TWI548665B - 負型光敏性樹脂組成物及其硬化物 - Google Patents
負型光敏性樹脂組成物及其硬化物 Download PDFInfo
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- TWI548665B TWI548665B TW101121919A TW101121919A TWI548665B TW I548665 B TWI548665 B TW I548665B TW 101121919 A TW101121919 A TW 101121919A TW 101121919 A TW101121919 A TW 101121919A TW I548665 B TWI548665 B TW I548665B
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- Prior art keywords
- resin composition
- epoxy resin
- negative photosensitive
- acid
- photosensitive resin
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims description 64
- 239000003822 epoxy resin Substances 0.000 claims description 60
- 229920000647 polyepoxide Polymers 0.000 claims description 60
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- 150000002989 phenols Chemical class 0.000 claims description 13
- 239000003505 polymerization initiator Substances 0.000 claims description 12
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 11
- 150000007519 polyprotic acids Polymers 0.000 claims description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- -1 hexafluoroantimonate Chemical compound 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 229920002120 photoresistant polymer Polymers 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 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 12
- 239000000243 solution Substances 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 7
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000001459 lithography Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 2
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 2
- LSTZTHCEEPHCNQ-UHFFFAOYSA-N 3-(2,5-dioxabicyclo[2.1.0]pentan-3-yloxy)-2,5-dioxabicyclo[2.1.0]pentane Chemical compound C1(C2C(O2)O1)OC1C2C(O2)O1 LSTZTHCEEPHCNQ-UHFFFAOYSA-N 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 210000004556 brain Anatomy 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- HGEPCTDTYIDUPS-UHFFFAOYSA-N diphenyl-(4-phenylsulfanylphenyl)phosphane Chemical compound S(c1ccccc1)c1ccc(cc1)P(c1ccccc1)c1ccccc1 HGEPCTDTYIDUPS-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 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
- 238000006116 polymerization reaction Methods 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 1
- JFWNSUSGQRQTSS-UHFFFAOYSA-N 1-(2,5-dioxabicyclo[2.1.0]pentan-3-yloxy)hexan-1-ol Chemical compound C1(C2C(O2)O1)OC(CCCCC)O JFWNSUSGQRQTSS-UHFFFAOYSA-N 0.000 description 1
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 1
- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-N 0.000 description 1
- SMLNDVNTPWRZJH-UHFFFAOYSA-N 1-chloro-4-(trimethoxymethyl)dodecane Chemical compound ClCCCC(C(OC)(OC)OC)CCCCCCCC SMLNDVNTPWRZJH-UHFFFAOYSA-N 0.000 description 1
- ZIKLJUUTSQYGQI-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxypropoxy)propane Chemical compound CCOCC(C)OCC(C)OCC ZIKLJUUTSQYGQI-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical class C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
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- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- DYVZSMLRTPVVHP-UHFFFAOYSA-N 2,4-di(propan-2-yl)thiophene Chemical compound CC(C)C1=CSC(C(C)C)=C1 DYVZSMLRTPVVHP-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- MFAWEYJGIGIYFH-UHFFFAOYSA-N 2-[4-(trimethoxymethyl)dodecoxymethyl]oxirane Chemical compound C(C1CO1)OCCCC(C(OC)(OC)OC)CCCCCCCC MFAWEYJGIGIYFH-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-UHFFFAOYSA-N 0.000 description 1
- ULMZOZMSDIOZAF-UHFFFAOYSA-N 3-hydroxy-2-(hydroxymethyl)propanoic acid Chemical compound OCC(CO)C(O)=O ULMZOZMSDIOZAF-UHFFFAOYSA-N 0.000 description 1
- DBXBTMSZEOQQDU-UHFFFAOYSA-N 3-hydroxyisobutyric acid Chemical compound OCC(C)C(O)=O DBXBTMSZEOQQDU-UHFFFAOYSA-N 0.000 description 1
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Description
本發明關於負型光阻。更詳細地，關於適合MEMS零件、微機械零件、μ-TAS(微型全分析系統)零件、微反應器零件、電子零件等之製造時所進行的凸塊形成、金屬柱形成、配線形成等精密加工以及LCD、PDP、電子紙、有機EL等的顯示器之製造的負型光敏性樹脂組成物。
MEMS(微機電系統)或微機械係集聚有微小的機械要素、電子電路、光學元件之裝置，許多的應用被檢討、實用化(參照非專利文獻1)。此等裝置由於一邊是以半導體製造技術為基礎的小型零件，一邊進行複雜且高度的動作，而成為掌握各種感測器、印表機頭、碟盤頭、通信用光開關、生物晶片等的微系統之關鍵的重要零件。於此領域的裝置中，與通常的半導體製造不同，需要能高縱橫比(縱橫比意味「構造體之高度/寬度」)之圖型化的光阻。
作為高縱橫比的構造體之製造方法，多採用稱為「LIGA製程」的光敏性樹脂組成物之藉由X射線微影術的圖型形成法(參照非專利文獻2)。然而，於LIGA製程中有需要高價的X射線裝置及需要長時間照射X射線等之缺點。由於省資源、節能、作業性提高、生產性提高等的迫切期望，便宜且生產性高的UV(紫外線)微影術系統之應用係受到注目。
然而，UV微影術系統中之以二萘醌-酚醛清漆反應為基礎之正型光阻，係不適合於要求50μm以上的厚膜之塗抹。如此地，在厚膜化有界限，因為一般地於光阻之曝光所用的近紫外區域波長(350~450nm)之二萘醌型(DNQ)光反應物係具有比較高的光吸收。又，於DNQ型光阻中由於特有的在顯像液中之曝光區域與非曝光區域之溶解性的差異，側壁係不成為直線形狀，倒是成為斜坡形狀。再者，已知由於光阻本身吸收照射光，在光阻的底部的照射強度係比表面還低，當光阻本身的光吸收能力極端地高時，底部的曝光不足係變顯著，側壁係成為斜坡形狀或畸變形狀。
專利文獻1中，記載由多官能雙酚A酚醛清漆環氧樹脂、光酸產生劑及芳香族鋶六氟銻酸鹽的碳酸伸丙酯溶液所成之負型的化學增幅型之厚膜光阻組成物，係在350~450nm波長範圍具有非常低的光吸收。藉由旋塗或簾幕塗覆等，將此光阻組成物塗佈於各種基板上後，藉由烘烤而使溶劑揮發，形成100μm或其以上的厚度之固體光阻層，更且使用接觸曝光、近接曝光、投影曝光等的各種曝光方法，通過光罩照射近紫外光，而施予微影術加工。接著，藉由浸漬在顯像液中，以溶解非曝光區域，可在基板上形成高解析的光罩之負圖像。又，對於在如聚酯薄膜之基材上所塗覆的如乾薄膜光阻之塗抹，亦揭示同樣的手法。然而，於此組成物的顯像中，使用有機溶劑，由於對環境的影響等，而希望能鹼顯像之可形成高縱橫比的構造體
之光阻之開發。又，專利文獻2、3及4中，揭示作為化學增幅型之厚膜光阻，在鹼水溶液中能顯像的光阻組成物，但由於發生熱所致的著色或經時所致的黃變，在要求透明性的領域中無法使用。
另一方面，專利文獻5中，揭示作為透明性優異的樹脂組成物，含有特定的環氧化合物之光學的立體造形用樹脂組成物。然而，該樹脂組成物由於無法在鹼水溶液中顯像，故無法使用半導體、LCD、MEMS等的既有之生產線，藉由微影術形成微細的圖型。
如此地，於近年來以LCD等的顯示器為首之電子紙、有機EL的隔壁材等之要求透明性的領域中，要求能鹼顯像，得到具有高縱橫比且透明性之構造體的光阻，但尚未發現完全滿足此等特性者。
[專利文獻1]美國專利第4882245號說明書
[專利文獻2]日本發明專利第3698499號公報
[專利文獻3]美國公開專利第20050147918號公報
[專利文獻4]特開平10-97068號公報
[專利文獻5]特開2010-265408號公報
[非專利文獻1]微機械，(股)產業技術服務中心發行
(2002年)
[非專利文獻2]高分子，第43卷，第564頁(1994年)
本發明之目的在於提供可得到具有高的透明性與耐熱性，同時熱所致的黃變著色少，高縱橫比之硬化物，高解析度、高感度之能鹼顯像的負型樹脂組成物。
本發明者等為了解決前述問題，專心致力地研究，結果發現藉由使用特定的環氧樹脂、鹼可溶性樹脂、光陽離子聚合引發劑所組合成的負光敏性樹脂組成物，可解決前述問題，終於完成本發明。
即，本發明關於：(1)一種負型光敏性樹脂組成物，其係含有在1分子中具有2個以上的環氧基之環氧樹脂(A)、鹼可溶性樹脂(B)及光陽離子聚合引發劑(C)所成之光敏性樹脂組成物，其中環氧樹脂(A)係藉由下述式(1)
所示的苯酚衍生物與表鹵代醇之反應而得之環氧樹脂。
(2)如前項(1)記載之負型光敏性樹脂組成物，其中鹼可溶性樹脂(B)係在1分子中具有1個以上的羧基之鹼可溶性樹脂。
(3)如前項(2)記載之負型光敏性樹脂組成物，其中鹼可溶性樹脂(B)係環氧樹脂(a)和單羧酸(b)之反應物、與多元酸或其酐(c)之反應物。
(4)一種硬化物，其係使前項(1)及至(3)中任一項之負型光敏性樹脂組成物硬化而得。
本發明之可鹼顯像的負型光敏性樹脂組成物之特徵為：高感度且具有高的解析度，該樹脂組成物的硬化物係一邊維持高的透明性，一邊耐熱性良好且熱所致的著色少。
以下，詳細說明本發明的實施形態。
本發明的負型光敏性樹脂組成物(以下亦僅記載為「本發明的樹脂組成物」)，係在1分子中具有2個以上的環氧基之環氧樹脂，含有由上述式(1)所示的苯酚衍生物與表鹵代醇之反應所得的環氧樹脂(A)(以下亦僅記載為「(A)成分」)、鹼可溶性樹脂(B)(以下亦僅記載為「(B)成分」)及光陽離子聚合引發劑(C)(以下亦僅記載為「(C)成分」)。
本發明的負型光敏性樹脂組成物所含有的(A)成分，係可使用式(1)所示的苯酚衍生物與表鹵代醇，藉由習知的環氧樹脂之合成方法而獲得。
作為一般的合成方法，例如可舉出於使式(1)所示的苯酚衍生物與表鹵代醇(環氧氯丙烷或環氧溴丙烷等)溶解於溶劑中而得之混合溶液中，添加氫氧化鈉等的鹼類，升溫至反應溫度為止，進行加成反應及閉環反應後，重複反應液的水洗、分離及水層的去除，最後自油層中餾去溶劑之方法。
已知藉由前述合成反應所用之式(1)所示的苯酚衍生物與表鹵代醇之使用比率，可得到(A)成分中的主成分不同之環氧樹脂(A)。例如，相對於苯酚衍生物的酚性羥基而言，使用過剩量的表鹵代醇時，得到以式(1)中的3個酚性羥基全部經環氧化之3官能環氧樹脂作為主成分之(A)成分，但隨著相對於酚性羥基而言，表鹵代醇的使用量變少，複數的苯酚衍生物之酚性羥基經由表鹵代醇鍵結，剩餘的酚性羥基經環氧化的分子量大之多官能環氧樹脂的含有率係增加。
作為得到以如此的分子量大之多官能環氧樹脂作為主成分之(A)成分的方法，除了藉由前述苯酚衍生物與表鹵代醇之使用比率來控制之方法，還可舉出使環氧樹脂(A)更與苯酚衍生物反應之方法。
作為本發明的樹脂組成物所含有的(A)成分，可使用以前述3官能的環氧樹脂或前述分子量大的多官能環氧樹
脂作為主成分之(A)成分，但較佳為以下述式(2)或式(3)中的任一者所示之環氧樹脂作為主成分。而且，根據GPC(凝膠滲透層析術)之測定結果，以聚苯乙烯換算所算出之式(2)所示的環氧樹脂與式(3)所示的環氧樹脂之面積比(式(2)的環氧樹脂/式(3)的環氧樹脂)，較佳為1~20之範圍，更佳為1.1~12之範圍。
作為環氧樹脂(A)的市售品之具體例，可舉出Techmore VG3101(PRINTEC製)及NC-6000(日本化藥製)。
作為本發明的樹脂組成物所含有的鹼可溶性樹脂(B)，只要可將在鹼水溶液中的顯像性(溶解性)賦予樹脂組成物，則沒有特別的限制，但在不損害本發明的效果之一個的硬化物之高透明性的意思中，較佳為鹼可溶性樹脂(B)本身的著色少者。作為(B)成分的具體例，可舉出苯酚酚醛清漆樹脂、鄰甲酚酚醛清漆樹脂、丙烯酸酯等之乙烯性
不飽和化合物的共聚物、由多元醇類與多元酸化合物所合成之聚酯樹脂、環氧樹脂與單羧酸和多元酸酐之反應物等，但從在鹼水溶液中的溶解性之觀點來看，較佳為在1分子中具有1個以上的羧基之化合物，更佳為環氧樹脂(a)和單羧酸(b)之反應物、與多元酸或其酐(c)之反應物。
作為鹼可溶性樹脂(B)之原料所使用的環氧樹脂(a)，例如可舉出酚醛清漆型環氧樹脂、雙酚型環氧樹脂、聯苯型環氧樹脂、三苯基甲烷型環氧樹脂、苯酚芳烷基型環氧樹脂等。具體地，可舉出雙酚A、雙酚F、雙酚S、硫二苯酚、茀雙酚、萜烯二苯酚、4,4’-聯苯酚、2,2’-聯苯酚、3,3’,5,5’-四甲基-[1,1’-聯苯基]-4,4’-二醇、氫醌、間苯二酚、萘二酚、三(4-羥基苯基)甲烷、1,1,2,2-四(4-羥基苯基)乙烷、酚類(苯酚、烷基取代苯酚、萘酚、烷基取代萘酚、二羥基苯、二羥基萘等)與甲醛、乙醛、苯甲醛、對羥基苯甲醛、鄰羥基苯甲醛、對羥基苯乙酮、鄰羥基苯乙酮、二環戊二烯、糠醛、4,4’-雙(氯甲基)-1,1’-聯苯、4,4’-雙(甲氧基甲基)-1,1’-聯苯、1,4-雙(氯甲基)苯或1,4-雙(甲氧基甲基)苯等之聚縮合物及此等之改性物、四溴雙酚A等的鹵化雙酚類以及醇類所衍生的環氧丙基醚化物、脂環式環氧樹脂等的固形或液狀環氧樹脂，惟不受此等所限定。然而，在不損害硬化物具有高的透明性之本發明的效果之意思中，較佳為環氧樹脂(a)本身的著色少者，作為特佳的環氧樹脂(a)，可舉出以雙酚A型環氧樹脂及上述式(2)或式(3)中任一者所示的環氧樹脂作為主成分之
環氧樹脂。
作為鹼可溶性樹脂(B)之原料所使用的單羧酸(b)，例如可舉出丙烯酸、甲基丙烯酸、巴豆酸、桂皮酸、丙烯酸二聚物等之乙烯性不飽和單羧酸、二羥甲基丙酸、二羥甲基乙酸、二羥甲基丁酸、二羥甲基戊酸、二羥甲基己酸等之含多羥基的單羧酸、羥基三甲基乙酸、對羥基苯甲酸等之含單羥基的單羧酸等。
作為鹼可溶性樹脂(B)之原料所使用的多元酸或其酐(c)，例如可舉出琥珀酸、馬來酸、苯二甲酸、四氫苯二甲酸、六氫苯二甲酸、甲基六氫苯二甲酸、甲基內亞甲基四氫苯二甲酸、偏苯三酸及苯均四酸等的多元酸，以及此等多元酸之酐。
於環氧樹脂(a)與單羧酸(b)之反應中，對於環氧樹脂(a)的環氧基1當量，較佳為使約0.1~1.5當量之單羧酸(b)反應。反應時，作為稀釋劑，較佳為使用甲基乙基酮、甲基異丁基酮、環戊酮、乙基溶纖劑乙酸酯、丁基溶纖劑乙酸酯、卡必醇乙酸酯、二乙二醇二甲基醚、溶劑油等的溶劑類。再者，為了促進反應，較佳為使用觸媒(例如三乙胺、苄基二甲基胺、氯化四甲銨、氯化甲基三乙銨、三苯基、三苯基膦等)、該觸媒的使用量，相對於反應原料混合物而言，較佳為0.01~10重量%，特佳為0.05~5重量%。為了防止反應中的聚合，較佳為使用聚合抑制劑(例如對甲氧基苯酚、氫醌、二丁基羥基甲苯、啡噻等)，其使用量相對於反應原料混合物而言，較佳為
0.01~2重量%，特佳為0.05~1重量%。反應溫度通常為60~150℃，反應時間通常為5~50小時。
相對於環氧樹脂(a)與單羧酸(b)之反應物中的羥基，藉由較佳地使羥基1每當量與0.05~1.00當量的多元酸或其酐(c)反應(酯化反應)，而由環氧樹脂(a)、單羧酸(b)及多元酸或其酐(c)得到鹼可溶性樹脂(B)。反應溫度為60~160℃。
如此所得之鹼可溶性樹脂(B)的酸價(mgKOH/g)較佳為30~160，特佳為50~150。再者，此處所言的酸價係依照JIS K-2501所測定之值。
本發明的樹脂組成物所含有的光陽離子聚合引發劑(C)，就是意味藉由活性能量線的照射而產生陽離子種之化學種，只要具有使環氧樹脂(A)硬化之充分性能者，則可沒有特別限制地使用。作為可使用的光陽離子聚合引發劑(C)，例如可舉出芳香族碘鎓錯鹽或芳香族鋶錯鹽。其中，作為芳香族碘鎓錯鹽之具體例，可舉出二苯基碘鎓四(五氟苯基)硼酸鹽、二苯基碘鎓六氟磷酸鹽、二苯基碘鎓六氟銻酸鹽、二(4-壬基苯基)碘鎓六氟磷酸鹽、甲苯基異丙苯基碘鎓四(五氟苯基)硼酸鹽(RHODIA公司製，商品名Roadsil光引發劑2074)、二(4-第三丁基)碘鎓三(三氟甲烷磺醯基)溴苯辛(BASF日本公司製，商品名CGI BBIC C1)等。
又，作為芳香族鋶錯鹽之具體例，可合適地使用4-(苯硫基)苯基二苯基鋶六氟銻酸鹽(SUN-APRO株式會社製
，商品名CPI-101A)、4-(苯硫基)苯基二苯基鋶三(五氟乙基)三氟磷酸鹽(SUN-APRO株式會社製，商品名CPI-210S)、4-{4-(2-氯苯甲醯基)苯硫基}苯基雙(4-氟苯基)鋶六氟銻酸鹽(旭電化工業株式會社製，商品名SP-172)、含有4-(苯硫基)苯基二苯基鋶六氟銻酸鹽的芳香族鋶六氟銻酸鹽之混合物(DOW化學公司製，商品名UVI-6976)及三苯基鋶三(三氟甲烷磺醯基)溴苯辛(BASF日本公司製，商品名CGI TPS C1)、三[4-(4-乙醯基苯基巰基)苯基]鋶三[(三氟甲基)磺醯基]溴苯辛(BASF日本公司製，商品名GSID26-1)、三[4-(4-乙醯基苯基)硫苯基]鋶四(五氟苯基)硼酸鹽(BASF日本公司製，商品名PAG-290)等。
於此等(C)成分之中，從加熱時樹脂不易著色，照射光時酸產生能力優異來看，較佳為4-(苯硫基)苯基二苯基鋶錯鹽。
其次，說明本發明的負型光敏性樹脂組成物中之各成分的配合比例。
本發明的樹脂組成物，當(A)成分、(B)成分及(C)成分的合計為100質量%時，通常含有10~90質量%，較佳含有10~80質量%，更佳含有20~50質量%的(A)成分，通常含有10~90質量%，較佳含有10~80質量%，更佳含有50~80質量%的(B)成分，通常含有0.1~15質量%，較佳含有1~10質量%的(C)成分。本發明的樹脂組成物中所用之光陽離子聚合引發劑(C)，由於在波長300~380nm的莫耳吸光係數高，特佳為按照使用樹脂組成物時
的膜厚，使用最合適的配合量。
於本發明的負型光敏性樹脂組成物中，以改良圖型的性能或光阻的反應性、硬化膜的物性等為目的，亦可添加與(A)成分或(B)成分有混合性的反應性環氧單體(D)(以下亦僅稱「(D)成分」)。此處所言的(D)成分，就是意味分子量比較小，在室溫下液狀或半固形狀之具有環氧基的化合物，作為其具體例，可舉出二乙二醇二環氧丙基醚、己二醇二環氧丙基醚、二羥甲基丙烷二環氧丙基醚、聚丙二醇二環氧丙基醚(株式會社ADEKA製，ED506)、三羥甲基丙烷三環氧丙基醚(株式會社ADEKA製，ED505)、三羥甲基丙烷三環氧丙基醚(低氯型，Nagase Chemtex株式會社製，EX321L)、季戊四醇四環氧丙基醚、雙酚A二環氧丙基醚、雙酚F二環氧丙基醚、3,4-環氧基環己烯基甲基-3’,4’-環氧基環己烯羧酸酯(DAICEL化學工業株式會社製，Celloxide 2021P)等。此等係可單獨或2種以上混合使用。當(D)成分為液狀時，相對於樹脂組成物的總量而言，若比20質量%還多地配合，則由於在溶劑去除後的皮膜發生發黏，而有變容易發生光罩黏附等之不適當。基於此點，本發明的樹脂組成物中之(D)成分的配合比例，相對於(A)成分、(B)成分及(C)成分之合計而言，較佳為20質量%以下。
於本發明的負型光敏性樹脂組成物中，為了降低樹脂組成物的黏度，提高塗膜性，可使用溶劑(E)。作為溶劑，只要是油墨、塗料等所通常使用的有機溶劑，可溶解樹
脂組成物的各構成成分者，則可沒有特別限制地使用。作為溶劑(E)之具體例，可舉出丙酮、乙基甲基酮、環己酮及環戊酮等的酮類、甲苯、二甲苯及四甲基苯等的芳香族烴類、二丙二醇二甲基醚及二丙二醇二乙基醚等的二醇醚類、醋酸乙酯、醋酸丁酯、丁基溶纖劑乙酸酯、卡必醇乙酸酯、丙二醇單甲基醚乙酸酯及γ-丁內酯等之酯類、甲醇、乙醇、溶纖劑及甲基溶纖劑等之醇類、辛烷及癸烷等之脂肪族烴、石油醚、石油腦、氫化石油腦及溶劑油等之石油系溶劑等。
此等溶劑係可單獨或混合2種以上使用。溶劑(E)成分係以在基材上塗佈時調整膜厚或塗佈性為目的而添加者，為了恰當地保持主成分的溶解性或成分的揮發性、組成物的液黏度等，其使用量較佳為佔樹脂組成物中的95質量%以下，特佳為10~90質量%。
於本發明的負型光敏性樹脂組成物中，更以提高對基板的組成物之密接性為目的，可使用與(A)成分或(B)成分有混合性之密接性賦予劑。作為密接性賦予劑，可使用矽烷偶合劑或鈦偶合劑等的偶合劑，較佳可舉出矽烷偶合劑。
作為矽烷偶合劑之具體例，可舉出3-氯丙基三甲氧基矽烷、乙烯基三氯矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基．三(2-甲氧基乙氧基)矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-
巰基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷等。此等密接性賦予劑係可單獨或組合2種以上使用。
當密接性賦予劑不具有與主成分之反應性時，除了在基材界面作用以外，由於在硬化物中照原樣地殘存，若過剩地使用，則有造成物性的降低等之不利影響之虞。視基材而定，從少量也發揮效果之點來看，在不造成不利影響之範圍內的使用係適當，其使用比例較佳為佔樹脂組成物中的15質量%以下，特佳為5質量%以下。
於本發明的負型光敏性樹脂組成物中，可更使用增感劑，以吸收紫外線，達成將所吸收的光能量供應給光陽離子聚合引發劑之任務。作為增感劑，例如較佳為噻噸酮類、在9位與10位具有烷氧基的蒽化合物(9,10-二烷氧基蒽衍生物)。作為前述烷氧基，例如可舉出甲氧基、乙氧基、丙氧基、丁氧基等之C1~C4的烷氧基。9,10-二烷氧基蒽衍生物可更具有取代基。作為取代基，例如可舉出氟原子、氯原子、溴原子、碘原子等之鹵素原子、甲基、乙基、丙基等之C1~C4的烷基或磺酸烷基酯基、羧酸烷基酯基等。作為磺酸烷基酯基或羧酸烷酯中的烷基，例如可舉出甲基、乙基、丙基等之C1~C4的烷基。此等取代基的取代位置較佳為2位。
作為噻噸酮類之具體例，可舉出2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2-氯噻噸酮、2,4-二異丙基噻噸酮等
，較佳為2,4-二乙基噻噸酮(商品名Kayacure DETX-S，日本化藥株式會社製)、2-異丙基噻噸酮。
作為9,10-二烷氧基蒽衍生物，例如可舉出9,10-二甲氧基蒽、9,10-二乙氧基蒽、9,10-二丙氧基蒽、9,10-二丁氧基蒽、9,10-二甲氧基-2-乙基蒽、9,10-二乙氧基-2-乙基蒽、9,10-二丙氧基-2-乙基蒽、9,10-二甲氧基-2-氯蒽、9,10-二甲氧基蒽-2-磺酸甲酯、9,10-二乙氧基蒽-2-磺酸甲酯、9,10-二甲氧基蒽-2-羧酸甲酯等。
此等增感劑係可單獨或2種以上混合而使用，最佳為2,4-二乙基噻噸酮、9,10-二甲氧基-2-乙基蒽及/或9,10-二丁氧基蒽之使用。為了以少量發揮效果，增感劑成分的使用比例，相對於光陽離子聚合引發劑(C)成分而言，較佳為30質量%以下，特佳為20質量%以下。
於本發明的負型光敏性樹脂組成物中，以減低來自光陽離子聚合引發劑(C)的離子所造成的不利影響為目的，亦可添加離子捕捉劑。作為離子捕捉劑之具體例，可舉出三甲氧基鋁、三乙氧基鋁、三異丙氧基鋁、異丙氧基二乙氧基鋁及三丁氧基鋁等之烷氧基鋁，三苯氧基鋁及三對甲基苯氧基鋁等之苯氧基鋁、三乙醯氧基鋁、三硬脂酸鋁、三丁酸鋁、三丙酸鋁、三乙醯基乙酸鋁、三個三氟乙醯基乙酸鋁、三乙基乙醯基乙酸鋁、二乙醯基丙酮酸酯雙三甲基乙醯基甲酸鋁及二異丙氧基(乙基乙醯基乙酸)鋁等之有機鋁化合物等。離子捕捉劑係可單獨或組合2種以上使用，而且其配合量相對於(A)成分、(B)成分及(C)成分之合
計而言為10質量%以下。
於本發明的負型光敏性樹脂組成物中，視需要可使用熱塑性樹脂、著色劑、增黏劑、消泡劑、均平劑等之各種添加劑。作為熱塑性樹脂，例如可舉出聚醚碸、聚苯乙烯、聚碳酸酯等。作為著色劑，例如可舉出酞花青藍、酞花青綠、碘綠、結晶紫、氧化鈦、碳黑、萘黑等。作為增黏劑，例如可舉出歐魯本(Orben)、有機性搬土(benton)、蒙脫石等。作為消泡劑，例如可舉出聚矽氧系、氟系及高分子系等之消泡劑。使用此等添加劑等時，其使用量在本發明的樹脂組成物中，例如各自大致的目標為0.1~30質量%左右，但可按照使用目的來適宜增減。
再者，當本發明的負型光敏性樹脂組成物所含有的(B)成分具有乙烯性不飽和雙鍵時，於光陽離子聚合引發劑(C)中亦可併用光自由基聚合引發劑。
於本發明的負型光敏性樹枝組成物中，例如可使用硫酸鋇、鈦酸鋇、氧化矽、無定形矽石、滑石、黏土、碳酸鎂、碳酸鈣、氧化鋁、氫氧化鋁、雲母粉等之無機填充劑。無機填充劑之含量係佔本發明的樹脂組成物中的0~60質量%。
本發明的負型光敏性樹脂組成物，係可藉由通常的方法，僅將(A)成分、(B)成分及(C)成分以及視需要添加的任意成分混合、攪拌而得，但按照需要亦可使用溶解器、均質機、3輥磨機等之分散機進行分散、混合。又，於混合後，可更使用篩網、薄膜過濾器等來過濾。
本發明的樹脂組成物較佳為以液狀使用。例如在矽、鋁、銅、ITO等之金屬基板、鉭酸鋰、玻璃、氧化矽、氮化矽等之陶瓷基板、聚醯亞胺、聚對苯二甲酸乙二酯等之基板上，以0.1~1000μm之厚度，使用旋塗機等，塗佈液狀的樹脂組成物，藉由在60~130℃熱處理5~60分鐘左右，以去除溶劑，而在基板上形成樹脂組成物層。於該樹脂組成物層上，載置具有指定圖型的光罩，照射紫外線，在50~130℃進行1~50分鐘左右的加熱處理後，使用顯像液，將未曝光部分在室溫~50℃、1~180分鐘左右的條件下顯像，形成圖型。接著，藉由在130~250℃進行加熱處理，得到滿足諸特性之硬化物。作為顯像液，例如可使用TMAH，氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉等之鹼性水溶液。又，亦可將在前述鹼類的水溶液加有甲醇、乙醇等之水溶性有機溶劑或界面活性劑的溶液作為顯像液使用。於顯像中可使用浸液型、噴霧型、噴淋型等之顯像裝置，視需要亦可進行超音波照射。尚且，作為使用本發明的樹脂組成物時較佳之基板，可舉出玻璃或ITO。
以下，藉由實施例來詳細說明本發明，惟此等實施例只不過用於適宜地說明本發明之例示，絕非限定本發明。再者，合成例及實施例中之份係質量份。
於具備攪拌機、回流冷卻管、攪拌裝置之燒瓶中，一邊進行氮沖洗，一邊添加TrisP-PA(式(1)所示的苯酚衍生物，本州化學株式會社製)141份、環氧氯丙烷370份及甲醇64份，於攪拌下溶解，升溫至70℃為止。接著，費90分鐘，分割添加鱗片狀的氫氧化鈉42份後，在70℃進行1小時反應。反應結束後，進行水洗，使用旋轉式蒸發器，在140℃於減壓下，自油層中餾去過剩的環氧氯丙烷、溶劑等。於殘留物中添加甲基異丁基酮400份及溶解，升溫至70℃。於攪拌下添加30%氫氧化鈉水溶液10份，進行1小時攪拌後，進行水洗直到洗淨水成為中性為止，使用旋轉式蒸發器，在180℃於減壓下，自所得之溶液中餾去甲基異丁基酮等，而得到含有前述式(2)的環氧樹脂作為主成分之環氧樹脂(A-1)。所得之環氧樹脂的環氧當量為205g/eq.，軟化點為58.8℃。尚且，根據GPC(凝膠滲透層析術)之測定結果，以聚苯乙烯換算所算出之式(2)所示的環氧樹脂與式(3)所示的環氧樹脂之面積比(式(2)的環氧樹脂/式(3)的環氧樹脂)約10。
除了將環氧氯丙烷變更為185份以外，與合成例1同樣地進行，得到環氧樹脂(A-2)。所得之環氧樹脂的環氧當量為233g/eq.，軟化點為70℃。尚且，根據GPC(凝膠滲透層析術)的測定結果，以聚苯乙烯換算所算出之式(2)所示的環氧樹脂與式(3)所示的環氧樹脂之面積比(式(2)的
環氧樹脂/式(3)的環氧樹脂)約3。
於具備攪拌機、回流冷卻管、攪拌裝置之燒瓶中，加入NER-1302(日本化藥製，雙酚A型環氧樹脂，環氧當量330g/eq.，軟化點70℃)330份、丙烯酸72.8份、二丁基羥基甲苯1.7份、氯化四甲銨0.9份及甲基異丁基酮173份，升溫至98℃為止。維持在98℃，進行反應直到反應液的酸價(mgKOH/g，去除溶劑後的固體成分酸價，以下同樣)成為3.0以下為止，冷卻至60℃為止。其次，加入四氫苯二甲酸酐150份及甲基異丁基酮64份，升溫至120℃為止。維持在120℃，進行反應直到反應液的酸價成為100為止，水洗後，一邊餾去甲基異丁基酮，一邊置換成丙二醇單甲基醚乙酸酯，而得到鹼可溶性樹脂(B-1)。
於具備攪拌機、回流冷卻管、攪拌裝置之燒瓶中，加入合成例2所合成之環氧樹脂(A-2)233份、丙烯酸72.8份、二丁基羥基甲苯1.3份、氯化四甲銨0.7份及甲基異丁基酮145份，升溫至98℃為止。維持在98℃，進行反應直到反應液的酸價成為3.0以下為止，冷卻至60℃為止。其次，加入四氫苯二甲酸酐152份及甲基異丁基酮51份，升溫至120℃為止。維持在120℃，進行反應直到反應液的酸價成為122為止，水洗後，一邊餾去甲基異丁基
酮，一邊置換成丙二醇單甲基醚乙酸酯，而得到鹼可溶性樹脂(B-2)。
尚且，於上述合成例中，樹脂的物性值係藉由以下的方法來測定。
環氧當量；JIS K-7236
軟化點；JIS K-7234
分子量；GPC(凝膠滲透層析術)
依照表1中記載的配合量，於附攪拌機的燒瓶中，在60℃將各成分攪拌混合1小時，得到本發明及比較用的樹脂組成物。
藉由旋塗機，將實施例1~9及比較例1的各樹脂組成物塗佈於基板(玻璃或ITO)上後，乾燥而得到具有表1中所示的膜厚(表1中的「塗佈後膜厚」係意味塗佈、乾燥後的膜厚)之樹脂組成物層。藉由熱板，將此樹脂組成物層在65℃預烘烤5分鐘及在95℃預烘烤10分鐘。然後，使用i線曝光裝置(Mask Aligner：USHIO電機公司製)，進行圖型曝光(軟接觸，i線)，藉由熱板在95℃進行6分鐘的曝光後烘烤，使用2.38質量%的TMAH溶液，藉由浸漬法在23℃進行5分鐘顯像處理，得到在基板上硬化
之樹脂圖型。
於前述圖型曝光中，將光罩轉印精度成為最佳的曝光量當作最合適曝光量，進行各自的樹脂組成物之感度評價。最合適曝光量之值愈小，表示感度愈高。表1中顯示結果。
於前述所得之最合適曝光量的圖型曝光中，使用1~50μm的線與間隙之光罩，於沒有殘渣下的經解像光阻圖型中，藉由測定對基板密接的最細圖型寬度，進行解像性的評價。表1中顯示結果。
將前述所得之硬化物(厚度：40μm)在230℃的空氣烘箱中加熱處理20分鐘後，以分光光度計(日本分光製V-650)，於厚度方向測定在波長450nm之透光率(%)。表1中顯示結果。
對在230℃的空氣烘箱中經20分鐘加熱處理之硬化物，使用TG/DTA(精工儀器製TG/DTA 6200)，以20℃/分鐘的升溫速度進行測定，藉由下述之判定基準來評價。下述
表1中顯示結果。
○：1%重量減少溫度為250℃以上
×：1%重量減少溫度未達250℃
(A-1)：合成例1所得之環氧樹脂
(A-2)：合成例2所得之環氧樹脂
(A-3)：EOCN-1020(日本化藥製，鄰甲酚酚醛清漆環氧樹脂，環氧當量197g/eq.，軟化點64℃)
(B-1)：合成例3所得之鹼可溶性樹脂
(B-2)：合成例4所得之鹼可溶性樹脂
(C-1)：CPI-210S(SUN-APRO株式會社製)
(C-2)：UVI-6976(DOW化學公司製)
(C-3)：OPPI(Hampford Research Products製)
(C-4)：BBI-103(MIDORI化學株式會社製)
(D)：Celloxide 2021P(DAICEL化學工業株式會社製)
(E)：丙二醇單甲基醚乙酸酯
(F)：Megafac F-470(DIC株式會社製)
(G)：S510(CHISSO株式會社製)
(H-1)：ANTHRACURE UVS-1331(川崎化成工業株式會社製)
(H-2)：9,10-二甲氧基-2-乙基蒽(ALDRICH公司製)
本發明的負型光敏性樹脂組成物，除了可鹼顯像且圖像解析度或感度優異，還有該樹脂組成物的硬化物係熱安定性、耐藥品及溶劑溶解性優異，而且保有加熱時的著色少之特性，適用於顯示器用途等之要求透明性的領域。
Claims (4)
- 一種負型光敏性樹脂組成物，其係含有在1分子中具有2個以上的環氧基之環氧樹脂(A)、鹼可溶性樹脂(B)及光陽離子聚合引發劑(C)所成之光敏性樹脂組成物，其中環氧樹脂(A)係藉由下述式(1)
- 如申請專利範圍第1項之負型光敏性樹脂組成物，其中鹼可溶性樹脂(B)係在1分子中具有1個以上的羧基之鹼可溶性樹脂。
- 如申請專利範圍第2項之負型光敏性樹脂組成物，其中鹼可溶性樹脂(B)係環氧樹脂(a)和單羧酸(b)之反應物、與多元酸或其酐(c)之反應物。
- 一種硬化物，其係使如申請專利範圍第1至3項中任一項之負型光敏性樹脂組成物硬化而得。
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