, compounds obtained by reacting an α, β -unsaturated carboxylic acid with a glycidyl group-containing compound, phthalic acid compounds, and the like. Among them, an acrylate compound having at least 2 (meth) acryloyl groups is preferable from the viewpoint of resolution, adhesiveness, and peeling time. The acrylate compound having at least 2 (meth) acryloyl groups may be di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, hexa (meth) acrylate, and the like. From the viewpoints of flexibility, resolution, adhesion and the like, for example, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and di (meth) acrylate having both ethylene oxide and polypropylene oxide are preferable (for example, "FA-023M, FA-024M, FA-027M, product name, manufactured by hitachi chemical industries co.).
Further, from the viewpoint of peelability and cured film flexibility, it is preferable to contain a compound having 1 ethylenically unsaturated bond such as 4-n-nonylphenoxy octaethylene glycol acrylate, 4-n-nonylphenoxy tetraethylene glycol acrylate, and γ -chloro- β -hydroxypropyl- β '-methacryloyloxyethyl-phthalate, and from the viewpoint of sensitivity, resolution, or adhesiveness, it is preferable to contain γ -chloro- β -hydroxypropyl- β' -methacryloyloxyethyl-phthalate.
In the present embodiment, the total content of all the compounds having an ethylenically unsaturated bond (B) in the photosensitive resin composition is preferably in the range of 1 to 70% by mass, more preferably 2 to 60% by mass, and even more preferably 4 to 50% by mass, from the viewpoints of improving the adhesiveness of the resist pattern, and suppressing curing failure of the resist pattern, delay in development time, cold flow, bleeding, or peeling delay of the cured resist.
(C) Photopolymerization initiator
(C) The photopolymerization initiator is a compound that polymerizes monomers using light. The photosensitive resin composition contains a compound generally known in the art as (C) a photopolymerization initiator.
The total content of the photopolymerization initiator (C) in the photosensitive resin composition is preferably in the range of 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, still more preferably 0.1 to 7% by mass, and particularly preferably 0.1 to 6% by mass. (C) The total content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and is preferably 20% by mass or less from the viewpoint of sufficiently transmitting light to the bottom surface of the resist layer to obtain good high resolution.
Examples of the photopolymerization initiator (C) include: quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkyl aminobenzoate esters, oxime esters, acridines (for example, 9-phenylacridine, bisazinylheptane, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine are preferable from the viewpoints of sensitivity, resolution, and adhesion), and further, there are included: hexaarylbiimidazole, pyrazoline compound, anthracene compound (preferably 9, 10-dibutoxyanthracene, 9, 10-diethoxyanthracene, 9, 10-diphenylanthracene, for example) from the viewpoint of sensitivity, resolution and adhesion, coumarin compound (preferably 7-diethylamino-4-methylcoumarin, for example) from the viewpoint of sensitivity, resolution and adhesion, N-arylamino acid or an ester compound thereof (preferably N-phenylglycine, for example, from the viewpoint of sensitivity, resolution and adhesion), halogen compound (tribromomethylphenylsulfone, for example), and the like. These can be used alone in 1 or a combination of 2 or more. Other, it is possible to use: 2, 2-dimethoxy-1, 2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, triphenylphosphine oxide, and the like.
Examples of the aromatic ketone include: benzophenone, Michler's ketone [4, 4' -bis (dimethylamino) benzophenone ], 4 '-bis (diethylamino) benzophenone, 4-methoxy-4' -dimethylamino benzophenone. These can be used alone in 1 or a combination of 2 or more. Among these, 4' -bis (diethylamino) benzophenone is preferable from the viewpoint of adhesion. Further, from the viewpoint of transmittance, the content of the aromatic ketone in the photosensitive resin composition is preferably in the range of 0.01 to 0.5 mass%, more preferably 0.02 to 0.3 mass%.
Examples of hexaarylbiimidazoles include: 2- (o-chlorophenyl) -4, 5-diphenylbiimidazole, 2 ', 5-tris- (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4', 5 '-diphenylbiimidazole, 2, 4-bis- (o-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -diphenylbiimidazole, 2,4, 5-tris- (o-chlorophenyl) -diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4, 5- (3, 4-dimethoxyphenyl) -biimidazole, 2' -bis- (2-fluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -biimidazole, 2,2 ' -bis- (2, 3-difluoromethylphenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2, 4-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2, 5-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2, 6-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2,3, 4-trifluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 '-bis- (2,3, 5-trifluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -biimidazole, 2' -bis- (2,3, 6-trifluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 '-bis- (2,4, 5-trifluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -biimidazole, 2' -bis- (2,4, 6-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2,3,4, 5-tetrafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2,3,4, 6-tetrafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, and 2,2 ' -bis- (2,3,4,5, 6-pentafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, and the like, and 1 kind or more thereof may be used alone or 2 or more kinds may be used in combination. From the viewpoint of high sensitivity, resolution and adhesion, 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer is preferable.
In the present embodiment, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably in the range of 0.05 to 7 mass%, more preferably 0.1 to 6 mass%, and still more preferably 1 to 4 mass%, from the viewpoint of improving the peeling property and/or sensitivity of the photosensitive resin layer.
The photosensitive resin composition preferably contains a pyrazoline compound as a photosensitizer from the viewpoint of the peeling property, sensitivity, resolution, or adhesion of the photosensitive resin layer.
From the above-mentioned viewpoint, the pyrazoline compound is preferably, for example, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline, 1-phenyl-3- (3, 5-dimethoxystyryl) -5- (3, 5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (3, 4-dimethoxystyryl) -5- (3, 4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 6-dimethoxystyryl) -5- (2, 6-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 5-dimethoxystyryl) -5- (2, 5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 3-dimethoxystyryl) -5- (2, 3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 4-dimethoxystyryl) -5- (2, 4-dimethoxyphenyl) -pyrazoline, etc., more preferably 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline.
The photosensitive resin composition may contain 1 or 2 or more pyrazoline compounds as a photosensitizer.
In the present embodiment, the content of the photosensitizer in the photosensitive resin composition is preferably in the range of 0.05 to 5 mass%, more preferably 0.1 to 3 mass%, from the viewpoint of improving the peeling property and/or sensitivity of the photosensitive resin layer.
(D) Additive agent
The photosensitive resin composition may contain additives such as a dye, a plasticizer, an antioxidant, and a stabilizer, as required. For example, additives listed in Japanese patent laid-open publication No. 2013-156369 can be used.
From the viewpoints of coloring property, color stability and exposure contrast, the photosensitive resin composition preferably contains tris (4-dimethylaminophenyl) methane [ leuco crystal violet ] and/or DIAMOND GREEN (AIZEN (registered trademark) DIAMOND GREEN GH manufactured by HODOGAYA CHEMICAL co., ltd.) as a dye.
In the present embodiment, the content of the dye in the photosensitive resin composition is preferably in the range of 0.001 to 3% by mass, more preferably 0.01 to 2% by mass, and still more preferably 0.02 to 1% by mass. The content of the dye is preferably 0.001% by mass or more from the viewpoint of obtaining good colorability, and is preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.
From the viewpoint of thermal stability or storage stability of the photosensitive resin composition, the photosensitive resin composition preferably contains a monomer selected from the group consisting of radical polymerization inhibitors such as nitrosophenylhydroxylamine aluminum salt, p-methoxyphenol, 4-tert-butylcatechol, 4-ethyl-6-tert-butylphenol, and the like; benzotriazoles such as 1:1 mixtures of 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole; carboxybenzotriazoles such as 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, 6-carboxy-1, 2, 3-benzotriazole and the like; and at least 1 of alkylene oxide compounds having a glycidyl group, such as neopentyl glycol diglycidyl ether, and the like, as a stabilizer. In addition, the ink may further include: 2-mercaptobenzimidazole, 1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 2-amino-5-mercapto-1, 3, 4-thiadiazole, 3-amino-5-mercapto-1, 2, 4-triazole, 3-mercaptotriazole, 4, 5-diphenyl-1, 3-oxadiazol-2-yl, 5-amino-1H-tetrazole, etc.
In the present embodiment, the total content of all the stabilizers in the photosensitive resin composition is preferably in the range of 0.001 to 3 mass%, more preferably 0.01 to 1 mass%, and still more preferably 0.05 to 0.7 mass%. The total content of the stabilizer is preferably 0.001 mass% or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3 mass% or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.
The above-mentioned additives may be used singly in 1 kind or in combination in 2 or more kinds.
< preparation of photosensitive resin composition >
In the present embodiment, a photosensitive resin composition preparation liquid can be formed by adding a solvent to a photosensitive resin composition. Suitable solvents include: ketones such as Methyl Ethyl Ketone (MEK), etc.; and alcohols such as methanol, ethanol, isopropanol, and the like. The solvent is preferably added to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid becomes 500 to 4000mPa · s at 25 ℃.
< photosensitive resin laminate >
In the present embodiment, a photosensitive resin laminate having a support and a photosensitive resin layer formed of the photosensitive resin composition laminated on the support can be provided. The photosensitive resin laminate may have a protective layer on the side of the photosensitive resin layer opposite to the support body side as needed.
The support is not particularly limited, and is preferably a transparent support that transmits light emitted from the exposure light source. Examples of such a support include: polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films may be stretched as necessary. The haze is preferably 0.01% to 5.0%, more preferably 0.01% to 2.5%, and further preferably 0.01% to 1.0%. The thinner the film thickness is, the more advantageous the image formability and the economical efficiency is, and the strength needs to be maintained, and it is preferably 10 to 30 μm.
In addition, an important characteristic of the protective layer used in the photosensitive resin laminate is that the adhesion force between the protective layer and the photosensitive resin layer is smaller than the adhesion force between the support and the photosensitive resin layer, and the protective layer can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film, or the like is preferable. For example, a film excellent in releasability as disclosed in Japanese patent application laid-open No. 59-202457 can be used. The thickness of the protective layer is preferably 10 to 100 μm, more preferably 10 to 50 μm.
In the present embodiment, the thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 5 μm to 100 μm, and more preferably 7 μm to 60 μm. The smaller the thickness of the photosensitive resin layer, the higher the resolution of the resist pattern, while the larger the thickness, the higher the strength of the cured film, and therefore, the thickness can be selected according to the application.
As a method for producing a photosensitive resin laminate by sequentially laminating a support, a photosensitive resin layer, and a desired protective layer, a known method can be used.
For example, the photosensitive resin composition preparation liquid is prepared, and then applied to a support using a bar coater or a roll coater and dried, thereby laminating a photosensitive resin layer formed from the photosensitive resin composition preparation liquid on the support. Further, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer as required.
< method for Forming resist Pattern >
The method for forming a resist pattern preferably includes the following steps in this order: a laminating step of laminating a photosensitive resin layer formed of the photosensitive resin composition on a support, an exposure step of exposing the photosensitive resin layer, and a developing step of developing the exposed photosensitive resin layer. An example of a specific method for forming a resist pattern in this embodiment will be described below.
First, in the laminating step, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heated and pressed against the surface of the substrate by a laminator to be laminated. Examples of the material of the substrate include: copper, stainless steel (SUS), glass, Indium Tin Oxide (ITO), and the like.
In the present embodiment, the photosensitive resin layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces as necessary. The heating temperature for lamination is usually 40 to 160 ℃. Further, by performing the heat pressure bonding in the case of laminating 2 times or more, the adhesion of the obtained resist pattern to the substrate can be improved. In the case of thermal pressure bonding, a two-stage laminator having two rollers may be used, or the pressure bonding may be performed by repeatedly passing the laminate of the substrate and the photosensitive resin layer through the rollers a plurality of times.
Next, in the exposure step, the photosensitive resin composition layer is exposed to active light using an exposure machine. The exposure may be performed after peeling off the support as needed. When exposure is performed through a photomask, the exposure amount can be determined according to the illuminance of the light source and the exposure time, and can be measured using a light meter. In the exposure process, direct image exposure may be performed. In the direct imaging exposure, exposure is performed on a substrate by a direct writing apparatus without using a photomask. As the light source, a semiconductor laser or an ultra-high pressure mercury lamp having a wavelength of 350nm to 410nm can be used. When the pattern is drawn by computer control, the exposure amount is determined according to the illumination of the exposure light source and the moving speed of the substrate. Exposure may also be performed by projecting an image of the photomask through a lens.
Next, in the developing step, the unexposed portion or the exposed portion of the exposed photosensitive resin layer is removed with a developing solution using a developing device. After exposure, when the support is present on the photosensitive resin layer, the support is removed. Next, the unexposed portion or the exposed portion is developed and removed using a developer solution containing an alkali aqueous solution, thereby obtaining a resist image.
As the aqueous alkali solution, Na is preferred2CO3、K2CO3And the like. The aqueous alkali solution may be selected depending on the characteristics of the photosensitive resin layer, and Na having a concentration of 0.2 to 2 mass% is usually used2CO3An aqueous solution. In the aqueous alkali solution, a surfactant, a defoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed. The temperature of the developing solution in the developing step is preferably kept constant within a range of 20 to 40 ℃.
The resist pattern can be obtained by the above steps, and the heating step may be performed at 100 to 300 ℃ as required. By performing this heating step, the chemical resistance of the resist pattern can be improved. In the heating step, a heating furnace using a hot air, infrared ray, or far infrared ray system may be used.
The photosensitive resin composition of the present embodiment can be used for forming a circuit of a printed board. Generally, as a circuit forming method of a printed substrate, a subtractive process and a semi-additive process (SAP) may be used.
The subtractive process is a method of forming a circuit by removing only a non-circuit portion from a conductor disposed on the entire surface of a substrate by etching.
The SAP is a method of forming a resist layer on a non-circuit portion disposed on a conductor seed layer over the entire surface of a substrate and then forming only a circuit portion by plating.
In the present embodiment, the photosensitive resin composition is more preferably used for the SAP.
< cured product of photosensitive resin composition >
In the present embodiment, the elongation of the cured product of the photosensitive resin composition is preferably 1mm or more, more preferably 2mm or more, and further preferably 3mm or more, in order to improve the flexibility of the resist pattern.
The elongation of the cured product was measured by the following method: a photosensitive resin laminate produced using the photosensitive resin composition was exposed to light through a rectangular mask of 5mm × 40mm, developed in a time 2 times the minimum development time, and the obtained cured resist layer was stretched at a speed of 100 mm/min using a tensile tester (ORIENTEC co., ltd., RTM-500).
In the present embodiment, the young's modulus of the cured product of the photosensitive resin composition is preferably in the range of 1.5Gpa or more and less than 8Gpa from the viewpoint of the resolution and flexibility of the resist pattern. In the present specification, the "young modulus" can be measured by nanoindentation using TOYO techinica co. Specifically, the "young's modulus" was measured using a TOYO techinica co., ltd. nanoindenter DCM for measuring the surface of the photosensitive resin composition on the substrate obtained by laminating the resin composition to be measured on the substrate, exposing the substrate, and developing the substrate. As a measurement Method, DCM Basic Hardness, Modulus, Tip Cal, Load control. msm (multiple Load-unload Method) was used, and the parameters of the indentation test were: the percentage Of unloading (Percent To Unload) is 90%, the Maximum Load (Maximum Load) is 1gf, the Load Rate Times the unloading Rate (Load Rate Multiple For Unload Rate) is 1, the Number Of Times Of loading (Number Of Times To Load) is 5, the Peak Hold Time (Peak Hold Time) is 10s, the Load Time (Time To Load) is 15s, and the Poisson's ratio (Poisson's ratio) is 0.25. The Young's modulus is a value of "modulus of elasticity under maximum Load (modules At Max Load)".
< method for producing conductor Pattern >
The method for manufacturing the conductor pattern preferably includes the following steps in this order: a laminating step of laminating a photosensitive resin layer formed of the photosensitive resin composition on a substrate such as a metal plate or a metal-coated insulating plate; an exposure step of exposing the photosensitive resin layer; a developing step of removing an unexposed portion or an exposed portion of the exposed photosensitive resin layer with a developing solution to obtain a substrate on which a resist pattern is formed; and a conductor pattern forming step of etching or plating the substrate on which the resist pattern is formed.
In the present embodiment, the method for manufacturing the conductor pattern is performed as follows: the method is carried out by using a metal plate or a metal-coated insulating plate as a substrate, forming a resist pattern by the above-described resist pattern forming method, and then performing a conductor pattern forming step. In the conductive pattern forming step, a conductive pattern is formed on the surface (for example, copper surface) of the substrate exposed by the development by a known etching method or plating method.
The present invention is suitably applied to the following applications, for example.
< method for producing Circuit Board >
After the conductor pattern is produced by the conductor pattern production method, a peeling step of peeling the resist pattern from the substrate with an aqueous solution having a stronger basicity than that of the developer is further performed, whereby a circuit board (for example, a printed circuit board) having a desired wiring pattern can be obtained.
In the production of a circuit board, a laminate of an insulating resin layer and a copper layer or a flexible substrate is used as a substrate. For SAP, a laminate of an insulating resin layer and a copper layer is preferably used. As for the SAP, the copper layer is preferably an electroless copper plating layer containing palladium as a catalyst. As for the SAP, it is also preferable to perform the conductor pattern forming process by a known plating method. In order to perform the modified semi-additive process (MSAP), the substrate is preferably a laminate of an insulating resin layer and a copper foil, and more preferably a copper-clad laminate.
The alkaline aqueous solution for stripping (hereinafter also referred to as "stripping solution") is not particularly limited, and an aqueous solution of NaOH or KOH having a concentration of 2 to 5 mass%, or an organic amine-based stripping solution is usually used. A small amount of a water-soluble solvent may be added to the stripping solution. Examples of the water-soluble solvent include alcohols. The temperature of the stripping solution in the stripping step is preferably in the range of 40 to 70 ℃.
In order to perform the SAP, the manufacturing method of the circuit board preferably further includes a process of removing palladium from the obtained circuit board.
< production of lead frame >
A metal plate of copper, a copper alloy, an iron alloy, or the like is used as a substrate, and after a resist pattern is formed by a resist pattern forming method, a lead frame is produced through the following steps. First, a step of etching the substrate exposed by the development is performed to form a conductor pattern. Then, a peeling step of peeling the resist pattern is performed by the same method as the method of manufacturing the circuit board, and a desired lead frame can be obtained.
< production of base Material having concave-convex Pattern >
The resist pattern formed by the resist pattern forming method can be used as a protective mask member when a substrate is processed by a sandblast method. In this case, examples of the substrate include: glass, silicon wafers, amorphous silicon, polycrystalline silicon, ceramics, sapphire, metallic materials, and the like. A resist pattern is formed on these substrates by the same method as the resist pattern forming method. Then, a base material having a fine uneven pattern on a substrate can be produced through a blast treatment step of blasting a blast material from above the formed resist pattern to cut the substrate to a target depth, and a peeling step of removing a resist pattern portion remaining on the substrate from the substrate with an alkali peeling liquid or the like.
In the blasting step, a known blasting material may be used, and for example, a material containing SiC or SiO may be used in general2、Al2O3、CaCO3Fine particles of 2 to 100 μm in particle diameter such as ZrO, glass and stainless steel.
< manufacture of semiconductor Package >
A semiconductor package can be manufactured by using a wafer on which a large scale integrated circuit (LSI) has been formed as a substrate, forming a resist pattern on the wafer by a resist pattern forming method, and then performing the following steps. First, a step of performing columnar plating of copper, solder, or the like on the opening exposed by development to form a conductor pattern is performed. Then, a peeling step of peeling off the resist pattern by the same method as the method for manufacturing the circuit board is performed, and a step of removing the thin metal layer in the portion other than the columnar plating by etching is further performed, whereby a desired semiconductor package can be obtained.
In the present embodiment, the photosensitive resin composition can be used for the production of a printed wiring board; manufacturing a lead frame for mounting an IC chip; metal foil precision processing such as metal mask manufacturing; manufacturing packages such as Ball Grid Arrays (BGAs) and Chip Scale Packages (CSPs); manufacturing a tape substrate such as a Chip On Film (COF) and Tape Automated Bonding (TAB); manufacturing a semiconductor bump; and the manufacture of partition walls for flat panel displays such as ITO electrodes, address electrodes, and electromagnetic wave shields.
The values of the parameters are measured by the measurement method in the examples described below, unless otherwise specified.
Examples
The measurement of the physical property values of the polymer, the calculation of the glass transition temperature of the polymer, and the production methods of the samples for evaluation in examples and comparative examples will be described, and the evaluation method and the evaluation results of the obtained samples will be shown.
(1) Measurement or calculation of physical property values
< measurement of the weight average molecular weight or number average molecular weight of Polymer >
The weight average molecular weight or number average molecular weight of the polymer was determined in terms of polystyrene using a polystyrene standard sample (Shorex STANDARD SM-105, Shorex, Japan) (pump: Gulliver, model PU-1580, column: Shorex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5)4 columns connected in series, and a mobile phase solvent: tetrahydrofuran, using a calibration curve based on polystyrene standards).
Further, the degree of dispersion of the polymer was calculated as the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).
< acid equivalent >
In the present specification, the acid equivalent means the mass (g) of the polymer having 1 equivalent of carboxyl group in the molecule. The acid equivalent was measured by a potentiometric titration method using a 0.1mol/L aqueous sodium hydroxide solution using a Hei Marsh automatic titrator (COM-555) manufactured by Hei Marsh industries, Ltd.
< glass transition temperature >
The glass transition temperature of an alkali-soluble polymer is a value determined by the following formula (Fox formula),
[ mathematical formula 1]
{ in formula (II), WiThe respective masses, Tg, of the comonomers constituting the alkali-soluble polymeriThe glass transition temperature, W, when the comonomers constituting the alkali-soluble polymer are each homopolymerstotalIs the total mass of the alkali-soluble polymer,
and n is the number of kinds of comonomers constituting the alkali-soluble polymer. }.
Wherein the glass transition temperature Tg is determinediIn the case of the Polymer, Brandrup, J.Immergut, E.H. eds. "Polymer handbook, Third edition, John wire, was used as the glass transition temperature of the homopolymer formed from the corresponding comonomer forming the alkali-soluble Polymer&sons, 1989, chapter VI, page 209 of polymers (Glass transition temperatures of polymers) ". In the examples, the Tg of the homopolymer formed from the comonomers used was calculatediShown in table 1.
< weight average molecular weight of (B) Compound having ethylenically unsaturated bond >
In examples I-1 to I-16 and comparative examples I-1 to I-3, the molecular weights were determined by calculation based on the molecular structures of the compounds (B) having an ethylenically unsaturated bond. When there are a plurality of (B) compounds having an ethylenically unsaturated bond, the molecular weight of each compound is determined by a weight average of the contents.
In examples II-1 to II-6 and comparative examples II-1 to II-5, the weight average molecular weight of the compound having an ethylenically unsaturated bond was determined in terms of POLYSTYRENE using 4 columns of Shodex (registered trademark) (K-801, K-802, KF-802.5, available from Showa Denko K.K.) in series, a mobile phase solvent of tetrahydrofuran, and a calibration curve based on a POLYSTYRENE standard sample (TSK standard POLYSTYRENE, available from Tosoh Corporation) by Gel Permeation Chromatography (GPC) (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) (K-801, K-802, KF-802.5, available from Japan K.K.).
< concentration of methacryloyl group in Compound having ethylenically unsaturated bond >
The number of moles of a methacryloyl group relative to 100g of the compound having an ethylenically unsaturated bond (B) was determined by calculation.
< concentration of Ethylene Oxide (EO) Unit in (B) Compound having ethylenically unsaturated bond >
The number of moles of Ethylene Oxide (EO) units relative to 100g of the compound (B) having an ethylenically unsaturated bond was determined by calculation.
(2) Method for producing sample for evaluation
The samples for evaluation were prepared as follows.
< production of photosensitive resin laminate >
The components shown in tables 2 to 5 below (wherein the numerals of the respective components indicate the amount of solid components (parts by mass)) and a solvent were sufficiently stirred and mixed to obtain a photosensitive resin composition preparation liquid. The names of the components shown in tables 2 and 4 in short are shown in tables 3 and 5 below, respectively. The prepared liquid was uniformly applied to the surface of a 16 μm-thick polyethylene terephthalate film (FB-40, made by Toray Industries, Inc.) using a bar coater as a support film, and dried in a dryer at 95 ℃ for 2.5 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 25 μm.
Next, a 19 μm thick polyethylene film (tamapol co., ltd., GF-818) was laminated as a protective layer on the surface of the photosensitive resin composition layer on the side where the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate.
< entire surface of substrate >
In examples I-1 to I-16 and comparative examples I-1 to I-3, sensitivity, image quality, adhesion, and chemical resistance were evaluatedA copper-clad laminate of 0.4mm thickness, in which a 35 μm rolled copper foil was laminated, was treated with a soft etchant (CPE-900, manufactured by Mitsubishi chemical Co., Ltd.), and 10 mass% H was used2SO4And cleaning the surface of the substrate.
In examples II-1 to II-6 and comparative examples II-1 to II-5, a 0.4mm thick copper-clad laminate laminated with 35 μm rolled copper foil was jet-washed and polished at a jet pressure of 0.2MPa using a grinding material (Japan Carlit Co., Ltd., manufactured by Ltd., Sakurundum R (registered trade name #220)) to prepare substrates for evaluation.
< lamination >
The photosensitive resin laminate was laminated on a copper-clad laminate having a surface adjusted and preheated to 60 ℃ by a hot roll laminator (AL-700, manufactured by asahi chemicals) at a roll temperature of 105 ℃ while peeling the polyethylene film of the photosensitive resin laminate, to obtain a test piece. The air pressure was set to 0.35MPa, and the lamination speed was set to 1.5 m/min.
< Exposure >
In examples I-1 to I-16 and comparative examples I-1 to I-3, the mask pattern for Direct Imaging (DI) exposure was formed at an illuminance of 85mW/cm by using a direct writing exposure machine (DE-1 DH, manufactured by Hitachi Via Mechanics, Ltd., light source: GaN blue-violet diode, dominant wavelength of 405. + -.5 nm) and using a Schonfigur 41-stage exposure scale or a predetermined mask pattern for Direct Imaging (DI) exposure2Exposure is performed under the conditions of (1). The exposure is performed with an exposure amount such that the maximum number of residual film steps in the development becomes 15 steps by performing the exposure using the schrader 41 step exposure scale as a mask.
In examples II-1 to II-6 and comparative examples II-1 to II-5, exposure was performed with an exposure amount shown in Table 4 using a chromium glass mask and a parallel light exposure machine (ORC MANUFACTURING CO., LTD., HM-801).
< development >
In examples I-1 to I-16 and comparative examples I-1 to I-3, the polyethylene terephthalate film of the exposed evaluation substrate was peeled off, and then 1% by mass Na was added thereto at 30 ℃ using an alkaline developing machine (a developing machine for dry film, manufactured by Fuji machine Co., Ltd.)2CO3The aqueous solution is carried out for a prescribed timeAnd spraying to dissolve and remove the unexposed part of the photosensitive resin layer. At this time, development was performed over a time 2 times the minimum development time, thereby producing a cured resist pattern. The minimum development time is the minimum time required for the photosensitive resin layer at the unexposed portion to be completely dissolved.
In examples II-1 to II-6 and comparative examples II-1 to II-5, the polyethylene terephthalate film was peeled from the photosensitive resin laminate, and then sprayed with 1% by mass of Na having a developing pressure of 0.15MPa for a predetermined time at 30 ℃ by a full cone nozzle using a developing device manufactured by Fuji machine K.K., using a full cone nozzle2CO3The unexposed portion of the photosensitive resin layer is dissolved and removed by developing with an aqueous solution. At this time, the minimum time required for the photosensitive resin layer of the unexposed portion to be completely dissolved was measured as the minimum development time, and development was performed in a time 2 times the minimum development time to produce a resist pattern. In this case, the washing step is carried out at a washing pressure of 0.15MPa using a flat nozzle in the same time as the developing step.
(3) Method for evaluating sample
< evaluation of sensitivity >
The substrate for sensitivity evaluation after 15 minutes from the lamination was exposed through a mask of a schmuth 41-stage exposure scale. The development was performed in a time 2 times the minimum development time, and the exposure amount of the highest residual film number of 15 steps was classified by the following criteria.
O (good): the exposure with the highest residual film grade of 15 grades is lower than 70mJ/cm2。
X (bad): the exposure amount of the highest residual film grade of 15 grades is 70mJ/cm2The above.
< resolution >
The substrate for resolution evaluation after 15 minutes from the lamination was exposed using drawing data of a line pattern having a ratio of the widths of the exposed portion and the unexposed portion of 1: 1. Development was performed with a development time 2 times the minimum development time to form a cured resist line.
In examples I-1 to I-16 and comparative examples I-1 to I-3, the minimum line width of the line in which the cured resist was normally formed was classified into a value having a resolution according to the following criteria.
O (good): the resolution value is 12 μm or less.
Δ (allowed): the resolution value is more than 12 μm and 17 μm or less.
X (bad): the resolution value exceeds 17 μm.
In examples II-1 to II-6 and comparative examples II-1 to II-5, the minimum line width of the line in which the cured resist was normally formed was classified into a value having a resolution according to the following criteria.
Very good: the resolution value is 7.5 μm or less.
O (good): the resolution value is more than 7.5 μm and 9 μm or less.
Δ (allowed): the resolution value exceeds 9 μm.
< FT-IR measurement >
The polyethylene film of the photosensitive resin laminate was peeled off, and then subjected to FT-IR (NiCOLET 380, manufactured by Thermo SCIENTIFIC) measurement.
Wave number of 810cm-1The peak height P of (b) was determined by measuring the absorbance by FT-IR before exposure. When the peak overlaps with other peaks, the rising points on both sides of the peak are connected to each other by a line, and the highest height from the line is measured.
The reaction rate Q of the olefinic double bond is determined by the following method. The polyethylene terephthalate film (support layer) side of the self-photosensitive resin laminate was exposed to light using a direct drawing exposure machine (DE-1 DH, manufactured by Hitachi Via Mechanics, Ltd., light source: GaN blue-violet diode (dominant wavelength 405. + -. 5 nm)). The illuminance at the time of exposure was set to 85mW/cm2. The exposure amount at this time is an exposure amount at which the maximum residual film number becomes 15 when the exposure is performed by using the schrader 41 stage exposure scale as a mask and then the development is performed by the above-described method. The reactivity Q of the ethylenic double bond of the cured resist layer obtained by the above procedure was 810cm in terms of wave number-1The disappearance rate (%) of the ethylenic double bond group was calculated from the peak heights before and after the exposure to light, and the reaction rate Q (%) was determined.
R is the film thickness (μm) of the photosensitive resin layer, and P × Q/R was obtained by calculation.
< adhesion >
In examples I-1 to I-16 and comparative examples I-1 to I-3, the substrate for resolution evaluation after 15 minutes from the lamination was exposed using drawing data of a line pattern having a ratio of the widths of an exposed portion and an unexposed portion of 1: 400. The development was performed with a development time 2 times the minimum development time, and the minimum line width of a line in which a cured resist was normally formed was classified into a value of adhesion according to the following criteria.
O (excellent): the value of the adhesion is 12 μm or less.
Δ (good): the value of the adhesion is more than 12 μm and 13 μm or less.
Δ (allowed): the value of the adhesion is more than 13 μm and not more than 15 μm.
X (bad): the value of the adhesion was more than 15 μm.
In examples II-1 to II-6 and comparative examples II-1 to II-5, the evaluation substrate after 15 minutes from the lamination was exposed through a chromium glass mask having a line pattern in which the width of the exposed portion and the unexposed portion was 1: 100. The development was performed in a time 2 times the minimum development time, and the minimum line width of the line in which the cured resist was normally formed was defined as a value of adhesion, and was classified as follows.
Very good: the value of the adhesion is 7.5 μm or less.
O (good): the value of the adhesion is more than 7.5 μm and 9 μm or less.
Δ (allowed): the value of the adhesion is more than 9 μm and less than 10 μm.
X (bad): the value of the adhesion is 10 μm or more.
< evaluation of chemical resistance >
A chemical reagent was prepared by mixing CupraPro S2100 mL manufactured by Atotech Japan K.K., 60mL of 98% sulfuric acid, and 840mL of pure water. The substrate for resolution evaluation after 15 minutes from lamination was exposed using drawing data of a line pattern having a ratio of the width of the exposed portion to the width of the unexposed portion of 1: 400. Development was performed with a development time 2 times the minimum development time, and immersed in a chemical heated to 40 ℃ for 5 minutes in a beaker. After the immersion, washing was performed with pure water to obtain the minimum line width of the line where the cured resist layer was normally formed as a value of chemical resistance. In table 2, only the case where the chemical resistance exceeded 17 μm was represented as "x (poor)".
< bleeding Property >
The photosensitive resin laminate wound in a roll was stored at 23 ℃ under a light-shielding condition, and the time until stickiness occurred on the surface of the support film (the outermost layer of the roll was excluded) due to bleeding was classified as follows, and the bleeding property was evaluated.
O (good): the time until stickiness is generated on the surface of the support film is more than 1 month
X (bad): the time until stickiness is generated on the surface of the support film is less than 1 month
(4) Evaluation results
The evaluation results are shown in tables 2 to 5 below. The photosensitive resin composition designed so that the chemical resistance is evaluated to be 17 μm or less is also excellent in adhesion of a resist pattern, resolution, and balance of a folded edge shape. Further, by using such a photosensitive resin composition, short-circuiting can be suppressed when a wiring pattern is formed by plating. As a result of copper plating after the evaluation of chemical resistance, it was presumed that short circuits were observed in the cured resist layer at a line width of 15 μm in the composition of comparative example I-1, but short circuits were not observed in the composition of example I-1, and that failures were reduced.
[ Table 1]
TABLE 1
[ Table 2]
[ Table 3]
[ Table 4]
[ Table 5]
Claims (21)
1. A photosensitive resin composition comprising:
(A) an alkali-soluble polymer;
(B) a compound having an ethylenically unsaturated bond; and the combination of (a) and (b),
(C) a photopolymerization initiator,
the composition contains a (meth) acrylate compound having 5 or more ethylenically unsaturated bonds and having an alkylene oxide chain as the (B) compound having an ethylenically unsaturated bond,
the weight average Tg of the glass transition temperature Tg of the alkali-soluble polymer (A)totalIs at least 30 ℃ and not more than 110 ℃,
a resist pattern obtained by forming a photosensitive resin layer made of the photosensitive resin composition on a substrate surface, exposing and developing the photosensitive resin layer with a chemical agent for evaluation of chemical resistance is immersed in the chemical agent at 40 ℃ for 5 minutes, and then the minimum line width of the cured resist line is 17 [ mu ] m or less,
the chemical reagent is prepared by mixing CupraPro S2100 mL, 98% sulfuric acid 60mL and pure water 840 mL.
2. The photosensitive resin composition according to claim 1, wherein when the photosensitive resin layer is formed on the surface of the substrate and exposed to an exposure amount at which the maximum residual film number in the case of exposure using a Schonfler 41 stage exposure scale as a mask and subsequent development becomes 15 stages,
in the FT-IR measurement, the wave number before exposure was 810cm-1Wherein the peak height is P, the reaction rate of the ethylenic double bond in the compound (B) having an ethylenic unsaturated bond after the exposure is Q, and the value of P x Q/R is 0.21 or more when the film thickness of the photosensitive resin layer is R.
3. The photosensitive resin composition according to claim 1 or 2, wherein the weight average molecular weight of the compound (B) having an ethylenically unsaturated bond is 760 or more.
4. The photosensitive resin composition according to claim 1 or 2, wherein the concentration of the methacryloyl group in the compound having an ethylenically unsaturated bond (B) is 0.20mol/100g or more.
5. The photosensitive resin composition according to claim 1 or 2, wherein the concentration of the ethylene oxide unit in the compound (B) having an ethylenically unsaturated bond is 0.80mol/100g or more.
6. The photosensitive resin composition according to claim 1 or 2, comprising a hexaarylbisimidazole compound as the (C) photopolymerization initiator.
7. The photosensitive resin composition according to claim 1, wherein the alkali-soluble polymer (A) has an acid equivalent of 100 to 600 and a weight average molecular weight of 5000 to 500000, and has an aromatic group in a side chain thereof.
8. The photosensitive resin composition according to claim 1, which contains a (meth) acrylate compound having 5 or more ethylenically unsaturated bonds and having an ethylene oxide chain as the (B) compound having an ethylenically unsaturated bond.
9. The photosensitive resin composition according to claim 1, which contains a (meth) acrylate compound having an ethylene oxide chain and a dipentaerythritol skeleton as the (B) compound having an ethylenically unsaturated bond.
10. The photosensitive resin composition according to claim 1, further comprising a compound represented by the following general formula (II) as the compound having an ethylenically unsaturated bond (B),
in the formula (II), R1And R2Each independently represents a hydrogen atom or a methyl group, A is C2H4B is C3H6，n1And n3Each independently is an integer of 1 to 39, and n1+n3Is an integer of 2 to 40, n2And n4Each independently is an integer of 0 to 29, and n2+n4The repeating units of- (A-O) -and- (B-O) -may be arranged randomly or in blocks, and in the case of blocks, either of- (A-O) -and- (B-O) -may be on the biphenyl side.
11. The photosensitive resin composition according to claim 1, further comprising a compound represented by the following general formula (I) as the compound having an ethylenically unsaturated bond (B),
in the formula (I), R3～R6Independently represents an alkyl group having 1 to 4 carbon atoms, X represents an alkylene group having 2 to 6 carbon atoms, and m1、m2、m3And m4Each independently is an integer of 0 to 40, m1+m2+m3+m41 to 40, and when m is1+m2+m3+m4Is 2 or moreIn the above, plural xs may be the same as or different from each other.
12. The photosensitive resin composition according to claim 1, which contains a hexaarylbisimidazole compound as the (C) photopolymerization initiator.
13. The photosensitive resin composition according to claim 1, which contains a pyrazoline compound as the (C) photopolymerization initiator.
14. The photosensitive resin composition of claim 1, which is used for direct image-wise exposure.
15. The photosensitive resin composition according to claim 1, wherein the weight average Tg of the glass transition temperature Tg of the alkali-soluble polymer (A) istotalThe temperature of the mixture is below 105 ℃,
the photosensitive resin composition contains (B1) a compound having at least 3 methacryloyl groups as the compound having an ethylenically unsaturated bond (B) in an amount of more than 0% by mass and 16% by mass or less relative to the total solid content of the photosensitive resin composition,
and 70% by mass or more of the (B) compound having an ethylenically unsaturated bond is a compound having a weight average molecular weight of 500 or more.
16. The photosensitive resin composition according to claim 15, wherein the compound (b1) having at least 3 methacryloyl groups has a weight average molecular weight of 500 or more.
17. The photosensitive resin composition according to claim 15 or 16, which contains (B2) a compound having an oxetane chain and 1 or 2 (meth) acryloyl groups as the (B) compound having an ethylenically unsaturated bond.
18. The photosensitive resin composition according to claim 17, wherein the compound (b2) having a butylene oxide chain and 1 or 2 (meth) acryloyl groups has a weight average molecular weight of 500 or more.
19. The photosensitive resin composition according to claim 15 or 16, which is used for a semi-additive process (SAP).
20. A method of forming a resist pattern, comprising:
a laminating step of laminating a photosensitive resin layer formed from the photosensitive resin composition according to any one of claims 1 to 19 on a support;
an exposure step of exposing the photosensitive resin layer; and
and a developing step of developing the exposed photosensitive resin layer.
21. A method of manufacturing a circuit board, comprising:
a laminating step of laminating a photosensitive resin layer formed from the photosensitive resin composition according to any one of claims 1 to 19 on a substrate;
an exposure step of exposing the photosensitive resin layer;
a developing step of developing the exposed photosensitive resin layer to obtain a substrate on which a resist pattern is formed;
a conductor pattern forming step of etching or plating the substrate on which the resist pattern is formed; and
a stripping step of stripping the resist pattern.
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| CN202210104954.1A CN114437251B (en) | 2015-04-08 | 2016-04-08 | Photosensitive resin composition |
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| JP2015079381 | 2015-04-08 | ||
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| PCT/JP2016/061610 WO2016163540A1 (en) | 2015-04-08 | 2016-04-08 | Photosensitive resin composition |
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| Publication number | Publication date |
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| JPWO2016163540A1 (en) | 2017-11-02 |
| KR20190047146A (en) | 2019-05-07 |
| JP7162030B2 (en) | 2022-10-27 |
| TW201947323A (en) | 2019-12-16 |
| TWI706222B (en) | 2020-10-01 |
| KR20170101263A (en) | 2017-09-05 |
| CN114437251A (en) | 2022-05-06 |
| WO2016163540A1 (en) | 2016-10-13 |
| TWI667539B (en) | 2019-08-01 |
| TW201701070A (en) | 2017-01-01 |
| CN107407880A (en) | 2017-11-28 |
| JP2020126251A (en) | 2020-08-20 |
| CN114437251B (en) | 2024-02-20 |
| KR102286107B1 (en) | 2021-08-04 |
| TW201812454A (en) | 2018-04-01 |
| JP7242748B2 (en) | 2023-03-20 |
| JP2021131556A (en) | 2021-09-09 |
| MY187481A (en) | 2021-09-23 |
| TWI620017B (en) | 2018-04-01 |
| KR101990230B1 (en) | 2019-06-17 |
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