KR102635564B1 - Positive photosensitive resist composition and insulation layer prepared from the same - Google Patents
Positive photosensitive resist composition and insulation layer prepared from the same Download PDFInfo
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- KR102635564B1 KR102635564B1 KR1020160054411A KR20160054411A KR102635564B1 KR 102635564 B1 KR102635564 B1 KR 102635564B1 KR 1020160054411 A KR1020160054411 A KR 1020160054411A KR 20160054411 A KR20160054411 A KR 20160054411A KR 102635564 B1 KR102635564 B1 KR 102635564B1
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- KR
- South Korea
- Prior art keywords
- group
- resin composition
- photosensitive resin
- resin
- carbon atoms
- Prior art date
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- 239000000203 mixture Substances 0.000 title description 11
- 238000009413 insulation Methods 0.000 title 1
- 239000011347 resin Substances 0.000 claims abstract description 80
- 229920005989 resin Polymers 0.000 claims abstract description 80
- 239000011342 resin composition Substances 0.000 claims abstract description 45
- 239000011230 binding agent Substances 0.000 claims abstract description 27
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 19
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 21
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 14
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000003504 photosensitizing agent Substances 0.000 claims description 9
- 150000007514 bases Chemical class 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 3
- 125000001412 tetrahydropyranyl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 description 70
- -1 quinonediazide compound Chemical class 0.000 description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 230000006870 function Effects 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000004611 light stabiliser Substances 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000001029 thermal curing Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- FZXRXKLUIMKDEL-UHFFFAOYSA-N 2-Methylpropyl propanoate Chemical compound CCC(=O)OCC(C)C FZXRXKLUIMKDEL-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- JVZRCNQLWOELDU-UHFFFAOYSA-N 4-Phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- FFOPEPMHKILNIT-UHFFFAOYSA-N Isopropyl butyrate Chemical compound CCCC(=O)OC(C)C FFOPEPMHKILNIT-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- QVQGTNFYPJQJNM-UHFFFAOYSA-N dicyclohexylmethanamine Chemical compound C1CCCCC1C(N)C1CCCCC1 QVQGTNFYPJQJNM-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- HOSJNFCDDCLEBM-UHFFFAOYSA-N (2-phenyloxetan-3-yl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1COC1C1=CC=CC=C1 HOSJNFCDDCLEBM-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RSHKWPIEJYAPCL-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1(CC)COC1 RSHKWPIEJYAPCL-UHFFFAOYSA-N 0.000 description 1
- RYNQKSJRFHJZTK-UHFFFAOYSA-N (3-methoxy-3-methylbutyl) acetate Chemical compound COC(C)(C)CCOC(C)=O RYNQKSJRFHJZTK-UHFFFAOYSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 description 1
- CNDOSNMFHUSKGN-UHFFFAOYSA-N 1-(2-hydroxyphenyl)pyrrole-2,5-dione Chemical compound OC1=CC=CC=C1N1C(=O)C=CC1=O CNDOSNMFHUSKGN-UHFFFAOYSA-N 0.000 description 1
- LJDGDRYFCIHDPX-UHFFFAOYSA-N 1-(2-methoxyphenyl)pyrrole-2,5-dione Chemical compound COC1=CC=CC=C1N1C(=O)C=CC1=O LJDGDRYFCIHDPX-UHFFFAOYSA-N 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- MRYQZMHVZZSQRT-UHFFFAOYSA-M tetramethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)C MRYQZMHVZZSQRT-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133345—Insulating layers
-
- 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
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
-
- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Liquid Crystal (AREA)
Abstract
본 발명은 포지티브형 감광성 수지 조성물 및 이로부터 제조된 절연막에 관한 것으로, 보다 상세하게는, 포지티브형 감광성 수지 조성물은 (a-1)페놀성 수산기 또는 카르복시기의 적어도 일부가 산분해성기로 보호된 수지, (a-2)실릴 에테르기를 포함하는 아크릴 수지 및 (a-3)에폭시기를 포함하는 아크릴 수지를 포함하는 바인더 수지를 포함하는 것을 특징으로 한다.The present invention relates to a positive photosensitive resin composition and an insulating film manufactured therefrom. More specifically, the positive photosensitive resin composition includes (a-1) a resin in which at least a portion of the phenolic hydroxyl group or carboxyl group is protected by an acid-decomposable group; It is characterized by comprising a binder resin containing (a-2) an acrylic resin containing a silyl ether group and (a-3) an acrylic resin containing an epoxy group.
Description
본 발명은 밀착성 및 균일성이 우수한 절연막을 얻을 수 있는 포지티브형 감광성 수지 조성물 및 이로부터 제조된 절연막에 관한 것이다.The present invention relates to a positive photosensitive resin composition capable of obtaining an insulating film with excellent adhesion and uniformity, and an insulating film manufactured therefrom.
박막 트랜지스터(TFT)형 액정표시장치 등의 디스플레이 장치에 있어서, TFT(Thin Film Transistor)회로를 보호하고, 절연시키기 위한 보호막으로는 종래에 실리콘 나이트라이드 등의 무기계 보호막이 이용되어 왔지만, 유전상수값이 높아서 개구율을 향상시키기 어려운 문제점이 있어서, 이를 극복하기 위하여 유전율이 낮은 유기 절연막의 수요가 증가하고 있는 추세에 있다.In display devices such as thin film transistor (TFT) type liquid crystal displays, inorganic protective films such as silicon nitride have conventionally been used as protective films to protect and insulate the TFT (Thin Film Transistor) circuit. There is a problem that it is difficult to improve the aperture ratio due to the high aperture ratio, and in order to overcome this problem, the demand for organic insulating films with low dielectric constant is increasing.
이러한 유기 절연막으로서, 광 및 전자선에 의해 화학 반응하여 특정 용매에 대한 용해도가 변화되는 고분자 화합물인 감광성 수지가 일반적으로 사용되며, 회로패턴의 미세가공은 상기 유기 절연막의 광반응에 의해 일어나는 고분자의 극성변화 및 가교반응에 의한다. 특히, 상기 유기 절연막 재료는 노광 후 알칼리 수용액 등의 용매에 대한 용해성의 변화 특성을 이용한다.As such an organic insulating film, a photosensitive resin, which is a polymer compound whose solubility in a specific solvent changes by chemical reaction with light and electron beams, is generally used, and the microprocessing of the circuit pattern is carried out by changing the polarity of the polymer caused by the photoreaction of the organic insulating film. Due to changes and cross-linking reactions. In particular, the organic insulating film material utilizes the property of changing solubility in solvents such as aqueous alkaline solutions after exposure.
상기 유기 절연막은 감광된 부분의 현상에 대한 용해도에 따라 포지티브형과 네가티브형으로 분류된다. 포지티브형 포토레지스트는 노광된 부분이 현상액에 의해 용해되며, 네가티브형 포토레지스트는 노광된 부분이 현상액에 녹지 않고 노광되지 아니한 부분이 용해되어 패턴이 형성되는 방식이다.The organic insulating film is classified into positive and negative types depending on the solubility of the photosensitive portion. In the case of positive type photoresist, the exposed portion is dissolved by the developer, while in the case of negative type photoresist, the exposed portion is not dissolved in the developer, but the unexposed portion is dissolved to form a pattern.
이 중에서, 포지티브형 유기 절연막은 알칼리 수용액을 사용함으로써, 네가티브형 유기 절연막에서 사용하던 유기 현상액의 사용을 배제할 수 있으므로, 작업 환경적인 측면에서 유리할 뿐 아니라, 이론적으로는 자외선에 노출되지 않은 부분의 팽윤 현상을 막을 수 있기 때문에 분해능이 향상되는 장점이 있다. 아울러, 유기막 형성 후, 박리액에 의한 제거가 용이하여, 공정 중 불량 패널 발생시 유기막 제거에 의해 기판 회수와 재사용성이 월등히 향상되는 장점이 있다.Among these, the positive-type organic insulating film uses an aqueous alkaline solution, which eliminates the use of the organic developer used in the negative-type organic insulating film, so it is not only advantageous in terms of the working environment, but also theoretically allows the use of an aqueous alkaline solution in areas that are not exposed to ultraviolet rays. There is an advantage in that resolution is improved because swelling phenomenon can be prevented. In addition, after the organic film is formed, it is easy to remove with a stripper, so when a defective panel occurs during the process, substrate recovery and reusability are greatly improved by removing the organic film.
특히, 이러한 유기 절연막으로서 액정표시장치의 절연막 등을 구성함에 있어, 상기 절연막은 절연성이 우수하여야 함은 물론, 기판 위에 코팅되었을 때 계면에서의 응력을 줄이기 위하여 낮은 열팽창성을 가져야 하고, 물리적으로 강인한 특성을 지녀야 하며 감도, 투과율 등이 우수해야 한다.In particular, when constructing the insulating film of a liquid crystal display device using such an organic insulating film, the insulating film must not only have excellent insulating properties, but also have low thermal expansion to reduce stress at the interface when coated on a substrate, and must be physically strong. It must have excellent characteristics and must have excellent sensitivity and transmittance.
그런데, 유기 절연막과 기판과의 밀착성을 향상시키기 위해 공정 중에 헥사메틸디실라잔 등을 기판 위에 처리하게 되는데, 이때, 헥사메틸디실라잔 처리라는 별도의 공정이 필요한 문제점이 있다.However, in order to improve the adhesion between the organic insulating film and the substrate, hexamethyldisilazane, etc., is treated on the substrate during the process. At this time, there is a problem that a separate process called hexamethyldisilazane treatment is required.
대한민국 공개특허 제10-2010-0066808호는 포지티브형 감광성 유-무기 하이브리드 절연막 조성물에 관한 것으로, 실록산 올리고머 화합물을 포함한다. 그러나, 상기 선행문헌들은 퀴논디아지드 화합물을 이용한 포지티브형 감광성 수지 조성물로 감도가 느린 단점이 있다.Republic of Korea Patent Publication No. 10-2010-0066808 relates to a positive photosensitive organic-inorganic hybrid insulating film composition, and includes a siloxane oligomer compound. However, the above prior literature has the disadvantage of slow sensitivity due to the positive type photosensitive resin composition using a quinonediazide compound.
또한, 대한민국 등록특허 제10-1404005호는 포지티브형 감방사선성 조성물, 표시 소자용 층간 절연막 및 그 형성 방법에 관한 것으로, 가수분해성 실란 화합물의 가수분해 축합물인 실록산 폴리머를 사용한다. 그러나, 상기 선행문헌은 고감도화가 어려운 문제가 있다.In addition, Republic of Korea Patent No. 10-1404005 relates to a positive radiation-sensitive composition, an interlayer insulating film for a display device, and a method of forming the same, using siloxane polymer, which is a hydrolytic condensate of a hydrolyzable silane compound. However, the above prior literature has a problem in that it is difficult to achieve high sensitivity.
본 발명은 특정 바인더 수지를 포함함으로써, 특히 실리콘 질화물(SiNx) 막 상에서의 밀착성 및 균일성이 우수한 포지티브형 감광성 수지 조성물 및 이로부터 제조된 절연막을 제공하는 것을 목적으로 한다.The purpose of the present invention is to provide a positive photosensitive resin composition with excellent adhesion and uniformity, especially on a silicon nitride (SiNx) film, by including a specific binder resin, and an insulating film manufactured therefrom.
상기 목적을 달성하기 위한 본 발명에 따른 포지티브형 감광성 수지 조성물은 (a-1)페놀성 수산기 또는 카르복시기의 적어도 일부가 산분해성기로 보호된 수지, (a-2)실릴 에테르기를 포함하는 아크릴 수지 및 (a-3)에폭시기를 포함하는 아크릴 수지를 포함하는 바인더 수지를 포함하는 것을 특징으로 한다.The positive photosensitive resin composition according to the present invention for achieving the above object includes (a-1) a resin in which at least part of the phenolic hydroxyl group or carboxyl group is protected with an acid-decomposable group, (a-2) an acrylic resin containing a silyl ether group, and (a-3) It is characterized by containing a binder resin containing an acrylic resin containing an epoxy group.
또한, 본 발명은 상기 포지티브형 감광성 수지 조성물로 제조된 절연막을 포함하는 것을 목적으로 한다.Additionally, the present invention aims to include an insulating film made from the positive-type photosensitive resin composition.
상기한 바와 같이 본 발명에 따른 포지티브형 감광성 수지 조성물 및 이로부터 제조된 절연막은 특정 바인더 수지를 포함함으로써, 헥사메틸디실라잔(hexamethyldisilazane) 미처리 조건에서도 실리콘 질화물 기판에서의 밀착성 및 균일성이 우수한 효과가 있다.As described above, the positive photosensitive resin composition according to the present invention and the insulating film manufactured therefrom contain a specific binder resin, thereby providing excellent adhesion and uniformity on a silicon nitride substrate even under hexamethyldisilazane untreated conditions. There is.
이하 본 발명을 상세히 설명하기로 한다.Hereinafter, the present invention will be described in detail.
<< 포지티브형positive type 감광성 수지 조성물> Photosensitive resin composition>
본 발명의 포지티브형 감광성 수지 조성물은 (a-1)페놀성 수산기 또는 카르복시기의 적어도 일부가 산분해성기로 보호된 수지, (a-2)실릴 에테르기를 포함하는 아크릴 수지 및 (a-3)에폭시기를 포함하는 아크릴 수지를 포함하는 바인더 수지를 포함하고, 광산발산제, 광증감제, 용매, 염기성 화합물, 커플링제, 계면활성제 및 첨가제 중 하나 이상을 더 포함한다.The positive photosensitive resin composition of the present invention includes (a-1) a resin in which at least part of the phenolic hydroxyl group or carboxyl group is protected by an acid-decomposable group, (a-2) an acrylic resin containing a silyl ether group, and (a-3) an epoxy group. It includes a binder resin including an acrylic resin, and further includes one or more of a photoacid emitter, a photosensitizer, a solvent, a basic compound, a coupling agent, a surfactant, and an additive.
바인더 수지binder resin
상기 바인더 수지는 (a-1)페놀성 수산기 또는 카르복시기의 적어도 일부가 산분해성기로 보호된 수지, (a-2)실릴 에테르기를 포함하는 아크릴 수지 및 (a-3)에폭시기를 포함하는 아크릴 수지를 포함하는 바인더 수지를 포함한다:The binder resin includes (a-1) a resin in which at least a portion of the phenolic hydroxyl group or carboxyl group is protected by an acid-decomposable group, (a-2) an acrylic resin containing a silyl ether group, and (a-3) an acrylic resin containing an epoxy group. A binder resin comprising:
(a-1) 수지는 페놀성 수산기 또는 카르복시기의 적어도 일부가 산분해성기로 보호된 수지로 노광 시 광산 발생제에 의해 산이 발생되어, 산분해성기를 탈리시켜 현상공정에서 용해성을 부여하는 기능을 한다. 상기 산분해성기의 예로는 알콕시기 또는 시클로알콕시기로 치환된 알킬기; 또는 테트라하이드로피라닐기를 들 수 있다.(a-1) Resin is a resin in which at least part of the phenolic hydroxyl group or carboxyl group is protected by an acid-decomposable group. When exposed, acid is generated by a photoacid generator, thereby desorbing the acid-decomposable group and providing solubility in the development process. Examples of the acid-decomposable group include an alkyl group substituted with an alkoxy group or a cycloalkoxy group; Or a tetrahydropyranyl group can be mentioned.
(a-1) 수지는 상기 작용기에 특별한 제한은 없으나, 하기 화학식 1로 표시되는 단량체를 포함하여 중합되는 수지를 예로 들 수 있다.(a-1) There is no particular limitation on the functional group of the resin, but examples include resins that are polymerized and contain a monomer represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서, R은 탄소수 1 내지 6의 알콕시기 또는 탄소수 4 내지 8의 시클로알콕시기로 치환 또는 비치환된 탄소수 1 내지 6의 알킬기; 또는 테트라하이드로피라닐기이다.In Formula 1, R is an alkyl group having 1 to 6 carbon atoms unsubstituted or substituted with an alkoxy group having 1 to 6 carbon atoms or a cycloalkoxy group having 4 to 8 carbon atoms; Or it is a tetrahydropyranyl group.
(a-1) 수지는 (산분해성기로 보호되지 않은) 페놀성 수산기 또는 카르복시기를 갖는 단량체로 형성된 반복단위를 더 포함할 수 있다. 그러한 단량체로는 전술한 카르복시기를 갖는 에틸렌성 불포화 단량체, 히드록시스티렌, 히드록시메틸스티렌 등을 예로 들 수 있다. (a-1) The resin may further include a repeating unit formed of a monomer having a phenolic hydroxyl group or a carboxyl group (not protected by an acid-decomposable group). Examples of such monomers include ethylenically unsaturated monomers having the above-mentioned carboxyl group, hydroxystyrene, and hydroxymethylstyrene.
(a-1) 수지는 중량평균분자량이 5,000 내지 35,000인 것이 바람직하며, 5,000 내지 20,000인 것이 보다 바람직하다. (a-1) 수지의 중량평균분자량이 상기 범위 미만일 경우에는 잔막율 저하 현상이 나타날 수 있으며, 상기 범위를 초과할 경우에는 잔사나 잔막 현상 등이 발생할 수 있다. (a-1) 수지의 중량평균분자량은 상기 범위인 것이 잔막율 개선 및 잔사 감소 측면에서 우수할 수 있다. (a-1) The resin preferably has a weight average molecular weight of 5,000 to 35,000, and more preferably 5,000 to 20,000. (a-1) If the weight average molecular weight of the resin is less than the above range, a decrease in the residual film rate may occur, and if it exceeds the above range, residue or residual film phenomena may occur. (a-1) The weight average molecular weight of the resin within the above range may be superior in terms of improving the residual film rate and reducing residue.
상기 (a-2) 수지는 실릴 에테르기를 포함하는 아크릴 수지로서, 하기 화학식 2로 표시되는 반복단위를 포함하는 수지일 수 있다.The resin (a-2) is an acrylic resin containing a silyl ether group, and may be a resin containing a repeating unit represented by the following formula (2).
[화학식 2][Formula 2]
식 중, R1, R2 및 R3은 서로 독립적으로 수소 또는 메틸기이며,In the formula, R 1 , R 2 and R 3 are independently hydrogen or methyl groups,
R4는 하기 화학식 3으로 표시되는 단량체에서 유래된 구조이며,R 4 is a structure derived from a monomer represented by the following formula (3),
[화학식 3][Formula 3]
R9는 탄수소 1 내지 6의 알킬렌기이며,R 9 is an alkylene group having 1 to 6 carbon atoms,
R10은 탄소수 1 내지 2의 알킬기이며,R 10 is an alkyl group having 1 to 2 carbon atoms,
R5는 (메타)아크릴산, 2-(메타)아크릴로일록시에틸석시네이트, 2-(메타)아크릴로일옥시에틸헥사히드로프탈레이트, 2-(메타)아크릴로일옥시에틸프탈레이트 및 2-(메타)아크릴로일옥시에틸석시네이트로 이루어진 군에서 선택되는 단량체에서 유래된 구조이며,R 5 is (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinate, 2-(meth)acryloyloxyethylhexahydrophthalate, 2-(meth)acryloyloxyethylphthalate and 2- It is a structure derived from a monomer selected from the group consisting of (meth)acryloyloxyethyl succinate,
R6은 하기 화학식 4로 표시되는 단량체에서 유래된 구조이며,R 6 is It is a structure derived from a monomer represented by the following formula 4,
[화학식 4][Formula 4]
R7은 탄소수 1 내지 6의 알킬렌기이며, R8은 탄소수 1 내지 6의 알킬기이고,R 7 is an alkylene group having 1 to 6 carbon atoms, R 8 is an alkyl group having 1 to 6 carbon atoms,
a=40 내지 80mol%, b=5 내지 45mol%, c=10 내지 55mol%이다.a=40 to 80 mol%, b=5 to 45 mol%, c=10 to 55 mol%.
이때, (a-2) 수지의 화학식 3을 포함함으로써, 헥사메틸디실라잔 미처리 조건에서도 실리콘 질화물 기판에서의 밀착성 및 균일성이 우수한 효과를 얻을 수 있다At this time, by including the formula (3) of the (a-2) resin, excellent adhesion and uniformity on the silicon nitride substrate can be obtained even under hexamethyldisilazane untreated conditions.
보다 상세하게는, (a-2) 수지의 화학식 4을 포함함으로써, 유기 절연막을 경화시키기 위한 열경화기로 후술할 (a-3) 수지에 사용된 에폭시 기와 동일한 역할을 한다. More specifically, by including the formula (4) of the (a-2) resin, it plays the same role as the epoxy group used in the (a-3) resin, which will be described later, as a thermal curing machine for curing the organic insulating film.
이때, 밀착성을 향상시키기 위해 기판 위에 헥사메틸디실라잔이라는 물질을 처리하게 되는데, 본 발명에서는 헥사메틸디실라잔 처리를 하지 않기 때문에, 공정 과정을 줄일 수 있기 때문에 공정 시간을 단축할 수 있는 특징이 있다.At this time, in order to improve adhesion, a material called hexamethyldisilazane is treated on the substrate. In the present invention, since hexamethyldisilazane treatment is not performed, the processing time can be shortened by reducing the processing steps. There is.
상기 (a-2) 수지는 바인더 수지 100중량부에 대하여, 10 내지 30중량부로 포함하는 것이 바람직하다. 상기 (a-2) 수지가 상기 범위 이내일 경우, 가공이 용이하며 밀착성이 우수할 수 있다. The resin (a-2) is preferably contained in an amount of 10 to 30 parts by weight based on 100 parts by weight of the binder resin. When the (a-2) resin is within the above range, processing is easy and adhesion can be excellent.
상기 (a-2) 수지는 중량평균분자량이 5,000 내지 30,000인 것이 바람직하며, 8,000 내지 20,000인 것이 보다 바람직하다. (a-2) 수지의 중량평균분자량이 상기 범위 미만일 경우에는 잔막율 저하 현상이 나타날 수 있으며, 상기 범위를 초과할 경우에는 잔사나 잔막 현상등이 발생할 수 있다. (a-2) 수지의 중량평균분자량은 상기 범위인 것이 현상성에 따른 잔사 감소 및 경시안정성 향상 측면에서 우수할 수 있다. The (a-2) resin preferably has a weight average molecular weight of 5,000 to 30,000, and more preferably 8,000 to 20,000. (a-2) If the weight average molecular weight of the resin is less than the above range, a decrease in the residual film rate may occur, and if it exceeds the above range, residue or residual film phenomena may occur. (a-2) The weight average molecular weight of the resin within the above range may be superior in terms of reducing residues due to developability and improving aging stability.
상기 (a-3) 수지는 에폭시기를 포함하는 아크릴 수지는 에폭시기를 포함하는 수지로서, 열경화를 가능하게 함으로써 보다 내구성이 높은 패턴의 형성이 가능하다. 열경화는 예를 들면 포스트-베이크 공정에서 수행될 수 있다.The (a-3) resin contains an epoxy group, and the acrylic resin contains an epoxy group, and enables thermal curing to form a more durable pattern. Thermal curing can be carried out, for example, in a post-bake process.
아크릴 수지에 에폭시기를 도입하기 위해서, 본 발명의 일 구현예에서 본 발명에 따른 a-3 수지는 하기 화학식 5로 표시되는 단량체를 포함하여 중합될 수 있다.In order to introduce an epoxy group into an acrylic resin, in one embodiment of the present invention, the a-3 resin according to the present invention may be polymerized including a monomer represented by the following formula (5).
[화학식 5][Formula 5]
상기 화학식 5에서, R11은 수소원자 또는 메틸기이고; R12는 탄소수 1 내지 6의 알킬렌기이고; R13 및 R14는 서로 독립적으로 수소 원자 또는 탄소수 1 내지 6의 알킬기이거나, 서로 연결되어 탄소수 3 내지 8의 고리를 형성할 수 있고; m은 1 내지 6의 정수임.In Formula 5, R 11 is a hydrogen atom or a methyl group; R 12 is an alkylene group having 1 to 6 carbon atoms; R 13 and R 14 may each independently be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or may be connected to each other to form a ring having 3 to 8 carbon atoms; m is an integer from 1 to 6.
화학식 5로 표시되는 단량체는 R12에 인접한 산소 원자를 포함하고 있는데, 사슬에 산소원자를 포함하고 있는 경우 단일 결합의 회전 반경이 커져 유리전이온도가 낮아져 흐름성이 개선되어 가공이 용이해진다.The monomer represented by Formula 5 contains an oxygen atom adjacent to R 12 . When the chain contains an oxygen atom, the radius of gyration of the single bond increases, lowering the glass transition temperature, improving flowability and making processing easier.
또한 화학식 5에서 m의 조정을 통해 단량체 길이의 조절이 가능한데, 이를 통해 형성한 패턴의 기울기를 조정할 수 있으며, 이 경우 패턴의 기울기를 낮추어 투명전극의 증착시 경화막의 탈락이나 크랙의 발생을 방지할 수 있다. 뿐만 아니라, 화학식 5로 표시되는 단량체는 중합되는 수지의 투과율을 개선할 수 있다. In addition, the length of the monomer can be adjusted by adjusting m in Formula 5, and through this, the slope of the formed pattern can be adjusted. In this case, the slope of the pattern can be lowered to prevent the falling off of the cured film or the occurrence of cracks during deposition of transparent electrodes. You can. In addition, the monomer represented by Formula 5 can improve the transmittance of the polymerized resin.
(a-3) 수지는 상기 화학식 5의 단량체 외에 아크릴 수지를 형성할 수 있는, 당분야에 공지된 단량체들을 사용하여 중합될 수 있다.(a-3) Resin can be polymerized using monomers known in the art that can form an acrylic resin in addition to the monomer of Chemical Formula 5.
예를 들면, 카르복시기를 갖는 에틸렌성 불포화 단량체를 사용할 수 있다. 카르복시기를 갖는 에틸렌성 불포화 단량체의 종류는 특별히 한정되지 않으나, 예를 들면, 아크릴산, 메타아크릴산, 크로톤산 등의 모노카르복실산류; 푸마르산, 메사콘산, 이타콘산 등의 디카르복실산류 및 이들의 무수물; ω-카르복시폴리카프로락톤모노(메타)아크릴레이트 등의 양 말단에 카르복시기와 수산기를 갖는 폴리머의 모노(메타)아크릴레이트류 등을 들 수 있으며, 바람직하게는 아크릴산 및 메타아크릴산일 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.For example, an ethylenically unsaturated monomer having a carboxyl group can be used. The type of ethylenically unsaturated monomer having a carboxyl group is not particularly limited, but examples include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid, and their anhydrides; Examples include polymer mono(meth)acrylates having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate, and preferably acrylic acid and methacrylic acid. These can be used alone or in combination of two or more types.
또한, 상기 단량체와 공중합 가능한 적어도 하나의 다른 단량체를 더 포함하여 중합될 수 있다. 예를 들면 스티렌, 비닐톨루엔, 메틸스티렌, p-클로로스티렌, o-메톡시스티렌, m-메톡시스티렌, p-메톡시스티렌, o-비닐벤질메틸에테르, m-비닐벤질메틸에테르, p-비닐벤질메틸에테르 등의 방향족 비닐 화합물; N-시클로헥실말레이미드, N-벤질말레이미드, N-페닐말레이미드, N-o-히드록시페닐말레이미드, N-m-히드록시페닐말레이미드, N-p-히드록시페닐말레이미드, N-o-메틸페닐말레이미드, N-m-메틸페닐말레이미드, N-p-메틸페닐말레이미드, N-o-메톡시페닐말레이미드, N-m-메톡시페닐말레이미드, N-p-메톡시페닐말레이미드 등의 N-치환 말레이미드계 화합물; 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, n-프로필(메타)아크릴레이트, i-프로필(메타)아크릴레이트, n-부틸(메타)아크릴레이트, i-부틸(메타)아크릴레이트, sec-부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트 등의 알킬(메타)아크릴레이트류; 시클로펜틸(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 2-메틸시클로헥실(메타)아크릴레이트, 트리시클로[5.2.1.0 2,6]데칸-8-일(메타)아크릴레이트, 2-디시클로펜타닐옥시에틸(메타)아크릴레이트, 이소보르닐(메타)아크릴레이트 등의 지환족(메타)아크릴레이트류; 페닐(메타)아크릴레이트, 벤질(메타)아크릴레이트 등의 아릴(메타)아크릴레이트류; 3-(메타크릴로일옥시메틸)옥세탄, 3-(메타크릴로일옥시메틸)-3-에틸옥세탄, 3-(메타크릴로일옥시메틸)-2-트리플루오로메틸옥세탄, 3-(메타크릴로일옥시메틸)-2-페닐옥세탄, 2-(메타크릴로일옥시메틸)옥세탄, 2-(메타크릴로일옥시메틸)-4-트리플루오로메틸옥세탄 등의 불포화 옥세탄 화합물; 탄소수 4 내지 16의 시클로알칸, 디시클로알칸 또는 트리시클로알칸고리로 치환된 (메타)아크릴레이트; 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.In addition, the polymerization may further include at least one other monomer copolymerizable with the monomer. For example, styrene, vinyltoluene, methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p- Aromatic vinyl compounds such as vinylbenzyl methyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m -N-substituted maleimide compounds such as methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-methoxyphenylmaleimide; Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, Alkyl (meth)acrylates such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate; Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6]decan-8-yl(meth)acrylate, 2- Alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate; Aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. unsaturated oxetane compounds; (meth)acrylate substituted with a cycloalkane, dicycloalkane, or tricycloalkane ring having 4 to 16 carbon atoms; etc. can be mentioned. These can be used alone or in combination of two or more types.
상기 (a-3) 수지는 바인더 수지 100중량부에 대하여, 20 내지 40중량부로 포함하는 것이 바람직하다. 상기 (a-3) 수지가 상기 범위 이내일 경우, 밀착성이 우수할 수 있다. The resin (a-3) is preferably contained in an amount of 20 to 40 parts by weight based on 100 parts by weight of the binder resin. When the (a-3) resin is within the above range, adhesion may be excellent.
(a-3) 수지는 중량평균분자량이 5,000 내지 40,000인 것이 바람직하며, 15,000 내지 30,000인 것이 보다 바람직하다.. (a-3) 수지의 중량평균분자량이 상기 범위 미만일 경우에는 잔막율 저하 현상이 나타날 수 있으며, 상기 범위를 초과할 경우에는 잔사 및 잔막 현상 등이 발생할 수 있다. (a-3) 수지의 중량평균분자량은 상기 범위 이내일 경우 현상성 개선 및 잔사 감소 측면에서 바람직하다.(a-3) The resin preferably has a weight average molecular weight of 5,000 to 40,000, and more preferably 15,000 to 30,000. (a-3) If the weight average molecular weight of the resin is less than the above range, the residual film rate decreases. may appear, and if the above range is exceeded, residue and remaining film phenomena may occur. (a-3) If the weight average molecular weight of the resin is within the above range, it is preferable in terms of improving developability and reducing residue.
상기 (a-1):(a-2):(a-3) 수지의 비율은 바인더 수지 100중량부에 대하여 40 내지 60 : 10 내지 30 : 20 내지 40 중량부인 것이 바람직하다. 상기 (a-1):(a-2): (a-3) 수지의 비율이 상기 범위 이내일 경우, 밀착성, 감도 및 투과율이 모두 우수할 수 있다. The ratio of the (a-1):(a-2):(a-3) resin is preferably 40 to 60:10 to 30:20 to 40 parts by weight based on 100 parts by weight of the binder resin. When the ratio of the (a-1):(a-2):(a-3) resin is within the above range, adhesion, sensitivity, and transmittance can all be excellent.
본 발명에 따른 바인더 수지는 전술한 3종의 수지를 혼합하여 패턴 형성 능은 저하시키지 않으면서 현상성을 현저하게 상승시켜 잔사를 감소시킬 수 있다. The binder resin according to the present invention can significantly increase developability and reduce residue by mixing the three types of resins described above without reducing pattern forming ability.
광산발생제Mineral generator
광산발생제는 활성광선 또는 방사선을 조사하여 산을 발생시키는 화합물이다.A photoacid generator is a compound that generates acid by irradiating actinic light or radiation.
광산발생제의 종류는 특별히 한정되지 않으며, 예를 들면 디아조늄염계, 포스포늄염계, 술포늄염계, 요오드늄염계, 이미드술포네이트계, 옥심술포네이트계, 디아조디술폰계, 디술폰계, 오르소-니트로벤질술포네이트계, 트라아진계 화합물 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The type of photoacid generator is not particularly limited, and examples include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, Ortho-nitrobenzylsulfonate-based compounds, triazine-based compounds, etc. can be mentioned. These can be used alone or in combination of two or more types.
광산발생제는 그 기능을 할 수 있는 범위 내에서는 그 함량이 특별히 한정되지 않으며, 예를 들면 바인더 수지 100중량부에 대하여 0.1 내지 20중량부로 포함될 수 있고, 바람직하게는 0.5 내지 10중량부로 포함될 수 있다. 광산발생제의 함량이 상기 범위 내이면 산의 촉매작용에 의한 화학 변화가 충분히 일어날 수 있고 조성물 도포시 균일하게 도포가 이루어질 수 있는 장점이 있다. The content of the photoacid generator is not particularly limited within the range in which it can perform its function. For example, it may be included in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin. there is. If the content of the photoacid generator is within the above range, there is an advantage that chemical changes due to the catalytic action of the acid can sufficiently occur and the composition can be applied uniformly.
광증감제photosensitizer
본 발명에 있어서, 필요에 따라 광산발생제와 함께 광증감제가 더 포함될 수도 있다.In the present invention, a photosensitizer may be further included along with the photoacid generator, if necessary.
광증감제는 광산발생제의 분해를 촉진하여 감도를 향상시키는 성분이다. 본 발명에 따른 광증감제는 특별히 한정되지 않으며, 예를 들면 다핵 방향족류, 크산텐류, 크산톤류, 시아닌류, 옥소놀류, 티아진류, 아크리딘류, 아크리돈류, 안트라퀴논류, 스쿠알륨류, 스티릴류, 베이스스티릴류, 쿠마린류, 안트라센류 화합물 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.A photosensitizer is an ingredient that improves sensitivity by promoting the decomposition of the photoacid generator. The photosensitizer according to the present invention is not particularly limited, and includes, for example, polynuclear aromatics, xanthenes, xanthons, cyanines, oxonols, thiazines, acridines, acridones, anthraquinones, and squaliums. , styryls, base styryls, coumarins, anthracene compounds, etc. These can be used alone or in combination of two or more types.
광증감제는 그 기능을 할 수 있는 범위 내에서는 그 함량이 특별히 한정되지 않으며, 예를 들면 바인더 수지 100중량부에 대하여 0.01 내지 60중량부로 포함될 수 있고, 바람직하게는 0.5 내지 10중량부로 포함될 수 있다. 광증감제의 함량이 상기 범위 내인 경우 분광 증감에 의한 감도의 향상 또는 투과율의 향상 효과를 최대화할 수 있는 장점이 있다.The content of the photosensitizer is not particularly limited within the range in which it can perform its function. For example, it may be included in an amount of 0.01 to 60 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin. there is. When the content of the photosensitizer is within the above range, there is an advantage in maximizing the effect of improving sensitivity or transmittance by spectral sensitization.
용매menstruum
용매의 종류는 특별히 한정되지 않으며, 상기 언급한 성분들을 용해시킬 수 있고, 적합한 건조속도를 가지며, 용매의 증발 후에 균일하고 매끄러운 코팅막을 형성할 수 있는 것이라면 어떤 용매나 사용할 수 있다.The type of solvent is not particularly limited, and any solvent can be used as long as it can dissolve the above-mentioned components, has an appropriate drying speed, and can form a uniform and smooth coating film after evaporation of the solvent.
구체적인 예로는 에테르류, 아세테이트류, 에스테르류, 케톤류, 아미드류, 락톤류 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Specific examples include ethers, acetates, esters, ketones, amides, and lactones. These can be used alone or in combination of two or more types.
에테르류의 구체적인 예로는 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노프로필에테르, 에틸렌글리콜모노부틸에테르 등의 에틸렌글리콜모노알킬에테르류; 에틸렌글리콜디메틸에테르, 에틸렌글리콜디에틸에테르, 에틸렌글리콜디프로필에테르 등의 에틸렌글리콜디알킬에테르류; 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노에틸에테르, 프로필렌글리콜모노프로필에테르, 프로필렌글리콜모노부틸에테르 등의 프로필렌글리콜모노알킬에테르류; 프로필렌글리콜디메틸에테르, 프로필렌글리콜디에틸에테르, 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노에틸에테르 등의 프로필렌글리콜디알킬에테르류; 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 디에틸렌글리콜에틸메틸에테르 등의 디에틸렌글리콜디알킬에테르류; 디프로필렌글리콜모노메틸에테르, 디프로필렌글리콜모노에틸에테르, 디프로필렌글리콜모노프로필에테르, 디프로필렌글리콜모노부틸에테르 등의 디프로필렌글리콜모노알킬에테르류; 디프로필렌글리콜디메틸에테르, 디프로필렌글리콜디에틸에테르, 디프로필렌글리콜에틸메틸에테르 등의 디프로필렌글리콜디알킬에테르류 등을 들 수 있다.Specific examples of ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether; Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether; and dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether.
아세테이트류의 구체적인 예로는 에틸렌글리콜모노메틸에테르아세테이트, 에틸렌글리콜모노에틸에테르아세테이트, 에틸렌글리콜모노프로필에테르아세테이트, 에틸렌글리콜모노부틸에테르아세테이트 등의 에틸렌글리콜모노알킬에테르아세테이트류; 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노프로필에테르아세테이트, 프로필렌글리콜모노부틸에테르아세테이트 등의 프로필렌글리콜모노알킬에테르아세테이트류; 디에틸렌글리콜모노메틸에테르아세테이트, 디에틸렌글리콜모노에틸에테르아세테이트, 디에틸렌글리콜모노프로필에테르아세테이트, 디에틸렌글리콜모노부틸에테르아세테이트 등의 디에틸렌글리콜모노알킬에테르아세테이트류; 디프로필렌글리콜모노메틸에테르아세테이트, 디프로필렌글리콜모노에틸에테르아세테이트, 디프로필렌글리콜모노프로필에테르아세테이트, 디프로필렌글리콜모노부틸에테르아세테이트 등의 디프로필렌글리콜모노알킬에테르아세테이트류;Specific examples of acetates include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate; Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, and diethylene glycol monobutyl ether acetate; Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, and dipropylene glycol monobutyl ether acetate;
프로필렌글리콜메틸에틸아세테이트 등의 프로필렌글리콜디알킬아세테이트류; 등을 들 수 있다.propylene glycol dialkyl acetates such as propylene glycol methyl ethyl acetate; etc. can be mentioned.
에스테르류의 구체적인 예로는 젖산메틸, 젖산에틸, 젖산n-프로필, 젖산이소프로필, 젖산n-부틸, 젖산이소부틸, 젖산n-아밀, 젖산이소아밀, 아세트산n-부틸, 아세트산이소부틸, 아세트산n-아밀, 아세트산이소아밀, 아세트산n-헥실, 아세트산2-에틸헥실, 프로피온산에틸, 프로피온산n-프로필, 프로피온산이소프로필, 프로피온산n-부틸, 프로피온산이소부틸, 부티르산메틸, 부티르산에틸, 부티르산에틸, 부티르산n-프로필, 부티르산이소프로필, 부티르산n-부틸, 히드록시아세트산에틸, 2-히드록시-2-메틸프로피온산에틸, 2-히드록시-3-메틸부티르산에틸, 메톡시아세트산에틸, 에톡시아세트산에틸, 3-메톡시프로피온산메틸, 3-메톡시프로피온산에틸, 3-에톡시프로피온산메틸, 3-에톡시프로피온산에틸, 3-메톡시부틸아세테이트, 3-메틸-3-메톡시부틸아세테이트, 3-메틸-3-메톡시부틸프로피오네이트, 3-메틸-3-메톡시부틸부티레이트, 아세토아세트산메틸, 아세토아세트산에틸, 피르브산메틸, 피르브산에틸, 디에틸렌글리콜메틸에틸에스테르 등을 들 수 있다.Specific examples of esters include methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate, n-butyl acetate, isobutyl acetate, and acetic acid. n-amyl, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate , 3-methoxymethyl propionate, ethyl 3-methoxypropionate, 3-ethoxymethyl propionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl -3-methoxybutylpropionate, 3-methyl-3-methoxybutyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, diethylene glycol methyl ethyl ester, etc.
케톤류의 구체적인 예로는 메틸에틸케톤, 메틸프로필케톤, 메틸-n-부틸케톤, 메틸이소부틸케톤, 2-헵탄온, 3-헵탄온, 4-헵탄온, 시클로헥산온 등을 들 수 있다.Specific examples of ketones include methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone.
아미드류의 구체적인 예로는 N-메틸포름아미드, N,N-디메틸포름아미드, N-메틸아세트아미드, N,N-디메틸아세트아미드, N-메틸피롤리돈 등을 들 수 있다.Specific examples of amides include N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone.
락톤류의 구체적인 예로는 γ-부티로락톤을 들 수 있다.Specific examples of lactones include γ-butyrolactone.
바람직하게는 도포성 및 절연막 피막의 막 두께의 균일성 측면에서 프로필렌글리콜메틸에테르아세테이트, 디에틸렌글리콜메틸에틸에스테르 또는 이들의 혼합물을 사용하는 것이 좋다.Preferably, in terms of applicability and uniformity of the thickness of the insulating film, propylene glycol methyl ether acetate, diethylene glycol methyl ethyl ester, or a mixture thereof is used.
용매는 그 기능을 할 수 있는 범위 내에서는 그 함량이 특별히 한정되지 않으며, 예를 들면 바인더 수지 100중량부에 대하여 200 내지 400 중량부로 포함될 수 있으며, 용매가 상기 범위 내로 포함될 경우, 고형분 함량 및 점도를 적정 수준으로 유지할 수 있어 코팅성이 증가될 수 있다.The content of the solvent is not particularly limited within the range in which it can perform its function. For example, it may be included in 200 to 400 parts by weight based on 100 parts by weight of the binder resin. When the solvent is contained within the above range, the solid content and viscosity can be maintained at an appropriate level, so coating properties can be increased.
염기성 화합물basic compound
염기성 화합물의 종류는 특별히 한정되지 않으며, 화학 증폭 레지스트로 사용되는 것 중에서 임의로 선택하여 사용할 수 있다. 구체적인 예로는 지방족 아민, 방향족 아민, 복소환식 아민, 제4급 암모늄히드록시드, 카르복시산의 제4급 암모늄염 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The type of basic compound is not particularly limited, and can be arbitrarily selected from those used as chemically amplified resists. Specific examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxide, and quaternary ammonium salts of carboxylic acids. These can be used alone or in combination of two or more types.
지방족 아민의 구체적인 예로는 트리메틸아민, 디에틸아민, 트리에틸아민, 디-n-프로필아민, 트리-n-프로필아민, 디-n-펜틸아민, 트리-n-펜틸아민, 디에탄올아민, 트리에탄올아민, 디시클로헥실아민, 디시클로헥실메틸아민 등을 들 수 있다.Specific examples of aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, and triethanol. Amine, dicyclohexylamine, dicyclohexylmethylamine, etc. can be mentioned.
방향족 아민의 구체적인 예로는 아닐린, 벤질아민, N,N-디메틸아닐린, 디페닐아민 등을 들 수 있다.Specific examples of aromatic amines include aniline, benzylamine, N,N-dimethylaniline, and diphenylamine.
복소환식 아민의 구체적인 예로는 피리딘, 2-메틸피리딘, 4-메틸피리딘, 2-에틸피리딘, 4-에틸피리딘, 2-페닐피리딘, 4-페닐피리딘, N-메틸-4-페닐피리딘, 4-디메틸아미노피리딘, 이미다졸, 벤즈이미다졸, 4-메틸이미다졸, 2-페닐벤즈이미다졸, 2,4,5-트리페닐이미다졸, 니코틴, 니코틴산, 니코틴산아미드, 퀴놀린, 8-옥시퀴놀린, 피라진, 피라졸, 피리다진, 푸린, 피롤리딘, 피페리딘, 1,5-디아자비시클로[4.3.0]-5-노넨, 1,8-디아자비시클로[5.3.0]-7-운데센 등을 들 수 있다.Specific examples of heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4- Dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinoline , pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.3.0]-7 -Undecene, etc. can be mentioned.
제4급 암모늄히드록시드의 구체적인 예로는 테트라메틸암모늄히드록시드, 테트라에틸암모늄히드록시드, 테트라-n-부틸암모늄히드록시드, 테트라-n-헥실암모늄히드록시드 등을 들 수 있다.Specific examples of quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
카르복시산의 제4급 암모늄염의 구체적인 예로는 테트라메틸암모늄아세테이트, 테트라메틸암모늄벤조에이트, 테트라-n-부틸암모늄아세테이트, 테트라-n-부틸암모늄벤조에이트 등을 들 수 있다.Specific examples of quaternary ammonium salts of carboxylic acids include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
염기성 화합물은 그 기능을 할 수 있는 범위 내에서는 그 함량이 특별히 한정되지 않으나, 바인더 수지 100중량부에 대하여 0.001 내지 1중량부 포함될 수 있고, 바람직하게는 0.005 내지 0.5중량부 포함될 수 있다. 염기성 화합물의 함량이 바인더 수지 100중량부에 대하여 0.001중량부 이상, 1중량부 이하로 포함되면 양호한 내열성 및 내용매성을 갖는 층간 절연막을 형성할 수 있는 장점이 있다.The content of the basic compound is not particularly limited within the range in which it can perform its function, but may be included in an amount of 0.001 to 1 part by weight, preferably 0.005 to 0.5 parts by weight, based on 100 parts by weight of the binder resin. If the content of the basic compound is 0.001 parts by weight or more and 1 part by weight or less based on 100 parts by weight of the binder resin, there is an advantage in forming an interlayer insulating film with good heat resistance and solvent resistance.
커플링제Coupling agent
커플링제는 기재가 되는 무기물, 예를 들면, 실리콘, 산화실리콘, 질화실리콘 등의 실리콘 화합물, 금, 구리, 알루미늄 등의 금속과 절연막과의 밀착성을 향상시키고, 기판과의 테이퍼각의 조정에도 유용하다.The coupling agent improves the adhesion between the inorganic material used as the substrate, such as silicon compounds such as silicon, silicon oxide, and silicon nitride, and metals such as gold, copper, and aluminum, and the insulating film, and is also useful for adjusting the taper angle with the substrate. do.
커플링제의 종류는 특별히 한정되지 않으며, 구체적인 예로는 γ-아미노프로필트리메톡시실란, γ-아미노프로필트리에톡시실란, γ-글리시독시프로필트리알콕시실란, γ-글리시독시프로필알킬디알콕시실란, γ-메타크릴옥시프로필트리알콕시실란, γ-메타크릴옥시프로필알킬디알콕시실란, γ-클로로프로필트리알콕시실란, γ-메르캅토프로필트리알콕시실란, β-(3,4-에폭시시클로헥실)에틸트리알콕시실란, 비닐트리알콕시실란 등이 사용될 수 있으며, 이들은 단독 또는 2종 이상 혼합되어 사용될 수 있으며, γ-글리시독시프로필트리알콕시실란을 사용하는 것이 보다 바람직하다.The type of coupling agent is not particularly limited, and specific examples include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, and γ-glycidoxypropylalkyl dialkoxy. Silane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β-(3,4-epoxycyclohexyl) ) Ethyltrialkoxysilane, vinyltrialkoxysilane, etc. may be used, and these may be used alone or in a mixture of two or more types, and it is more preferable to use γ-glycidoxypropyltrialkoxysilane.
계면활성제Surfactants
계면활성제는 기판과 감광성 수지 조성물의 밀착성을 개선시키는 성분이다.Surfactant is an ingredient that improves the adhesion between the substrate and the photosensitive resin composition.
계면활성제의 종류는 특별히 한정되지 않으며, 불소 함유 계면활성제, 비이온 계면활성제, 양이온 계면활성제, 음이온 계면활성제 및 실리콘 계면활성제와 같은 각종 계면활성제를 사용할 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The type of surfactant is not particularly limited, and various surfactants such as fluorine-containing surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. These can be used alone or in combination of two or more types.
불소 함유 계면활성제의 구체적인 예로는 MAGAFAC F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 및 F781(상품명, DIC Corporation 제품), FLUORAD FC430, FC431 및 FC171(상품명, Sumitomo 3M Limited 제품), SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 및 KH-40(상품명, Asahi Glass Co., Ltd. 제품), SOLSPERSE 20000(상품명, Lubrizol Japan Limited 제품) 등을 들 수 있다.Specific examples of fluorine-containing surfactants include MAGAFAC F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 and F781 (trade name, product of DIC Corporation); FLUORAD FC430, FC431 and FC171 (trade name, Sumitomo 3M Limited product), SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 and KH- 40 (brand name, product of Asahi Glass Co., Ltd.), SOLSPERSE 20000 (brand name, product of Lubrizol Japan Limited), etc.
비이온 계면활성제의 구체적인 예로는 글리세롤, 트리메틸롤프로판과 트리메틸롤 에탄, 및 그것들의 에톡실레이트 또는 프로폭시레이트(예를 들면, 글리세롤프로폭실레이트 또는 글리세린에톡실레이트); PLURONIC L10, L31, L61, L62, 10R5, 17R2 및 25R2, 및 TETRONIC 304, 701, 704, 901, 904 및 150R1(상품명, BASF 제품)과 같은 폴리옥시에틸렌라우릴에테르, 폴리옥시에틸렌스테아릴에테르, 폴리옥시에틸렌올레일에테르, 폴리옥시에틸렌옥틸페닐에테르, 폴리옥시에틸렌노닐페닐에테르, 폴리에틸렌글리콜 디라우레이트, 폴리에틸렌글리콜 디스테아레이트, 소르비탄 지방산에스테르 등을 들 수 있다.Specific examples of nonionic surfactants include glycerol, trimethylolpropane and trimethylol ethane, and their ethoxylates or propoxylates (e.g., glycerolpropoxylate or glycerinethoxylate); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, such as PLURONIC L10, L31, L61, L62, 10R5, 17R2 and 25R2, and TETRONIC 304, 701, 704, 901, 904 and 150R1 (trade name, BASF product); Examples include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.
양이온 계면활성제의 구체적인 예로는 EFKA-745(상품명, Morishita & Co., Ltd. 제품)와 같은 프탈로사이아닌변성 화합물, KP341(상품명, Shin-Etsu Chemical Co., Ltd. 제품)과 같은 오가노실록산 폴리머; POLYFLOW No.75, No.90, No.95(상품명, Kyoeisha Chemical Co., Ltd. 제품)와 같은 (메타)아크릴산계 (코)폴리머, W001(상품명, Yusho Co., Ltd. 제품) 등을 들 수 있다.Specific examples of cationic surfactants include phthalocyanine-modified compounds such as EFKA-745 (trade name, manufactured by Morishita & Co., Ltd.), organochemicals such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) siloxane polymer; (meth)acrylic acid-based (co)polymers such as POLYFLOW No.75, No.90, No.95 (trade name, product of Kyoeisha Chemical Co., Ltd.), W001 (product name, product of Yusho Co., Ltd.), etc. I can hear it.
음이온 계면활성제의 구체적인 예로는 W004, W005, W017(상품명, Yusho Co., Ltd. 제품) 등을 들 수 있다.Specific examples of anionic surfactants include W004, W005, and W017 (brand name, manufactured by Yusho Co., Ltd.).
실리콘 계면활성제의 구체적인 예로는 TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA 및 SH8400(상품명, Dow Corning Toray Co., Ltd. 제품), TSF-4440, 4300, 4445, 4460 및 4452(상품명, Momentive Performance Materials Inc. 제품), KP341, KF6001 및 KF6002(상품명, Shin-Etsu Chemical Co., Ltd. 제품), BYK307, 323 및 330(상품명, BYK Chemie 제품) 등을 들 수 있다.Specific examples of silicone surfactants include TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA and SH8400 (trade name, Dow Corning Toray Co., Ltd.), TSF-4440, 4300, 4445, 4460 and 4452 ( Examples include product name, Momentive Performance Materials Inc.), KP341, KF6001 and KF6002 (brand name, product of Shin-Etsu Chemical Co., Ltd.), BYK307, 323 and 330 (product name, product of BYK Chemie), etc.
계면활성제는 그 기능을 할 수 있는 범위 내에서는 그 함량이 특별히 한정되지 않으나, 바인더 수지 100중량부에 대하여 0.01 내지 5중량부 포함될 수 있고, 바람직하게는 0.05 내지 3중량부 포함될 수 있다. 계면활성제의 함량이 상기 범위 내로 포함될 경우에는 기판과 수지 조성물의 밀착성을 개선효과를 극대화할 수 있는 장점이 있다. The content of the surfactant is not particularly limited within the range in which it can perform its function, but may be included in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the binder resin. When the content of the surfactant is included within the above range, there is an advantage in maximizing the effect of improving the adhesion between the substrate and the resin composition.
첨가제additive
본 발명의 감광성 수지 조성물은 그 밖에 일반적으로 열가교제, 광안정제, 광경화촉진제, 할레이션 방지제(레벨링제), 소포제 등과 같은 첨가제를 본 발명의 목적을 벗어나지 않는 범위 내에서 더 포함할 수 있다.The photosensitive resin composition of the present invention may further generally include additives such as a heat crosslinking agent, a light stabilizer, a photocuring accelerator, an anti-halation agent (leveling agent), an anti-foaming agent, etc., within the range that does not deviate from the purpose of the present invention.
열가교제는 조성물로서 절연막을 형성할 때 UV조사와 열처리를 통하여 가교 반응이 원활하게 발생하도록 하며, 내열성을 향상시키는 성분이다.Thermal crosslinking agent is a composition that allows crosslinking reaction to occur smoothly through UV irradiation and heat treatment when forming an insulating film, and is an ingredient that improves heat resistance.
열가교제의 종류는 특별히 한정되지 않으며, 구체적인 예로는 폴리아크릴레이트 수지, 에폭시 수지, 페놀수지, 멜라민 수지, 유기산, 아민 화합물, 무수 화합물 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The type of thermal crosslinking agent is not particularly limited, and specific examples include polyacrylate resin, epoxy resin, phenol resin, melamine resin, organic acid, amine compound, anhydride compound, etc. These can be used alone or in combination of two or more types.
열가교제는 그 기능을 할 수 있는 범위 내에서는 그 함량이 특별히 한정되지 않으나, 바인더 수지 100중량부에 대하여 0.01내지 5중량부 포함될 수 있고, 바람직하게는 0.1 내지 3중량부 포함될 수 있다. 열가교제의 함량이 바인더 수지 100중량부에 대하여 0.01중량부 이상, 5중량부 이하로 포함되면 내열성 향상 효과가 최대화되는 장점이 있다.The content of the thermal crosslinking agent is not particularly limited within the range in which it can perform its function, but may be included in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the binder resin. If the content of the thermal crosslinking agent is 0.01 parts by weight or more and 5 parts by weight or less based on 100 parts by weight of the binder resin, the effect of improving heat resistance is maximized.
광안정제는 감광성 수지 조성물의 내광성을 개선시키는 성분이다.A light stabilizer is a component that improves the light resistance of the photosensitive resin composition.
광안정제의 종류는 특별히 한정되지 않으며, 구체적인 예로는 벤조트리아졸계, 트리아진계, 벤조페논계, 힌더드아미노에테르(hindered aminoether)계, 힌더드아민계 화합물 등을 들 수 있다. 이들은 단독 또는 2종이상 혼합하여 사용 가능하다.The type of light stabilizer is not particularly limited, and specific examples include benzotriazole-based, triazine-based, benzophenone-based, hindered aminoether-based, and hindered amine-based compounds. These can be used alone or in combination of two or more types.
광안정제는 그 기능을 할 수 있는 범위 내에서는 그 함량이 특별히 한정되지 않으나, 바인더 수지 100중량부에 대하여 0.01 내지 5중량부 포함될 수 있고, 바람직하게는 0.1 내지 3중량부 포함될 수 있다. 광안정제의 함량이 바인더 수지 100중량부에 대하여 0.01중량부 이상, 5중량부 이하로 포함되면 내광성 개선 효과가 최대화되는 장점이 있다.The content of the light stabilizer is not particularly limited within the range in which it can perform its function, but may be included in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the binder resin. If the content of the light stabilizer is 0.01 parts by weight or more and 5 parts by weight or less based on 100 parts by weight of the binder resin, the effect of improving light resistance is maximized.
<절연막><Insulating film>
본 발명은 상기 감광성 수지 조성물로 제조된 절연막이 형성될 수 있다.In the present invention, an insulating film made of the photosensitive resin composition can be formed.
이때, 절연막은 기판상에 형성되며, 기판으로, 액정표시장치용 또는 유기발광 표시장치용 기판이 있으며, 석영 또는 투명 수지 기판 등을 사용할 수 있다.At this time, the insulating film is formed on a substrate, and the substrate may be a substrate for a liquid crystal display device or an organic light emitting display device, and a quartz or transparent resin substrate may be used.
기판 제조에 적용되는 투명 수지의 종류는 특별히 한정되지 않으며, 예를 들면 폴리이미드 수지, 아크릴 수지, 폴리아크릴레이트 수지, 폴리카보네이트 수지, 폴리에테르 수지, 폴리에틸렌 테레프탈레이트 수지, 술폰산 수지 등이 있다. 이들은 단독으로 또는 2종 이상 혼합하여 사용될 수 있다. The type of transparent resin applied to manufacturing the substrate is not particularly limited, and examples include polyimide resin, acrylic resin, polyacrylate resin, polycarbonate resin, polyether resin, polyethylene terephthalate resin, and sulfonic acid resin. These can be used individually or in combination of two or more types.
기판상에 게이트 전극 또는 소스/드레인 전극이 형성될 수 있으며, 그 위에 상기 절연막이 형성될 수 있다. 또한, 기판 상에 유기 절연막 또는 무기 절연막이 형성되고, 그 위에 상기 절연막이 형성될 수도 있다.A gate electrode or source/drain electrode may be formed on the substrate, and the insulating film may be formed thereon. Additionally, an organic insulating film or an inorganic insulating film may be formed on the substrate, and the insulating film may be formed on the insulating film.
유기 절연막은 아크릴계 수지, 폴리이미드계 수지, 폴리아미드계 수지, 실록산계 수지, 감광성 아크릴 카르복실기를 포함하는 수지, 노볼락 수지, 알칼리 가용성 수지 등으로 된 절연막일 수 있다. 또한, 무기 절연막은 실리콘 산화물(SiOx), 실리콘 질화물(SiNx), 실리콘 산질화물(SiOxNy), 실리콘 산탄화물(SiOxCy), 실리콘 탄질화물(SiCxNy), 알루미늄 산화물(AlOx), 티타늄 산화물(TiOx), 탄탈륨 산화물(TaOx), 마그네슘 산화물(MgOx), 아연산화물(ZnOx), 하프늄 산화물(HfOx), 지르코늄 산화물(ZrOx), 티타늄 산화물(TiOx)일 수 있으나, 본 발명에서는 실리콘 질화물, 실리콘 산질화물, 실리콘 산화물이 본 발명의 감광성 수지 조성물로 형성된 절연막과의 밀착성 증대 효과가 두드러진다는 점에서 가장 바람직하다.The organic insulating film may be an insulating film made of acrylic resin, polyimide resin, polyamide resin, siloxane resin, resin containing a photosensitive acrylic carboxyl group, novolak resin, alkali-soluble resin, etc. In addition, inorganic insulating films include silicon oxide (SiOx), silicon nitride (SiNx), silicon oxynitride (SiOxNy), silicon oxycarbide (SiOxCy), silicon carbonitride (SiCxNy), aluminum oxide (AlOx), titanium oxide (TiOx), It may be tantalum oxide (TaOx), magnesium oxide (MgOx), zinc oxide (ZnOx), hafnium oxide (HfOx), zirconium oxide (ZrOx), or titanium oxide (TiOx), but in the present invention, silicon nitride, silicon oxynitride, and silicon The oxide is most preferable in that it has a noticeable effect of increasing adhesion to the insulating film formed from the photosensitive resin composition of the present invention.
본 발명의 일 실시형태에서, 상기 실리콘 질화물 절연막상에 상기 절연막이 형성될 수 있다. 실리콘 질화물은 일반적으로 유기 절연막과 밀착성이 우수하지 않기 때문에, 종래 실리콘 질화물로 된 절연막 상에 유기 절연막을 형성하기 위하여 밀착성 개선을 위한 전처리 공정, 예를 들어 HMDS 도포 등이 필요하였다. 그렇지만 본 발명에 따른 감광성 수지 조성물로 형성된 절연막은 실리콘 질화물과의 밀착성이 우수하므로 전처리 공정이 생략될 수 있다.In one embodiment of the present invention, the insulating film may be formed on the silicon nitride insulating film. Since silicon nitride generally does not have excellent adhesion to organic insulating films, a pretreatment process to improve adhesion, such as HMDS application, was required to form an organic insulating film on a conventional silicon nitride insulating film. However, since the insulating film formed from the photosensitive resin composition according to the present invention has excellent adhesion to silicon nitride, the pretreatment process can be omitted.
본 발명의 상기 절연막의 두께는 특별히 한정되지 않으며, 예를 들면 0.5 내지 100㎛일 수 있다.The thickness of the insulating film of the present invention is not particularly limited and may be, for example, 0.5 to 100 μm.
본 발명에 의한 절연막 형성방법은, 본 발명의 감광성 수지 조성물을 디스플레이 장치의 기판 상부에 또는 기판 위에 형성된 소오스/드레인 또는 실리콘 질화물층 상부에 도포하는 단계; 감광성 수지 조성물을 선굽기(pre-bake)하는 단계; 감광성 수지 조성물을 선택적으로 노광, 현상하여 패턴을 형성하는 단계; 형성된 패턴을 열처리하는 단계를 포함할 수 있다.The method of forming an insulating film according to the present invention includes the steps of applying the photosensitive resin composition of the present invention on the top of the substrate of a display device or on the source/drain or silicon nitride layer formed on the substrate; Pre-bake the photosensitive resin composition; forming a pattern by selectively exposing and developing the photosensitive resin composition; It may include heat treating the formed pattern.
기판으로서, 액정표시장치, 유기 EL 등에 통상적으로 사용되는 유리 또는 투명 플라스틱 수지가 주로 사용되나, 사용되는 디스플레이 장치의 특성에 따라 특별히 제한되지 아니한다. 예를 들어, 유리 기판 등의 절연기판상에 게이트 전극을 구성하는 금속막이 형성되며, 그 금속막이 표면층으로 되어 있는 것을 사용할 수 있다.As a substrate, glass or transparent plastic resin commonly used in liquid crystal displays, organic EL, etc. is mainly used, but is not particularly limited depending on the characteristics of the display device used. For example, a metal film constituting a gate electrode is formed on an insulating substrate such as a glass substrate, and the metal film serves as a surface layer.
감광성 수지 조성물을 기판 등의 상부에 도포하는 방법은 특별히 한정되지 않으며 예를 들면 스프레이 코팅법, 롤 코팅법, 토출노즐식 도포법 등의 슬릿노즐을 이용한 코팅법, 중앙 적하 스핀법 등의 회전도포법, 익스트루젼 코팅법, 바 코팅법 등이 있으며, 두가지 이상의 코팅방법을 조합하여 코팅할 수 있다.The method of applying the photosensitive resin composition to the upper part of the substrate is not particularly limited, and examples include spray coating, roll coating, coating using a slit nozzle such as a discharge nozzle coating method, and rotational coating such as the central drop spin method. There are coating methods, extrusion coating methods, and bar coating methods, and two or more coating methods can be combined to coat.
도포된 막 두께는 도포 방법, 조성물의 고형분 농도, 점도 등에 따라 달라지지만, 통상, 건조 후 막 두께가 0.5 내지 100㎛이 되도록 도포한다. The applied film thickness varies depending on the application method, solid concentration of the composition, viscosity, etc., but is usually applied so that the film thickness after drying is 0.5 to 100㎛.
이후에 수행되는 선굽기 단계는, 도막 형성 후에 유동성이 없는 도막을 얻기 위해 진공, 적외선, 또는 열을 가하여 용매를 휘발시키는 공정이다. 가열조건은 각 성분의 종류나 배합 등에 따라 달라지지만, 열판(핫플레이트, hot plate) 가열의 경우에는 60 내지 130℃로 5 내지 500초간 수행될 수 있고, 열 오븐을 사용하는 경우에는 60 내지 140℃로 20 내지 1,000초간 수행될 수 있다.The pre-baking step performed afterwards is a process of volatilizing the solvent by applying vacuum, infrared rays, or heat to obtain a non-fluid coating film after forming the coating film. Heating conditions vary depending on the type or combination of each ingredient, but in the case of hot plate heating, it can be performed at 60 to 130 ° C for 5 to 500 seconds, and when using a heat oven, it can be performed at 60 to 140 ° C. It can be performed at ℃ for 20 to 1,000 seconds.
다음, 선택적 노광 공정은 엑시머 레이저, 원자외선, 자외선, 가시광선, 전자선, X선 또는 g-선(파장 436nm), i-선(파장 365nm), h-선(파장 405nm) 또는 이들의 혼합 광선을 조사하면서 수행된다. 노광은 접촉식(contact), 근접식(porximity), 투영식(projection) 노광법 등으로 수행될 수 있다.Next, the selective exposure process is performed using excimer laser, deep ultraviolet ray, ultraviolet ray, visible light, electron beam, It is carried out while investigating. Exposure may be performed using contact, proximity, or projection exposure methods.
본 발명에서는 알칼리 현상을 수행한 후에 감광성 수지 조성물을 열처리(고온 소성)하는 단계를 수행한다. 상기 고온 소성을 위한 감광성 수지 조성물의 구성에 열가교제 등이 적용되는 것이다. 상기 열처리 단계는 핫플레이트 또는 오븐 등의 가열장치를 이용하여 150 내지 350℃ 온도 하에서 30분 내지 3시간 수행될 수 있다. 상기 열처리를 마친 후에는 완전히 가교 경화된 패턴이 얻어진다.In the present invention, a step of heat treatment (high temperature firing) of the photosensitive resin composition is performed after performing alkaline development. A thermal crosslinking agent, etc. is applied to the composition of the photosensitive resin composition for high temperature firing. The heat treatment step may be performed for 30 minutes to 3 hours at a temperature of 150 to 350°C using a heating device such as a hot plate or oven. After completing the heat treatment, a completely cross-linked and hardened pattern is obtained.
<화상표시장치><Image display device>
또한, 본 발명은 상기 절연막을 구비한 화상표시장치를 제공한다.Additionally, the present invention provides an image display device including the above insulating film.
본 발명의 절연막은 통상의 액정 표시 장치뿐만 아니라, 전계 발광 표시 장치, 플라스마 표시 장치, 전계 방출 표시 장치 등 각종 화상 표시 장치에 적용이 가능하다.The insulating film of the present invention can be applied to various image display devices such as electroluminescence display devices, plasma display devices, and field emission display devices, as well as ordinary liquid crystal display devices.
화상표시장치는 상기 절연막 외에 당분야에서 통상적으로 사용되는 구성을 더 포함할 수 있다.The image display device may further include components commonly used in the art in addition to the insulating film.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred embodiments are presented to aid understanding of the present invention, but these examples are only illustrative of the present invention and do not limit the scope of the appended claims, and are examples within the scope and technical idea of the present invention. It is obvious to those skilled in the art that various changes and modifications are possible, and it is natural that such changes and modifications fall within the scope of the appended patent claims.
실시예Example 1 내지 14 및 1 to 14 and 비교예Comparative example 1 내지 3 1 to 3
하기 표 1에 기재된 조성 및 함량을 갖는 감광성 수지 조성물을 제조하였다.A photosensitive resin composition having the composition and content shown in Table 1 below was prepared.
(A)binder resin
(A)
(B)/
광증감제
(C)Mineral generator
(B)/
photosensitizer
(C)
(D)menstruum
(D)
화합물
(E)basic
compound
(E)
(F)Coupling agent
(F)
(G)Surfactants
(G)
A1-1. (a) / (b) = 60 / 40 A1-1. (a) / (b) = 60 / 40
A1-2. (a) / (b) = 70 / 30 A1-2. (a) / (b) = 70 / 30
A2-1: (a)/(b)/(c) = 20/60/20 A2-1: (a)/(b)/(c) = 20/60/20
A2-2: (a)/(b)/(c) = 30/50/20 A2-2: (a)/(b)/(c) = 30/50/20
A3-1: (a)/(b)/(c)/(d) = 15/10/50/25A3-1: (a)/(b)/(c)/(d) = 15/10/50/25
A3-2: (a)/(b)/(c)/(d) = 25/15/30/30A3-2: (a)/(b)/(c)/(d) = 25/15/30/30
(B)(B)
(C)(C)
(D1) 프로필렌 글리콜 메틸 에틸 아세테이트(D1) propylene glycol methyl ethyl acetate
(D2) 디에틸렌 글리콜 메틸 에틸 에스터(D2) Diethylene glycol methyl ethyl ester
(E) 디시클로헥실메틸아민(E) dicyclohexylmethylamine
(F) KBM-403(γ-글리시독시프로필트리알콕시실란)(F) KBM-403 (γ-glycidoxypropyltrialkoxysilane)
(G1) SH-8400(G1) SH-8400
(G2) F-475(G2)F-475
실험예Experiment example
실시예 1 내지 14 및 비교예 1 내지 3에 따라 제조된 수지 조성물에 대하여 하기와 같은 평가를 진행하였으며, 그 결과를 하기 표 2에 기재하였다.The resin compositions prepared according to Examples 1 to 14 and Comparative Examples 1 to 3 were evaluated as follows, and the results are shown in Table 2 below.
(1) 감도 측정(1) Sensitivity measurement
0.7mm 두께의 유리 기판(코닝1737, 코닝社 제조) 위에, 스피너로 실시예 및 비교예의 감광성 수지 조성물을 각각 도포하고, 100℃의 핫플레이트 상에서 125초간 가열하여 용매를 휘발시켜, 두께 4.0㎛의 감광성 수지 조성물층을 형성하였다.The photosensitive resin compositions of Examples and Comparative Examples were applied with a spinner on a 0.7 mm thick glass substrate (Corning 1737, manufactured by Corning Co., Ltd.), heated on a hot plate at 100°C for 125 seconds to volatilize the solvent, and a 4.0 μm thick layer was formed. A photosensitive resin composition layer was formed.
이후에 직경 10㎛의 콘택트홀 패턴을 얻기 위해, 노광부가 10㎛의 변을 갖는 사각 패턴 개구부를 갖는 마스크를 이용하여 i선 스텝퍼(NSR-205i11D, 니콘(주))로 노광을 실시하였다.Afterwards, in order to obtain a contact hole pattern with a diameter of 10 ㎛, exposure was performed with an i-line stepper (NSR-205i11D, Nikon Co., Ltd.) using a mask with a square pattern opening with a side of 10 ㎛.
노광 후의 기판을 2.38% 테트라메틸암모늄히드록시드 수용액을 현상액으로 23℃에서 40초 동안 퍼들 현상을 행하고, 230℃의 오븐에서 30분간 가열하여 경화된 막을 얻었다.The substrate after exposure was subjected to puddle development at 23°C for 40 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution as a developer, and then heated in an oven at 230°C for 30 minutes to obtain a cured film.
이후에 기판을 수직으로 절삭하고 각 조성에서 10㎛ 콘택트홀이 되는 노광량을 감도로 선택하였다.Afterwards, the substrate was cut vertically, and the exposure amount that produces a 10㎛ contact hole in each composition was selected as the sensitivity.
(2) 패턴 각도(2) Pattern angle
얻어진 패턴을 수직으로 절삭하고, 기판과의 각도를 광학 사진으로부터 산출하였다.The obtained pattern was cut vertically, and the angle with the substrate was calculated from an optical photograph.
(3) 투과율 측정(3) Transmittance measurement
얻어진 막의 400nm에서의 투과율을 분광광도계로 측정하였다.The transmittance at 400 nm of the obtained film was measured with a spectrophotometer.
(4) 밀착성 평가(4) Adhesion evaluation
실리콘 질화물이 증착된 글래스 기판상에 헥사메틸디실라잔 용액을 도포하지 않은 상태에서 스피너로 실시예 1 내지 14 및 비교예 1 내지 3의 감광성 수지 조성물을 각각 도포하고, 100℃의 핫플레이트 상에서 125초간 가열하여 용제를 휘발시켜, 두께 4.0㎛의 감광성 수지 조성물층을 형성하였다. 이후에 5-20 um Hole 패턴이 있는 마스크를 사용하여, i선 스텝퍼(NSR-205i11D, 니콘(주))로 노광을 실시하였다. 노광 후의 기판을 2.38% 테트라메틸암모늄히드록시드 수용액을 현상액으로 23℃에서 40초 동안 퍼들 현상을 행하고 패턴의 박리 여부를 확인하였다.The photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 3 were applied using a spinner without applying the hexamethyldisilazane solution on the glass substrate on which silicon nitride was deposited, and the photosensitive resin compositions were heated to 125°C on a hot plate at 100°C. The solvent was volatilized by heating for a second to form a photosensitive resin composition layer with a thickness of 4.0 μm. Afterwards, exposure was performed with an i-line stepper (NSR-205i11D, Nikon Co., Ltd.) using a mask with a 5-20 um hole pattern. The substrate after exposure was subjected to puddle development at 23°C for 40 seconds using a 2.38% tetramethylammonium hydroxide aqueous developer solution, and it was confirmed whether the pattern was peeled off.
<평가기준><Evaluation criteria>
◎: 패턴이 전 영역에서 전혀 박리되지 않음◎: The pattern does not peel off at all in the entire area.
○: 패턴이 일부 영역에서 미세하게 박리됨○: The pattern is slightly peeled in some areas.
△: 상당 부분의 패턴이 박리됨△: A significant portion of the pattern is peeled off
X: 패턴 전 영역이 박리됨X: The entire pattern is peeled off
상기 표 2를 참고하면, 실시예 1 내지 14의 감광성 수지 조성물로 형성한 절연막은 밀착성이 매우 우수하며, 감도 및 투과율도 매우 우수하였고, 적정 패턴 각도를 나타낸 것을 알 수 있다. 그러나, 실릴 에테르기를 포함하는 아크릴 수지를 사용하지 않은 비교예 1 내지 비교예 3의 감광성 수지 조성물로 형성한 절연막은 밀착성이 매우 떨어지는 결과를 나타낸 것을 알 수 있다.Referring to Table 2, it can be seen that the insulating film formed from the photosensitive resin composition of Examples 1 to 14 had excellent adhesion, excellent sensitivity and transmittance, and showed an appropriate pattern angle. However, it can be seen that the insulating film formed from the photosensitive resin composition of Comparative Examples 1 to 3 without using the acrylic resin containing a silyl ether group showed very poor adhesion.
Claims (14)
상기 (a-1) 수지는 하기 화학식 1을 포함하여 중합되는 것을 특징으로 하는 포지티브형 감광성 수지 조성물:
[화학식 1]
(상기 화학식 1에서, R은 탄소수 1 내지 6의 알콕시기 또는 탄소수 4 내지 8의 시클로알콕시기로 치환 또는 비치환된 탄소수 1 내지 6의 알킬기; 또는 테트라하이드로피라닐기임).(a-1) a resin in which at least part of the phenolic hydroxyl group or carboxyl group is protected by an acid-decomposable group, (a-2) an acrylic resin containing a silyl ether group, and (a-3) a binder resin containing an acrylic resin containing an epoxy group. A positive photosensitive resin composition comprising:
The (a-1) resin is a positive photosensitive resin composition, characterized in that the polymerization comprises the following formula (1):
[Formula 1]
(In Formula 1, R is an alkyl group with 1 to 6 carbon atoms substituted or unsubstituted with an alkoxy group with 1 to 6 carbon atoms or a cycloalkoxy group with 4 to 8 carbon atoms; or a tetrahydropyranyl group).
상기 (a-2) 수지는 하기 화학식 2로 표시되는 반복단위를 포함하는 것을 특징으로 하는 포지티브형 감광성 수지 조성물:
[화학식 2]
(상기 화학식 2에서, R1, R2 및 R3은 서로 독립적으로 수소 또는 메틸기이며,
R4는 하기 화학식 3으로 표시되는 단량체에서 유래된 구조이며,
[화학식 3]
R7은 탄수소 1 내지 6의 알킬렌기이며,
R8은 탄소수 1 내지 2의 알킬기이며,
R5는 (메타)아크릴산, 2-(메타)아크릴로일록시에틸석시네이트, 2-(메타)아크릴로일옥시에틸헥사히드로프탈레이트, 2-(메타)아크릴로일옥시에틸프탈레이트 및 2-(메타)아크릴로일옥시에틸석시네이트로 이루어진 군에서 선택되는 단량체에서 유래된 구조이며,
R6은 하기 화학식 3로 표시되는 단량체에서 유래된 구조이며,
[화학식 4]
R9는 탄소수 1 내지 6의 알킬렌기이며,
R10은 탄소수 1 내지 6의 알킬기이고,
a=40 내지 80mol%, b=5 내지 45mol%, c=10 내지 55mol%).According to paragraph 1,
The (a-2) resin is a positive photosensitive resin composition, characterized in that it contains a repeating unit represented by the following formula (2):
[Formula 2]
(In Formula 2, R 1 , R 2 and R 3 are independently hydrogen or methyl groups,
R 4 is a structure derived from a monomer represented by the following formula (3),
[Formula 3]
R 7 is an alkylene group having 1 to 6 carbon atoms,
R 8 is an alkyl group having 1 to 2 carbon atoms,
R 5 is (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinate, 2-(meth)acryloyloxyethylhexahydrophthalate, 2-(meth)acryloyloxyethylphthalate and 2- It is a structure derived from a monomer selected from the group consisting of (meth)acryloyloxyethyl succinate,
R 6 is It is a structure derived from a monomer represented by the following formula 3,
[Formula 4]
R 9 is an alkylene group having 1 to 6 carbon atoms,
R 10 is an alkyl group having 1 to 6 carbon atoms,
a=40 to 80 mol%, b=5 to 45 mol%, c=10 to 55 mol%).
상기 (a-3) 수지는 하기 화학식 5로 표시되는 단량체를 포함하여 중합되는 것을 특징으로 하는 포지티브형 감광성 수지 조성물:
[화학식 5]
(상기 화학식 5에서, R11은 수소원자 또는 메틸기이고; R12는 탄소수 1 내지 6의 알킬렌기이고; R13 및 R14는 서로 독립적으로 수소 원자 또는 탄소수 1 내지 6의 알킬기이거나, 서로 연결되어 탄소수 3 내지 8의 고리를 형성할 수 있고; m은 1 내지 6의 정수임).According to paragraph 1,
A positive photosensitive resin composition, characterized in that the resin (a-3) is polymerized by including a monomer represented by the following formula (5):
[Formula 5]
(In Formula 5, R 11 is a hydrogen atom or a methyl group; R 12 is an alkylene group having 1 to 6 carbon atoms; R 13 and R 14 are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or are connected to each other Can form a ring with 3 to 8 carbon atoms; m is an integer from 1 to 6).
상기 감광성 수지 조성물은
광산발생제, 광증감제, 용매, 염기성 화합물, 커플링제, 계면활성제 및 첨가제 중 하나 이상를 더 포함하는 포지티브형 감광성 수지 조성물.According to paragraph 1,
The photosensitive resin composition is
A positive photosensitive resin composition further comprising one or more of a photoacid generator, a photosensitizer, a solvent, a basic compound, a coupling agent, a surfactant, and an additive.
상기 (a-2) 수지는 바인더 수지 100중량부에 대하여, 10 내지 30중량부로 포함하는 것을 특징으로 하는 포지티브형 감광성 수지 조성물.According to paragraph 1,
A positive photosensitive resin composition characterized in that the (a-2) resin is contained in an amount of 10 to 30 parts by weight based on 100 parts by weight of the binder resin.
상기 (a-3) 수지는 바인더 수지 100중량부에 대하여, 20 내지 40중량부로 포함하는 것을 특징으로 하는 포지티브형 감광성 수지 조성물.According to paragraph 1,
A positive photosensitive resin composition characterized in that the (a-3) resin is contained in an amount of 20 to 40 parts by weight based on 100 parts by weight of the binder resin.
상기 (a-1):(a-2):(a-3)의 비율은 바인더 수지 100중량부에 대하여 40 내지 60 : 10 내지 30 : 20 내지 40 중량부인 것을 특징으로 하는 포지티브형 감광성 수지 조성물.In claim 1,
Positive type photosensitive resin composition, characterized in that the ratio of (a-1):(a-2):(a-3) is 40 to 60:10 to 30:20 to 40 parts by weight based on 100 parts by weight of the binder resin. .
상기 (a-1) 수지의 중량평균 분자량은 5,000 내지 35,000인 것을 특징으로 하는 포지티브형 감광성 수지 조성물.In claim 1,
A positive type photosensitive resin composition, characterized in that the weight average molecular weight of the resin (a-1) is 5,000 to 35,000.
상기 (a-2) 수지의 중량평균 분자량은 5,000 내지 30,000인 것을 특징으로 하는 포지티브형 감광성 수지 조성물.According to paragraph 1,
A positive type photosensitive resin composition, characterized in that the weight average molecular weight of the resin (a-2) is 5,000 to 30,000.
상기 (a-3) 수지의 중량평균 분자량은 5,000 내지 40,000인 것을 특징으로 하는 포지티브형 감광성 수지 조성물.According to paragraph 1,
A positive type photosensitive resin composition, characterized in that the weight average molecular weight of the resin (a-3) is 5,000 to 40,000.
상기 절연막은 기재 상의 실리콘 질화물층 상에 형성된 것을 특징으로 하는 절연막.According to clause 12,
The insulating film is characterized in that it is formed on a silicon nitride layer on a substrate.
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