CN107407880A - Photosensitive polymer combination - Google Patents
Photosensitive polymer combination Download PDFInfo
- Publication number
- CN107407880A CN107407880A CN201680019911.6A CN201680019911A CN107407880A CN 107407880 A CN107407880 A CN 107407880A CN 201680019911 A CN201680019911 A CN 201680019911A CN 107407880 A CN107407880 A CN 107407880A
- Authority
- CN
- China
- Prior art keywords
- photosensitive polymer
- polymer combination
- compound
- ethylenic unsaturated
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 129
- 150000001875 compounds Chemical class 0.000 claims abstract description 109
- 229920005989 resin Polymers 0.000 claims abstract description 65
- 239000011347 resin Substances 0.000 claims abstract description 65
- 239000000758 substrate Substances 0.000 claims abstract description 56
- 239000003513 alkali Substances 0.000 claims abstract description 46
- 229920002521 macromolecule Polymers 0.000 claims abstract description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 17
- 238000005260 corrosion Methods 0.000 claims abstract description 11
- 230000007797 corrosion Effects 0.000 claims abstract description 11
- -1 methylacryloyl Chemical group 0.000 claims description 96
- 238000000034 method Methods 0.000 claims description 93
- 239000010410 layer Substances 0.000 claims description 52
- 239000002585 base Substances 0.000 claims description 44
- 230000008569 process Effects 0.000 claims description 41
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical class COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 40
- 238000004519 manufacturing process Methods 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 125000002947 alkylene group Chemical group 0.000 claims description 23
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 22
- 229920002120 photoresistant polymer Polymers 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 230000009477 glass transition Effects 0.000 claims description 16
- 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 15
- 239000000470 constituent Substances 0.000 claims description 12
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical group CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 11
- 238000003475 lamination Methods 0.000 claims description 11
- 238000007747 plating Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 150000003219 pyrazolines Chemical class 0.000 claims description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 235000003642 hunger Nutrition 0.000 claims description 6
- 230000009257 reactivity Effects 0.000 claims description 6
- 230000007261 regionalization Effects 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000003384 imaging method Methods 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 230000006978 adaptation Effects 0.000 description 48
- 239000000203 mixture Substances 0.000 description 21
- 239000000178 monomer Substances 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 19
- 229920001577 copolymer Polymers 0.000 description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 230000035945 sensitivity Effects 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000011241 protective layer Substances 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 238000011161 development Methods 0.000 description 9
- 230000018109 developmental process Effects 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 238000007792 addition Methods 0.000 description 8
- 238000007711 solidification Methods 0.000 description 8
- 230000008023 solidification Effects 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000001976 improved effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 235000011194 food seasoning agent Nutrition 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 229940106691 bisphenol a Drugs 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- SYOANZBNGDEJFH-UHFFFAOYSA-N 2,5-dihydro-1h-triazole Chemical compound C1NNN=C1 SYOANZBNGDEJFH-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 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
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 238000003556 assay Methods 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
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 3
- 238000005422 blasting Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000001259 photo etching Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical class CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical class OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 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
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000003884 phenylalkyl group Chemical group 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 230000008093 supporting effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000003021 water soluble solvent Substances 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
- NJXYTXADXSRFTJ-UHFFFAOYSA-N 1,2-Dimethoxy-4-vinylbenzene Chemical class COC1=CC=C(C=C)C=C1OC NJXYTXADXSRFTJ-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 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
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical class COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 1
- QQHQTCGEZWTSEJ-UHFFFAOYSA-N 1-ethenyl-4-propan-2-ylbenzene Chemical class CC(C)C1=CC=C(C=C)C=C1 QQHQTCGEZWTSEJ-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 class SN1C=CN=N1 MACMNSLOLFMQKL-UHFFFAOYSA-N 0.000 description 1
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical class SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 1
- NEBBLNDVSSWJLL-UHFFFAOYSA-N 2,3-bis(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(OC(=O)C(C)=C)COC(=O)C(C)=C NEBBLNDVSSWJLL-UHFFFAOYSA-N 0.000 description 1
- 125000001617 2,3-dimethoxy phenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C(OC([H])([H])[H])=C1[H] 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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-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
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical group C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- HPSGLFKWHYAKSF-UHFFFAOYSA-N 2-phenylethyl prop-2-enoate Chemical compound C=CC(=O)OCCC1=CC=CC=C1 HPSGLFKWHYAKSF-UHFFFAOYSA-N 0.000 description 1
- LZHCVNIARUXHAL-UHFFFAOYSA-N 2-tert-butyl-4-ethylphenol Chemical class 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
- LCYDMVAVSPMZIQ-UHFFFAOYSA-N 3-(oxiran-2-yl)propane-1,2-diol Chemical class OCC(O)CC1CO1 LCYDMVAVSPMZIQ-UHFFFAOYSA-N 0.000 description 1
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 1
- CPHGOBGXZQKCKI-UHFFFAOYSA-N 4,5-diphenyl-1h-imidazole Chemical compound N1C=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 CPHGOBGXZQKCKI-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical class NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 description 1
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical class C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- CSCGRSSBEBRMOA-UHFFFAOYSA-N ClOC1=C(C=CC=C1)C=1NC(=C(N1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical class ClOC1=C(C=CC=C1)C=1NC(=C(N1)C1=CC=CC=C1)C1=CC=CC=C1 CSCGRSSBEBRMOA-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 description 1
- 101000598921 Homo sapiens Orexin Proteins 0.000 description 1
- 101001123245 Homo sapiens Protoporphyrinogen oxidase Proteins 0.000 description 1
- 101001134276 Homo sapiens S-methyl-5'-thioadenosine phosphorylase Proteins 0.000 description 1
- 206010020466 Hunger Diseases 0.000 description 1
- 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 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 1
- VRBYVBRQIDNSEK-UHFFFAOYSA-N NCC1=C(C=CC=C1)C=1C2=CC=CC=C2N=C2C=CC=CC12 Chemical compound NCC1=C(C=CC=C1)C=1C2=CC=CC=C2N=C2C=CC=CC12 VRBYVBRQIDNSEK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 102100022050 Protein canopy homolog 2 Human genes 0.000 description 1
- 102100029028 Protoporphyrinogen oxidase Human genes 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- ZCZFEIZSYJAXKS-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COC(=O)C=C ZCZFEIZSYJAXKS-UHFFFAOYSA-N 0.000 description 1
- XAKBSHICSHRJCL-UHFFFAOYSA-N [CH2]C(=O)C1=CC=CC=C1 Chemical group [CH2]C(=O)C1=CC=CC=C1 XAKBSHICSHRJCL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000005115 alkyl carbamoyl group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 150000001356 alkyl thiols Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000010165 autogamy Effects 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 229940059082 douche Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000003551 oxepanyl group Chemical group 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 235000012771 pancakes Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical class OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (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 kind of photosensitive polymer combination, it contains alkali solubility macromolecule；Compound with ethylenic unsaturated bond；And Photoepolymerizationinitiater initiater, and utilize for evaluate the chemical reagent of chemical reagent resistance to formed on the surface of the substrate as photo-sensitive resin that the photosensitive polymer combination is formed and carry out it is exposed and developed obtained from after corrosion-resisting pattern handles, the minimum feature for solidifying layer line against corrosion is less than 17 μm.
Description
Technical field
The present invention relates to photosensitive polymer combination etc..
Background technology
All the time, printed circuit board (PCB) is generally manufactured by photoetching process.In photoetching process, first, to being layered on substrate
Photosensitive polymer combination layer carry out pattern exposure.The exposure portion of photosensitive polymer combination carries out polymerizing curable (for minus
Situation) or become soluble in developer solution (for the situation of eurymeric).Then, unexposed portion is removed (for minus using developer solution
Situation) or exposure portion (for the situation of eurymeric) and corrosion-resisting pattern is formed on substrate.And then implement etching or plating and shape
Into conductive pattern, then corrosion-resisting pattern is removed from strippable substrate.By passing through these processes, conductive pattern is formed on substrate.
, can any one of with the following method generally in photosensitive resin coating composition on substrate on photoetching process：
By the solution coating of photosensitive polymer combination on substrate and make its dry method；Or photonasty tree is laminated on substrate
The method of lipid layer stack (hereinafter also referred to as " dry film resist layer "), the photoresist layered product are by stacking gradually support
Body, the layer formed by photosensitive polymer combination (hereinafter also referred to as " photo-sensitive resin ") and protective layer as needed and
Obtain.Use the latter mostly in the manufacturing of printed circuit boards.
With the miniaturization of the routing space of printed circuit board (PCB) in recent years, constantly require there are various spies for dry film resist layer
Property.For example, in order to improve the adaptation of corrosion-resisting pattern and resolution ratio, and in the stage untill before developing procedure, make to cover
The corrosion-resisting pattern of lid through hole is not easy to break, it is proposed that following photosensitive polymer combination：It, which includes to have respectively, was derived from for two seasons penta
(methyl) acrylate compounds of the skeleton of tetrol are as the compound with ethylenic unsaturated bond, and pyrazoline compounds
As sensitising agent (patent document 1).
In order to improve the adaptation of corrosion-resisting pattern and resolution ratio, and suppress in developing procedure the production of the residue of corrosion-resisting pattern bottom
It is raw, it is also proposed that following photosensitive polymer combination：It includes (methyl) acrylic acid with the skeleton from dipentaerythritol
Ester compounds and two (methyl) acrylate compounds (patent document 2) with bisphenol A-type skeleton and alkylene oxide chain.
The substrate formed with corrosion-resisting pattern is etched or the conductive pattern formation process of plating in or the process before, have
The chemical reagent such as Shi Liyong degreasers clean corrosion-resisting pattern and substrate.In the comparison before and after the contact with chemical reagent, it is desirable to
Suppress the change of corrosion-resisting pattern shape.
However, the viewpoint such as chemical proofing from corrosion-resisting pattern, the photoresist group described in patent document 1 and 2
Compound still has the leeway of improvement.
And then in order to improve the characteristic of resist layer, it is proposed that various photosensitive polymer combinations (patent document 3~6).
In patent document 3, from the viewpoint of the flanging shape, resolution ratio and residual film ratio of corrosion-resisting pattern, it have studied following photosensitive
Property resin combination：It includes pentaerythrite poly-alkoxyl tetramethyl acrylate as the chemical combination with ethylenic unsaturated bond
Thing.
In patent document 4, from the flanging shape of corrosion-resisting pattern, resolution ratio, adaptation, minimum developing time and exudative viewpoint
Set out, as the monomer in photosensitive polymer combination, have studied following combination：Ethylene-oxide-modified pentaerythrite is carried out
Four (methyl) acrylate, bisphenol-A is set to carry out two (methyl) acrylate and dipentaerythritol obtained from alkylene oxide modification
The combination of (methyl) acrylate.
Following photosensitive polymer combination has been recorded in patent document 5 and 6：It is included with the glass transition more than 106 DEG C
The alkali solubility macromolecule of temperature.
However, in the manufacture of printed circuit board (PCB) etc., when solidifying the excessive high hardness of resist layer, because in development treatment or in conveying
Physical impact and corrosion-resisting pattern is fractureed, as a result have wiring pattern yield be deteriorated worry.Therefore, for solidifying resist layer,
In order to maintain to the closely sealed of base material, it is expected that flexibility is good.In addition, although dry film resist layer batches protected for web-like sometimes
Deposit, but when the constituent of dry film resist layer is attached to support membrane surface because oozing out, be difficult to stable wiring diagram sometimes
Case produces.
However, the photosensitive polymer combination described in for patent document 3~6, is carried from the flexibility for improving corrosion-resisting pattern
High adhesion, and from the viewpoint of suppressing the oozing out of constituent of dry film resist layer, still there is the leeway of improvement.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2012-048202 publications
Patent document 2：International Publication No. 2015/012272
Patent document 3：Japanese Unexamined Patent Publication 2013-156369 publications
Patent document 4：Japanese Unexamined Patent Publication 2014-081440 publications
Patent document 5：Japanese Unexamined Patent Publication 2013-117716 publications
Patent document 6：Japanese Unexamined Patent Publication 2014-191318 publications
The content of the invention
Problems to be solved by the invention
Completed the present invention be directed to the background technology of described above, the problem to be solved by the present invention is that offer adaptation,
The excellent photosensitive polymer combination of at least one of resolution ratio and bin stability.
The solution used to solve the problem
The inventors discovered that can solve above-mentioned problem by following technical method.
A kind of photosensitive polymer combination, it contains：
(A) alkali solubility macromolecule；
(B) there is the compound of ethylenic unsaturated bond；With,
(C) Photoepolymerizationinitiater initiater,
The chemical reagent evaluated with chemical reagent resistance to forming what is formed by the photosensitive polymer combination on the surface of the substrate
Photo-sensitive resin and carry out it is exposed and developed obtained from after corrosion-resisting pattern (resist pattern) handled, solidification
The minimum feature of layer line against corrosion is less than 17 μm.
According to the photosensitive polymer combination described in [1], photosensitive resin bed is formed on aforesaid base plate surface, with
Highest residual film level when 41 grades of stage exposure guide rules of Si Tufei (Stouffer) are exposed as mask, then developed
When number is exposed as 15 grades of light exposure to the photo-sensitive resin,
In FT-IR measure, by the wave number 810cm before exposure-1The peak height at place is set to P, will carry out foregoing after foregoing exposure
(B) reactivity of the olefinic double bond in the compound with ethylenic unsaturated bond is set to Q, by the thickness of photosensitive resin bed
The value of P × Q/R when being set to R is more than 0.21.
According to the photosensitive polymer combination described in [1] or [2], wherein, the high molecular vitrifying of foregoing (A) alkali solubility turns
Temperature Tg weighed average TgtotalFor less than 110 DEG C.
According to the photosensitive polymer combination any one of [1]~[3], wherein, foregoing (B) has olefinic unsaturated
The weight average molecular weight of the compound of key is more than 760.
According to the photosensitive polymer combination any one of [1]~[4], wherein, foregoing (B) has olefinic unsaturated
The concentration of methylacryloyl in the compound of key is more than 0.20mol/100g.
According to the photosensitive polymer combination any one of [1]~[5], wherein, foregoing (B) has olefinic unsaturated
The concentration of ethylene oxide unit in the compound of key is more than 0.80mol/100g.
According to the photosensitive polymer combination any one of [1]~[6], it makees comprising hexa-aryl bi-imidazole compound
For foregoing (C) Photoepolymerizationinitiater initiater.
A kind of photosensitive polymer combination, it contains：
(A) alkali solubility macromolecule；
(B) there is the compound of ethylenic unsaturated bond；With,
(C) Photoepolymerizationinitiater initiater,
The weighed average Tg of the high molecular glass transition temperature Tg of foregoing (A) alkali solubilitytotalFor less than 110 DEG C,
And contain (methyl) acrylate compounds with more than 3 ethylenic unsaturated bonds as foregoing (B) with olefinic not
The compound of saturated bond.
According to the photosensitive polymer combination described in [8], it contains with more than 5 ethylenic unsaturated bonds and with ring
(methyl) acrylate compounds of oxygen alkane chain have the compound of ethylenic unsaturated bond as foregoing (B).
According to the photosensitive polymer combination described in [8] or [9], wherein, foregoing (A) alkali solubility macromolecule have 100~
600 acid equivalent and 5000~500000 weight average molecular weight, and there is aromatic series base in its side chain.
According to the photosensitive resin combination any one of [8]~[10], it has more than 5 olefinic insatiable hungers
(methyl) acrylate compounds with key and with ethylene oxide chain are as the foregoing chemical combination of (B) with ethylenic unsaturated bond
Thing.
According to the photosensitive resin combination any one of [8]~[11], it contains with ethylene oxide chain
(methyl) acrylate compounds with dipentaerythritol skeleton are as the compound of foregoing (B) with ethylenic unsaturated bond.
According to the photosensitive polymer combination any one of [8]~[12], it is also containing shown in following logical formula (II)s
Compound as foregoing (B) have ethylenic unsaturated bond compound,
In formula (II), R1And R2Separately represent hydrogen atom or methyl, A C2H4, B C3H6, n1And n3Separately
For 1~39 integer, and n1+n3For 2~40 integer, n2And n4The separately integer for 0~29, and n2+n4For 0~30
Integer ,-(A-O)-and-(B-O)-repeat unit arrangement can be can also be randomly block, in the situation for block
Under, any one of-(A-O)-and-(B-O)-are in xenyl side.}.
According to the photosensitive polymer combination any one of [8]~[13], it is also containing shown in following logical formula (I)s
Compound has the compound of ethylenic unsaturated bond as foregoing (B),
In formula (I), R3~R6The alkyl of carbon number 1~4 is separately represented, X represents the alkylidene of carbon number 2~6, m1、m2、m3
And m4The separately integer for 0~40, m1+m2+m3+m4For 1~40, and m1+m2+m3+m4For more than 2 when, multiple X can be with
It is same to each other or different to each other }.
According to the photosensitive polymer combination any one of [8]~14, it contains hexa-aryl bi-imidazole compound work
For foregoing (C) Photoepolymerizationinitiater initiater.
According to the photosensitive polymer combination any one of [8]~[15], it contains before pyrazoline compounds are used as
State (C) Photoepolymerizationinitiater initiater.
According to the photosensitive polymer combination any one of [8]~[16], it is used for direct imaging exposure.
According to the photosensitive polymer combination described in [8], wherein, the high molecular glass transition temperature of foregoing (A) alkali solubility
Spend Tg weighed average TgtotalFor less than 105 DEG C,
Relative to photosensitive resin combination solid constituent total amount more than 0 mass % and for below 16 mass % model
Enclose and contain the compound of (b1) with least three methylacryloyl as the foregoing compound of (B) with ethylenic unsaturated bond,
And more than the 70 mass % in the foregoing compound of (B) with ethylenic unsaturated bond are with more than 500 Weight-average molecular
The compound of amount.
According to the photosensitive polymer combination described in [18], wherein, foregoing (b1) has at least three methylacryloyl
Compound has more than 500 weight average molecular weight.
According to the photosensitive polymer combination described in [18] or [19], it, which contains (b2), has epoxy butane chain and 1 or 2
The compound of individual (methyl) acryloyl group has the compound of ethylenic unsaturated bond as foregoing (B).
According to the photosensitive polymer combination described in [20], wherein, foregoing (b2) has epoxy butane chain and 1 or 2
The compound of (methyl) acryloyl group has more than 500 weight average molecular weight.
The effect of invention
According to the present invention it is possible to provide at least one of adaptation, resolution ratio and bin stability excellent photoresist
Composition.
Embodiment
Hereinafter, it is specifically described for the mode (hreinafter referred to as " present embodiment ") for implementing the present invention.
<Photosensitive polymer combination>
In present embodiment, photosensitive polymer combination contains：(A) change of alkali solubility macromolecule, (B) with ethylenic unsaturated bond
Compound and (C) Photoepolymerizationinitiater initiater.According to required, photosensitive polymer combination can also contain (D) additive it is such its
His composition.
The first embodiment of the present invention is a kind of photosensitive polymer combination, and it is designed as follows：Use chemically-resistant
The chemical reagent of agents evaluation to forming the photo-sensitive resin formed by photosensitive polymer combination, simultaneously on the surface of the substrate
After corrosion-resisting pattern obtained from being exposed and developing is handled, the minimum feature for solidifying layer line against corrosion is less than 17 μm.It is logical
Cross using this photosensitive polymer combination, when forming wiring pattern by plating, short circuit can be suppressed.Alternatively, it is also possible to
Suppress coating and slip into (Japanese：め っ I is dived り), so as to obtain the excellent wiring pattern of linearity.That is, of the invention is photosensitive
The adaptation and/or excellent in resolution of property resin combination.The minimum feature for solidifying layer line against corrosion is preferably less than 16 μm, more excellent
Elect less than 15 μm, more preferably less than 12 μm, particularly preferably less than 10 μm as, be most preferably less than 8 μm.Solidify against corrosion
The assay method and condition of the minimum feature of layer line illustrate in the chemical reagent resistance evaluation of embodiment.
Second embodiment of the present invention is a kind of photosensitive polymer combination, wherein, the high molecular vitrifying of (A) alkali solubility turns
Temperature Tg weighed average TgtotalFor less than 110 DEG C, and contain (methyl) third with more than 3 ethylenic unsaturated bonds
Enoic acid ester compounds have the compound of ethylenic unsaturated bond as (B).By containing TgtotalFor less than 110 DEG C (A) alkali soluble
Property macromolecule and (methyl) acrylate compounds with more than 3 ethylenic unsaturated bonds, reactivity can be improved, in addition,
Due to the tendency that crosslinking density rises, and unreacted (B) composition is not easy to remain, and therefore, its result has photoresist group
Compound provides the tendency of at least one of adaptation, resolution ratio and bin stability excellent corrosion-resisting pattern.
The photo-sensitive resin formed by the photosensitive polymer combination of present embodiment is formed on the surface of the substrate, by this figure
Highest residual film series when 41 grades of stage exposure guide rules of expense are exposed as mask, then developed turns into 15 grades of exposure
When amount is exposed to photo-sensitive resin, photo-sensitive resin preferably meets the relation shown in following formula.
P×Q/R≥0.21
{ in formula, for photo-sensitive resin, in FT-IR measure, P represents the wave number 810cm before exposure-1The peak height at place, Q tables
Show that (B) has the reactivity of olefinic double bond after exposure in the compound of ethylenic unsaturated bond, and R represents thickness.}
Value shown in formula P × Q/R of described above be more preferably more than 0.22, more than 0.23, more than 0.24, more than 0.25 or
More than 0.27.The assay method and condition of value shown in formula P × Q/R illustrate in embodiment.
(A) alkali solubility macromolecule
(A) alkali solubility macromolecule is the macromolecule being dissolvable in water in alkaline matter.In present embodiment, from the viewpoint of alkali-developable
Set out, photosensitive polymer combination preferably has carboxyl, more preferably comprising copolymer carboxyl group-containing monomer as copolymer composition.
In present embodiment, for photosensitive polymer combination, the viewpoint of high-resolution and flanging shape from corrosion-resisting pattern goes out
Send out and then from the viewpoint of the chemical proofing of corrosion-resisting pattern, as (A) alkali solubility macromolecule, preferably comprise with virtue
The copolymer of fragrant race's base, particularly preferably containing the copolymer in side chain with aromatic series base.It should be noted that as this virtue
Fragrant race's base, such as can enumerate：Substituted or unsubstituted phenyl, substituted or unsubstituted aralkyl.
The ratio shared in (A) composition as the copolymer with aromatic series base, preferably more than 50 mass %, be preferably 60
More than quality %, it is preferably more than 70 mass %, preferably more than 80 mass %, preferably more than 90 mass %, or
100 mass %.
In addition, from the viewpoint of the high-resolution and flanging shape of corrosion-resisting pattern so corrosion-resisting pattern chemical proofing
From the viewpoint of, as the copolymerization ratio of the comonomer with aromatic series base in the copolymer with aromatic series base, preferably
For more than 20 mass %, preferably more than 30 mass %, preferably more than 40 mass %, preferably more than 50 mass %, preferably
For more than 60 mass %, preferably more than 70 mass %, preferably more than 80 mass %.As the upper limit of copolymerization ratio, do not have
Special limitation, from the viewpoint of alkali solubility is maintained, preferably below 95 mass %, it is more preferably below 90 mass %.
As the foregoing comonomer with aromatic series base, such as can enumerate：Monomer, styrene, Yi Jike with aralkyl
Styrene derivative (such as methyl styrene, vinyltoluene, t-butoxystyrene, the acetyloxy phenyl second being polymerize
Alkene, 4- vinyl benzoic acids, styrene dimer thing, styrene terpolymer etc.).Wherein, the monomer or benzene preferably with aralkyl
Ethene, the more preferably monomer with aralkyl.
As aralkyl, can enumerate：Substituted or unsubstituted phenylalkyl (not including benzyl), substituted or unsubstituted benzyl
Deng preferably substituted or unsubstituted benzyl.
As the comonomer with phenylalkyl, can enumerate：(methyl) phenylethyl acrylate etc..
As the comonomer with benzyl, can enumerate：(methyl) acrylate with benzyl, such as (methyl) acrylic acid benzyl
Ester, (methyl) acrylic acid benzyl chloride ester etc.；Vinyl monomer with benzyl, such as vinyl chloride, vinyl benzyl alcohol.Its
In, preferred (methyl) benzyl acrylate.
Copolymer of the side chain with aromatic series base (particularly preferred benzyl) preferably by make the monomer with aromatic series base, with it is aftermentioned
At least one kind of polymerization at least one kind of and/or aftermentioned second comonomer in first monomer and obtain.
(A) alkali solubility macromolecule in addition to side chain has the copolymer of aromatic series base is preferably by making in aftermentioned first monomer
It is at least one kind of polymerization and obtain, more preferably by make in the first monomer it is at least one kind of, with it is at least one kind of common in aftermentioned second comonomer
Gather and obtain.
First monomer is the monomer for having in molecule carboxyl.As the first monomer, such as can enumerate：(methyl) acrylic acid, rich horse
Acid, cinnamic acid, crotonic acid, itaconic acid, 4- vinyl benzoic acids, maleic anhydride, acid half ester etc..Among these, preferred (first
Base) acrylic acid.
It should be noted that in this specification, " (methyl) acrylic acid " refers to acrylic or methacrylic acid, " (methyl) propylene
Acyl group " refers to acryloyl group or methylacryloyl, and " (methyl) acrylate " refers to " acrylate " or " methacrylic acid
Ester ".
The copolymerization ratio of first monomer is using the gross mass of whole monomer components as benchmark, preferably 10~50 mass %.From table
From the viewpoint of revealing viewpoint, control edge-melting of good developability etc., it is more than 10 mass % preferably to make the copolymerization ratio.
It is excellent from the viewpoint of the high-resolution and the viewpoint of flanging shape and then the chemical proofing of corrosion-resisting pattern of corrosion-resisting pattern
Choosing makes the copolymerization ratio be below 50 mass %, in these viewpoints, more preferably below 30 mass %, further preferred 25 matter
Measure below %, particularly preferred below 22 mass %, most preferably below 20 mass %.
Second comonomer is nonacid, and to have the monomer of at least one polymerism unsaturated group in molecule.It is single as second
Body, such as can enumerate：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) propylene
Isopropyl propionate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) propylene
Sour 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) cyclohexyl acrylate, (methyl) 2-EHA
Deng (methyl) esters of acrylic acid；The esters of the vinyl alcohols such as vinyl acetate；And (methyl) acrylonitrile etc..Wherein, preferred (first
Base) methyl acrylate, (methyl) 2-EHA and (methyl) n-butyl acrylate.
In present embodiment, (A) alkali solubility macromolecule can be prepared via a method which：Make one or more monomers of described above
It is polymerize by known polymerization, preferably addition polymerization, more preferably radical polymerization to prepare.
From the viewpoint of the chemical proofing of corrosion-resisting pattern, adaptation, high-resolution or flanging shape, tool is preferably comprised
Have aralkyl monomer and/or styrene as monomer, such as preferably by methacrylic acid, benzyl methacrylate and styrene
The copolymer of formation；The copolymer formed by methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene
Deng.
From the viewpoint of the chemical proofing of corrosion-resisting pattern, adaptation, high-resolution or flanging shape, asked by Fox formulas
The high molecular glass transition temperature of (A) alkali solubility gone out is (overall on the mixture when (A) composition includes a variety of copolymers
Glass transition temperature Tg, i.e. the weighed average Tg of glass transition temperaturetotal) be preferably less than 110 DEG C, be more preferably
Less than 107 DEG C, less than 105 DEG C, less than 100 DEG C, less than 95 DEG C, less than 90 DEG C or less than 80 DEG C.For (A) alkali solubility macromolecule
The lower limit of glass transition temperature (Tg) there is no particular limitation, from the viewpoint of control edge-melting, preferably 30 DEG C
Above, more preferably more than 50 DEG C, more preferably more than 60 DEG C.
(A) the high molecular acid equivalent of alkali solubility (when (A) composition includes a variety of copolymers, the acid equivalent overall on the mixture)
From the viewpoint of the resistance to developability of photo-sensitive resin and the resolution ratio and adaptation of corrosion-resisting pattern, preferably 100 with
On, from the viewpoint of the developability of photo-sensitive resin and fissility, preferably less than 600.(A) the high molecular acid of alkali solubility
Equivalent is more preferably 200~500, more preferably 250~450.
(A) the high molecular weight average molecular weight of alkali solubility (when (A) composition includes a variety of copolymers, the weight overall on the mixture
Average molecular weight) it is preferably 5000~500000.(A) the high molecular weight average molecular weight of alkali solubility is from equably can maintaining dry film to resist
Lose layer thickness, obtain to the patience of developer solution from the viewpoint of, preferably more than 5000, from maintain dry film resist layer development
The viewpoint of the viewpoint of property, the viewpoint of the high-resolution of corrosion-resisting pattern and flanging shape and then the chemical proofing of corrosion-resisting pattern
Set out, preferably less than 500000.(A) the high molecular weight average molecular weight of alkali solubility is more preferably 10000~200000, further
Preferably 20000~130000,30000~100000 are particularly preferably, is most preferably 40000~70000.(A) alkali solubility is high
The decentralization of molecule is preferably 1.0~6.0.
In present embodiment, the high molecular content of (A) alkali solubility in photosensitive polymer combination is with photosensitive polymer combination
Solid constituent total amount as benchmark (following, be same in respectively containing composition as long as no especially expressing), preferably 10
The mass % of quality %~90, more preferably in the mass % of 20 mass %~80, further preferably the mass %'s of 40 mass %~60
In the range of.(A) the high molecular content of alkali solubility is from the viewpoint of the alkali-developable for maintaining photo-sensitive resin, preferably 10 matter
Measure more than %, from the performance as erosion resistant is given full play to the corrosion-resisting pattern that is formed by exposure viewpoint, corrosion-resisting pattern
High-resolution and the viewpoint of flanging shape and then the chemical proofing of corrosion-resisting pattern from the viewpoint of, preferably 90 matter
Measure below %, more preferably below 70 mass %, more preferably below 60 mass %.
(B) there is the compound of ethylenic unsaturated bond
(B) compound with ethylenic unsaturated bond be due in its structure with ethylenically unsaturated group and with polymerism
Compound.
From the viewpoint of the chemical proofing of corrosion-resisting pattern, adaptation, high-resolution or flanging shape, present embodiment
Photosensitive polymer combination preferably comprises (methyl) acrylate compounds with more than 3 ethylenic unsaturated bonds and is used as (B)
Compound with ethylenic unsaturated bond.Now, ethylenic unsaturated bond is more preferably derived from methylacryloyl.
(methyl) acrylate compounds with more than 3 ethylenic unsaturated bonds are for example as with ethylene oxide chain and two seasons
(methyl) acrylate compounds or (b1) of penta 4 ol skeletons have at least three methylacryloyl compound and rear
Narration.
From the viewpoint of the chemical proofing of corrosion-resisting pattern, adaptation, high-resolution or flanging shape, present embodiment
Photosensitive polymer combination preferably comprises (methyl) acrylic acid with more than 5 ethylenic unsaturated bonds and with alkylene oxide chain
Ester compounds have the compound of ethylenic unsaturated bond as (B).Now, ethylenic unsaturated bond is more preferably derived from methacryl
Base, and alkylene oxide chain is more preferably ethylene oxide chain.
(methyl) acrylate compounds with more than 5 ethylenic unsaturated bonds and with alkylene oxide chain for example as with
(methyl) acrylate compounds of ethylene oxide chain and dipentaerythritol skeleton and be described later.
From the viewpoint of the chemical proofing of corrosion-resisting pattern, adaptation, high-resolution or flanging shape, (B) has olefinic
The concentration of methylacryloyl in the compound of unsaturated bond is preferably more than 0.20mol/100g, more preferably 0.30mol/
More than 100g, more preferably more than 0.35mol/100g, particularly preferably more than 0.40mol/100g.Methylacryloyl
As long as the higher limit of concentration can ensure that polymerism and alkali-developable, then do not limit, for example, can be 0.90mol/100g with
Lower or below 0.80mol/100g.
From the same viewpoint, (B) has concentration/(methyl of the methylacryloyl in the compound of ethylenic unsaturated bond
The concentration of concentration+acryloyl group of acryloyl group) value be preferably more than 0.50, more preferably more than 0.60, further preferably
For more than 0.80, particularly preferably more than 0.90, most preferably more than 0.95.
From the viewpoint of the chemical proofing of corrosion-resisting pattern, adaptation, high-resolution or flanging shape, (B) has olefinic
The concentration of ethylene oxide unit in the compound of unsaturated bond is preferably more than 0.80mol/100g, more preferably 0.90mol/
More than 100g, more preferably more than 1.00mol/100g, particularly preferably more than 1.10mol/100g.Ethylene oxide unit
As long as the higher limit of concentration can ensure that chemical proofing, adaptation and the resolution ratio of corrosion-resisting pattern, then do not limit, such as
Can be below 1.60mol/100g, below 1.50mol/100g, below 1.45mol/100g or below 1.40mol/100g.
In present embodiment, go out from the viewpoint of the chemical proofing of corrosion-resisting pattern, adaptation, high-resolution or flanging shape
Hair, photosensitive polymer combination preferably comprise (methyl) acrylate compounds with alkylene oxide chain and dipentaerythritol skeleton
There is the compound of ethylenic unsaturated bond as (B).As alkylene oxide chain, such as can enumerate：Ethylene oxide chain, expoxy propane
Chain, epoxy butane chain, epoxypentane chain, oxepane chain etc..When photosensitive polymer combination includes multiple alkylene oxide chains, they
Can with it is mutually the same can also be different.From the above point of view, as alkylene oxide chain, more preferably ethylene oxide chain, expoxy propane
Chain or epoxy butane chain, further preferred ethylene oxide chain or expoxy propane chain, particularly preferred ethylene oxide chain.
In photosensitive polymer combination, by the way that (A) alkali solubility macromolecule is applied in combination and there is alkylene oxide chain and dipentaerythritol
(methyl) acrylate compounds of skeleton, so as to have the chemical proofing for keeping corrosion-resisting pattern, adaptation and resolution ratio
Balanced tendency.
(methyl) acrylate compounds with alkylene oxide chain and dipentaerythritol skeleton refer to that using alkylidene epoxide will be more
Dipentaerythritol compound obtained from least one in individual hydroxyl is modified and the ester of (methyl) acrylic acid.Can also be right
6 hydroxyls in dipentaerythritol skeleton are modified using alkylidene epoxide.The quantity of ester bond in the molecule of ester one can be 1
~6, preferably 6.
As (methyl) acrylate compounds with alkylene oxide chain and dipentaerythritol skeleton, such as can enumerate：In two seasons
Averagely 4~30 moles of addition, average 6~24 moles or six (first averagely obtained from 10~14 mol of alkylene oxide on penta tetrol
Base) acrylate.
Specifically, as (methyl) acrylate compounds with alkylene oxide chain and dipentaerythritol skeleton, from resist pattern
From the viewpoint of the chemical proofing of case, adaptation, high-resolution or flanging shape, shown in preferably following logical formula (III)s
Compound,
{ in formula, R separately represents hydrogen atom or methyl, and n is 0~30 integer, and whole n total value is more than 1 }.
In logical formula (III), preferably whole n average value is that more than 4 or n is respectively more than 1.As R, preferably methyl.
From the viewpoint of the chemical proofing of corrosion-resisting pattern, there are alkylene oxide chain and two seasons in photosensitive polymer combination
The content of (methyl) acrylate compounds of penta 4 ol skeletons is preferably in the mass % of 1 mass %~50, more preferably in 5 mass %
~40 mass %, further preferably in the range of the mass % of 7 mass %~30.
In present embodiment, bin stability is improved in order to suppress the oozing out for constituent of dry film resist layer, (B) is had
The solid constituent total amount of the compound of ethylenic unsaturated bond has 70 in the compound of ethylenic unsaturated bond as benchmark, (B)
More than quality %, preferably more than 80 mass %, more preferably more than 90 mass %, further preferred 100 mass % be with 500 with
On weight average molecular weight compound.From suppress ooze out and the chemical proofing of corrosion-resisting pattern from the viewpoint of, (B) has alkene
The weight average molecular weight for belonging to the compound of unsaturated bond is preferably more than 760, more preferably more than 800, more preferably 830 with
Above, particularly preferably more than 900.(B) weight average molecular weight of the compound with ethylenic unsaturated bond can be by embodiment
The method of record is measured.
Adaptation is improved in order to improve the flexibility of corrosion-resisting pattern, and suppresses oozing out for the constituent of dry film resist layer, is felt
Photosensitive resin composition preferably comprises the compound of (b1) with least three methylacryloyl as (B) with olefinic insatiable hunger
With the compound of key.
(b1) with least three methylacryloyl compound from suppress ooze out from the viewpoint of, have preferably more than 500,
More preferably more than 700, further preferred more than 900 weight average molecular weight.
There is the compound of at least three methylacryloyl on (b1), the quantity of methylacryloyl be preferably more than 4,5 with
It is upper or more than 6.Compound with least three methylacryloyl can be with alkylene oxide chain, such as ethylene oxide chain, epoxy
Propane chain or combinations thereof.
There is the compound of at least three methylacryloyl as (b1), can enumerate：Trimethyl acrylic ester, such as ethyoxyl
Change glycerol trimethacrylate, ethoxylation isocyanuric acid trimethyl acrylic ester, pentaerythritol acrylate trimethyl, three
TRIM is (for example, from flexibility, adaptation and suppress from the viewpoint of oozing out, preferably in three hydroxyls
On methylpropane trimethyl acrylic ester obtained from the oxirane of average 21 moles of addition or on trimethylolpropane plus
Into trimethyl acrylic ester obtained from average 30 moles oxirane) etc.；Tetramethyl acrylate, such as two trihydroxy methyls
Propane tetramethyl acrylate, pentaerythritol tetramethylacrylate, dipentaerythritol tetramethyl acrylate etc.；Pentamethyl third
Olefin(e) acid ester, such as dipentaerythritol pentamethacrylates；Hexamethacrylate, such as dipentaerythritol hexamethyl propylene
Acid esters etc..Among these, preferably tetramethyl acrylate, pentamethacrylates or hexamethacrylate.
As tetramethyl acrylate, preferably pentaerythritol tetramethylacrylate.Pentaerythritol tetramethylacrylate can be with
For tetramethyl acrylate obtained from amounting to 1~40 mole of alkylene oxide in 4 terminal additions of pentaerythrite etc..
Tetramethyl acrylate is more preferably the tetramethyl acrylate compounds shown in following logical formula (I)s,
In formula, R3~R6The alkyl of carbon number 1~4 is separately represented, X represents the alkylidene of carbon number 2~6, m1、m2、m3And m4
The separately integer for 0~40, m1+m2+m3+m4For 1~40, and m1+m2+m3+m4For more than 2 when, multiple X can be each other
It is identical or different }.
Although being not intended to be limited to theory, it is considered that：Tetramethyl acrylate compounds shown in logical formula (I) pass through tool
There is group R3~R6, and with H2The tetraacrylate of C=CH-CO-O- parts is compared, and can suppress water-disintegrable in aqueous slkali.From
The resolution ratio of raising corrosion-resisting pattern, specifically wire shaped, more specifically the flanging shape of line and the adaptation of resist layer
From the viewpoint of, preferably use the photosensitive polymer combination for including the tetramethyl acrylate compounds shown in logical formula (I).
In logical formula (I), group R3~R6In at least one be preferably methyl, and more preferably group R3~R6All methyl.
On corrosion-resisting pattern, from the viewpoint of required resolution ratio, flanging shape and residual film ratio is obtained, lead in formula (I), X is excellent
Elect-CH as2-CH2-。
On corrosion-resisting pattern, from the viewpoint of required resolution ratio, flanging shape and residual film ratio is obtained, lead in formula (I), m1、
m2、m3And m4It is preferred that separately be 1~20 integer, more preferably 2~10 integer.And then in logical formula (I), m1+m2+
m3+m4Preferably 1~36 or 4~36.
As the compound shown in logical formula (I), such as can enumerate：Pentaerythrite (poly-) alkoxy tetramethyl acrylate etc..Separately
Outside, in this specification, " pentaerythrite (poly-) alkoxy tetramethyl acrylate " includes：In above-mentioned logical formula (I), m1+m2+m3+
m4=1 " pentaerythrite alkoxy tetramethyl acrylate " and m1+m2+m3+m4=2~40 " pentaerythrite poly-alkoxyl four
Both methacrylates ".As the compound shown in logical formula (I), can enumerate：Japanese Unexamined Patent Publication 2013-156369 publications
In enumerate compound, such as pentaerythrite (poly-) alkoxy tetramethyl acrylate.
As hexamethacrylate compound, preferably 1~24 mole of ring is amounted in 6 terminal additions of dipentaerythritol
Hexamethacrylate obtained from oxidative ethane, in 6 terminal additions of dipentaerythritol amount to 1~10 mole of 6-caprolactone
Obtained from hexamethacrylate.
Relative to the solid constituent total amount of photosensitive polymer combination, (b1) has the compound of at least three methylacryloyl
Content be preferably greater than 0 mass % and be below 16 mass %.When the content is more than 0 mass %, there is resolution ratio raising,
For below 16 mass % when, have solidification resist layer flexibility improved, and splitting time shorten tendency.The content is more excellent
Elect as more than 2 mass % and below 15 mass %, more preferably more than 4 mass % and below 12 mass %.
Photosensitive polymer combination preferably comprises the chemical combination of (b2) with epoxy butane chain and 1 or 2 (methyl) acryloyl group
Thing has the compound of ethylenic unsaturated bond as (B).
(b2) there is the compound of epoxy butane chain and 1 or 2 (methyl) acryloyl group from the viewpoint of suppression is oozed out, tool
Have preferably more than 500, more preferably more than 700, further preferred more than 1000 molecular weight.
There is the compound of epoxy butane chain and 1 or 2 (methyl) acryloyl group as (b2), can enumerate：Polytetramethylene
Glycol (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate etc..
Specifically, the compound of (b2) with epoxy butane chain and 1 or 2 (methyl) acryloyl group be with preferably 1~
20, more preferably 4~15, the C of further preferred 6~124H8O (methyl) acrylate or two (methyl) acrylate.
Relative to the solid constituent total amount of photosensitive polymer combination, (b2) has epoxy butane chain and 1 or 2 (methyl) third
The content of the compound of enoyl- is preferably greater than 0 mass % and is below 20 mass %.
Photosensitive polymer combination can contain (b3) and be used as (B) with alkene with the compound of aromatic rings and ethylenic unsaturated bond
Belong to the compound of unsaturated bond.
(b3) compound with aromatic rings and ethylenic unsaturated bond can also be with alkylene oxide chain.Aromatic rings is preferably with from double
Being introduced to of form of the O divalent aromatic bases such as phenol A divalence skeleton, the divalence skeleton from naphthalene, phenylene, methylphenylene
In compound.Alkylene oxide chain can be ethylene oxide chain, expoxy propane chain or combinations thereof.Ethylenic unsaturated bond is preferably with (first
Base) form of acryloyl group is introduced in compound.
Specifically, it can use the compound shown in following logical formula (II)s that there is aromatic rings and ethylenic unsaturated bond as (b3)
Compound,
In formula (II), R1And R2Separately represent hydrogen atom or methyl, A C2H4, B C3H6, n1And n3Separately
For 1~39 integer, and n1+n3For 2~40 integer, n2And n4The separately integer for 0~29, and n2+n4For 0~30
Integer, it can also be randomly block that the arrangement of-(A-O)-and-(B-O)-repeat unit, which can be, in the situation for block
Under, any one of-(A-O)-and-(B-O)-are in xenyl side.}.
From the viewpoint of resolution ratio and adaptation, such as preferably in the average each 5 moles ring of the both ends of bisphenol-A difference addition
The dimethylacrylate of polyethylene glycol obtained from oxidative ethane, the average each 2 moles epoxy of addition is distinguished at the both ends of bisphenol-A
The dimethylacrylate of polyethylene glycol obtained from ethane, the average each 1 mole epoxy second of addition is distinguished at the both ends of bisphenol-A
Dimethylacrylate of polyethylene glycol obtained from alkane etc..
In addition, as the foregoing compound with aromatic rings, alkylene oxide chain and ethylenic unsaturated bond, above-mentioned formula can be used
(II) aromatic rings in has the compound of hetero atom and/or substituent.
As hetero atom, such as can enumerate：Halogen atom etc., and substituent is used as, it can enumerate：Alkyl, the carbon number of carbon number 1~20
3~10 cycloalkyl, the aryl of carbon number 6~18, phenacyl, amino, the alkyl amino of carbon number 1~10, carbon number 2~20
Dialkyl amido, nitro, cyano group, carbonyl, sulfydryl, the alkyl thiol of carbon number 1~10, aryl, hydroxyl, the hydroxyl of carbon number 1~20
Acyl group that alkyl, carboxyl, the carboxyalkyl that the carbon number of alkyl is 1~10, the carbon number of alkyl are 1~10, the alcoxyl of carbon number 1~20
Base, the alkoxy carbonyl of carbon number 1~20, the alkyl-carbonyl of carbon number 2~10, the alkenyl of carbon number 2~10, the N- of carbon number 2~10
Alkyl-carbamoyl or group comprising heterocycle or aryl obtained from being substituted using these substituents etc..These take
Condensed ring can be formed for base, or, the hydrogen atom in these substituents can be substituted by hetero atoms such as halogen atoms.Formula
(II) when the aromatic rings in has multiple substituents, multiple substituents can be with identical or different.
Relative to the solid constituent total amount of photosensitive polymer combination, (b3) has the compound of aromatic rings and ethylenic unsaturated bond
Content be preferably greater than 0 mass % and be below 50 mass %.When the content is more than 0 mass %, there are resolution ratio and adaptation to obtain
To improved tendency, from the viewpoint of developing time and edge-melting (edge fusion), preferably below 50 mass %.
Described above have alkylene oxide chain and (methyl) acrylate compounds of dipentaerythritol skeleton and (b1)~
(b3) compound can separately using or be applied in combination.In photosensitive polymer combination, there is olefinic insatiable hunger as (B)
With the compound of key, it can also not only contain (methyl) acrylate compounds with alkylene oxide chain and dipentaerythritol skeleton
And (b1)~(b3) compounds, also containing other compounds.
As other compounds, can enumerate：Acrylate compounds with least one (methyl) acryloyl group, with amino
(methyl) acrylate of formic acid ester bond, make alpha, beta-unsaturated carboxylic acid and polyol reaction obtained from compound, make α, β-no
Saturated carboxylic acid and compound, phthalic acid based compound etc. obtained from the compound reaction containing glycidyl.Wherein, from point
From the viewpoint of resolution, adaptation and splitting time, the preferred acrylate chemical combination with least two (methyl) acryloyl group
Thing.Acrylate compounds with least two (methyl) acryloyl group can be two (methyl) acrylate, three (methyl) third
Olefin(e) acid ester, four (methyl) acrylate, five (methyl) acrylate, six (methyl) acrylate etc..From flexibility, resolution ratio,
The viewpoints such as adaptation are set out, for example, preferably polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate,
With both oxirane and PPOX two (methyl) acrylate (such as " FA-023M, FA-024M, FA-027M,
ProductName, Hitachi Chemical Co., Ltd.'s manufacture ").
In addition, from the viewpoint of fissility, cured film flexibility, the glycol propylene of 4- n-nonyls phenoxy group eight acid is preferably comprised
Ester, 4- n-nonyl phenoxy group tetraethylene glycols acrylate, γ-adjacent benzene of chloro- beta-hydroxy propyl group-β '-methacryloxyethyls-
The such compound with 1 ethylenic unsaturated bond of dicarboxylic acid esters, from the viewpoint of sensitivity, resolution ratio or adaptation,
Preferably comprise γ-chloro- beta-hydroxy propyl group-β '-methacryloxyethyl-phthalic acid ester.
In present embodiment, from the adaptation for improving corrosion-resisting pattern, and the solidification for suppressing corrosion-resisting pattern bad, developing time is prolonged
Late, cold flow or ooze out or solidify resist layer stripping delay so from the viewpoint of, the whole in photosensitive polymer combination
(B) have ethylenic unsaturated bond compound total content preferably in the mass % of 1 mass %~70, more preferably in 2 mass %
~60 mass %, further preferably in the range of the mass % of 4 mass %~50.
(C) Photoepolymerizationinitiater initiater
(C) Photoepolymerizationinitiater initiater is to make the compound that monomer polymerize using light.Photosensitive polymer combination contains this technology
Commonly known compound is used as (C) Photoepolymerizationinitiater initiater in field.
The total content of (C) Photoepolymerizationinitiater initiater in photosensitive polymer combination is preferably in 0.01~20 mass %, more preferably exist
The mass % of 0.05 mass %~10, further preferably in the mass % of 0.1 mass %~7, particularly preferably in the matter of 0.1 mass %~6
In the range of amount %.(C) total content of Photoepolymerizationinitiater initiater is from the viewpoint of enough sensitivity is obtained, preferably 0.01 matter
More than % is measured, from making light fully pass through to resist layer bottom surface, and from the viewpoint of obtaining good high-resolution, preferably 20
Below quality %.
As (C) Photoepolymerizationinitiater initiater, can enumerate：Quinones, aromatic series ketone, acetophenones, acylphosphine oxide class, benzoin or
Benzoin ethers, dialkyl group ketal class, thioxanthene ketone class, dialkylaminobenzoic acid esters class, oxime esters, acridine (from sensitivity,
From the viewpoint of resolution ratio and adaptation, such as preferably 9- phenylacridines, double acridine base heptanes, 9- (p-methylphenyl) a word used for translation
Pyridine, 9- (aminomethyl phenyl) acridine), and then can enumerate：Six aryl bisglyoxalines, pyrazoline compounds, anthracene compound are (from sensitive
From the viewpoint of degree, resolution ratio and adaptation, such as preferably 9,10- dibutoxies anthracene, 9,10- diethoxies anthracene, 9,10-
Diphenylanthrancene), coumarin compound is (from the viewpoint of sensitivity, resolution ratio and adaptation, such as preferably 7- diethyl
Amino -4- methylcoumarins), N- aryl amino acids or its ester compounds (go out from the viewpoint of sensitivity, resolution ratio and adaptation
Hair, such as preferably N-phenylglycine) and halogen compounds (such as trisbromomethyl phenyl sulfone) etc..They can be independent
Using a kind or two or more is applied in combination.Other, can use：2,2- dimethoxy -1,2- diphenylethane -1- ketone, 2- first
Base -1- (4- methyl mercaptos phenyl) -2- morpholinopropane -1- ketone, 2,4,6- trimethylbenzoy-diphenies-phosphine oxide, triphen
Base phosphine oxide etc..
As aromatic series ketone, such as can enumerate：Benzophenone, Michler's keton [4,4 '-bis- (dimethylamino) benzophenone], 4,
4 '-bis- (diethylamino) benzophenone, 4- methoxyl groups -4 '-dimethylamino benzophenone.They can be used alone
Or two or more is applied in combination.Among these, from the viewpoint of adaptation, preferably 4,4 '-bis- (diethylamino) hexichol first
Ketone.And then from the viewpoint of transmissivity, the content of the aromatic series ketone in photosensitive polymer combination is preferably in 0.01 matter
Measure the mass % of %~0.5, further preferably in the range of the mass % of 0.02 mass %~0.3.
As the example of six aryl bisglyoxalines, can enumerate：2- (Chloro-O-Phenyl) -4,5- diphenyl bisglyoxaline, 2,2 ', 5- tri--(adjacent
Chlorphenyl) -4- (3,4- Dimethoxyphenyls) -4 ', 5 '-diphenyl bisglyoxaline, 2,4- pairs-(Chloro-O-Phenyl) -5- (3,4- diformazans
Phenyl)-diphenyl bisglyoxaline, 2,4,5- tri--(Chloro-O-Phenyl)-diphenyl bisglyoxaline, 2- (Chloro-O-Phenyl)-bis- -4,5-
(3,4- Dimethoxyphenyls)-bisglyoxaline, 2,2 '-bis--(2- fluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-connection miaow
Azoles, 2,2 '-bis--(2,3- difluoromethyls phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-bisglyoxaline, 2,2 '-it is bis--(2,
4- difluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-bisglyoxalines, 2,2 '-bis--(2,5- difluorophenyls) -4,4 ', 5,
5 '-four-(3- methoxyphenyls)-bisglyoxalines, 2,2 '-bis--(2,6- difluorophenyls) -4,4 ', 5,5 '-four-(3- methoxybenzenes
Base)-bisglyoxaline, 2,2 '-bis--(2,3,4- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-bisglyoxaline, 2,2 ' -
Double-(2,3,5- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-bisglyoxaline, 2,2 '-bis--(2,3,6- trifluoro-benzenes
Base) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-bisglyoxalines, 2,2 '-bis--(2,4,5- trifluorophenyls) -4,4 ', 5,5 '-four -
(3- methoxyphenyls)-bisglyoxaline, 2,2 '-bis--(2,4,6- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-connection
Imidazoles, 2,2 '-bis--(2,3,4,5- tetrafluoros phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-bisglyoxaline, 2,2 '-it is bis- -
(2,3,4,6- tetrafluoros phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-bisglyoxaline and 2,2 '-bis--(2,3,4,5,6-
Pentafluorophenyl group) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-bisglyoxalines etc., they can be used alone or be applied in combination 2
More than kind.From the viewpoint of high sensitivity, resolution ratio and adaptation, preferably 2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazoles two
Aggressiveness.
In present embodiment, in photosensitive polymer combination the content of hexa-aryl bi-imidazole compound from improve photo-sensitive resin
Peel property and/or sensitivity from the viewpoint of, preferably in the mass % of 0.05 mass %~7, more preferably 0.1 mass %~
6 mass %, further preferably in the range of the mass % of 1 mass %~4.
From the viewpoint of the peel property of photo-sensitive resin, sensitivity, resolution ratio or adaptation, photosensitive resin composition
Thing preferably comprises pyrazoline compounds as sensitising agent.
As pyrazoline compounds, from the above point of view, such as preferably 1- phenyl -3- (4- tert-butyl-styrenes base) -5-
(4- tbutyl-phenyls)-pyrazoline, 1- (4- (benzoxazole -2- bases) phenyl) -3- (4- tert-butyl-styrenes base) -5- (4-
Tbutyl-phenyl)-pyrazoline, 1- phenyl -3- (4- xenyls) -5- (4- tbutyl-phenyls)-pyrazoline, 1- phenyl -3- (4-
Xenyl) -5- (4- t-octyls-phenyl)-pyrazoline, 1- phenyl -3- (4- isopropyl styrenes base) -5- (4- cumenes
Base)-pyrazoline, 1- phenyl -3- (4- methoxyl-styrenes) -5- (4- methoxyphenyls)-pyrazoline, 1- phenyl -3- (3,5-
Dimethoxy-styryl) -5- (3,5- Dimethoxyphenyls)-pyrazoline, 1- phenyl -3- (3,4 dimethoxy styrenes
Base) -5- (3,4- Dimethoxyphenyls)-pyrazoline, 1- phenyl -3- (2,6- dimethoxy-styryls) -5- (2,6- dimethoxies
Base phenyl)-pyrazoline, 1- phenyl -3- (2,5- dimethoxy-styryls) -5- (2,5- Dimethoxyphenyls)-pyrazoline, 1-
Phenyl -3- (2,3- dimethoxy-styryls) -5- (2,3- Dimethoxyphenyls)-pyrazoline, 1- phenyl -3- (2,4- diformazans
Epoxide styryl) -5- (2,4- Dimethoxyphenyl)-pyrazoline etc., more preferably 1- phenyl -3- (4- xenyls) -5- (4-
Tbutyl-phenyl)-pyrazoline.
Photosensitive polymer combination can contain one kind or two or more pyrazoline compounds as sensitising agent.
In present embodiment, the content of the sensitising agent in photosensitive polymer combination is from the peel property for improving photo-sensitive resin
And/or from the viewpoint of sensitivity, preferably in the mass % of 0.05 mass %~5, more preferably the mass %'s of 0.1 mass %~3
In the range of.
(D) additive
Photosensitive polymer combination can contain the additives such as dyestuff, plasticizer, antioxidant, stabilizer needed for.Such as
The additive enumerated in Japanese Unexamined Patent Publication 2013-156369 publications can be used.
From the viewpoint of coloring, form and aspect stability and exposure contrast, photosensitive polymer combination preferably comprises three (4- bis-
Methylamino phenyl) methane [leuco crystal violet] and/or diamond green (HODOGAYA CHEMICAL CO., LTD. AIZEN
(registration mark) DIAMOND GREEN GH) it is used as dyestuff.
In present embodiment, the content of the dyestuff in photosensitive polymer combination preferably in the mass % of 0.001 mass %~3, more
It is preferred that in the mass % of 0.01 mass %~2, further preferably in the range of the mass % of 0.02 mass %~1.The content of dyestuff
From the viewpoint of good coloring is obtained, preferably more than 0.001 mass %, from the sensitivity for maintaining photo-sensitive resin
From the viewpoint of, preferably below 3 mass %.
From the viewpoint of the heat endurance of photosensitive polymer combination or bin stability, photosensitive polymer combination preferably wraps
Containing selected from by radical polymerization inhibitor, such as nitrosophenylhydroxylamine aluminium salt, p methoxy phenol, 4- tert-butyl os benzene two
Phenol, 4- ethyl -6- tert-butyl phenols etc.；Benzotriazole, such as 1- (2- di-n-butyls amino methyl) -5- carboxyl benzotriazoles
With the 1 of 1- (2- di-n-butyls amino methyl) -6- carboxyl benzotriazoles:1 mixture etc.；Carboxyl benzotriazole class, such as 4- carboxylics
Base-l, 2,3 triazole, 5- carboxyls-l, 2,3 triazole, 6- carboxyls-l, 2,3 triazole etc.；And with shrink
Glyceryl oxirane compounds, the composition such as neopentylglycol diglycidyl ether group at least one as stabilizer.
In addition, can also contain：2-mercaptobenzimidazole, 1H-TETRAZOLE, 1- methyl -5- sulfydryls -1H-TETRAZOLE, 2- amino -5- mercaptos
Base -1,3,4- thiadiazoles, 3- amino -5- sulfydryl -1,2,4- triazoles, 3- sulfydryl -1,2,4- triazoles, 3- mercapto-triazoles, 4,5- bis-
Phenyl -1,3- diazole -2- bases, 5- amino -1H-TETRAZOLE etc..
In present embodiment, the total content of whole stabilizers in photosensitive polymer combination is preferably in 0.001 mass %~3
Quality %, more preferably in the mass % of 0.01 mass %~1, further preferably in the range of the mass % of 0.05 mass %~0.7.
The total content of stabilizer to photosensitive polymer combination from the viewpoint of good bin stability is assigned, and preferably 0.001
More than quality %, from the viewpoint of the sensitivity for maintaining photo-sensitive resin, preferably below 3 mass %.
The additive of described above can be used alone or two or more is applied in combination.
<Photosensitive polymer combination seasoning liquid>
In present embodiment, by adding solvent to photosensitive polymer combination, photosensitive polymer combination allotment can be formed
Liquid.As suitable solvent, can enumerate：Ketone, such as MEK (MEK)；And alcohols, such as methanol, ethanol, isopropanol
Deng.It is preferred that turn into the side of 500mPa seconds~4000mPa seconds at 25 DEG C with the viscosity of photosensitive polymer combination seasoning liquid
Formula, add a solvent in photosensitive polymer combination.
<Photoresist layered product>
In present embodiment, it is possible to provide a kind of photoresist layered product, its have supporter and be laminated on supporter by
The photo-sensitive resin that above-mentioned photosensitive polymer combination is formed.Photoresist layered product can be in photonasty tree needed for
Lipid layer has protective layer with support side opposite side.
As supporter, have no particular limits, preferably make the light transmissive transparent supporting body from exposure light source radiation.It is used as this
Kind supporter, such as can enumerate：Pet film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride
Copolymer film, polyvinylidene chloride film, vinylidene chloride are copolymerized film, polymethyl methacrylate copolymer film, gathered
Styrene film, polyacrylonitrile film, styrol copolymer film, polyamide film and cellulose derivative film.These
Film can carry out overstretching as needed.Mist degree is preferably 0.01%~5.0%, is more preferably 0.01%~2.5%, enters one
Step is preferably 0.01%~1.0%.For the thickness of film, film is thinner more to be had in terms of image formative and economy
Profit, due to need maintain intensity, preferably 10 μm~30 μm.
In addition, the key property of the protective layer used in photoresist layered product is, protective layer and photo-sensitive resin
Closing force is less than the closing force of supporter and photo-sensitive resin, can be easily peeled off.As protective layer, such as preferred polyethylene
Film, polypropylene film etc..Such as excellent thin of fissility described in Japanese Unexamined Patent Application 59-202457 publications can be used
Film.The thickness of protective layer is preferably 10 μm~100 μm, more preferably 10 μm~50 μm.
In present embodiment, the thickness of the photo-sensitive resin in photoresist layered product is preferably 5 μm~100 μm, more excellent
Elect 7 μm~60 μm as.The thickness of photo-sensitive resin is smaller, and the resolution ratio of corrosion-resisting pattern more improves, and on the other hand, thickness is bigger
Solidification film strength more improves, and therefore, can be selected according to purposes.
As stack gradually supporter, photo-sensitive resin and according to required protective layer come make photoresist stacking
The method of body, known method can be used.
For example, preparing above-mentioned photosensitive polymer combination seasoning liquid, then it is coated on using bar coater or roll coater on supporter
And make its drying, so as to be laminated the photo-sensitive resin formed by photosensitive polymer combination seasoning liquid on supporter.And then
According to required, by being laminated protective layer on photo-sensitive resin, photoresist layered product can be made.
<Corrosion-resisting pattern forming method>
The forming method of corrosion-resisting pattern preferably includes following process successively：It is photosensitive by being formed by above-mentioned photosensitive polymer combination
Property resin bed is laminated in the lamination process of supporter, the exposure process being exposed to photo-sensitive resin and to exposure
The developing procedure that photo-sensitive resin is developed.The specific method of corrosion-resisting pattern is formed in present embodiment described below
One.
First, it is laminated in process, photo-sensitive resin is formed on substrate using laminating machine.Specifically, in photoresist
When layered product has protective layer, after peeling off protective layer, photo-sensitive resin heating is crimped on substrate surface using laminating machine and
It is laminated.As the material of substrate, such as can enumerate：Copper, stainless steel (SUS), glass, tin indium oxide (ITO) etc..
In present embodiment, photo-sensitive resin can only be laminated to the one side of substrate surface or can also be laminated as needed
In two-sided.Heating-up temperature during lamination is usually 40 DEG C~160 DEG C.In addition, by carrying out heating pressure during more than 2 times laminations
Connect, adaptation of the gained corrosion-resisting pattern to substrate can be improved.During heating crimping, it can use with the two two-part layers for connecting roller
Press can also make the sandwich of substrate and photo-sensitive resin repeatedly repeatedly from roller by being crimped.
Then, in exposure process, photoresist group layer is exposed under active light using exposure machine.Exposure can be according to institute
Carried out after supporter need to be peeled off.When being exposed by photomask, light exposure can according to light illumination and time for exposure come
It is determined that it can be measured using quantometer.In exposure process, direct imaging exposure can be carried out.In direct imaging exposure, no
It is exposed using photomask using direct drawing apparatus on substrate.As light source, wavelength 350nm~410nm can be used
Semiconductor laser or ultrahigh pressure mercury lamp.When controlling depicting pattern using computer, light exposure according to the illumination of exposure light source and
The translational speed of substrate and determine.Can also be by making the image of photomask be projected by lens to be exposed.
Then, it is unexposed in the photo-sensitive resin after being exposed using developing apparatus using developer solution removal in developing procedure
Portion or exposure portion.When having supporter after exposure, on photo-sensitive resin, remove it.Then, using being formed by aqueous alkali
Developer solution, unexposed portion or exposure portion development are removed, obtain resist pattern picture.
As aqueous alkali, preferably Na2CO3、K2CO3Deng the aqueous solution.Aqueous alkali can be according to the spy of photo-sensitive resin
Property selected, usually using the Na of the mass % of 0.2 mass %~2 concentration2CO3The aqueous solution.In aqueous alkali, it can mix
Surfactant, defoamer, a small amount of organic solvent etc. for promoting development.The temperature of developer solution in developing procedure preferably exists
Keep constant in the range of 20 DEG C~40 DEG C.
Corrosion-resisting pattern can be obtained by above-mentioned operation, according to required, heating process can also be carried out at 100 DEG C~300 DEG C.It is logical
Cross and implement the heating process, the chemical proofing of corrosion-resisting pattern can be improved.In heating process, can use using hot blast,
The heating furnace of infrared ray or far infrared mode.
The photosensitive polymer combination of present embodiment can be used for the circuit to form printed base plate.Usually as printed base plate
Circuit forming method, abatement technique and half additive process (SAP) can be used.
Abatement technique is that the conductor that substrate entire surface is placed in by etching autogamy only removes inverter circuit part to form the side of circuit
Method.
SAP is that the inverter circuit part on the conductor seed layer of substrate entire surface is configured at forms resist layer, then passes through plating
The method for only forming circuit part.
In present embodiment, photosensitive polymer combination is more preferably used for SAP.
<The solidfied material of photosensitive polymer combination>
In present embodiment, in order to improve the flexibility of corrosion-resisting pattern, the elongation of the solidfied material of photosensitive polymer combination is excellent
Elect more than 1mm, more preferably more than 2mm, more preferably more than 3mm as.
The elongation of solidfied material is measured by the following method：To the photoresist made using photosensitive polymer combination
Layered product is exposed by 5mm × 40mm rectangular mask, and then is carried out with 2 times of the time of minimum developing time
Development, using cupping machine (ORIENTEC Co., Ltd.s system, RTM-500) with solid obtained by the speed tensile of 100mm/ minutes
Change resist layer.
In present embodiment, the resolution ratio and flexibility of the Young's modulus of the solidfied material of photosensitive polymer combination from corrosion-resisting pattern
From the viewpoint of, preferably in the range of 1.5Gpa is less than 8GPa.In this specification, " Young's modulus " can use
TOYO TECHNICA Co., Ltd. nano-hardness tester (Nano Indenter) DCM is determined by Nanoindentation.It is specific and
Speech, on " Young's modulus ", using TOYO TECHNICA Co., Ltd.s nano-hardness tester DCM for by measure object resin
The photosensitive polymer combination surface on substrate that composition layer is pressed on substrate and is exposed, develops and obtain is surveyed
It is fixed.It is (multiple using DCM Basic Hardness, Modulus, Tip Cal, Load Control.msm as mensuration mode
Loading-unloading mode, MultiLoad Method), the parameter of indentation test is：Unload percentage (Percent To
Unload)=90%, maximum load (Maximum Load)=1gf, load factor multiply unloading rate (Load Rate Multiple
For Unload Rate)=1, loading number (Number Of Times to Load)=5, peak holding time (Peak
Hold time)=10s, load time (Time To Load)=15s, Poisson's ratio (Poisson's ratio)=0.25.Poplar
Family name's modulus is the value of " modulus of elasticity (Modulas At Max Load) under maximum load ".
<The manufacture method of conductive pattern>
The manufacture method of conductive pattern preferably includes following process successively：Process is laminated, in metallic plate, metal film coated insulation board etc.
The photo-sensitive resin formed by above-mentioned photosensitive polymer combination is laminated on substrate；Exposure process, photo-sensitive resin is entered
Row exposure；Developing procedure, unexposed portion or the exposure portion of the photo-sensitive resin of exposure are removed by using developer solution, obtains shape
Into the substrate for having corrosion-resisting pattern；And conductive pattern formation process, the substrate formed with corrosion-resisting pattern is etched or plating.
In present embodiment, the manufacture method of conductive pattern is carried out as follows：Made by using metallic plate or metal film coated insulation board
For substrate, after corrosion-resisting pattern is formed by above-mentioned corrosion-resisting pattern forming method, by conductive pattern formation process, so as to enter
OK.In conductive pattern formation process, known etching method is being used on the substrate surface (such as copper face) that exposes by development
Or plating method and form conductive pattern.
And then the present invention is for example suitably adapted to following purposes.
<The manufacture method of circuit board>
After conductive pattern is manufactured by the manufacture method of conductive pattern, further utilized has highly basic compared with developer solution
The aqueous solution of property and from the stripping process of strippable substrate corrosion-resisting pattern, it is possible thereby to obtain the circuit with required wiring pattern
Plate (such as printed circuit board (PCB)).
In the manufacture of circuit board, substrate is used as using the layered product or flexible substrate of insulating resin layer and layers of copper.In order to carry out
SAP, preferably using insulating resin layer and the layered product of layers of copper.On SAP, layers of copper is preferably comprising chemistry palladium as catalyst
Copper plate.On SAP, it is also preferred that carrying out conductive pattern formation process by known plating method.Add to carry out modified form half
Into technique (MSAP), substrate is preferably the layered product of insulating resin layer and copper foil, more preferably copper-clad laminated board.
On the aqueous alkali (hereinafter also referred to as " stripper ") of stripping, have no particular limits, usually using 2 mass %
The NaOH or KOH of~5 mass % the concentration aqueous solution or organic amine system stripper.It can be added in stripper a small amount of
Water-soluble solvent.As water-soluble solvent, such as alcohol etc. can be enumerated.The temperature of stripper in stripping process is preferably at 40 DEG C
In the range of~70 DEG C.
In order to carry out SAP, the manufacture method of circuit board preferably also includes the process that palladium removing is gone from gained circuit board.
<The manufacture of lead frame>
Using the metallic plate of copper, copper alloy or iron-based alloy etc. as substrate, resist pattern is formed by corrosion-resisting pattern forming method
After case, lead frame is made by following process.First, enter to be about to by developing the substrate etch that exposes so as to form conductor figure
The process of case.Then, enter to be about to the stripping process that corrosion-resisting pattern peels off with the method same with the manufacture method of circuit board, can be with
Lead frame needed for obtaining.
<The manufacture of base material with relief pattern>
When and the corrosion-resisting pattern formed may be used as that substrate is implemented to process by blasting method by corrosion-resisting pattern forming method
Protection mask member.Now, as substrate, such as can enumerate：Glass, Silicon Wafer, non-crystalline silicon, polysilicon, ceramics, Lan Bao
Stone, metal material etc..Corrosion-resisting pattern is formed by the method same with corrosion-resisting pattern forming method on these substrates.Then,
It is cut to the blasting treatment process of target depth by blowing sand-blast material above the corrosion-resisting pattern formed and uses alkali
Stripper etc. removes the stripping process of the corrosion-resisting pattern part remained on substrate from substrate, and can manufacture has on substrate
The base material of fine relief pattern.
In blasting treatment process, known sand-blast material can be used, such as can generally use comprising SiC, SiO2、Al2O3、
CaCO3, ZrO, glass, stainless steel etc. 2 μm~100 μm of particle diameter particulate.
<The manufacture of semiconductor package body>
The wafer finished using the formation of large scale integrated circuit (LSI) is existed as substrate by corrosion-resisting pattern forming method
After forming corrosion-resisting pattern on wafer, by following process, it is possible thereby to manufacture semiconductor package body.First, carry out to by aobvious
The column plating of copper, solder etc. is implemented in shadow and the opening portion exposed, so as to form the process of conductive pattern.Then, carry out with
The stripping process that the same method of the manufacture method of circuit board peels off corrosion-resisting pattern, further removed by etching except column is plated
Coated with the process of the thin metal layer of outer part, it is possible thereby to obtain required semiconductor package body.
In present embodiment, photosensitive polymer combination can be used for the manufacture of printed circuit board (PCB)；IC chip carrying lead frame
Manufacture；The metal foil Precision Machinings such as metal mask manufacture；The packaging bodies such as ball grid array (BGA), chip size packages body (CSP)
Manufacture；The manufacture of the belt base plates such as chip on film (COF), carrier band automatic welding (TAB)；The manufacture of semiconductor projection；And ITO
The manufacture of the partition wall of the flat-panel monitors such as electrode, addressing electrode, electromagnetic wave shield.
It should be noted that the value on above-mentioned each parameter, in the case of no special declaration, according in aftermentioned embodiment
Assay method is measured.
Embodiment
For the determining of high molecular physics value, the calculating of high molecular glass transition temperature and embodiment and comparative example
The preparation method of sample for evaluation illustrate, then, evaluation method and its evaluation result for gained sample are shown.
(1) measure of physics value or calculating
<The measure of high molecular weight average molecular weight or number-average molecular weight>
High molecular weight average molecular weight or number-average molecular weight are the gel permeation chromatographs using Japan Spectroscopy Corporation
(GPC) (pump：Gulliver, PU-1580 type, post：Showa Denko K. K Shodex (registration mark) (KF-807, KF-
806M, KF-806M, KF-802.5) 4 pieces series connection；Mobile phase solvent：Tetrahydrofuran；Using (clear based on polystyrene standard sample
With electrician Co. Ltd. system Shodex STANDARD SM-105) calibration curve) with polystyrene convert and obtain.
And then ratio (weight average molecular weight/number equal molecule of the high molecular decentralization with weight average molecular weight relative to number-average molecular weight
Amount) form calculate.
<Acid equivalent>
In this specification, acid equivalent refers to the quality (gram) of the polymer of the carboxyl with 1 equivalent in molecule.Use flat natural pond industry
The flat natural pond automatic titration device (COM-555) of Co. Ltd. system, passes through potential difference using 0.1mol/L sodium hydrate aqueous solution
Titration determines acid equivalent.
<Glass transition temperature>
The high molecular glass transition temperature of alkali solubility is the value obtained according to following formula (Fox formulas),
[mathematical expression 1]
In formula, WiTo form the respective quality of the high molecular comonomer of alkali solubility, TgiIt is high molecular common to form alkali solubility
Polycondensation monomer is respectively glass transition temperature during homopolymer, WtotalFor the high molecular gross mass of alkali solubility,
And n is the quantity for the species for forming the high molecular comonomer of alkali solubility.}.
Wherein, glass transition temperature Tg is obtainediWhen, form what the high molecular comonomer of alkali solubility was formed as by corresponding
The glass transition temperature of homopolymer, " the polymer handbook third edition is compiled using Brandrup, J.Immergut, E.H.
(Polymer handbook, Third edition), John wiley＆sons, 1989, VI chapter ＜ polymer of page 209
The value shown in glass transition temperature (Glass transition temperatures of polymers) ＞ ".Need
It is bright, the Tg for the homopolymer that will be formed in embodiment used in calculating by each comonomeriIt is shown in table 1.
<(B) weight average molecular weight of the compound with ethylenic unsaturated bond>
In embodiment I-1~I-16 and Comparative Example I -1~I-3, there is the molecule knot of the compound of ethylenic unsaturated bond according to (B)
Structure is calculated, and thus obtains molecular weight.When the compound that a variety of (B) have ethylenic unsaturated bond be present, by each chemical combination
The molecular weight of thing is weighted average and obtained according to content.
In addition, in embodiment II-1~II-6 and Comparative Example I I-1~II-5, have the weight of the compound of ethylenic unsaturated bond equal
Molecular weight is to utilize Japan Spectroscopy Corporation's gel permeation chromatograph (GPC) (pump：Gulliver, PU-1580 type, post：It is clear
With 4 series connection of electrician's Co. Ltd. system Shodex (registration mark) (K-801, K-801, K-802, KF-802.5), flowing mixes
Agent：Tetrahydrofuran, using based on polystyrene standard sample (Tosoh Corporation TSK standard
POLYSTYRENE calibration curve)) so that polystyrene converts and obtains.
<(B) concentration of the methylacryloyl in the compound with ethylenic unsaturated bond>
Molal quantity of the methylacryloyl relative to the compound 100g of (B) with ethylenic unsaturated bond is obtained by calculating.
<(B) concentration of oxirane (EO) unit in the compound with ethylenic unsaturated bond>
Mole of oxirane (EO) unit relative to the compound 100g of (B) with ethylenic unsaturated bond is obtained by calculating
Number.
(2) preparation method of sample for evaluation
Sample for evaluation makes as follows.
<The making of photoresist layered product>
By the composition shown in table 2 below~5, (wherein, the numeral of each composition represents the compounding amount (quality in terms of solid constituent
Part).) and solvent be sufficiently stirred, be obtained by mixing photosensitive polymer combination seasoning liquid.To be represented in table 2 and 4 with writing a Chinese character in simplified form into
The title divided is shown in Table 3 below and 5.As support membrane, the pet film of 16 μ m-thicks is used
(Toray Industries, Inc. systems, FB-40), is equably coated with the seasoning liquid using bar coater, at 95 DEG C on the surface
Dried 2.5 minutes in drying machine, form photosensitive polymer combination layer.The dry thickness of photosensitive polymer combination layer is 25 μ
m。
Then, it is bonded in not being laminated on the surface of pet film side for photosensitive polymer combination layer
As the polyethylene film (Tamapoly Co., Ltd.s system, GF-818) of 19 μ m-thicks of protective layer, photoresist stacking is obtained
Body.
<The whole face of substrate>
In embodiment I-1~I-16 and Comparative Example I -1~I-3, as sensitivity, image, adaptation and chemical reagent resistance
Evaluation substrate, using soft etchant (Ling Jiang KCCs system, CPE-900) to being laminated with 35 μm of rolled copper foils
Copper-clad laminated board thick 0.4mm is handled, and utilizes 10 mass %H2SO4Cleaning base plate surface.
In addition, in embodiment II-1~II-6 and Comparative Example I I-1~II-5, using removing material (Japan Carlit Co.,
Ltd. make, Sakurundum R (registration mark #220)), it is thick to the 0.4mm for being laminated with 35 μm of rolled copper foils to spray 0.2MPa
Copper-clad laminated board carry out jet douche grinding, thus make evaluation substrate.
<Lamination>
While the polyethylene film of photoresist layered product is peeled off, while utilizing hot roll laminator (Asahi Kasei Corporation
System, AL-700) photoresist layered product is laminated at 105 DEG C of roll temperature carries out surface and adjust and be preheated to 60 DEG C
On copper-clad laminated board, so as to obtain test film.Air pressure is set to 0.35MPa, laminate speed is set to 1.5m/ minutes.
<Exposure>
In embodiment I-1~I-16 and Comparative Example I -1~I-3, directly description exposure machine (Hitachi Via are utilized
Mechanics, Ltd. system, DE-1DH, light source：GaN royal purple diodes, 405 ± 5nm of dominant wavelength) and take 41 grades of ranks using this figure
Segmentation exposure guide rule or the mask pattern of defined direct imaging (DI) exposure, in illumination 85mW/cm2Under conditions of exposed
Light.Highest residual film series when exposure is so that this foregoing figure 41 grades of stage exposure guide rules of expense are exposed as mask, developed
Carried out as 15 grades of light exposures.
In addition, in embodiment II-1~II-6 and Comparative Example I I-1~II-5, using chromium glass mask, parallel exposing machine is utilized
(ORC MANUFACTURING CO., LTD. systems, HM-801) is exposed with the light exposure shown in table 4.
<Development>
In embodiment I-1~I-16 and Comparative Example I -1~I-3, by the polyethylene terephthalate of the evaluation substrate of exposure
After film is peeled off, using alkaline development machine (Fuji Kiko KK's system, dry film developing machine) by 30 DEG C of 1 mass %
Na2CO3The aqueous solution is sprayed with the stipulated time, and the unexposed portion of photo-sensitive resin is dissolved and removed.Now, after most
2 times of the time of small developing time is developed, so as to make solidification corrosion-resisting pattern.It should be noted that minimum developing time
Refer to that the photo-sensitive resin of unexposed portion is completely dissolved the required minimum time.
In addition, in embodiment II-1~II-6 and Comparative Example I I-1~II-5, from photo-sensitive resin stack by poly- terephthaldehyde
After sour glycol ester film is peeled off, using Fuji Kiko KK's developing apparatus, using the nozzle of full cone with spray of developing
0.15MPa is pressed to be sprayed 30 DEG C of 1 mass %Na with the stipulated time2CO3The aqueous solution is developed, and dissolving removes photoresist
The unexposed portion of layer.Now, the photo-sensitive resin for determining unexposed portion is completely dissolved the required minimum time as most
Small developing time, developed with 2 times of the time of minimum developing time and make corrosion-resisting pattern.Now, washing step is profit
Sprayed 0.15MPa to be washed with pancake nozzle and handled with developing procedure within the same time.
(3) evaluation method of sample
<Sensitivity evaluation>
The mask that sensitivity evaluation substrate after lamination after 15 minutes is taken into 41 grades of stage exposure guide rules by this figure enters
Row exposure.Developed with 2 times of the time of minimum developing time, be 15 grades of exposure to highest residual film series by following benchmark
Light quantity is classified.
Zero (good)：Highest residual film series is that 15 grades of light exposure is less than 70mJ/cm2。
× (bad)：The light exposure that highest residual film series is 15 grades is 70mJ/cm2More than.
<Resolution ratio>
The use of the width with exposure portion and unexposed portion is 1:The description data of the line pattern of 1 ratio to will lamination after by
Resolution ratio evaluation after 15 minutes is exposed with substrate.Developed with 2 times of developing time of minimum developing time, so as to
Formed and solidify layer line against corrosion.
In embodiment I-1~I-16 and Comparative Example I -1~I-3, according to following benchmark to solidification layer line against corrosion will be normally formed
The value that minimum feature is set to resolution ratio is classified.
Zero (good)：The value of resolution ratio is less than 12 μm.
△ (permission)：The value of resolution ratio is more than 12 μm and for less than 17 μm.
× (bad)：The value of resolution ratio is more than 17 μm.
In addition, in embodiment II-1~II-6 and Comparative Example I I-1~II-5, it is anti-to solidification will be normally formed according to following benchmark
The value that the minimum feature of erosion layer line is set to resolution ratio is classified.
◎ (extremely good)：The value of resolution ratio is less than 7.5 μm.
Zero (good)：The value of resolution ratio is more than 7.5 μm and for less than 9 μm.
△ (permission)：The value of resolution ratio is more than 9 μm.
<FT-IR is determined>
After the polyethylene film of photoresist layered product is peeled off, progress FT-IR (Thermo SCIENTIFIC systems,
NICOLET 380) measure.
Wave number 810cm-1The peak height P at place using FT-IR by determining absorbance to obtain before exposure.At the peak and other peaks
When overlapping, the rising point of the both sides at the peak is connected to each other with line, measures the maximum height away from the line.
The reactivity Q of olefinic double bond is obtained by the following method.From the polyethylene terephthalate of photo-sensitive resin stack
Ester film (supporting layer) side uses directly description exposure machine (Hitachi Via Mechanics, Ltd. systems, DE-1DH, light source：
GaN royal purple diode (405 ± 5nm of dominant wavelength)) it is exposed.Illumination during exposure is set to 85mW/cm2.On exposure now
Light quantity, using by preceding method by this figure expense 41 grades of stage exposure guide rules be exposed as mask, then developed when
Highest residual film series is carried out as 15 grades of light exposure.Olefinic double bond for solidifying resist layer obtained from being operated as more than
Reactivity Q, according to wave number 810cm-1Peak height before and after the exposure at place calculates the disappearance rate (%) of olefinic double bond base, obtains reaction
Rate Q (%).
R is the thickness (μm) of photo-sensitive resin, and P × Q/R is obtained by calculating.
<Adaptation>
The use of the width with exposure portion and unexposed portion is 1 in embodiment I-1~I-16 and Comparative Example I -1~I-3:400
The description data of the line pattern of ratio are to the resolution ratio evaluation after lamination after 15 minutes is exposed with substrate.With minimum
2 times of developing time of developing time is developed, according to following benchmark to will normally form the minimum line for solidifying layer line against corrosion
The value that width is set to adaptation is classified.
Zero (extremely good)：The value of adaptation is less than 12 μm.
Zero △ (good)：The value of adaptation is more than 12 μm and for less than 13 μm.
△ (permission)：The value of adaptation is more than 13 μm and for less than 15 μm.
× (bad)：The value of adaptation is more than 15 μm.
In addition, in embodiment II-1~II-6 and Comparative Example I I-1~II-5, pass through the width with exposure portion and unexposed portion
For 1:The chromium glass mask of the line pattern of 100 ratio is exposed to the evaluation after lamination after 15 minutes with substrate.With
2 times of the time of minimum developing time is developed, and will be normally formed the minimum feature that solidifies layer line against corrosion and is set to adaptation
Value, is classified as described below.
◎ (extremely good)：The value of adaptation is less than 7.5 μm.
Zero (good)：The value of adaptation is more than 7.5 μm and for less than 9 μm.
△ (permission)：The value of adaptation is more than 9 μm and less than 10 μm.
× (bad)：The value of adaptation is more than 10 μm.
<Chemical reagent resistance is evaluated>
Atotech Japan K.K. CupraPro S2 100mL, 98% sulfuric acid 60mL and pure water 840mL are mixed,
Make chemical reagent.The use of the width with exposure portion and unexposed portion is 1:The description data pair of the line pattern of 400 ratio
Resolution ratio evaluation after lamination after 15 minutes is exposed with substrate.Entered with 2 times of developing time of minimum developing time
Row development, is impregnated 5 minutes with beaker in 40 DEG C of chemical reagent is heated to.After dipping, cleaned, obtained just using pure water
Value of the minimum feature for solidifying layer line against corrosion as chemical reagent resistance is commonly formed.It should be noted that in table 2, only by resistance toization
Situation of the agents value more than 17 μm is learned to be expressed as " × (bad) ".
<It is exudative>
The photoresist layered product batched as web-like is preserved under 23 DEG C, dark conditions, pair until supported because oozing out
Time untill film surface (outermost layer for not including roller wherein) generation is tacky is carried out as follows classification, and evaluates exudative.
Zero (good)：It it is more than 1 month until the time untill the generation of support membrane surface is tacky
× (bad)：It is less than 1 month until the time untill the generation of support membrane surface is tacky
(4) evaluation result
Evaluation result is shown in table 2 below~5.The photonasty tree designed in a manner of chemical reagent resistance is evaluated as below 17 μm
The harmony of the adaptation of the corrosion-resisting pattern of oil/fat composition, resolution ratio or flanging shape is also excellent.In addition, by using this
Photosensitive polymer combination, when forming wiring pattern by plating, short circuit can be suppressed.Evaluated in chemical reagent resistance laggard
Row copper facing, as a result for the composition of Comparative Example I -1, in the partially observable short circuit of 15 μm of the line width of solidification resist layer, but for
Embodiment I-1 composition, do not observe short circuit, so as to speculate can reduce it is bad.
[table 1]
Table 1
[table 2]
[table 3]
[table 4]
[table 5]
Claims (24)
1. a kind of photosensitive polymer combination, it contains：
(A) alkali solubility macromolecule；
(B) there is the compound of ethylenic unsaturated bond；With,
(C) Photoepolymerizationinitiater initiater,
The chemical reagent evaluated with chemical reagent resistance to forming what is formed by the photosensitive polymer combination on the surface of the substrate
Photo-sensitive resin and carry out it is exposed and developed obtained from after corrosion-resisting pattern handled, solidify the minimum line of layer line against corrosion
A width of less than 17 μm.
2. photosensitive polymer combination according to claim 1, the photoresist is formed on the substrate surface
Layer, using this figure expense 41 grades of stage exposure guide rules be exposed as mask, then developed when highest residual film series into
When being exposed for 15 grades of light exposures to the photo-sensitive resin,
In FT-IR measure, by the wave number 810cm before exposure-1The peak height at place is set to P, will carry out after the exposure described in (B)
The reactivity of olefinic double bond in compound with ethylenic unsaturated bond is set to Q, and the thickness of the photo-sensitive resin is set
For R when P × Q/R value be more than 0.21.
3. photosensitive polymer combination according to claim 1 or 2, wherein, the high molecular vitrifying of (A) alkali solubility
Transition temperature Tg weighed average TgtotalFor less than 110 DEG C.
4. according to photosensitive polymer combination according to any one of claims 1 to 3, wherein, (B) has olefinic insatiable hunger
Weight average molecular weight with the compound of key is more than 760.
5. according to photosensitive polymer combination according to any one of claims 1 to 4, wherein, (B) has olefinic insatiable hunger
Concentration with the methylacryloyl in the compound of key is more than 0.20mol/100g.
6. according to photosensitive polymer combination according to any one of claims 1 to 5, wherein, (B) has olefinic insatiable hunger
Concentration with the ethylene oxide unit in the compound of key is more than 0.80mol/100g.
7. according to photosensitive polymer combination according to any one of claims 1 to 6, it includes hexa-aryl bi-imidazole compound
As (C) Photoepolymerizationinitiater initiater.
8. a kind of photosensitive polymer combination, it contains：
(A) alkali solubility macromolecule；
(B) there is the compound of ethylenic unsaturated bond；With,
(C) Photoepolymerizationinitiater initiater,
The weighed average Tg of the high molecular glass transition temperature Tg of (A) alkali solubilitytotalFor less than 110 DEG C,
And contain (methyl) acrylate compounds with more than 3 ethylenic unsaturated bonds be used as described in (B) with olefinic not
The compound of saturated bond.
9. photosensitive polymer combination according to claim 8, it contains with more than 5 ethylenic unsaturated bonds and had
There is the compound that (methyl) acrylate compounds of alkylene oxide chain as described in (B) have ethylenic unsaturated bond.
10. photosensitive polymer combination according to claim 8 or claim 9, wherein, (A) the alkali solubility macromolecule has 100
~600 acid equivalent and 5000~500000 weight average molecular weight, and there is aromatic series base in its side chain.
11. the photosensitive polymer combination according to any one of claim 8~10, it contains with more than 5
Ethylenic unsaturated bond and (methyl) acrylate compounds with ethylene oxide chain be used as described in (B) there is olefinic unsaturation
The compound of key.
12. the photosensitive polymer combination according to any one of claim 8~11, it contains with oxirane
(methyl) acrylate compounds of chain and dipentaerythritol skeleton (B) as described in have the compound of ethylenic unsaturated bond.
13. the photosensitive polymer combination according to any one of claim 8~12, it also contains following logical formula (II) institutes
The compound shown (B) as described in has the compound of ethylenic unsaturated bond,
In formula (II), R1And R2Separately represent hydrogen atom or methyl, A C2H4, B C3H6, n1And n3It is separately
1~39 integer, and n1+n3For 2~40 integer, n2And n4The separately integer for 0~29, and n2+n4For 0~30
Integer ,-(A-O)-and-(B-O)-repeat unit arrangement can be can also be randomly block, in the situation for block
Under, any one of-(A-O)-and-(B-O)-are in xenyl side.
14. the photosensitive polymer combination according to any one of claim 8~13, it also contains following logical formula (I) institutes
The compound shown (B) as described in has the compound of ethylenic unsaturated bond,
In formula (I), R3~R6The alkyl of carbon number 1~4 is separately represented, X represents the alkylidene of carbon number 2~6, m1、m2、m3And
m4The separately integer for 0~40, m1+m2+m3+m4For 1~40, and work as m1+m2+m3+m4For more than 2 when, multiple X can
To be same to each other or different to each other.
15. the photosensitive polymer combination according to any one of claim 8~14, it contains hexa-aryl bi-imidazole chemical combination
(C) Photoepolymerizationinitiater initiater described in thing conduct.
16. the photosensitive polymer combination according to any one of claim 8~15, it contains pyrazoline compounds conduct
(C) Photoepolymerizationinitiater initiater.
17. the photosensitive polymer combination according to any one of claim 8~16, it is used for direct imaging exposure.
18. photosensitive polymer combination according to claim 8, wherein, the high molecular vitrifying of (A) alkali solubility turns
Temperature Tg weighed average TgtotalFor less than 105 DEG C,
Relative to the photosensitive polymer combination solid constituent total amount more than 0 mass % and for below 16 mass % model
Enclose and contain the compound of (b1) with least three methylacryloyl compound of (B) with ethylenic unsaturated bond as described in,
And more than the 70 mass % in the compound of (B) with ethylenic unsaturated bond are with more than 500 Weight-average molecular
The compound of amount.
19. photosensitive polymer combination according to claim 18, wherein, (b1) has at least three metering system
The compound of acyl group has more than 500 weight average molecular weight.
20. the photosensitive polymer combination according to claim 18 or 19, it, which contains (b2), has epoxy butane chain and 1
Or the compound of 2 (methyl) acryloyl groups (B) as described in has the compound of ethylenic unsaturated bond.
21. photosensitive polymer combination according to claim 20, wherein, (b2) has epoxy butane chain and 1
Or the compound of 2 (methyl) acryloyl groups has more than 500 weight average molecular weight.
22. the photosensitive polymer combination according to any one of claim 18~21, it is used for half additive process
(SAP)。
23. a kind of forming method of corrosion-resisting pattern, it includes：
The photo-sensitive resin formed as the photosensitive polymer combination any one of claim 1~22 is laminated in branch
The lamination process of support body；
The exposure process being exposed to the photo-sensitive resin；And
The developing procedure to be developed to the photo-sensitive resin of the exposure.
24. a kind of manufacture method of circuit board, it includes：
The photo-sensitive resin formed as the photosensitive polymer combination any one of claim 1~22 is laminated in base
The lamination process of plate；
The exposure process being exposed to the photo-sensitive resin；
The photo-sensitive resin of the exposure is developed, and obtains the developing procedure of the substrate formed with corrosion-resisting pattern；
Substrate formed with the corrosion-resisting pattern is etched or the conductive pattern formation process of plating；And
The stripping process that the corrosion-resisting pattern is peeled off.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210104954.1A CN114437251B (en) | 2015-04-08 | 2016-04-08 | Photosensitive resin composition |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-079381 | 2015-04-08 | ||
| JP2015079381 | 2015-04-08 | ||
| JP2015-166570 | 2015-08-26 | ||
| JP2015166570 | 2015-08-26 | ||
| PCT/JP2016/061610 WO2016163540A1 (en) | 2015-04-08 | 2016-04-08 | Photosensitive resin composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210104954.1A Division CN114437251B (en) | 2015-04-08 | 2016-04-08 | Photosensitive resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107407880A true CN107407880A (en) | 2017-11-28 |
| CN107407880B CN107407880B (en) | 2022-02-08 |
Family
ID=57073148
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210104954.1A Active CN114437251B (en) | 2015-04-08 | 2016-04-08 | Photosensitive resin composition |
| CN201680019911.6A Active CN107407880B (en) | 2015-04-08 | 2016-04-08 | Photosensitive resin composition |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210104954.1A Active CN114437251B (en) | 2015-04-08 | 2016-04-08 | Photosensitive resin composition |
Country Status (6)
| Country | Link |
|---|---|
| JP (3) | JPWO2016163540A1 (en) |
| KR (2) | KR102286107B1 (en) |
| CN (2) | CN114437251B (en) |
| MY (1) | MY187481A (en) |
| TW (3) | TWI667539B (en) |
| WO (1) | WO2016163540A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019128256A1 (en) * | 2017-12-27 | 2019-07-04 | 太阳油墨（苏州）有限公司 | Curable resin composition, dry film, cured product, and printed circuit board |
| CN112352197A (en) * | 2018-06-22 | 2021-02-09 | 旭化成株式会社 | Photosensitive resin composition and method for forming resist pattern |
| CN112368642A (en) * | 2018-06-22 | 2021-02-12 | 旭化成株式会社 | Photosensitive resin composition and method for forming resist pattern |
| CN114503030A (en) * | 2019-10-08 | 2022-05-13 | 东京应化工业株式会社 | Negative photosensitive resin composition, photosensitive resist film, pattern forming method, cured film and manufacturing method, and roller |
| CN116209571A (en) * | 2020-08-07 | 2023-06-02 | 株式会社力森诺科 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI666518B (en) * | 2016-12-30 | 2019-07-21 | 奇美實業股份有限公司 | Photosensitive resin composition and uses thereof |
| JP6981864B2 (en) * | 2017-01-30 | 2021-12-17 | 旭化成株式会社 | A method for manufacturing a photosensitive resin composition, a photosensitive resin laminate, a substrate on which a resist pattern is formed, and a circuit board. |
| WO2018159629A1 (en) * | 2017-03-01 | 2018-09-07 | 旭化成株式会社 | Photosensitive resin composition |
| CN115524922A (en) * | 2017-03-29 | 2022-12-27 | 旭化成株式会社 | Photosensitive resin composition |
| JPWO2020013111A1 (en) * | 2018-07-11 | 2021-08-19 | 富士フイルム株式会社 | Chemical solution, chemical solution container |
| CN112534351A (en) * | 2018-08-09 | 2021-03-19 | 旭化成株式会社 | Photosensitive resin composition and method for forming resist pattern |
| JP7300619B2 (en) * | 2019-01-11 | 2023-06-30 | 太陽ホールディングス株式会社 | Laminated structures, dry films, cured products thereof, and electronic components |
| US20220362110A1 (en) * | 2019-09-19 | 2022-11-17 | Kuraray Noritake Dental Inc. | Dental curable composition |
| WO2021095784A1 (en) * | 2019-11-11 | 2021-05-20 | 旭化成株式会社 | Photosensitive resin composition and photosensitive resin multilayer body |
| CN116847983A (en) * | 2021-02-26 | 2023-10-03 | 太阳控股株式会社 | Laminated structure and flexible printed circuit board |
| JPWO2022181485A1 (en) * | 2021-02-26 | 2022-09-01 | ||
| KR20240031514A (en) * | 2022-08-30 | 2024-03-08 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using the same and color filter |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007133349A (en) * | 2005-10-14 | 2007-05-31 | Hitachi Chem Co Ltd | Photosensitive film roll |
| CN1989456A (en) * | 2004-07-30 | 2007-06-27 | 日立化成工业株式会社 | Photosensitive film, photosensitive film laminate and photosensitive film roll |
| CN102331684A (en) * | 2010-07-13 | 2012-01-25 | 日立化成工业株式会社 | Photosensitive element, formation method of corrosion-resisting pattern, manufacture method of printing circuit wiring board and printing circuit wiring board |
| CN102937776A (en) * | 2007-12-18 | 2013-02-20 | 旭化成电子材料株式会社 | Negative photosensitive resin laminate and use of negative photosensitive resin laminate |
| CN103091985A (en) * | 2011-10-31 | 2013-05-08 | 日立化成工业株式会社 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board |
Family Cites Families (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3619852B2 (en) * | 1999-06-08 | 2005-02-16 | ニチゴー・モートン株式会社 | Photosensitive resin composition and dry film resist using the same |
| WO2003042758A1 (en) * | 2001-11-12 | 2003-05-22 | Asahi Kasei Emd Corporation | Photosensitive resin composition and applications thereof |
| JP4535851B2 (en) * | 2004-11-19 | 2010-09-01 | 旭化成イーマテリアルズ株式会社 | Photopolymerizable resin composition |
| JP4646759B2 (en) | 2005-09-20 | 2011-03-09 | 旭化成イーマテリアルズ株式会社 | Pattern forming material, pattern forming apparatus and pattern forming method |
| JP4936848B2 (en) * | 2006-10-16 | 2012-05-23 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition and laminate thereof |
| EP2096493A4 (en) * | 2006-12-19 | 2010-11-17 | Hitachi Chemical Co Ltd | Photosensitive element |
| JP2008202022A (en) * | 2007-01-23 | 2008-09-04 | Fujifilm Corp | Curable composition for optical nano imprint lithography, and pattern forming method using the same |
| JP5164982B2 (en) * | 2007-06-18 | 2013-03-21 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition, flexographic printing plate, and method for producing flexographic printing plate |
| TWI536094B (en) * | 2007-12-25 | 2016-06-01 | Asahi Kasei Emd Corp | Photosensitive resin laminate |
| JP5396833B2 (en) * | 2008-11-28 | 2014-01-22 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition, spacer and protective film for liquid crystal display element, and method for forming them |
| WO2011013664A1 (en) * | 2009-07-29 | 2011-02-03 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition, photosensitive resin laminate, and method for forming resist pattern |
| KR101548791B1 (en) * | 2009-09-25 | 2015-08-31 | 아사히 가세이 이-매터리얼즈 가부시키가이샤 | Photosensitive resin composition for resist material, and photosensitive resin laminate |
| JP5526868B2 (en) * | 2010-03-03 | 2014-06-18 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition, display element spacer and protective film, and method for forming them |
| JP5570275B2 (en) * | 2010-03-31 | 2014-08-13 | 旭化成イーマテリアルズ株式会社 | Dry film resist roll |
| KR20120002864A (en) * | 2010-07-01 | 2012-01-09 | 동우 화인켐 주식회사 | A black photosensitive resin composition, color filter and liquid crystal display device having the same |
| JP6022749B2 (en) | 2010-07-30 | 2016-11-09 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for producing resist pattern, method for producing lead frame, and method for producing printed wiring board |
| JP5771944B2 (en) * | 2010-10-18 | 2015-09-02 | Jsr株式会社 | Manufacturing method of color filter |
| KR20150017384A (en) | 2010-12-24 | 2015-02-16 | 아사히 가세이 이-매터리얼즈 가부시키가이샤 | Photosensitive resin composition |
| JP5835014B2 (en) * | 2011-03-31 | 2015-12-24 | Jsr株式会社 | Pixel pattern forming method and color filter manufacturing method |
| JP6229256B2 (en) | 2011-10-31 | 2017-11-15 | 日立化成株式会社 | Photosensitive element, resist pattern forming method, and printed wiring board manufacturing method |
| JP5948539B2 (en) * | 2012-01-27 | 2016-07-06 | 旭化成株式会社 | Photosensitive resin composition |
| JP2013195681A (en) * | 2012-03-19 | 2013-09-30 | Mitsubishi Chemicals Corp | Photosensitive resin composition, color filter, liquid crystal display device, and organic el display |
| JP5853806B2 (en) * | 2012-03-23 | 2016-02-09 | Jsr株式会社 | Radiation sensitive resin composition, cured film and method for forming cured film |
| JP6019791B2 (en) * | 2012-06-19 | 2016-11-02 | 日立化成株式会社 | Partition wall forming material, photosensitive element using the same, partition wall forming method, and image display device manufacturing method |
| JP5826135B2 (en) * | 2012-08-23 | 2015-12-02 | 富士フイルム株式会社 | Colored radiation-sensitive composition and color filter using the same |
| JP6063200B2 (en) | 2012-10-15 | 2017-01-18 | 旭化成株式会社 | Photosensitive resin composition |
| JP6120560B2 (en) * | 2012-12-26 | 2017-04-26 | 第一工業製薬株式会社 | Color filter, black matrix, or curable resin composition for circuit formation |
| JP6135314B2 (en) * | 2012-12-26 | 2017-05-31 | Jsr株式会社 | Coloring composition, color filter and display element |
| JP6257164B2 (en) | 2013-03-28 | 2018-01-10 | 旭化成株式会社 | Method for forming resist pattern |
| KR20150143679A (en) * | 2013-05-27 | 2015-12-23 | 후지필름 가부시키가이샤 | Method for producing color filter, composition for forming base layer, and organic el display device |
| KR102162752B1 (en) | 2013-07-23 | 2020-10-07 | 히타치가세이가부시끼가이샤 | Photosensitive resin composition for projection exposure, photosensitive element, method for forming resist pattern, process for producing printed wiring board and process for producing lead frame |
| WO2015178462A1 (en) * | 2014-05-21 | 2015-11-26 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition and method for forming circuit pattern |
-
2016
- 2016-04-08 WO PCT/JP2016/061610 patent/WO2016163540A1/en active Application Filing
- 2016-04-08 TW TW106146049A patent/TWI667539B/en active
- 2016-04-08 TW TW105111187A patent/TWI620017B/en active
- 2016-04-08 KR KR1020197012465A patent/KR102286107B1/en active IP Right Grant
- 2016-04-08 MY MYUI2017703393A patent/MY187481A/en unknown
- 2016-04-08 KR KR1020177020557A patent/KR101990230B1/en active IP Right Grant
- 2016-04-08 TW TW108122448A patent/TWI706222B/en active
- 2016-04-08 CN CN202210104954.1A patent/CN114437251B/en active Active
- 2016-04-08 JP JP2017511104A patent/JPWO2016163540A1/en active Pending
- 2016-04-08 CN CN201680019911.6A patent/CN107407880B/en active Active
-
2020
- 2020-03-31 JP JP2020064645A patent/JP7162030B2/en active Active
-
2021
- 2021-04-30 JP JP2021077956A patent/JP7242748B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1989456A (en) * | 2004-07-30 | 2007-06-27 | 日立化成工业株式会社 | Photosensitive film, photosensitive film laminate and photosensitive film roll |
| JP2007133349A (en) * | 2005-10-14 | 2007-05-31 | Hitachi Chem Co Ltd | Photosensitive film roll |
| CN102937776A (en) * | 2007-12-18 | 2013-02-20 | 旭化成电子材料株式会社 | Negative photosensitive resin laminate and use of negative photosensitive resin laminate |
| CN102331684A (en) * | 2010-07-13 | 2012-01-25 | 日立化成工业株式会社 | Photosensitive element, formation method of corrosion-resisting pattern, manufacture method of printing circuit wiring board and printing circuit wiring board |
| CN103091985A (en) * | 2011-10-31 | 2013-05-08 | 日立化成工业株式会社 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019128256A1 (en) * | 2017-12-27 | 2019-07-04 | 太阳油墨（苏州）有限公司 | Curable resin composition, dry film, cured product, and printed circuit board |
| CN112352197A (en) * | 2018-06-22 | 2021-02-09 | 旭化成株式会社 | Photosensitive resin composition and method for forming resist pattern |
| CN112368642A (en) * | 2018-06-22 | 2021-02-12 | 旭化成株式会社 | Photosensitive resin composition and method for forming resist pattern |
| CN114503030A (en) * | 2019-10-08 | 2022-05-13 | 东京应化工业株式会社 | Negative photosensitive resin composition, photosensitive resist film, pattern forming method, cured film and manufacturing method, and roller |
| CN116209571A (en) * | 2020-08-07 | 2023-06-02 | 株式会社力森诺科 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102286107B1 (en) | 2021-08-04 |
| MY187481A (en) | 2021-09-23 |
| JP2020126251A (en) | 2020-08-20 |
| TW201812454A (en) | 2018-04-01 |
| TW201947323A (en) | 2019-12-16 |
| JP2021131556A (en) | 2021-09-09 |
| CN114437251B (en) | 2024-02-20 |
| CN114437251A (en) | 2022-05-06 |
| KR101990230B1 (en) | 2019-06-17 |
| WO2016163540A1 (en) | 2016-10-13 |
| TWI706222B (en) | 2020-10-01 |
| TW201701070A (en) | 2017-01-01 |
| TWI667539B (en) | 2019-08-01 |
| TWI620017B (en) | 2018-04-01 |
| CN107407880B (en) | 2022-02-08 |
| JPWO2016163540A1 (en) | 2017-11-02 |
| KR20170101263A (en) | 2017-09-05 |
| JP7242748B2 (en) | 2023-03-20 |
| JP7162030B2 (en) | 2022-10-27 |
| KR20190047146A (en) | 2019-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107407880A (en) | Photosensitive polymer combination | |
| CN108027559B (en) | Photosensitive resin composition | |
| CN105793778B (en) | Photosensitive resin composition and photosensitive resin laminate | |
| TWI392967B (en) | Photosensitive resin composition and laminate | |
| KR101548791B1 (en) | Photosensitive resin composition for resist material, and photosensitive resin laminate | |
| JP2008287227A (en) | Photosensitive resin composition and laminate | |
| CN110446976A (en) | Photosensitive polymer combination | |
| CN101779165B (en) | Photosensitive resin composition and laminate thereof | |
| CN102007452B (en) | Photosensitive resin composition and layered object obtained therewith | |
| JP2009069465A (en) | Photosensitive resin composition | |
| TWI412884B (en) | Photosensitive resin composition, photosensitive resin laminate, photoresist pattern forming method and manufacturing method of conductor pattern, printed wiring board, lead frame, substrate and semiconductor package | |
| KR20090082240A (en) | Photosensitive resin composition and layered product | |
| CN109690404A (en) | Photosensitive polymer combination and photoresist laminated body | |
| CN103477283B (en) | Photosensitive polymer combination and its layered product | |
| JP2010113349A (en) | Photosensitive resin composition | |
| JP2010271395A (en) | Photosensitive resin composition, photosensitive resin laminate, resist pattern forming method and method for producing conductor pattern | |
| JP6630088B2 (en) | Photosensitive resin composition | |
| TW202125104A (en) | Photosensitive resin composition and photosensitive resin multilayer body | |
| JP2011075706A (en) | Photosensitive resin composition, photosensitive resin laminate, resist pattern-forming method, and method for producing conductor pattern, printed wiring board, lead frame, substrate with uneven pattern and semiconductor package |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |