JP2007246559A - Side chain unsaturated polymer, radiation sensitive resin composition and spacer of liquid crystal displaying element - Google Patents
Side chain unsaturated polymer, radiation sensitive resin composition and spacer of liquid crystal displaying element Download PDFInfo
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- JP2007246559A JP2007246559A JP2006068010A JP2006068010A JP2007246559A JP 2007246559 A JP2007246559 A JP 2007246559A JP 2006068010 A JP2006068010 A JP 2006068010A JP 2006068010 A JP2006068010 A JP 2006068010A JP 2007246559 A JP2007246559 A JP 2007246559A
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- resin composition
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- sensitive resin
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- 125000006850 spacer group Chemical group 0.000 title claims abstract description 77
- 229920000642 polymer Polymers 0.000 title claims abstract description 62
- 230000005855 radiation Effects 0.000 title claims abstract description 56
- 239000011342 resin composition Substances 0.000 title claims abstract description 41
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 42
- -1 isocyanate compound Chemical class 0.000 claims abstract description 144
- 150000001875 compounds Chemical class 0.000 claims abstract description 81
- 229920001577 copolymer Polymers 0.000 claims abstract description 48
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 239000012948 isocyanate Substances 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 13
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 7
- 125000003566 oxetanyl group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 35
- 230000015572 biosynthetic process Effects 0.000 claims description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 11
- 238000011161 development Methods 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 16
- 238000011084 recovery Methods 0.000 abstract description 12
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 62
- 239000010408 film Substances 0.000 description 52
- 239000000243 solution Substances 0.000 description 46
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 14
- 239000004094 surface-active agent Substances 0.000 description 14
- 229940022663 acetate Drugs 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical class N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- AGJAUFUNZWHLKE-UHFFFAOYSA-N (2E,4E)-N-isobutyl-2,4-tetradecadienamide Natural products CCCCCCCCCC=CC=CC(=O)NCC(C)C AGJAUFUNZWHLKE-UHFFFAOYSA-N 0.000 description 7
- 125000005907 alkyl ester group Chemical group 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 6
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 6
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 6
- 125000004849 alkoxymethyl group Chemical group 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- CSVRUJBOWHSVMA-UHFFFAOYSA-N oxolan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCO1 CSVRUJBOWHSVMA-UHFFFAOYSA-N 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 230000001588 bifunctional effect Effects 0.000 description 5
- 125000003709 fluoroalkyl group Chemical group 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 4
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- MHDULSOPQSUKBQ-UHFFFAOYSA-N 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound ClC1=CC=CC=C1C(N1C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC=CC=2)Cl)=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 MHDULSOPQSUKBQ-UHFFFAOYSA-N 0.000 description 3
- MSYGLXDTNDBHDG-UHFFFAOYSA-N 2-(3-hydroxy-2,2-dimethylpropoxy)carbonyloxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(=O)OCC(C)(C)CO MSYGLXDTNDBHDG-UHFFFAOYSA-N 0.000 description 3
- NEGNTDZGFTWAEQ-UHFFFAOYSA-N 2-(dimethylamino)-2-ethyl-1-(4-methylphenyl)-3-(4-morpholin-4-ylphenyl)propane-1,3-dione Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(N(C)C)(CC)C(=O)C1=CC=C(C)C=C1 NEGNTDZGFTWAEQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XFOFBPRPOAWWPA-UHFFFAOYSA-N 6-hydroxyhexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCO XFOFBPRPOAWWPA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- FARWYUGFTNOIPS-UHFFFAOYSA-N [2-(trifluoromethyl)oxetan-3-yl]methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1COC1C(F)(F)F FARWYUGFTNOIPS-UHFFFAOYSA-N 0.000 description 3
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- YSBPNMOAQMQEHE-UHFFFAOYSA-N (2-methyloxiran-2-yl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1(C)CO1 YSBPNMOAQMQEHE-UHFFFAOYSA-N 0.000 description 2
- MRHSWHWXWMJQSP-UHFFFAOYSA-N (2-phenyloxetan-2-yl)methyl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C1(COC(=O)C(=C)C)CCO1 MRHSWHWXWMJQSP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- RWEAGLZFYKQPLZ-UHFFFAOYSA-N 1-[4,5-diphenyl-2-(2,4,6-trichlorophenyl)imidazol-2-yl]-4,5-diphenyl-2-(2,4,6-trichlorophenyl)imidazole Chemical compound ClC1=CC(Cl)=CC(Cl)=C1C(N1C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC(Cl)=CC=2Cl)Cl)=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 RWEAGLZFYKQPLZ-UHFFFAOYSA-N 0.000 description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- JKQRNTIBBOTABS-UHFFFAOYSA-N 2-(2,4-dichlorophenyl)-1-[2-(2,4-dichlorophenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound ClC1=CC(Cl)=CC=C1C(N1C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC(Cl)=CC=2)Cl)=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 JKQRNTIBBOTABS-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- WDEBWWPTHLWOJV-UHFFFAOYSA-N 2-(3-hydroxy-2,2-dimethylpropoxy)carbonyloxyethyl prop-2-enoate Chemical compound OCC(COC(=O)OCCOC(C=C)=O)(C)C WDEBWWPTHLWOJV-UHFFFAOYSA-N 0.000 description 2
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- ZQAXBTFXHKKQHN-UHFFFAOYSA-N 2-n-(propoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound CCCOCNC1=NC(N)=NC(N)=N1 ZQAXBTFXHKKQHN-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 2
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
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- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Liquid Crystal (AREA)
Abstract
Description
本発明は、特に液晶表示素子におけるスペーサーの形成に極めて好適な側鎖不飽和重合体、それを含む感放射線性樹脂組成物、スペーサーとその形成方法および液晶表示素子に関する。 The present invention relates to a side chain unsaturated polymer, particularly suitable for forming a spacer in a liquid crystal display device, a radiation-sensitive resin composition containing the polymer, a spacer, a method for forming the spacer, and a liquid crystal display device.
液晶表示素子には、従来から、2枚の基板間の間隔(セルギャップ)を一定に保つため、所定の粒径を有するガラスビーズ、プラスチックビーズ等のスペーサーが使用されているが、これらのスペーサーは、ガラス基板などの透明基板上にランダムに散布されるため、画素形成領域にスペーサーが存在すると、スペーサーの写り込み現象を生じたり、入射光が散乱を受け、液晶表示素子としてのコントラストが低下するという問題があった。
そこで、このような問題を解決するために、スペーサーをフォトリソグラフィーにより形成する方法が採用されるようになってきた。この方法は、感放射線性樹脂組成物を基板上に塗布し、所定のマスクを介して例えば紫外線を露光したのち現像して、ドット状やストライプ状のスペーサーを形成するものであり、画素形成領域以外の所定の場所にのみスペーサーを形成することができるため、前述したような問題は基本的には解決される。
Conventionally, spacers such as glass beads and plastic beads having a predetermined particle diameter have been used for liquid crystal display elements in order to keep the distance (cell gap) between two substrates constant. Is randomly distributed on a transparent substrate such as a glass substrate, so if there is a spacer in the pixel formation area, the spacer will be reflected, or the incident light will be scattered and the contrast of the liquid crystal display element will be reduced. There was a problem to do.
Therefore, in order to solve such a problem, a method of forming a spacer by photolithography has been adopted. In this method, a radiation-sensitive resin composition is applied onto a substrate, exposed to, for example, ultraviolet rays through a predetermined mask, and then developed to form a dot-like or stripe-like spacer. Since the spacer can be formed only at a predetermined place other than the above, the above-described problem is basically solved.
近年、液晶表示素子の大面積化や生産性の向上等の観点から、マザーガラス基板の大型化(例えば、1,500×1800mm、さらに1870×2,200mm程度)が進んでいる。しかし、従来の基板サイズでは、マスクサイズよりも基板サイズが小さいため、一括露光方式で対応が可能であったが、大型基板では、この基板サイズと同程度のマスクサイズを作製することはほぼ不可能であり、一括露光方式では対応が困難である。
そこで、大型基板に対応可能な露光方式として、ステップ露光方式が提唱されている。しかし、ステップ露光方式では、一枚の基板に数回露光され、各露光毎に、位置合せやステップ移動に時間を要するため、一括露光方式に比較して、スループットの低減が問題視されている。
また、一括露光方式では、3,000J/m2程度の露光量が可能であるが、ステップ露光方式では各回の露光量をより低くすることが必要であり、スペーサーの形成に使用される従来の感放射線性樹脂組成物では、1,200J/m2以下の露光量で十分なスペーサー形状および膜厚を達成することが困難であった。
In recent years, from the viewpoint of increasing the area of liquid crystal display elements and improving productivity, the size of mother glass substrates has been increasing (for example, about 1,500 × 1,800 mm, and further about 1,870 × 2,200 mm). However, with the conventional substrate size, the substrate size is smaller than the mask size, so it was possible to cope with the batch exposure method. However, with a large substrate, it is almost impossible to produce a mask size comparable to this substrate size. It is possible, and it is difficult to cope with the batch exposure method.
Therefore, a step exposure method has been proposed as an exposure method that can be applied to a large substrate. However, in the step exposure method, since a single substrate is exposed several times, and each exposure requires time for alignment and step movement, reduction of throughput is regarded as a problem compared to the batch exposure method. .
Further, in the batch exposure method, an exposure amount of about 3,000 J / m 2 is possible, but in the step exposure method, it is necessary to lower the exposure amount each time, and the conventional exposure method used for forming the spacer is used. In the radiation sensitive resin composition, it has been difficult to achieve a sufficient spacer shape and film thickness with an exposure amount of 1,200 J / m 2 or less.
また基板の大型化に伴い工程で不良が発生したとき、カラーフィルター上に形成された配向膜を剥離して再利用する必要がある。配向膜の剥離にはアルカリの剥離液が使用されるので、この剥離液に対してスペーサーは耐性が必要となってくる。すなわち配向膜の剥離時に下層のスペーサーは膨潤や溶解により膜厚変化が起こらないことが望ましく、また弾性特性などの物理的性質も剥離前と同等の性質を示すことが必要とされる。
しかしながら、従来の感放射線性樹脂組成物では剥離液浸漬時の溶解又は剥離によってスペーサー部分もダメージを受け配向膜の剥離が困難又は使用できる剥離液の種類が限定されるものであった。
また生産性向上の観点から、液晶パネルのガラスを張り合わせる前に液晶材をガラス表面にたらす工程技術“ODF(One Drop Fill)法”が導入されている。
この手法により、大幅に時間を節約することができる。例えば、従来の方法では30インチパネル用に液晶を充填するには約5日間要するが、ODF法を導入すればたったの2時間で済み、大幅な生産性向上が可能となる。
Further, when a defect occurs in the process as the substrate becomes larger, the alignment film formed on the color filter must be peeled off and reused. Since an alkaline stripping solution is used for stripping the alignment film, the spacer needs to be resistant to the stripping solution. That is, it is desirable that the lower spacer does not change in thickness due to swelling or dissolution when the alignment film is peeled off, and physical properties such as elastic properties are required to exhibit the same properties as before peeling.
However, in the conventional radiation-sensitive resin composition, the spacer portion is damaged by dissolution or peeling at the time of immersing the peeling liquid, and the kind of the peeling liquid that can hardly be used or the peeling of the alignment film is limited.
Also, from the viewpoint of improving productivity, a process technology “ODF (One Drop Fill) method” in which a liquid crystal material is applied to the glass surface before the glass of the liquid crystal panel is laminated is introduced.
This approach can save a lot of time. For example, in the conventional method, it takes about 5 days to fill the liquid crystal for a 30-inch panel. However, if the ODF method is introduced, only 2 hours are required, and the productivity can be greatly improved.
従来の張り合わせ方式では、TFTアレイとカラーフィルターを張り合わせる時、荷重をかけるため、その荷重によりスペーサーが均等に押され、スペーサーの高さ均一性が保たれていた。しかし、ODF法では、最初は基板の重さによる荷重と大気圧だけで張り合わせるため、従来法に比較して、初期の張り合わせ荷重が小さい。したがって、小さい荷重でスペーサーが押されても、均等に押されことで高さ均一性を発現することが重要とされている。そのためには、スペーサーの柔軟性が必要とされている。スペーサーの高さが不均一になるとセルギャップの均一性が保てなくなり、セル内に隙間が発生し表示ムラの原因となる。そこで、圧縮荷重による柔軟性と高い回復率を併せ持つスペーサー材が必要となる。 In the conventional bonding method, since a load is applied when the TFT array and the color filter are bonded together, the spacer is pressed evenly by the load, and the height uniformity of the spacer is maintained. However, in the ODF method, the initial bonding load is smaller than the conventional method because the bonding is performed only by the load due to the weight of the substrate and the atmospheric pressure. Therefore, even if the spacer is pushed with a small load, it is important to develop height uniformity by being pushed evenly. For this purpose, the flexibility of the spacer is required. If the height of the spacer is not uniform, the cell gap cannot be kept uniform, causing a gap in the cell and causing display unevenness. Therefore, a spacer material having both flexibility due to compressive load and a high recovery rate is required.
特許文献1では、感光性樹脂組成物中に、イミド基と水酸基を有する共重合性樹脂に、(メタ)アクリロイルオキシアルキルイソシアネート化合物を反応させて得られた光重合性官能基を構成単位として有する共重合性樹脂を用いることで高感度化、高回復率化等のスペーサーとしての性能向上を達成できることが開示されている。しかし、柔軟性に関しては考慮されていない。
以上のように、従来の感放射線性樹脂組成物では、光重合性官能基を構成単位として有する共重合性樹脂を用いることで、高感度化と高回復率化は可能であるが、高感度化と高回復率化に加え、さらに柔軟性を併せ持つスペーサーを与える材料とはいえない。
As described above, in the conventional radiation-sensitive resin composition, high sensitivity and high recovery rate can be achieved by using a copolymerizable resin having a photopolymerizable functional group as a structural unit. In addition to increasing the recovery rate and increasing the recovery rate, it cannot be said that it is a material that gives a spacer having more flexibility.
そこで、本発明の課題は、高感度で、1,200J/m2以下の露光量でも十分なスペーサー形状が得られ、柔軟性と高回復率、ラビング耐性、透明基板との密着性、耐熱性等に優れ、かつ配向膜剥離時の剥離液耐性を十分に示す液晶表示素子用スペーサーを形成することができる感放射線性樹脂組成物を提供することにある。 Therefore, the object of the present invention is to obtain a sufficient spacer shape with high sensitivity and an exposure amount of 1,200 J / m 2 or less, flexibility and high recovery rate, rubbing resistance, adhesion to a transparent substrate, and heat resistance. Another object of the present invention is to provide a radiation-sensitive resin composition capable of forming a spacer for a liquid crystal display element that is excellent in the above-mentioned and sufficiently exhibits the resistance to a peeling solution when peeling off an alignment film.
本発明の他の課題は、当該感放射線性樹脂組成物の樹脂成分として有用な側鎖不飽和重合体等を提供することにある。 Another object of the present invention is to provide a side chain unsaturated polymer useful as a resin component of the radiation sensitive resin composition.
本発明のさらに他の課題は、上記感放射線性樹脂組成物から形成された液晶表示用スペーサーおよびそれを備えた液晶表示素子を提供することにある。 Still another object of the present invention is to provide a liquid crystal display spacer formed from the above radiation sensitive resin composition and a liquid crystal display element including the same.
本発明のさらに他の課題は、上記液晶表示用スペーサーの形成方法を提供することにある。 Still another object of the present invention is to provide a method for forming the above-mentioned liquid crystal display spacer.
本発明によると、前記課題は、第一に、
(a1)不飽和カルボン酸および/または不飽和カルボン酸無水物、
(a2)下記式(1)〜(4)のそれぞれで表される水酸基含有不飽和化合物よりなる群から選ばれる少なくとも1つの化合物、(a3)下記式(5)または(6)で示されるオキセタニル基含有不飽和化合物、および(a4)(a1)及び(a2)及び(a3)以外の他の不飽和化合物の共重合体に、下記式(7)で表されるイソシアネート化合物を反応させて得られる重合体、によって達成される。
According to the present invention, the problem is firstly
(A1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride,
(A2) at least one compound selected from the group consisting of hydroxyl group-containing unsaturated compounds represented by the following formulas (1) to (4), (a3) oxetanyl represented by the following formula (5) or (6) It is obtained by reacting an isocyanate compound represented by the following formula (7) with a copolymer of a group-containing unsaturated compound and an unsaturated compound other than (a4) (a1) and (a2) and (a3). Achieved by the polymer.
(式中、Rは水素原子またはメチル基を示し、aは1以上の整数である。) (In the formula, R represents a hydrogen atom or a methyl group, and a is an integer of 1 or more.)
(式中、Rは水素原子またはメチル基を示し、b、cはそれぞれ独立に1〜12の整数である。) (In the formula, R represents a hydrogen atom or a methyl group, and b and c are each independently an integer of 1 to 12.)
(式中、Rは水素原子またはメチル基を示し、d、eはそれぞれ独立に1〜12の整数である。) (In the formula, R represents a hydrogen atom or a methyl group, and d and e are each independently an integer of 1 to 12.)
(式中、Rは水素原子またはメチル基を示し、f、gはそれぞれ独立に0〜6の整数であり、Wは下記式(I)〜(IV)のそれぞれで表される脂環式構造のいずれかを有する2価の基を示す。) (In the formula, R represents a hydrogen atom or a methyl group, f and g are each independently an integer of 0 to 6, and W is an alicyclic structure represented by each of the following formulas (I) to (IV)). A divalent group having any of
(ここで、式(5)および式(6)のR0は水素原子または炭素数1〜4のアルキル基であり、R1は水素原子または炭素数1〜4のアルキル基であり、R2、R3、R4およびR5はそれぞれ独立に水素原子、フッ素原子、炭素数1〜4のアルキル基、フェニル基、または炭素数1〜4のパーフロロアルキル基であり、そしてhは1〜6の整数である。) (Here, R 0 in Formula (5) and Formula (6) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and h is 1 to (It is an integer of 6.)
(式中、Rは水素原子またはメチル基を示し、jは1〜12の整数である。)
本発明によると、前記課題は、第二に、
〔A〕重合体、〔B〕重合性不飽和化合物および〔C〕感放射線性重合開始剤を含有することを特徴とする感放射線性樹脂組成物、によって達成される。
(In the formula, R represents a hydrogen atom or a methyl group, and j is an integer of 1 to 12.)
According to the present invention, the problem is secondly,
It is achieved by a radiation sensitive resin composition comprising [A] a polymer, [B] a polymerizable unsaturated compound, and [C] a radiation sensitive polymerization initiator.
本発明によると、前記課題は、第三に
前記感放射線性樹脂組成物からなる、液晶表示素子用スペーサーの形成に用いられる感放射線性樹脂組成物(以下「液晶表示素子用スペーサー用感放射線性樹脂組成物」という。)によって達成される。
According to the present invention, the above-mentioned problem is thirdly the radiation-sensitive resin composition (hereinafter referred to as “radiation-sensitive liquid crystal display element spacer for liquid crystal display element”) used for forming a spacer for a liquid crystal display element, comprising the radiation sensitive resin composition. It is achieved by “resin composition”).
本発明によると、前記課題は、第四に
液晶表示素子用スペーサー用感放射線性樹脂組成物から形成されてなる液晶表示素子用スペーサーによって達成される。
According to the present invention, fourthly, the above-mentioned object is achieved by a spacer for a liquid crystal display element formed from a radiation-sensitive resin composition for a spacer for a liquid crystal display element.
本発明によると、前記課題は、第五に
少なくとも以下の工程を以下に記載の順序で含むことを特徴とする液晶表示素子用スペーサーの形成方法によって達成される。
(イ)液晶表示素子用スペーサー用感放射線性樹脂組成物の塗膜を基板上に形成する工程、
(ロ)該被膜の少なくとも一部に露光する工程、
(ハ)露光後の該被膜を現像する工程、および
(ニ)現像後の該被膜を加熱する工程。
According to the present invention, fifthly, the above object is achieved by a method for forming a spacer for a liquid crystal display element, comprising at least the following steps in the order described below.
(A) forming a coating film of a radiation sensitive resin composition for spacers for liquid crystal display elements on a substrate;
(B) exposing at least a part of the coating;
(C) a step of developing the coated film after exposure, and (d) a step of heating the coated film after development.
本発明によると、前記課題は、第六に
前記液晶表示素子用スペーサーを具備する液晶表示素子、によって達成される。
According to the present invention, the object is achieved sixth by a liquid crystal display device comprising the liquid crystal display device spacer.
本発明の感放射線性樹脂組成物は、高感度かつ高解像度で、1,200J/m2以下の露光量でも十分なパターン形状が得られ、弾性回復性、ラビング耐性、透明基板との密着性、耐熱性等にも優れ、さらに配向膜剥離時の剥離液耐性を十分に示す液晶表示素子用スペーサーを形成することができる。
本発明の液晶表示素子は、パターン形状、弾性回復性、ラビング耐性、透明基板との密着性、耐熱性等の諸性能に優れたスペーサーを具備するものであり、長期にわたり高い信頼性を表現することができる。
The radiation-sensitive resin composition of the present invention has high sensitivity and high resolution, and a sufficient pattern shape can be obtained even with an exposure amount of 1,200 J / m 2 or less. Elastic recovery, rubbing resistance, adhesion to a transparent substrate In addition, it is possible to form a spacer for a liquid crystal display element that is excellent in heat resistance and the like, and that sufficiently exhibits the resistance to a peeling solution when the alignment film is peeled off.
The liquid crystal display element of the present invention comprises a spacer having excellent performance such as pattern shape, elastic recovery, rubbing resistance, adhesion to a transparent substrate, heat resistance, etc., and expresses high reliability over a long period of time. be able to.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
感放射線性樹脂組成物
−〔A〕重合体−
本発明の重合体は、(a1)不飽和カルボン酸および/または不飽和カルボン酸無水物、(a2)上記式(1)〜(4)のそれぞれで表わされる水酸基含有不飽和化合物よりなる群から選ばれる少なくとも1つの化合物、および(a3)上記式(5)または(6)で示されるオキセタニル基含有不飽和化合物、および(a4)(a1)及び(a2)及び(a3)以外の他の不飽和化合物からなる共重合体(以下、「共重合体〔α〕」という。)に、上記式(7)で表されるイソシアネート化合物(以下、「不飽和イソシアナート化合物」という。)を反応させて得られる重合体(以下、「〔A〕重合体」という。)からなる。
Radiation-sensitive resin composition- [A] polymer-
The polymer of the present invention comprises (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, and (a2) a hydroxyl group-containing unsaturated compound represented by each of the above formulas (1) to (4). At least one selected compound, and (a3) an oxetanyl group-containing unsaturated compound represented by the above formula (5) or (6), and (a4) other than (a1), (a2) and (a3) A copolymer composed of a saturated compound (hereinafter referred to as “copolymer [α]”) is reacted with an isocyanate compound represented by the above formula (7) (hereinafter referred to as “unsaturated isocyanate compound”). A polymer (hereinafter referred to as “[A] polymer”).
共重合体〔α〕を構成する各成分のうち、(a1)不飽和カルボン酸および/または不飽和カルボン酸無水物(以下、これらをまとめて「(a1)不飽和カルボン酸系化合物」という。)としては、例えば、アクリル酸、メタクリル酸、クロトン酸、2−アクリロイルオキシエチルコハク酸、2−メタクリロイルオキシエチルコハク酸、2−アクリロイルオキシエチルヘキサヒドロフタル酸、2−メタクリロイルオキシエチルヘキサヒドロフタル酸の如きモノカルボン酸;
マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸の如きジカルボン酸;
前記ジカルボン酸の無水物等を挙げることができる。
Among the components constituting the copolymer [α], (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (hereinafter these are collectively referred to as “(a1) unsaturated carboxylic acid compound”. ), For example, acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid Monocarboxylic acids such as
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
The anhydride of the said dicarboxylic acid etc. can be mentioned.
これらの(a1)不飽和カルボン酸系化合物のうち、共重合反応性、得られる〔A〕重合体のアルカリ現像液に対する溶解性および入手が容易である点から、アクリル酸、メタクリル酸、2−メタクリロイルオキシエチルヘキサヒドロフタル酸等が好ましい。
共重合体〔α〕において、(a1)不飽和カルボン酸系化合物は、単独でまたは2種以上を混合して使用することができる。
共重合体〔α〕において、(a1)不飽和カルボン酸系化合物に由来する繰り返し単位の含有率は、共重合体〔α〕に基いて好ましくは1〜50重量%、さらに好ましくは5〜40重量%、特に好ましくは10〜30重量%である。(a1)不飽和カルボン酸系化合物に由来する繰り返し単位の含有率が1重量%未満では、不飽和イソシアナート化合物(7)との反応により得られる重合体のアルカリ現像液に対する溶解性が低下する傾向があり、一方50重量%を超えると、該重合体のアルカリ現像液に対する溶解性が大きくなりすぎるおそれがある。
Among these (a1) unsaturated carboxylic acid-based compounds, copolymerization reactivity, solubility of the resulting [A] polymer in an alkaline developer, and easy availability, acrylic acid, methacrylic acid, 2- Methacryloyloxyethyl hexahydrophthalic acid is preferred.
In the copolymer [α], the (a1) unsaturated carboxylic acid compound can be used alone or in admixture of two or more.
In the copolymer [α], the content of the repeating unit derived from the (a1) unsaturated carboxylic acid compound is preferably 1 to 50% by weight, more preferably 5 to 40 based on the copolymer [α]. % By weight, particularly preferably 10 to 30% by weight. (A1) If the content of the repeating unit derived from the unsaturated carboxylic acid compound is less than 1% by weight, the solubility of the polymer obtained by the reaction with the unsaturated isocyanate compound (7) in an alkaline developer is lowered. On the other hand, if it exceeds 50% by weight, the solubility of the polymer in an alkaline developer may be too high.
また、(a2)前記式(1)〜(4)のそれぞれで表される不飽和化合物よりなる群から選ばれる水酸基含有不飽和化合物としては、例えば、前記式(1)で表される化合物としては、アクリル酸5−ヒドロキシペンチルエステル、アクリル酸6−ヒドロキシヘキシルエステル、アクリル酸7−ヒドロキシヘプチルエステル、アクリル酸8−ヒドロキシオクチルエステル、アクリル酸9−ヒドロキシノニルエステル、アクリル酸10−ヒドロキシデシルエステル、アクリル酸11−ヒドロキシウンデシルエステル、アクリル酸12−ヒドロキシト゛デシルエステルの如きアクリル酸ヒドロキシアルキルエステル;
メタクリル酸5−ヒドロキシペンチルエステル、メタクリル酸6−ヒドロキシヘキシルエステル、メタクリル酸7−ヒドロキシヘプチルエステル、メタクリル酸8−ヒドロキシオクチルエステル、メタクリル酸9−ヒドロキシノニルエステル、メタクリル酸10−ヒドロキシデシルエステル、メタクリル酸11−ヒドロキシウンデシルエステル、メタクリル酸12−ヒドロキシト゛デシルエステルの如きメタクリル酸ヒドロキシアルキルエステル等を挙げることができる。
式(1)において、aは5以上が好ましい。
Moreover, (a2) As a hydroxyl-containing unsaturated compound chosen from the group which consists of an unsaturated compound represented by each of said Formula (1)-(4), for example, as a compound represented by said Formula (1) Are acrylic acid 5-hydroxypentyl ester, acrylic acid 6-hydroxyhexyl ester, acrylic acid 7-hydroxyheptyl ester, acrylic acid 8-hydroxyoctyl ester, acrylic acid 9-hydroxynonyl ester, acrylic acid 10-hydroxydecyl ester, Acrylic acid hydroxyalkyl esters such as acrylic acid 11-hydroxyundecyl ester, acrylic acid 12-hydroxydodecyl ester;
Methacrylic acid 5-hydroxypentyl ester, methacrylic acid 6-hydroxyhexyl ester, methacrylic acid 7-hydroxyheptyl ester, methacrylic acid 8-hydroxyoctyl ester, methacrylic acid 9-hydroxynonyl ester, methacrylic acid 10-hydroxydecyl ester, methacrylic acid Examples include 11-hydroxyundecyl ester and methacrylic acid hydroxyalkyl ester such as methacrylic acid 12-hydroxydodecyl ester.
In the formula (1), a is preferably 5 or more.
また、前記式(2)で表される化合物としては、例えば、アクリル酸2−(6−ヒドロキシエチルヘキサノイルオキシ)エチルエステル、アクリル酸3−(6−ヒドロキシエチルヘキサノイルオキシ)プロピルエステル、アクリル酸4−(6−ヒドロキシエチルヘキサノイルオキシ)ブチルエステル、アクリル酸5−(6−ヒドロキシエチルヘキサノイルオキシ)ペンチルエステル、アクリル酸6−(6−ヒドロキシエチルヘキサノイルオキシ)へキシルエステルの如きアクリル酸(6−ヒドロキシエチルヘキサノイルオキシ)アルキルエステル;
メタクリル酸2−(6−ヒドロキシエチルヘキサノイルオキシ)エチルエステル、メタクリル酸3−(6−ヒドロキシエチルヘキサノイルオキシ)プロピルエステル、メタクリル酸4−(6−ヒドロキシエチルヘキサノイルオキシ)ブチルエステル、メタクリル酸5−(6−ヒドロキシエチルヘキサノイルオキシ)ペンチルエステル、メタクリル酸6−(6−ヒドロキシエチルヘキサノイルオキシ)へキシルエステルの如きメタクリル酸(6−ヒドロキシエチルヘキサノイルオキシ)アルキルエステルを挙げることができる。
また、(メタ)アクリル酸(6−ヒドロキシエチルヘキサノイルオキシ)アルキルエステルの市販品としては、商品名で、PLACCEL FM1D、FM2D(ダイセル化学工業(株)製)等を挙げることができる。
Examples of the compound represented by the formula (2) include acrylic acid 2- (6-hydroxyethylhexanoyloxy) ethyl ester, acrylic acid 3- (6-hydroxyethylhexanoyloxy) propyl ester, and acrylic acid. Acrylics such as 4- (6-hydroxyethylhexanoyloxy) butyl ester, 5- (6-hydroxyethylhexanoyloxy) pentyl ester, 6- (6-hydroxyethylhexanoyloxy) hexyl ester of acrylic acid Acid (6-hydroxyethylhexanoyloxy) alkyl ester;
Methacrylic acid 2- (6-hydroxyethylhexanoyloxy) ethyl ester, methacrylic acid 3- (6-hydroxyethylhexanoyloxy) propyl ester, methacrylic acid 4- (6-hydroxyethylhexanoyloxy) butyl ester, methacrylic acid Mention may be made of methacrylic acid (6-hydroxyethylhexanoyloxy) alkyl esters such as 5- (6-hydroxyethylhexanoyloxy) pentyl ester and methacrylic acid 6- (6-hydroxyethylhexanoyloxy) hexyl ester. .
Moreover, as a commercial item of (meth) acrylic acid (6-hydroxyethylhexanoyloxy) alkyl ester, PLACEL FM1D, FM2D (made by Daicel Chemical Industries, Ltd.), etc. can be mentioned by a brand name.
また、前記式(3)で表される化合物としては、例えば、アクリル酸2−(3−ヒドロキシ−2,2−ジメチル−プロポキシカルボニルオキシ)−エチルエステル、アクリル酸3−(3−ヒドロキシ−2,2−ジメチル−プロポキシカルボニルオキシ)−プロピルエステル、アクリル酸4−(3−ヒドロキシ−2,2−ジメチル−プロポキシカルボニルオキシ)−ブチルエステル、アクリル酸5−(3−ヒドロキシ−2,2−ジメチル−プロポキシカルボニルオキシ)−ペンチルエステル、アクリル酸6−(3−ヒドロキシ−2,2−ジメチル−プロポキシカルボニルオキシ)−ヘキシルエステルの如きアクリル酸(3−ヒドロキシ−2,2−ジメチル−プロポキシカルボニルオキシ)−アルキルエステル、
メタクリル酸2−(3−ヒドロキシ−2,2−ジメチル−プロポキシカルボニルオキシ)−エチルエステル、メタクリル酸3−(3−ヒドロキシ−2,2−ジメチル−プロポキシカルボニルオキシ)−プロピルエステル、メタクリル酸4−(3−ヒドロキシ−2,2−ジメチル−プロポキシカルボニルオキシ)−ブチルエステル、メタクリル酸5−(3−ヒドロキシ−2,2−ジメチル−プロポキシカルボニルオキシ)−ペンチルエステル、メタクリル酸6−(3−ヒドロキシ−2,2−ジメチル−プロポキシカルボニルオキシ)−ヘキシルエステルの如きメタクリル酸(3−ヒドロキシ−2,2−ジメチル−プロポキシカルボニルオキシ)−アルキルエステル等を挙げることができる。
また、(メタ)アクリル酸(3−ヒドロキシ−2,2−ジメチル−プロポキシカルボニルオキシ)−アルキルエステルの市販品としては、商品名で、HEMAC1(ダイセル化学工業(株)製)等を挙げることができる。
Examples of the compound represented by the formula (3) include acrylic acid 2- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -ethyl ester and acrylic acid 3- (3-hydroxy-2). , 2-dimethyl-propoxycarbonyloxy) -propyl ester, acrylic acid 4- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -butyl ester, acrylic acid 5- (3-hydroxy-2,2-dimethyl) Acrylic acid (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) such as -propoxycarbonyloxy) -pentyl ester, acrylic acid 6- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -hexyl ester -Alkyl esters,
Methacrylic acid 2- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -ethyl ester, methacrylic acid 3- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -propyl ester, methacrylic acid 4- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -butyl ester, methacrylic acid 5- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -pentyl ester, methacrylic acid 6- (3-hydroxy And methacrylic acid (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -alkyl ester such as -2,2-dimethyl-propoxycarbonyloxy) -hexyl ester.
Moreover, as a commercial item of (meth) acrylic acid (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -alkyl ester, HEMAC1 (manufactured by Daicel Chemical Industries, Ltd.) and the like can be mentioned as trade names. it can.
さらに、前記式(4)で表される化合物としては、例えば、アクリル酸4−ヒドロキシ−シクロヘキシルエステル、アクリル酸4−ヒドロキシメチル−シクロヘキシルメチルエステル、アクリル酸4−ヒドロキシエチル−シクロヘキシルエチルエステル、アクリル酸3−ヒドロキシ−ビシクロ[2.2.1]ヘプト−5−エン−2−イルエステル、アクリル酸3−ヒドロキシメチル−ビシクロ[2.2.1]ヘプト−5−エン−2−イルメチルエステル、アクリル酸3−ヒドロキシエチル−ビシクロ[2.2.1]ヘプト−5−エン−2−イルエチルエステル、アクリル酸8−ヒドロキシ−ビシクロ[2.2.1]ヘプト−5−エン−2−イルエステル、アクリル酸2−ヒドロキシ−オクタヒドロ−4,7−メタノ−インデン−5−イルエステル、アクリル酸2−ヒドロキシメチル−オクタヒドロ−4,7−メタノ−インデン−5−イルメチルエステル、アクリル酸2−ヒドロキシエチル−オクタヒドロ−4,7−メタノ−インデン−5−イルエチルエステル、アクリル酸3−ヒドロキシ−アダマンタン−1−イルエステル、アクリル酸3−ヒドロキシメチル−アダマンタン−1−イルメチルエステル、アクリル酸3−ヒドロキシエチル−アダマンタン−1−イルエチルエステルの如き脂環式構造を有するアクリル酸ヒドロキシアルキルエステル;
メタクリル酸4−ヒドロキシ−シクロヘキシルエステル、メタクリル酸4−ヒドロキシメチル−シクロヘキシルメチルエステル、メタクリル酸4−ヒドロキシエチル−シクロヘキシルエチルエステル、メタクリル酸3−ヒドロキシ−ビシクロ[2.2.1]ヘプト−5−エン−2−イルエステル、メタクリル酸3−ヒドロキシメチル−ビシクロ[2.2.1]ヘプト−5−エン−2−イルメチルエステル、メタクリル酸3−ヒドロキシエチル−ビシクロ[2.2.1]ヘプト−5−エン−2−イルエチルエステル、メタクリル酸8−ヒドロキシ−ビシクロ[2.2.1]ヘプト−5−エン−2−イルエステル、メタクリル酸2−ヒドロキシ−オクタヒドロ−4,7−メタノ−インデン−5−イルエステル、メタクリル酸2−ヒドロキシメチル−オクタヒドロ−4,7−メタノ−インデン−5−イルメチルエステル、メタクリル酸2−ヒドロキシエチル−オクタヒドロ−4,7−メタノ−インデン−5−イルエチルエステル、メタクリル酸3−ヒドロキシ−アダマンタン−1−イルエステル、メタクリル酸3−ヒドロキシメチル−アダマンタン−1−イルメチルエステル、メタクリル酸3−ヒドロキシエチル−アダマンタン−1−イルエチルエステルの如き脂環式構造を有するメタクリル酸ヒドロキシアルキルエステル;
Furthermore, examples of the compound represented by the formula (4) include acrylic acid 4-hydroxy-cyclohexyl ester, acrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, acrylic acid 4-hydroxyethyl-cyclohexyl ethyl ester, and acrylic acid. 3-hydroxy-bicyclo [2.2.1] hept-5-en-2-yl ester, acrylic acid 3-hydroxymethyl-bicyclo [2.2.1] hept-5-en-2-ylmethyl ester, Acrylic acid 3-hydroxyethyl-bicyclo [2.2.1] hept-5-en-2-ylethyl ester, acrylic acid 8-hydroxy-bicyclo [2.2.1] hept-5-en-2-yl Esters, 2-hydroxy-octahydro-4,7-methano-indene-5-yl acrylate Acrylic acid 2-hydroxymethyl-octahydro-4,7-methano-inden-5-ylmethyl ester, acrylic acid 2-hydroxyethyl-octahydro-4,7-methano-inden-5-ylethyl ester, acrylic acid Acrylic acid having an alicyclic structure such as 3-hydroxy-adamantan-1-yl ester, acrylic acid 3-hydroxymethyl-adamantan-1-ylmethyl ester, acrylic acid 3-hydroxyethyl-adamantan-1-ylethyl ester Hydroxyalkyl esters;
Methacrylic acid 4-hydroxy-cyclohexyl ester, Methacrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, Methacrylic acid 4-hydroxyethyl-cyclohexyl ethyl ester, Methacrylic acid 3-hydroxy-bicyclo [2.2.1] hept-5-ene 2-yl ester, methacrylic acid 3-hydroxymethyl-bicyclo [2.2.1] hept-5-en-2-ylmethyl ester, methacrylic acid 3-hydroxyethyl-bicyclo [2.2.1] hept- 5-En-2-ylethyl ester, methacrylic acid 8-hydroxy-bicyclo [2.2.1] hept-5-en-2-yl ester, methacrylic acid 2-hydroxy-octahydro-4,7-methano-indene -5-yl ester, 2-hydroxymethyl methacrylate Octahydro-4,7-methano-inden-5-ylmethyl ester, 2-hydroxyethyl methacrylate-octahydro-4,7-methano-inden-5-ylethyl ester, 3-hydroxy-adamantan-1-yl methacrylate Methacrylic acid hydroxyalkyl esters having an alicyclic structure such as esters, methacrylic acid 3-hydroxymethyl-adamantan-1-ylmethyl ester, methacrylic acid 3-hydroxyethyl-adamantan-1-ylethyl ester;
上記式(1)〜(4)のそれぞれで表されるこれらの水酸基含有不飽和化合物のうち、共重合反応性およびイソシアネート化合物との反応性の点から、アクリル酸6−ヒドロキシヘキシルエステル、メタクリル酸6−ヒドロキシヘキシルエステル、アクリル酸2−(6−ヒドロキシエチルヘキサノイルオキシ)エチルエステル、メタクリル酸2−(6−ヒドロキシエチルヘキサノイルオキシ)エチルエステル、アクリル酸2−(3−ヒドロキシ−2,2−ジメチル−プロポキシカルボニルオキシ)−エチルエステル、メタクリル酸2−(3−ヒドロキシ−2,2−ジメチル−プロポキシカルボニルオキシ)−エチルエステル、アクリル酸4−ヒドロキシメチル−シクロヘキシルメチルエステル、メタクリル酸4−ヒドロキシメチル−シクロヘキシルメチルエステル、アクリル酸3−ヒドロキシメチル−アダマンタン−1−イルメチルエステル、メタクリル酸3−ヒドロキシメチル−アダマンタン−1−イルメチルエステル等が好ましい。 Among these hydroxyl group-containing unsaturated compounds represented by the above formulas (1) to (4), from the viewpoint of copolymerization reactivity and reactivity with isocyanate compounds, acrylic acid 6-hydroxyhexyl ester, methacrylic acid 6-hydroxyhexyl ester, acrylic acid 2- (6-hydroxyethylhexanoyloxy) ethyl ester, methacrylic acid 2- (6-hydroxyethylhexanoyloxy) ethyl ester, acrylic acid 2- (3-hydroxy-2,2 -Dimethyl-propoxycarbonyloxy) -ethyl ester, methacrylic acid 2- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -ethyl ester, acrylic acid 4-hydroxymethyl-cyclohexylmethyl ester, methacrylic acid 4-hydroxy Methyl-cyclohe Sill methyl ester, acrylic acid 3-hydroxymethyl - adamantan-1-yl methyl ester, methacrylic acid 3-hydroxymethyl - adamantan-1-yl methyl ester, and the like are preferable.
共重合体〔α〕において、(a2)の水酸基含有不飽和化合物は、単独でまたは2種以上を混合して使用することができる。
共重合体〔α〕において、(a2)の水酸基含有不飽和化合物に由来する繰り返し単位の含有率は、共重合体〔α〕に基づいて、好ましくは1〜50重量%、さらに好ましくは3〜40重量%、特に好ましくは5〜30重量%である。(a2)水酸基含有不飽和化合物に由来する繰り返し単位の含有率が1重量%未満では、不飽和イソシアネート化合物(7)の重合体への導入率が低下して、感度が低下する傾向があり、一方50重量%を超えると、不飽和イソシアネート化合物(7)との反応により得られる重合体の保存安定性が低下する傾向がある。
In the copolymer [α], the hydroxyl group-containing unsaturated compound (a2) can be used alone or in admixture of two or more.
In the copolymer [α], the content of the repeating unit derived from the hydroxyl group-containing unsaturated compound (a2) is preferably 1 to 50% by weight, more preferably 3 to 3, based on the copolymer [α]. It is 40% by weight, particularly preferably 5 to 30% by weight. (A2) If the content of the repeating unit derived from the hydroxyl group-containing unsaturated compound is less than 1% by weight, the introduction rate of the unsaturated isocyanate compound (7) into the polymer tends to decrease, and the sensitivity tends to decrease. On the other hand, when it exceeds 50% by weight, the storage stability of the polymer obtained by the reaction with the unsaturated isocyanate compound (7) tends to be lowered.
式(5)で示される化合物(a3)としては、例えば3−(メタクリロイルオキシメチル)オキセタン、3−(メタクリロイルオキシメチル)−3−エチルオキセタン、3−(メタクリロイルオキシメチル)−2−メチルオキセタン、3−(メタクリロイルオキシメチル)−2−トリフロロメチルオキセタン、3−(メタクリロイルオキシメチル)−2−ペンタフロロエチルオキセタン、3−(メタクリロイルオキシメチル)−2−フェニルオキセタン、3−(メタクリロイルオキシメチル)−2,2−ジフロロオキセタン、3−(メタクリロイルオキシメチル)−2,2,4−トリフロロオキセタン、3−(メタクリロイルオキシメチル)−2,2,4,4−テトラフロロオキセタン、3−(メタクリロイルオキシエチル)オキセタン、3−(メタクリロイルオキシエチル)−3−エチルオキセタン、2−エチル−3−(メタクリロイルオキシエチル)オキセタン、3−(メタクリロイルオキシエチル)−2−トリフロロメチルオキセタン、3−(メタクリロイルオキシエチル)−2−ペンタフロロエチルオキセタン、3−(メタクリロイルオキシエチル)−2−フェニルオキセタン、2,2−ジフロロ−3−(メタクリロイルオキシエチル)オキセタン、3−(メタクリロイルオキシエチル)−2,2,4−トリフロロオキセタン、3−(メタクリロイルオキシエチル)−2,2,4,4−テトラフロロオキセタン等のメタクリル酸エステル; Examples of the compound (a3) represented by the formula (5) include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- ( Methacryloyloxyethyl) oxetane, 3 (Methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxyethyl) -2-penta Fluoroethyloxetane, 3- (methacryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2,2,4-trifluorooxetane, Methacrylic acid esters such as 3- (methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane;
3−(アクリロイルオキシメチル)オキセタン、3−(アクリロイルオキシメチル)−3−エチルオキセタン、3−(アクリロイルオキシメチル)−2−メチルオキセタン、3−(アクリロイルオキシメチル)−2−トリフロロメチルオキセタン、3−(アクリロイルオキシメチル)−2−ペンタフロロエチルオキセタン、3−(アクリロイルオキシメチル)−2−フェニルオキセタン、3−(アクリロイルオキシメチル)−2,2−ジフロロオキセタン、3−(アクリロイルオキシメチル)−2,2,4−トリフロロオキセタン、3−(アクリロイルオキシメチル)−2,2,4,4−テトラフロロオキセタン、3−(アクリロイルオキシエチル)オキセタン、3−(アクリロイルオキシエチル)−3−エチルオキセタン、2−エチル−3−(アクリロイルオキシエチル)オキセタン、3−(アクリロイルオキシエチル)−2−トリフロロメチルオキセタン、3−(アクリロイルオキシエチル)−2−ペンタフロロエチルオキセタン、3−(アクリロイルオキシエチル)−2−フェニルオキセタン、2,2−ジフロロ−3−(アクリロイルオキシエチル)オキセタン、3−(アクリロイルオキシエチル)−2,2,4−トリフロロオキセタン、3−(アクリロイルオキシエチル)−2,2,4,4−テトラフロロオキセタン等のアクリル酸エステルが挙げられる。 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) ) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -3 -Ethyloxetane, 2-ethyl-3 (Acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (acryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxyethyl) -2,2,4,4-tetra Acrylic esters such as fluorooxetane are mentioned.
式(6)で示される化合物(a3)としては、例えば2−(メタクリロイルオキシメチル)オキセタン、2−メチル−2−(メタクリロイルオキシメチル)オキセタン、3−メチル−2−(メタクリロイルオキシメチル)オキセタン、4−メチル−2−(メタクリロイルオキシメチル)オキセタン、2−(メタクリロイルオキシメチル)−2−トリフロロメチルオキセタン、2−(メタクリロイルオキシメチル)−3−トリフロロメチルオキセタン、2−(メタクリロイルオキシメチル)−4−トリフロロメチルオキセタン、2−(メタクリロイルオキシメチル)−2−ペンタフロロエチルオキセタン、2−(メタクリロイルオキシメチル)−3−ペンタフロロエチルオキセタン、2−(メタクリロイルオキシメチル)−4−ペンタフロロエチルオキセタン、2−(メタクリロイルオキシメチル)−2−フェニルオキセタン、2−(メタクリロイルオキシメチル)−3−フェニルオキセタン、2−(メタクリロイルオキシメチル)−4−フェニルオキセタン、2,3−ジフロロ−2−(メタクリロイルオキシメチル)オキセタン、2,4−ジフロロ−2−(メタクリロイルオキシメチル)オキセタン、3,3−ジフロロ−2−(メタクリロイルオキシメチル)オキセタン、3,4−ジフロロ−2−(メタクリロイルオキシメチル)オキセタン、4,4−ジフロロ−2−(メタクリロイルオキシメチル)オキセタン、2−(メタクリロイルオキシメチル)−3,3,4−トリフロロオキセタン、2−(メタクリロイルオキシメチル)−3,4,4−トリフロロオキセタン、2−(メタクリロイルオキシメチル)−3,3,4,4−テトラフロロオキセタン、 Examples of the compound (a3) represented by the formula (6) include 2- (methacryloyloxymethyl) oxetane, 2-methyl-2- (methacryloyloxymethyl) oxetane, 3-methyl-2- (methacryloyloxymethyl) oxetane, 4-methyl-2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -3-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -2-pentafluoroethyl oxetane, 2- (methacryloyloxymethyl) -3-pentafluoroethyloxetane, 2- (methacryloyloxymethyl) -4-pentafluoroe Luoxetane, 2- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) -3-phenyloxetane, 2- (methacryloyloxymethyl) -4-phenyloxetane, 2,3-difluoro-2- ( Methacryloyloxymethyl) oxetane, 2,4-difluoro-2- (methacryloyloxymethyl) oxetane, 3,3-difluoro-2- (methacryloyloxymethyl) oxetane, 3,4-difluoro-2- (methacryloyloxymethyl) oxetane 4,4-Difluoro-2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -3,3,4-trifluorooxetane, 2- (methacryloyloxymethyl) -3,4,4-trifluoro Oxetane, 2- (meta Leroy oxy methyl) 3,3,4,4-tetrafluoroethane oxetane,
2−(メタクリロイルオキシエチル)オキセタン、2−(2−(2−メチルオキセタニル))エチルメタクリレート、2−(2−(3−メチルオキセタニル))エチルメタクリレート、2−(メタクリロイルオキシエチル)−2−メチルオキセタン、2−(メタクリロイルオキシエチル)−4−メチルオキセタン、2−(メタクリロイルオキシエチル)−2−トリフロロメチルオキセタン、2−(メタクリロイルオキシエチル)−3−トリフロロメチルオキセタン、2−(メタクリロイルオキシエチル)−4−トリフロロメチルオキセタン、2−(メタクリロイルオキシエチル)−2−ペンタフロロエチルオキセタン、2−(メタクリロイルオキシエチル)−3−ペンタフロロエチルオキセタン、2−(メタクリロイルオキシエチル)−4−ペンタフロロエチルオキセタン、2−(メタクリロイルオキシエチル)−2−フェニルオキセタン、2−(メタクリロイルオキシエチル)−3−フェニルオキセタン、2−(メタクリロイルオキシエチル)−4−フェニルオキセタン、2,3−ジフロロ−2−(メタクリロイルオキシエチル)オキセタン、2,4−ジフロロ−2−(メタクリロイルオキシエチル)オキセタン、3,3−ジフロロ−2−(メタクリロイルオキシエチル)オキセタン、3,4−ジフロロ−2−(メタクリロイルオキシエチル)オキセタン、4,4−ジフロロ−2−(メタクリロイルオキシエチル)オキセタン、2−(メタクリロイルオキシエチル)−3,3,4−トリフロロオキセタン、2−(メタクリロイルオキシエチル)−3,4,4−トリフロロオキセタン、2−(メタクリロイルオキシエチル)−3,3,4,4−テトラフロロオキセタン等のメタクリル酸エステル; 2- (methacryloyloxyethyl) oxetane, 2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (methacryloyloxyethyl) -2-methyl Oxetane, 2- (methacryloyloxyethyl) -4-methyloxetane, 2- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 2- (methacryloyloxyethyl) -3-trifluoromethyloxetane, 2- (methacryloyloxy) Ethyl) -4-trifluoromethyloxetane, 2- (methacryloyloxyethyl) -2-pentafluoroethyloxetane, 2- (methacryloyloxyethyl) -3-pentafluoroethyloxetane, 2- (methacryloyloxyethyl) -4- N-tafluoroethyloxetane, 2- (methacryloyloxyethyl) -2-phenyloxetane, 2- (methacryloyloxyethyl) -3-phenyloxetane, 2- (methacryloyloxyethyl) -4-phenyloxetane, 2,3-difluoro- 2- (methacryloyloxyethyl) oxetane, 2,4-difluoro-2- (methacryloyloxyethyl) oxetane, 3,3-difluoro-2- (methacryloyloxyethyl) oxetane, 3,4-difluoro-2- (methacryloyloxy) Ethyl) oxetane, 4,4-difluoro-2- (methacryloyloxyethyl) oxetane, 2- (methacryloyloxyethyl) -3,3,4-trifluorooxetane, 2- (methacryloyloxyethyl) -3,4,4 -Trifluorooxeta , 2- (methacryloyloxyethyl) 3,3,4,4 methacrylic esters tetrafluoroethane oxetane, and the like;
2−(アクリロイルオキシメチル)オキセタン、2−メチル−2−(アクリロイルオキシメチル)オキセタン、3−メチル−2−(アクリロイルオキシメチル)オキセタン、4−メチル−2−(アクリロイルオキシメチル)オキセタン、2−(アクリロイルオキシメチル)−2−トリフロロメチルオキセタン、2−(アクリロイルオキシメチル)−3−トリフロロメチルオキセタン、2−(アクリロイルオキシメチル)−4−トリフロロメチルオキセタン、2−(アクリロイルオキシメチル)−2−ペンタフロロエチルオキセタン、2−(アクリロイルオキシメチル)−3−ペンタフロロエチルオキセタン、2−(アクリロイルオキシメチル)−4−ペンタフロロエチルオキセタン、2−(アクリロイルオキシメチル)−2−フェニルオキセタン、2−(アクリロイルオキシメチル)−3−フェニルオキセタン、2−(アクリロイルオキシメチル)−4−フェニルオキセタン、2,3−ジフロロ−2−(アクリロイルオキシメチル)オキセタン、2,4−ジフロロ−2−(アクリロイルオキシメチル)オキセタン、3,3−ジフロロ−2−(アクリロイルオキシメチル)オキセタン、3,4−ジフロロ−2−(アクリロイルオキシメチル)オキセタン、4,4−ジフロロ−2−(アクリロイルオキシメチル)オキセタン、2−(アクリロイルオキシメチル)−3,3,4−トリフロロオキセタン、2−(アクリロイルオキシメチル)−3,4,4−トリフロロオキセタン、2−(アクリロイルオキシメチル)−3,3,4,4−テトラフロロオキセタン、 2- (acryloyloxymethyl) oxetane, 2-methyl-2- (acryloyloxymethyl) oxetane, 3-methyl-2- (acryloyloxymethyl) oxetane, 4-methyl-2- (acryloyloxymethyl) oxetane, 2- (Acryloyloxymethyl) -2-trifluoromethyloxetane, 2- (acryloyloxymethyl) -3-trifluoromethyloxetane, 2- (acryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyloxymethyl) 2-Pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -3-pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -4-pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -2-phenyloxet 2- (acryloyloxymethyl) -3-phenyloxetane, 2- (acryloyloxymethyl) -4-phenyloxetane, 2,3-difluoro-2- (acryloyloxymethyl) oxetane, 2,4-difluoro-2 -(Acryloyloxymethyl) oxetane, 3,3-difluoro-2- (acryloyloxymethyl) oxetane, 3,4-difluoro-2- (acryloyloxymethyl) oxetane, 4,4-difluoro-2- (acryloyloxymethyl) ) Oxetane, 2- (acryloyloxymethyl) -3,3,4-trifluorooxetane, 2- (acryloyloxymethyl) -3,4,4-trifluorooxetane, 2- (acryloyloxymethyl) -3,3 , 4,4-tetrafluorooxetane,
2−(アクリロイルオキシエチル)オキセタン、2−(2−(2−メチルオキセタニル))エチルメタクリレート、2−(2−(3−メチルオキセタニル))エチルメタクリレート、2−(アクリロイルオキシエチル)−2−メチルオキセタン、2−(アクリロイルオキシエチル)−4−メチルオキセタン、2−(アクリロイルオキシエチル)−2−トリフロロメチルオキセタン、2−(アクリロイルオキシエチル)−3−トリフロロメチルオキセタン、2−(アクリロイルオキシエチル)−4−トリフロロメチルオキセタン、2−(アクリロイルオキシエチル)−2−ペンタフロロエチルオキセタン、2−(アクリロイルオキシエチル)−3−ペンタフロロエチルオキセタン、2−(アクリロイルオキシエチル)−4−ペンタフロロエチルオキセタン、2−(アクリロイルオキシエチル)−2−フェニルオキセタン、2−(アクリロイルオキシエチル)−3−フェニルオキセタン、2−(アクリロイルオキシエチル)−4−フェニルオキセタン、2,3−ジフロロ−2−(アクリロイルオキシエチル)オキセタン、2,4−ジフロロ−2−(アクリロイルオキシエチル)オキセタン、3,3−ジフロロ−2−(アクリロイルオキシエチル)オキセタン、3,4−ジフロロ−2−(アクリロイルオキシエチル)オキセタン、4,4−ジフロロ−2−(アクリロイルオキシエチル)オキセタン、2−(アクリロイルオキシエチル)−3,3,4−トリフロロオキセタン、2−(アクリロイルオキシエチル)−3,4,4−トリフロロオキセタン、2−(アクリロイルオキシエチル)−3,3,4,4−テトラフロロオキセタン等のアクリル酸エステルが挙げられる。 2- (acryloyloxyethyl) oxetane, 2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (acryloyloxyethyl) -2-methyl Oxetane, 2- (acryloyloxyethyl) -4-methyloxetane, 2- (acryloyloxyethyl) -2-trifluoromethyloxetane, 2- (acryloyloxyethyl) -3-trifluoromethyloxetane, 2- (acryloyloxy) Ethyl) -4-trifluoromethyloxetane, 2- (acryloyloxyethyl) -2-pentafluoroethyloxetane, 2- (acryloyloxyethyl) -3-pentafluoroethyloxetane, 2- (acryloyloxyethyl) -4- Pentafluoroethyl Xetane, 2- (acryloyloxyethyl) -2-phenyloxetane, 2- (acryloyloxyethyl) -3-phenyloxetane, 2- (acryloyloxyethyl) -4-phenyloxetane, 2,3-difluoro-2- ( Acryloyloxyethyl) oxetane, 2,4-difluoro-2- (acryloyloxyethyl) oxetane, 3,3-difluoro-2- (acryloyloxyethyl) oxetane, 3,4-difluoro-2- (acryloyloxyethyl) oxetane 4,4-Difluoro-2- (acryloyloxyethyl) oxetane, 2- (acryloyloxyethyl) -3,3,4-trifluorooxetane, 2- (acryloyloxyethyl) -3,4,4-trifluoro Oxetane, 2- (acryloyloxyethyl)- , Acrylic acid esters such as 3,4,4-tetrafluoroethane oxetane.
これらのうち、3−(メタクリロイルオキシメチル)オキセタン、3−(メタクリロイルオキシメチル)−2−トリフロロメチルオキセタン、3−(メタクリロイルオキシメチル)−2−フェニルオキセタン、2−(メタクリロイルオキシメチル)オキセタン、2−(メタクリロイルオキシメチル)−4−トリフロロメチルオキセタンなどが、得られる感光性樹脂組成物のプロセスマージンが広く、かつ、得られるスペーサーの耐薬品性を高める点から好ましく用いられる。これらは、単独であるいは組み合わせて用いられる。
共重合体〔α〕において、(a3)に由来する繰り返し単位の含有率は、好ましくは3〜70重量%、より好ましくは5〜50重量%、さらに好ましくは5〜40重量%である。この場合、(a3)に由来する繰り返し単位の含有率が3重量%未満では、剥離液耐性が低下する傾向があり、一方70重量%を超えると、アルカリ水溶液に溶解しにくくなる。
Among these, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane and the like are preferably used from the viewpoint that the process margin of the obtained photosensitive resin composition is wide and the chemical resistance of the obtained spacer is increased. These may be used alone or in combination.
In the copolymer [α], the content of the repeating unit derived from (a3) is preferably 3 to 70% by weight, more preferably 5 to 50% by weight, and further preferably 5 to 40% by weight. In this case, when the content of the repeating unit derived from (a3) is less than 3% by weight, the resistance to the stripping solution tends to be lowered. On the other hand, when the content exceeds 70% by weight, it becomes difficult to dissolve in the alkaline aqueous solution.
また、(a4)他の不飽和化合物としては、例えば、
アクリル酸メチル、アクリル酸n−プロピル、アクリル酸i−プロピル、アクリル酸n−ブチル、アクリル酸sec−ブチル、アクリル酸t−ブチルの如きアクリル酸アルキルエステル;
メタクリル酸メチル、メタクリル酸エチル、メタクリル酸n−プロピル、メタクリル酸i−プロピル、メタクリル酸n−ブチル、メタクリル酸sec−ブチル、メタクリル酸t−ブチルの如きメタクリル酸アルキルエステル;
アクリル酸グリシジル、アクリル酸2−メチルグリシジル、4−ヒドロキシブチルアクリレートグリシジルエーテル、アクリル酸3,4−エポキシブチル、アクリル酸6,7−エポキシヘプチル、アクリル酸3,4−エポキシシクロヘキシルの如きアクリル酸エポキシ(シクロ)アルキルエステル;
メタクリル酸グリシジル、メタクリル酸2−メチルグリシジル、メタクリル酸3,4−エポキシブチル、メタクリル酸6,7−エポキシヘプチル、メタクリル酸3,4−エポキシシクロヘキシルの如きメタクリル酸エポキシ(シクロ)アルキルエステル;
α―エチルアクリル酸グリシジル、α―n−プロピルアクリル酸グリシジル、α―n−ブチルアクリル酸グリシジル、α―エチルアクリル酸6,7−エポキシヘプチル、α―エチルアクリル酸3,4−エポキシシクロヘキシルの如き他のα―アルキルアクリル酸エポキシ(シクロ)アルキルエステル;
o−ビニルベンジルグリシジルエーテル、m−ビニルベンジルグリシジルエーテル、p−ビニルベンジルグリシジルエーテルの如きグリシジルエーテル;
アクリル酸シクロヘキシル、アクリル酸2−メチルシクロヘキシル、アクリル酸トリシクロ[ 5.2.1.02,6] デカン−8−イル、アクリル酸2−(トリシクロ[ 5.2.1.02,6] デカン−8−イルオキシ)エチル、アクリル酸イソボロニルの如きアクリル酸脂環式エステル;
メタクリル酸シクロヘキシル、メタクリル酸2−メチルシクロヘキシル、メタクリル酸トリシクロ[ 5.2.1.02,6] デカン−8−イル、メタクリル酸2−(トリシクロ[ 5.2.1.02,6] デカン−8−イルオキシ)エチル、メタクリル酸イソボロニルの如きメタクリル酸脂環式エステル;
アクリル酸フェニル、アクリル酸ベンジルの如きアクリル酸のアリールエステルあるいはアラルキルエステル;
メタクリル酸フェニル、メタクリル酸ベンジルの如きメタクリル酸のアリールエステルあるいはアラルキルエステル;
マレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジエチルの如き不飽和ジカルボン酸ジアルキルエステル;
アクリル酸テトラヒドロフラン−2−イル、アクリル酸テトラヒドロピラン−2−イル、アクリル酸2−メチルテトラヒドロピラン−2−イルの如き含酸素複素5員環あるいは含酸素複素6員環を有するアクリル酸エステル;
メタクリル酸テトラヒドロフラン−2−イル、メタクリル酸テトラヒドロピラン−2−イル、メタクリル酸2−メチルテトラヒドロピラン−2−イルの如き含酸素複素5員環あるいは含酸素複素6員環を有するメタクリル酸エステル;
スチレン、α−メチルスチレン、m−メチルスチレン、p−メチルスチレン、p−メトキシスチレンの如きビニル芳香族化合物;
1,3−ブタジエン、イソプレン、2,3−ジメチル−1,3−ブタジエンの如き共役ジエン系化合物のほか、
アクリロニトリル、メタクリロニトリル、アクリルアミド、メタクリルアミド、塩化ビニル、塩化ビニリデン、酢酸ビニル
等を挙げることができる。
Moreover, as (a4) other unsaturated compounds, for example,
Alkyl acrylates such as methyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate;
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate;
Acrylic epoxies such as glycidyl acrylate, 2-methylglycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl acrylate (Cyclo) alkyl esters;
Methacrylic acid epoxy (cyclo) alkyl esters such as glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate;
α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylate 6,7-epoxyheptyl, α-ethyl acrylate 3,4-epoxycyclohexyl, etc. Other α-alkyl acrylic acid epoxy (cyclo) alkyl esters;
Glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether;
Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo acrylate [5.2.1.0 2,6 ] decan-8-yl, 2- (tricyclo [5.2.1.0 2,6 ] acrylate Acrylic alicyclic esters such as decan-8-yloxy) ethyl, isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 2,6 ] decane-8-yl, methacrylic acid 2- (tricyclo [5.2.1.0 2,6 ] Decane-8-yloxy) ethyl, methacrylic acid alicyclic esters such as isobornyl methacrylate;
Aryl or aralkyl esters of acrylic acid such as phenyl acrylate, benzyl acrylate;
Aryl or aralkyl esters of methacrylic acid such as phenyl methacrylate or benzyl methacrylate;
Unsaturated dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Acrylic acid ester having an oxygen-containing hetero 5-membered ring or oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl acrylate, tetrahydropyran-2-yl acrylate, 2-methyltetrahydropyran-2-yl acrylate;
Methacrylate esters having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl methacrylate, tetrahydropyran-2-yl methacrylate, 2-methyltetrahydropyran-2-yl methacrylate;
Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene;
In addition to conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene,
Examples include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, and vinyl acetate.
これらの(a4)他の不飽和化合物のうち、共重合反応性および得られる〔A〕重合体のアルカリ水溶液に対する溶解性の点から、メタクリル酸n−ブチル、メタクリル酸2−メチルグリシジル、メタクリル酸ベンジル、メタクリル酸トリシクロ[ 5.2.1.02,6 ] デカン−8−イル、スチレン、p−メトキシスチレン、メタクリル酸テトラヒドロフラン−2−イル、1,3−ブタジエン等が好ましい。 Among these (a4) other unsaturated compounds, n-butyl methacrylate, 2-methylglycidyl methacrylate, methacrylic acid, from the viewpoint of copolymerization reactivity and solubility of the obtained [A] polymer in an aqueous alkali solution Benzyl, tricyclomethacrylate [5.2.1.0 2,6 ] decan-8-yl, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene and the like are preferable.
共重合体〔α〕において、(a4)他の不飽和化合物は、単独でまたは2種以上を混合して使用することができる。
共重合体〔α〕において、(a4)他の不飽和化合物に由来する繰り返し単位の含有率は、共重合体〔α〕に基いて、好ましくは10〜70重量%、さらに好ましくは20〜50重量%、特に好ましくは30〜50重量%である。(a4)他の不飽和化合物に由来する繰り返し単位の含有率が10重量%未満では、不飽和イソシアネート化合物(7)との反応により得られる重合体の保存安定性が低下する傾向があり、一方70重量%を超えると、該重合体のアルカリ現像液に対する溶解性が低下する傾向がある。また、(メタ)アクリル酸エポキシ(シクロ)アルキルエステル類を使用する時は、含有率10重量%以下が好ましく、10重量%以上では、保存安定性が低下する傾向がある。
共重合体〔α〕は、例えば、(a1)不飽和カルボン酸系化合物、(a2)の水酸基含有不飽和化合物、(a3)のオキセタニル基含有不飽和化合物、および(a4)他の不飽和化合物を、適当な溶媒中、ラジカル重合開始剤の存在下で重合することにより製造することができる。
In the copolymer [α], (a4) other unsaturated compounds can be used alone or in admixture of two or more.
In the copolymer [α], (a4) the content of repeating units derived from other unsaturated compounds is preferably 10 to 70% by weight, more preferably 20 to 50%, based on the copolymer [α]. % By weight, particularly preferably 30 to 50% by weight. (A4) When the content of the repeating unit derived from another unsaturated compound is less than 10% by weight, the storage stability of the polymer obtained by the reaction with the unsaturated isocyanate compound (7) tends to decrease, If it exceeds 70% by weight, the solubility of the polymer in an alkaline developer tends to be lowered. Further, when (meth) acrylic acid epoxy (cyclo) alkyl esters are used, the content is preferably 10% by weight or less, and if it is 10% by weight or more, the storage stability tends to decrease.
The copolymer [α] includes, for example, (a1) an unsaturated carboxylic acid compound, (a2) a hydroxyl group-containing unsaturated compound, (a3) an oxetanyl group-containing unsaturated compound, and (a4) other unsaturated compounds. Can be produced by polymerizing in a suitable solvent in the presence of a radical polymerization initiator.
前記重合に用いられる溶媒としては、例えば、
メタノール、エタノール、n−プロパノール、i−プロパノールの如きアルコール;
テトラヒドロフラン、ジオキサンの如きエーテル;
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノ−n−プロピルエーテル、エチレングリコールモノ−n−ブチルエーテルの如きエチレングリコールモノアルキルエーテル;
エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテル、エチレングリコールモノ−n−プロピルエーテルアセテート、エチレングリコールモノ−n−ブチルエーテルアセテートの如きエチレングリコールモノアルキルエーテルアセテート;
エチレングリコールモノメチルエーテルプロピオネート、エチレングリコールモノエチルエーテルプロピオネート、エチレングリコールモノ−n−プロピルエーテルプロピオネート、エチレングリコールモノ−n−ブチルエーテルプロピオネートの如きエチレングリコールモノアルキルエーテルプロピオネート;
ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテルの如きジエチレングリコールアルキルエーテル;
プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ−n−プロピルエーテル、プロピレングリコールモノ−n−ブチルエーテルの如きプロピレングリコールモノアルキルエーテル;
ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテル、ジプロピレングリコールメチルエチルエーテルの如きジプロピレングリコールアルキルエーテル;
プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノ−n−プロピルエーテルアセテート、プロピレングリコールモノ−n−ブチルエーテルアセテートの如きプロピレングリコールモノアルキルエーテルアセテート;
プロピレングリコールモノメチルエーテルプロピオネート、プロピレングリコールモノエチルエーテルプロピオネート、プロピレングリコールモノ−n−プロピルエーテルプロピオネート、プロピレングリコールモノ−n−ブチルエーテルプロピオネートの如きプロピレングリコールモノアルキルエーテルプロピオネート;
トルエン、キシレンの如き芳香族炭化水素;
メチルエチルケトン、2−ペンタノン、3−ペンタノン、シクロヘキサノン、4−ヒドロキシ−4−メチル−2−ペンタノンの如きケトン;
2−メトキシプロピオン酸メチル、2−メトキシプロピオン酸エチル、2−メトキシプロピオン酸n−プロピル、2−メトキシプロピオン酸n−ブチル、2−エトキシプロピオン酸メチル、2−エトキシプロピオン酸エチル、2−エトキシプロピオン酸n−プロピル、2−エトキシプロピオン酸n−ブチル、2−n−プロポキシプロピオン酸メチル、2−n−プロポキシプロピオン酸エチル、2−n−プロポキシプロピオン酸n−プロピル、2−n−プロポキシプロピオン酸n−ブチル、2−n−ブトキシプロピオン酸メチル、2−n−ブトキシプロピオン酸エチル、2−n−ブトキシプロピオン酸n−プロピル、2−n−ブトキシプロピオン酸n−ブチル、3−メトキシプロピオン酸メチル、3−メトキシプロピオン酸エチル、3−メトキシプロピオン酸n−プロピル、3−メトキシプロピオン酸n−ブチル、3−エトキシプロピオン酸メチル、3−エトキシプロピオン酸エチル、3−エトキシプロピオン酸n−プロピル、3−エトキシプロピオン酸n−ブチル、3−n−プロポキシプロピオン酸メチル、3−n−プロポキシプロピオン酸エチル、3−n−プロポキシプロピオン酸n−プロピル、3−n−プロポキシプロピオン酸n−ブチル、3−n−ブトキシプロピオン酸メチル、3−n−ブトキシプロピオン酸エチル、3−n−ブトキシプロピオン酸n−プロピル、3−n−ブトキシプロピオン酸n−ブチルの如きアルコキシプロピオン酸アルキルや、
酢酸メチル、酢酸エチル、酢酸n−プロピル、酢酸n−ブチル、ヒドロキシ酢酸メチル、ヒドロキシ酢酸エチル、ヒドロキシ酢酸n−プロピル、ヒドロキシ酢酸n−ブチル、酢酸4−メトキシブチル、酢酸3−メトキシブチル、酢酸2−メトキシブチル、酢酸3−エトキシブチル、酢酸3−プロキシブチル、乳酸メチル、乳酸エチル、乳酸n−プロピル、乳酸n−ブチル、2−ヒドロキシ−2−メチルプロピオン酸メチル、2−ヒドロキシ−2−メチルプロピオン酸エチル、3−ヒドロキシプロピオン酸メチル、3−ヒドロキシプロピオン酸エチル、3−ヒドロキシプロピオン酸n−プロピル、3−ヒドロキシプロピオン酸n−ブチル、2−ヒドロキシ−3−メチルブタン酸メチル、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸n−プロピル、メトキシ酢酸n−ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル、エトキシ酢酸n−プロピル、エトキシ酢酸n−ブチル、n−プロポキシ酢酸メチル、n−プロポキシ酢酸エチル、n−プロポキシ酢酸n−プロピル、n−プロポキシ酢酸n−ブチル、n−ブトキシ酢酸メチル、n−ブトキシ酢酸エチル、n−ブトキシ酢酸n−プロピル、n−ブトキシ酢酸n−ブチルの如き他のエステル
等を挙げることができる。
As the solvent used for the polymerization, for example,
Alcohols such as methanol, ethanol, n-propanol, i-propanol;
Ethers such as tetrahydrofuran and dioxane;
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate;
Ethylene glycol monoalkyl ether propionates such as ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propionate, ethylene glycol mono-n-butyl ether propionate;
Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether;
Dipropylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate;
Propylene glycol monoalkyl ether propionates such as propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol mono-n-propyl ether propionate, propylene glycol mono-n-butyl ether propionate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone;
Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxypropion N-propyl acid, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate, 2-n-propoxypropionic acid n-butyl, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, 3-methoxy N-propyl propionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, n-butyl 3-ethoxypropionate, 3-n -Methyl propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, methyl 3-n-butoxypropionate, 3-n- Alkyl alkoxypropionates such as ethyl butoxypropionate, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate,
Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, 4-methoxybutyl acetate, 3-methoxybutyl acetate, acetic acid 2 -Methoxybutyl, 3-ethoxybutyl acetate, 3-proxybutyl acetate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl propionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, Ethoxy methoxyacetate, methoxyacetic acid -Propyl, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, n-butyl ethoxyacetate, methyl n-propoxyacetate, ethyl n-propoxyacetate, n-propyloxyacetate n-propyl, n -Other esters such as n-butyl propoxyacetate, methyl n-butoxyacetate, ethyl n-butoxyacetate, n-butoxyacetate, n-butyloxybutoxyacetate, and the like.
これらの溶媒のうち、ジエチレングリコールアルキルエーテル、プロピレングリコールモノアルキルエーテルアセテート、アルコキシプロピオン酸アルキル、酢酸エステル等が好ましい。
前記溶媒は、単独でまたは2種以上を混合して使用することができる。
Of these solvents, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, acetate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.
また、前記ラジカル重合開始剤としては、特に限定されるものではなく、例えば、2,2’−アゾビスイソブチロニトリル、2,2’−アゾビス−(2,4−ジメチルバレロニトリル)、2,2’−アゾビス−(4−メトキシ−2,4−ジメチルバレロニトリル)、4,4’−アゾビス(4―シアノバレリン酸)、ジメチル−2,2’−アゾビス(2−メチルプロピオネート)、2,2’−アゾビス(4−メトキシ−2,4−ジメチルバレロニトリル)等のアゾ化合物;ベンゾイルペルオキシド、ラウロイルペルオキシド、t−ブチルペルオキシピバレート、1,1−ビス(t−ブチルペルオキシ)シクロヘキサンの如き有機過酸化物;過酸化水素等を挙げることができる。 In addition, the radical polymerization initiator is not particularly limited. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2 , 2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), dimethyl-2,2′-azobis (2-methylpropionate), Azo compounds such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1-bis (t-butylperoxy) cyclohexane And organic peroxides such as hydrogen peroxide.
また、ラジカル重合開始剤として過酸化物を用いる場合には、それと還元剤とを併用して、レドックス型開始剤としてもよい。
これらのラジカル重合開始剤は、単独でまたは2種以上を混合して使用することができる。
このようにして得られた共重合体〔α〕は、溶液のまま〔A〕重合体の製造に供しても、また一旦溶液から分離して〔A〕重合体の製造に供してもよい。
Moreover, when using a peroxide as a radical polymerization initiator, it is good also as a redox type initiator combining it and a reducing agent.
These radical polymerization initiators can be used alone or in admixture of two or more.
The copolymer [α] thus obtained may be used as it is in the production of the [A] polymer, or once separated from the solution and used in the production of the [A] polymer.
共重合体〔α〕のゲルパーミエーションクロマトグラフィ(GPC)によるポリスチレン換算重量平均分子量(以下、「Mw」という。)は、好ましくは2,000〜100,000、より好ましくは5,000〜50,000である。この場合、Mwが2,000未満であると、得られる被膜のアルカリ現像性、残膜率等が低下したり、またパターン形状、耐熱性等が損なわれたりするおそれがあり、一方100,000を超えると、解像度が低下したり、パターン形状が損なわれたりするおそれがある。
本発明における〔A〕重合体は、共重合体〔α〕に、不飽和イソシアナート化合物(7)を反応させることにより得られる。
The polystyrene equivalent weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer [α] by gel permeation chromatography (GPC) is preferably 2,000 to 100,000, more preferably 5,000 to 50, 000. In this case, if the Mw is less than 2,000, there is a risk that the alkali developability, the remaining film ratio, etc. of the resulting film may be reduced, and the pattern shape, heat resistance, etc. may be impaired. If it exceeds 1, the resolution may be reduced, or the pattern shape may be impaired.
The [A] polymer in the present invention can be obtained by reacting the unsaturated isocyanate compound (7) with the copolymer [α].
不飽和イソシアナート化合物(7)としては、例えば、
2−アクリロイルオキシエチルイソシアネート、3−アクリロイルオキシプロピルイソシアネート、4−アクリロイルオキシブチルイソシアネート、6−アクリロイルオキシヘキシルイソシアネート、8−アクリロイルオキシオクチルイソシアネート、10−アクリロイルオキシデシルイソシアネートの如きアクリル酸誘導体;
2−メタクリロイルオキシエチルイソシアネート、3−メタクリロイルオキシプロピルイソシアネート、4−メタクリロイルオキシブチルイソシアネート、6−メタクリロイルオキシヘキシルイソシアネート、8−メタクリロイルオキシオクチルイソシアネート、10−メタクリロイルオキシデシルイソシアネートの如きメタクリル酸誘導体
を挙げることができる。
Examples of the unsaturated isocyanate compound (7) include:
Acrylic acid derivatives such as 2-acryloyloxyethyl isocyanate, 3-acryloyloxypropyl isocyanate, 4-acryloyloxybutyl isocyanate, 6-acryloyloxyhexyl isocyanate, 8-acryloyloxyoctyl isocyanate, 10-acryloyloxydecyl isocyanate;
Mention may be made of methacrylic acid derivatives such as 2-methacryloyloxyethyl isocyanate, 3-methacryloyloxypropyl isocyanate, 4-methacryloyloxybutyl isocyanate, 6-methacryloyloxyhexyl isocyanate, 8-methacryloyloxyoctyl isocyanate, 10-methacryloyloxydecyl isocyanate. it can.
また、2−アクリロイルオキシエチルイソシアネートの市販品としては、商品名で、カレンズAOI(昭和電工(株)製)、2−メタクリロイルオキシエチルイソシアネートの市販品としては、商品名で、カレンズMOI(昭和電工(株)製)を挙げることができる。
これらの不飽和イソシアナート化合物(7)のうち、共重合体〔α〕との反応性の点から、2−アクリロイルオキシエチルイソシアネート、2−メタクリロイルオキシエチルイソシアネート等が好ましい。
〔A〕重合体において、不飽和イソシアナート化合物(7)は、単独でまたは2種以上を混合して使用することができる。
本発明において、共重合体〔α〕と不飽和イソシアナート化合物(7)との反応は、例えば、ジラウリン酸ジ−n−ブチルすず(IV)等の触媒やp−メトキシフェノール等の重合禁止剤を含む共重合体〔α〕溶液に、室温または加温下で、攪拌しつつ、不飽和イソシアナート化合物(7)を投入することによって実施することができる。
Moreover, as a commercial item of 2-acryloyloxyethyl isocyanate, it is a trade name, Karenz AOI (made by Showa Denko KK), and as a commercial item of 2-methacryloyloxyethyl isocyanate, it is a brand name, Karenz MOI (Showa Denko) (Made by Co., Ltd.).
Of these unsaturated isocyanate compounds (7), 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and the like are preferable from the viewpoint of reactivity with the copolymer [α].
[A] In the polymer, the unsaturated isocyanate compound (7) can be used alone or in admixture of two or more.
In the present invention, the reaction between the copolymer [α] and the unsaturated isocyanate compound (7) is carried out, for example, by a catalyst such as di-n-butyltin (IV) dilaurate or a polymerization inhibitor such as p-methoxyphenol. The unsaturated isocyanate compound (7) can be added to the copolymer [α] solution containing, while stirring at room temperature or under heating.
〔A〕重合体を製造する際の不飽和イソシアナート化合物(7)の使用量は、共重合体〔α〕中の(a2)水酸基含有不飽和化合物に対して、好ましくは0.1〜95重量%、さらに好ましくは10〜90重量%、特に好ましくは 25〜90重量%である。不飽和イソシアナート化合物(7)の使用量が0.1重量%未満では、感度ならびに弾性特性向上への効果が小さく、一方95重量%を超えると、未反応の不飽和イソシアナート化合物(7)が残存し、得られる重合体溶液や感放射線性樹脂組成物の保存安定性が低下する傾向がある。
〔A〕重合体は、カルボキシル基および/またはカルボン酸無水物基および重合性不飽和結合を有しており、アルカリ現像液に対して適度の溶解性を有するとともに、特別な硬化剤を併用しなくとも加熱により容易に硬化することができるものであり、〔A〕重合体を含有する感放射線性樹脂組成物は、現像する際に現像残りおよび膜減りを生じることなく、所定形状のスペーサーを容易に形成することができる。
本発明の感放射線性樹脂組成物は、〔A〕重合体を必須成分とするものであるが、さらに、下記する〔B〕重合性不飽和化合物および〔C〕感放射線性重合開始剤を含有する。
[A] The amount of the unsaturated isocyanate compound (7) used in producing the polymer is preferably 0.1 to 95 with respect to the (a2) hydroxyl group-containing unsaturated compound in the copolymer [α]. % By weight, more preferably 10 to 90% by weight, particularly preferably 25 to 90% by weight. When the amount of the unsaturated isocyanate compound (7) used is less than 0.1% by weight, the effect of improving the sensitivity and the elastic properties is small. On the other hand, when it exceeds 95% by weight, the unreacted unsaturated isocyanate compound (7) is used. Remain and the storage stability of the resulting polymer solution and radiation-sensitive resin composition tends to decrease.
[A] The polymer has a carboxyl group and / or a carboxylic anhydride group and a polymerizable unsaturated bond, has an appropriate solubility in an alkali developer, and is used in combination with a special curing agent. Can be easily cured by heating, and [A] the radiation-sensitive resin composition containing the polymer has a predetermined-shaped spacer without developing residue and film loss during development. It can be formed easily.
The radiation-sensitive resin composition of the present invention comprises [A] a polymer as an essential component, and further contains the following [B] polymerizable unsaturated compound and [C] a radiation-sensitive polymerization initiator. To do.
−〔B〕重合性不飽和化合物−
〔B〕重合性不飽和化合物は、感放射線性重合開始剤の存在下における放射線の露光により重合する不飽和化合物からなる。
このような〔B〕重合性不飽和化合物としては、特に限定されるものではないが、例えば、単官能、2官能または3官能以上の(メタ)アクリル酸エステルが、共重合性が良好であり、得られるスペーサーの強度が向上する点から好ましい。
-[B] polymerizable unsaturated compound-
[B] The polymerizable unsaturated compound comprises an unsaturated compound that is polymerized by exposure to radiation in the presence of a radiation-sensitive polymerization initiator.
Such a [B] polymerizable unsaturated compound is not particularly limited. For example, a monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid ester has good copolymerizability. From the viewpoint of improving the strength of the obtained spacer.
前記単官能(メタ)アクリル酸エステルとしては、例えば、2−ヒドロキシエチルアクリレート、2−ヒドロキシエチルメタクリレート、ジエチレングリコールモノエチルエーテルアクリレート、ジエチレングリコールモノエチルエーテルメタクリレート、イソボロニルアクリレート、イソボロニルメタクリレート、3−メトキシブチルアクリレート、3−メトキシブチルメタクリレート、(2−アクリロイルオキシエチル)(2−ヒドロキシプロピル)フタレート、(2−メタクリロイルオキシエチル)(2−ヒドロキシプロピル)フタレート、ω−カルボキシ−ポリカプロラクトンモノアクリレート等を挙げることができる。また市販品として、商品名で、例えば、アロニックスM−101、同M−111、同M−114(以上、東亜合成(株)製);KAYARAD TC−110S、同 TC−120S(以上、日本化薬(株)製);ビスコート158、同2311(以上、大阪有機化学工業(株)製)、アロニックスM−5300(東亜合成株 製)等を挙げることができる。 Examples of the monofunctional (meth) acrylic acid ester include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, isobornyl acrylate, isobornyl methacrylate, 3- Methoxybutyl acrylate, 3-methoxybutyl methacrylate, (2-acryloyloxyethyl) (2-hydroxypropyl) phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, ω-carboxy-polycaprolactone monoacrylate, etc. Can be mentioned. As commercial products, for example, Aronix M-101, M-111, M-114 (above, manufactured by Toa Gosei Co., Ltd.); KAYARAD TC-110S, TC-120S (above, Nippon Kayaku) Medicine Co., Ltd.); Biscote 158, 2311 (above, Osaka Organic Chemical Industry Co., Ltd.), Aronix M-5300 (Toagosei Co., Ltd.), and the like.
また、前記2官能(メタ)アクリル酸エステルとしては、例えば、エチレングリコールジアクリレート、エチレングリコールジメタクリレート、ジエチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、テトラエチレングリコールジアクリレート、テトラエチレングリコールジメタクリレート、1,6−ヘキサンジオールジアクリレート、1,6−ヘキサンジオールジメタクリレート、1,9−ノナンジオールジアクリレート、1,9−ノナンジオールジメタクリレート、ビスフェノキシエタノールフルオレンジアクリレート、ビスフェノキシエタノールフルオレンジメタクリレート等を挙げることがでる。また市販品として、商品名で、例えば、アロニックスM−210、同M−240、同M−6200(以上、東亜合成(株)製)、KAYARAD HDDA、同 HX−220、同 R−604(以上、日本化薬(株)製)、ビスコート260、同312、同335HP(以上、大阪有機化学工業(株)製)等を挙げることができる。 Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6- Examples include hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange methacrylate. Also, as commercial products, for example, Aronix M-210, M-240, M-6200 (above, manufactured by Toa Gosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (or more). , Nippon Kayaku Co., Ltd.), Biscoat 260, 312 and 335HP (Osaka Organic Chemical Co., Ltd.).
さらに、前記3官能以上の(メタ)アクリル酸エステルとしては、例えば、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールテトラメタクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールペンタメタクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヘキサメタクリレート、トリ(2−アクリロイルオキシエチル)フォスフェート、トリ(2−メタクリロイルオキシエチル)フォスフェートや、9官能以上の(メタ)アクリル酸エステル類として、直鎖アルキレン基および脂環式構造を有し、かつ2個以上のイソシアネート基を有する化合物と、分子内に1個以上の水酸基を有し、かつ3個、4個あるいは5個のアクリロイルオキシ基および/またはメタクリロイルオキシ基を有する化合物とを反応させて得られる多官能ウレタンアクリレート系化合物等を挙げることができる。 Furthermore, as the trifunctional or higher functional (meth) acrylic acid ester, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, Dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, and more than 9 functional groups (Meth) acrylic acid esters of linear alkylene groups and alicyclic And a compound having two or more isocyanate groups, one or more hydroxyl groups in the molecule, and three, four or five acryloyloxy groups and / or methacryloyloxy groups The polyfunctional urethane acrylate type compound etc. which are obtained by making it react with a compound can be mentioned.
3官能以上の(メタ)アクリル酸エステルの市販品としては、商品名で、例えば、アロニックスM−309、同M−400、同M−405、同M−450、同M−7100、同M−8030、同M−8060、同TO−1450(以上、東亜合成(株)製)、KAYARAD TMPTA、同 DPHA、同 DPCA−20、同 DPCA−30、同 DPCA−60、同 DPCA−120(以上、日本化薬(株)製)、ビスコート295、同300、同360、同GPT、同3PA、同400(以上、大阪有機化学工業(株)製)や、多官能ウレタンアクリレート系化合物を含有する市販品として、ニューフロンティア R−1150(第一工業製薬(株)製)、KAYARAD DPHA−40H(日本化薬(株)製)、アロニックスTO−1382(東亜合成)等を挙げることができる。 Commercially available products of trifunctional or higher functional (meth) acrylic acid esters are trade names, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M- 8030, M-8060, TO-1450 (above, manufactured by Toa Gosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-60, (above, Nippon Kayaku Co., Ltd.), Biscoat 295, 300, 360, GPT, 3PA, 400 (above, Osaka Organic Chemical Industry Co., Ltd.) and commercial products containing polyfunctional urethane acrylate compounds New Frontier R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD DPHA-40H (Nippon Kayaku Co., Ltd.), Aronix TO -1382 (Toa Gosei) and the like.
これらの単官能、2官能または3官能以上の(メタ)アクリル酸エステルのうち、3官能以上の(メタ)アクリル酸エステルがさらに好ましく、特に、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレートや、多官能ウレタンアクリレート系化合物を含有する市販品等が好ましい。
前記単官能、2官能または3官能以上の(メタ)アクリル酸エステルは、単独でまたは2種以上を混合して使用することができる。
Among these monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid esters, trifunctional or higher functional (meth) acrylic acid esters are more preferable, and in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol. Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and commercial products containing polyfunctional urethane acrylate compounds are preferred.
The monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid esters can be used alone or in admixture of two or more.
本発明の感放射線性樹脂組成物において、〔B〕重合性不飽和化合物の使用量は、〔A〕重合体100重量部に対して、好ましくは1〜200重量部、さらに好ましくは3〜150重量部である。〔B〕重合性不飽和化合物の使用量が1重量部未満では、現像時に現像残りが発生するおそれがあり、一方200重量部を超えると、得られるスペーサーの密着性が低下する傾向がある。 In the radiation-sensitive resin composition of the present invention, the amount of the [B] polymerizable unsaturated compound used is preferably 1 to 200 parts by weight, more preferably 3 to 150 parts per 100 parts by weight of the [A] polymer. Parts by weight. [B] If the amount of the polymerizable unsaturated compound used is less than 1 part by weight, there may be a residual image during development. On the other hand, if it exceeds 200 parts by weight, the adhesion of the resulting spacer tends to decrease.
−〔C〕感放射線性重合開始剤−
〔C〕感放射線性重合開始剤は、可視光線、紫外線、遠紫外線、荷電粒子線、X線等の放射線の露光により、〔B〕重合性不飽和化合物の重合を開始しうる活性種を発生する成分からなる。
このような〔C〕感放射線性重合開始剤としては、O−アシルオキシム系化合物、アセトフェノン系化合物、ビイミダゾール系化合物、ベンゾイン系化合物、ベンゾフェノン系化合物、α−ジケトン系化合物、多核キノン系化合物、キサントン系化合物、ホスフィン系化合物、トリアジン系化合物等を挙げることができる。
-[C] Radiation sensitive polymerization initiator-
[C] Radiation sensitive polymerization initiator generates [B] active species capable of initiating polymerization of polymerizable unsaturated compounds upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, charged particle beam, and X-ray. It consists of the component to do.
Examples of such [C] radiation sensitive polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, Examples include xanthone compounds, phosphine compounds, triazine compounds, and the like.
O−アシルオキシム系化合物としては、9.H.−カルバゾール系のO−アシルオキシム型重合開始剤が好ましい。例えば、1−〔9−エチル−6−ベンゾイル−9.H.−カルバゾール−3−イル〕−ノナン−1,2−ノナン−2−オキシム−O−ベンゾアート、1−〔9−エチル−6−ベンゾイル−9.H.−カルバゾール−3−イル〕−ノナン−1,2−ノナン−2−オキシム−O−アセタート、1−〔9−エチル−6−ベンゾイル−9.H.−カルバゾール−3−イル〕−ペンタン−1,2−ペンタン−2−オキシム−O−アセタート、1−〔9−エチル−6−ベンゾイル−9.H.−カルバゾール−3−イル〕−オクタン−1−オンオキシム−O−アセタート、1−〔9−エチル−6−(2−メチルベンゾイル)−9.H.−カルバゾール−3−イル〕−エタン−1−オンオキシム−O−ベンゾアート、1−〔9−エチル−6−(2−メチルベンゾイル)−9.H.−カルバゾール−3−イル〕−エタン−1−オンオキシム−O−アセタート、1−〔9−エチル−6−(1,3,5−トリメチルベンゾイル)−9.H.−カルバゾール−3−イル〕−エタン−1−オンオキシム−O−ベンゾアート、1−〔9−ブチル−6−(2−エチルベンゾイル)−9.H.−カルバゾール−3−イル〕−エタン−1−オンオキシム−O−ベンゾアート等を挙げることができる。 As the O-acyloxime compound, 9. H. A carbazole-based O-acyloxime polymerization initiator is preferred. For example, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-benzoate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -pentane-1,2-pentane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate and the like.
これらのO−アシルオキシム化合物のうち、特に1−〔9−エチル−6−(2−メチルベンゾイル)−9.H.−カルバゾール−3−イル〕−エタン−1−オンオキシム−O−アセタートが好ましい。
前記O−アシルオキシム化合物は、単独でまたは2種以上を混合して使用することができる。本発明において、O−アシルオキシム化合物を用いることにより、1,500J/m2以下の露光量でも十分な感度、密着性を有したスペーサーを得ることを可能にする。
前記アセトフェノン系化合物としては、例えば、α−ヒドロキシケトン系化合物、α−アミノケトン系化合物等を挙げることができる。
Of these O-acyloxime compounds, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate is preferred.
The O-acyloxime compounds can be used alone or in admixture of two or more. In the present invention, by using an O-acyloxime compound, it is possible to obtain a spacer having sufficient sensitivity and adhesion even with an exposure amount of 1,500 J / m 2 or less.
Examples of the acetophenone compound include an α-hydroxyketone compound and an α-aminoketone compound.
前記α−ヒドロキシケトン系化合物としては、例えば、1−フェニル−2−ヒドロキシ−2−メチルプロパン−1−オン、1−(4−i−プロピルフェニル)−2−ヒドロキシ−2−メチルプロパン−1−オン、4−(2−ヒドロキシエトキシ)フェニル−(2−ヒドロキシ−2−プロピル)ケトン、1−ヒドロキシシクロヘキシルフェニルケトン等を挙げることができる。また前記α−アミノケトン系化合物としては、例えば、2−メチル−1−(4−メチルチオフェニル)−2−モルホリノプロパン−1−オン、2−ベンジル−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタン−1−オン、2−(4−メチルベンゾイル)−2−(ジメチルアミノ)−1−(4−モルフォリノフェニル)−ブタン−1−オン等を挙げることができ、これら以外の化合物として、例えば、2,2−ジメトキシアセトフェノン、2,2−ジエトキシアセトフェノン、2,2−ジメトキシ−2−フェニルアセトフェノン等を挙げることができる。 Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1 -On, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone and the like can be mentioned. Examples of the α-aminoketone compound include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). ) -Butan-1-one, 2- (4-methylbenzoyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one, etc., and other compounds Examples thereof include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and the like.
これらのアセトフェノン系化合物のうち、特に、2−メチル−1−(4−メチルチオフェニル)−2−モルホリノプロパン−1−オン、2−(4−メチルベンゾイル)−2−(ジメチルアミノ)−1−(4−モルフォリノフェニル)−ブタン−1−オンが好ましい。
本発明においては、アセトフェノン系化合物を併用することにより、感度、スペーサー形状や圧縮強度をさらに改善することが可能となる。
Among these acetophenone compounds, in particular, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- (4-methylbenzoyl) -2- (dimethylamino) -1- (4-Morpholinophenyl) -butan-1-one is preferred.
In the present invention, the sensitivity, spacer shape and compressive strength can be further improved by using an acetophenone compound in combination.
また、前記ビイミダゾール系化合物としては、例えば、2,2’−ビス(2−クロロフェニル)−4,4’,5,5’−テトラキス(4−エトキシカルボニルフェニル)−1,2’−ビイミダゾール、2,2’−ビス(2−ブロモフェニル)−4,4’,5,5’−テトラキス(4−エトキシカルボニルフェニル)−1,2’−ビイミダゾール、2,2’−ビス(2−クロロフェニル)−4,4’,5,5’−テトラフェニル−1,2’−ビイミダゾール、2,2’−ビス(2,4−ジクロロフェニル)−4,4’,5,5’−テトラフェニル−1,2’−ビイミダゾール、2,2’−ビス(2,4,6−トリクロロフェニル)−4,4’,5,5’−テトラフェニル−1,2’−ビイミダゾール、2,2’−ビス(2−ブロモフェニル)−4,4’,5,5’−テトラフェニル−1,2’−ビイミダゾール、2,2’−ビス(2,4−ジブロモフェニル)−4,4’,5,5’−テトラフェニル−1,2’−ビイミダゾール、2,2’−ビス(2,4,6−トリブロモフェニル)−4,4’,5,5’−テトラフェニル−1,2’−ビイミダゾール等を挙げることができる。 Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole. 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2- Chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl -1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2 '-Bis (2-bromophenyl)- , 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like can be mentioned. .
これらのビイミダゾール系化合物のうち、2,2’−ビス(2−クロロフェニル)−4,4’,5,5’−テトラフェニル−1,2’−ビイミダゾール、2,2’−ビス(2,4−ジクロロフェニル)−4,4’,5,5’−テトラフェニル−1,2’−ビイミダゾール、2,2’−ビス(2,4,6−トリクロロフェニル)−4,4’,5,5’−テトラフェニル−1,2’−ビイミダゾール等が好ましく、特に2,2’−ビス(2,4−ジクロロフェニル)−4,4’,5,5’−テトラフェニル−1,2’−ビイミダゾールが好ましい。 Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole and the like are preferable, and in particular, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′. -Biimidazole is preferred.
本発明においては、ビイミダゾール系化合物を併用することにより、感度、解像度や密着性をさらに改善することが可能となる。
また、ビイミダゾール系化合物を併用する場合、それを増感するため、ジアルキルアミノ基を有する脂肪族系または芳香族系の化合物(以下、「アミノ系増感剤」という。)を添加することができる。
アミノ系増感剤としては、例えば、N−メチルジエタノールアミン、4,4’−ビス(ジメチルアミノ)ベンゾフェノン、4,4’−ビス(ジエチルアミノ)ベンゾフェノン、p−ジメチルアミノ安息香酸エチル、p−ジメチルアミノ安息香酸i−アミル等を挙げることができる。
これらのアミノ系増感剤のうち、特に4,4’−ビス(ジエチルアミノ)ベンゾフェノンが好ましい。
前記アミノ系増感剤は、単独でまたは2種以上を混合して使用することができる。
In the present invention, it is possible to further improve sensitivity, resolution and adhesion by using a biimidazole compound in combination.
When a biimidazole compound is used in combination, an aliphatic or aromatic compound having a dialkylamino group (hereinafter referred to as “amino sensitizer”) may be added to sensitize it. it can.
Examples of amino sensitizers include N-methyldiethanolamine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, ethyl p-dimethylaminobenzoate, p-dimethylamino. Examples include i-amyl benzoate.
Of these amino sensitizers, 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amino sensitizers can be used alone or in admixture of two or more.
さらに、ビイミダゾール系化合物とアミノ系増感剤とを併用する場合、水素供与化合物として、チオール系化合物を添加することができる。ビイミダゾール系化合物は前記アミノ系増感剤によって増感されて開裂し、イミダゾールラジカルを発生するが、そのままでは高い重合開始能が発現されず、得られるスペーサーが逆テーパ形状のような好ましくない形状となる場合が多い。しかし、ビイミダゾール系化合物とアミノ系増感剤とが共存する系に、チオール系化合物を添加することにより、イミダゾールラジカルにチオール系化合物から水素ラジカルが供与される結果、イミダゾールラジカルが中性のイミダゾールに変換されるとともに、重合開始能の高い硫黄ラジカルを有する成分が発生し、それによりスペーサーの形状をより好ましい順テーパ状にすることができる。 Further, when a biimidazole compound and an amino sensitizer are used in combination, a thiol compound can be added as a hydrogen donor compound. The biimidazole compound is sensitized and cleaved by the amino sensitizer to generate an imidazole radical, but as it is, high polymerization initiating ability is not expressed, and the resulting spacer has an unfavorable shape such as a reverse taper shape. In many cases. However, by adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, hydrogen radicals are donated from the thiol compound to the imidazole radical, so that the imidazole radical is neutral imidazole. In addition, a component having a sulfur radical having a high polymerization initiating ability is generated, whereby the spacer can have a more preferable forward taper shape.
前記チオール系化合物としては、例えば、2−メルカプトベンゾチアゾール、2−メルカプトベンゾオキサゾール、2−メルカプトベンゾイミダゾール、2−メルカプト−5−メトキシベンゾチアゾール、2−メルカプト−5−メトキシベンゾイミダゾール等の芳香族系化合物;3−メルカプトプロピオン酸、3−メルカプトプロピオン酸メチル、3−メルカプトプロピオン酸エチル、3−メルカプトプロピオン酸オクチルの如き脂肪族系モノチオール;3,6−ジオキサ−1,8−オクタンジチオール、ペンタエリストールテトラ(メルカプトアセテート)、ペンタエリストールテトラ(3−メルカプトプロピオネート)の如き2官能以上の脂肪族系チオールを挙げることができる。
これらのチオール系化合物のうち、特に2−メルカプトベンゾチアゾールが好ましい。
Examples of the thiol compound include aromatics such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole. Compounds: aliphatic monothiols such as 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate; 3,6-dioxa-1,8-octanedithiol, Bifunctional or higher aliphatic thiols such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate) can be exemplified.
Of these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.
本発明の感放射線性樹脂組成物において、他の感放射線性重合開始剤の使用割合は、全感放射線性重合開始剤100重量部に対して、好ましくは100重量部以下、さらに好ましくは80重量部以下、特に好ましくは60重量部以下である。この場合、他の感放射線性重合開始剤の使用割合が100重量部を超えると、本発明の所期の効果が損なわれるおそれがある。
また、ビイミダゾール系化合物とアミノ系増感剤とを併用する場合、アミノ系増感剤の添加量は、ビイミダゾール系化合物100重量部に対して、好ましくは0.1〜50重量部、さらに好ましくは1〜20重量部である。アミノ系増感剤の添加量が0.1重量部未満では、感度、解像度や密着性の改善効果が低下する傾向があり、一方50重量部を超えると、得られるスペーサーの形状が損なわれる傾向がある。
In the radiation-sensitive resin composition of the present invention, the use ratio of the other radiation-sensitive polymerization initiator is preferably 100 parts by weight or less, more preferably 80 parts by weight with respect to 100 parts by weight of the total radiation-sensitive polymerization initiator. Part or less, particularly preferably 60 parts by weight or less. In this case, if the use ratio of the other radiation-sensitive polymerization initiator exceeds 100 parts by weight, the intended effect of the present invention may be impaired.
Further, when the biimidazole compound and the amino sensitizer are used in combination, the addition amount of the amino sensitizer is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the biimidazole compound. Preferably it is 1-20 weight part. If the addition amount of the amino sensitizer is less than 0.1 parts by weight, the effect of improving the sensitivity, resolution and adhesion tends to be reduced. On the other hand, if it exceeds 50 parts by weight, the shape of the resulting spacer tends to be impaired. There is.
また、ビイミダゾール系化合物とアミノ系増感剤とを併用する場合、チオール系化合物の添加量は、ビイミダゾール系化合物100重量部に対して、好ましくは0.1〜50重量部、さらに好ましくは1〜20重量部である。チオール系化合物の添加量が0.1重量部未満では、スペーサーの形状の改善効果が低下したり、膜減りを生じやすくなる傾向があり、一方50重量部を超えると、得られるスペーサーの形状が損なわれる傾向がある。 In addition, when a biimidazole compound and an amino sensitizer are used in combination, the addition amount of the thiol compound is preferably 0.1 to 50 parts by weight, more preferably 100 parts by weight of the biimidazole compound. 1 to 20 parts by weight. If the amount of the thiol compound added is less than 0.1 parts by weight, the effect of improving the spacer shape tends to be reduced or the film tends to be reduced. There is a tendency to be damaged.
−添加剤−
本発明の感放射線性樹脂組成物には、本発明の所期の効果を損なわない範囲内で、必要に応じて、前記成分以外にも、界面活性剤、接着助剤、保存安定剤、耐熱性向上剤等の添加剤を配合することもできる。
前記界面活性剤は、塗布性を改善する作用を有する成分であり、フッ素系界面活性剤およびシリコーン系界面活性剤が好ましい。
前記フッ素系界面活性剤としては、末端、主鎖および側鎖の少なくともいずれかの部位にフルオロアルキル基あるいはフルオロアルキレン基を有する化合物が好ましく、その具体例としては、1,1,2,2−テトラフロロオクチル(1,1,2,2−テトラフルオロ−n−プロピル)エーテル、1,1,2,2−テトラフルオロ−n−オクチル(n−ヘキシル)エーテル、オクタエチレングリコールジ(1,1,2,2−テトラフルオロ−n−ブチル)エーテル、ヘキサエチレングリコール(1,1,2,2,3,3−ヘキサフルオロ−n−ペンチル)エーテル、オクタプロピレングリコールジ(1,1,2,2−テトラフルオロ−n−ブチル)エーテル、ヘキサプロピレングリコールジ(1,1,2,2,3,3−ヘキサフルオロ−n−ペンチル)エーテル、1,1,2,2,3,3−ヘキサフルオロ−n−デカン、1,1,2,2,8,8,9,9,10,10−デカフルオロ−n−ドデカン、パーフルオロ−n−ドデシルスルホン酸ナトリウムや、フルオロアルキルベンゼンスルホン酸ナトリウム、フルオロアルキルホスホン酸ナトリウム、フルオロアルキルカルボン酸ナトリウム、フルオロアルキルポリオキシエチレンエーテル、ジグリセリンテトラキス(フルオロアルキルポリオキシエチレンエーテル)、フルオロアルキルアンモニウムヨージド、フルオロアルキルベタイン、フルオロアルキルポリオキシエチレンエーテル、パーフルオロアルキルポリオキシエタノール、パーフルオロアルキルアルコキシレート、フッ素系アルキルエステル等を挙げることができる。
-Additives-
In the radiation-sensitive resin composition of the present invention, a surfactant, an adhesion assistant, a storage stabilizer, a heat resistance, in addition to the above components, if necessary, within a range that does not impair the intended effect of the present invention. Additives such as property improvers can also be blended.
The said surfactant is a component which has the effect | action which improves coating property, and a fluorine-type surfactant and a silicone type surfactant are preferable.
The fluorine-based surfactant is preferably a compound having a fluoroalkyl group or a fluoroalkylene group at at least one of the terminal, main chain and side chain, and specific examples thereof include 1,1,2,2- Tetrafluorooctyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, octaethylene glycol di (1,1 , 2,2-tetrafluoro-n-butyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2, 2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro-n- Nethyl) ether, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane, Sodium perfluoro-n-dodecyl sulfonate, sodium fluoroalkylbenzene sulfonate, sodium fluoroalkyl phosphonate, sodium fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl Ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, fluorine alkyl ester and the like can be mentioned.
また、フッ素系界面活性剤の市販品としては、商品名で、例えば、BM−1000、同−1100(以上、BM CHEMIE社製)、メガファックF142D、同F172、同F173、同F183、同F178、同F191、同F471、同F476(以上、大日本インキ化学工業(株)製)、フロラードFC 170C、同FC−171、同FC−430、同FC−431(以上、住友スリーエム(株)製)、サーフロンS−112、同S−113、同S−131、同S−141、同S−145、同S−382、同SC−101、同SC−102、同SC−103、同SC−104、同SC−105、同SC−106(以上、旭硝子(株)製)、エフトップEF301、同EF303、同EF352(以上、新秋田化成(株)製)、フタージェントFT−100、同FT−110、同FT−140A、同FT−150、同FT−250、同FT−251、同FTX−251、同FTX−218、同FT−300、同FT−310、同FT−400S(以上、(株)ネオス製)等を挙げることができる。 Moreover, as a commercial item of a fluorine-type surfactant, it is a brand name, for example, BM-1000, the same -1100 (above, the product made from BM CHEMIE), MegaFuck F142D, the same F172, the same F173, the same F183, the same F178. F191, F471, F476 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC 170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M Limited) ), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-103 104, SC-105, SC-106 (above, manufactured by Asahi Glass Co., Ltd.), F-top EF301, EF303, EF352 (above, manufactured by Shin-Akita Kasei Co., Ltd.), lid Agent FT-100, FT-110, FT-140A, FT-150, FT-250, FT-251, FTX-251, FTX-218, FT-300, FT-310, FT-400S (above, manufactured by Neos Co., Ltd.) and the like.
前記シリコーン系界面活性剤としては、市販品として、商品名で、例えば、トーレシリコーンDC3PA、同DC7PA、同SH11PA、同SH21PA、同SH28PA、同SH29PA、同SH30PA、同SH−190、同SH−193、同SZ−6032、同SF−8428、同DC−57、同DC−190(以上、東レ・ダウコーニング・シリコーン(株)製)、TSF−4440、同−4300、同−4445、同−4446、同−4460、同−4452(以上、GE東芝シリコーン(株)製)等を挙げることができる。 The silicone-based surfactant is a commercially available product, for example, Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193. SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, -4300, -4445, -4446 -4460, -4442 (above, manufactured by GE Toshiba Silicone Co., Ltd.), and the like.
さらに、前記以外の界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテルの如きポリオキシエチレンアルキルエーテル;ポリオキシエチレンn−オクチルフェニルエーテル、ポリオキシエチレンn−ノニルフェニルエーテルの如きポリオキシエチレンアリールエーテル;ポリオキシエチレンジラウレート、ポリオキシエチレンジステアレートの如きポリオキシエチレンジアルキルエステル等のノニオン系界面活性剤や、市販品として、商品名で、例えば、KP341(信越化学工業(株)製)、ポリフローNo.57、同No.95(共栄社化学(株)製)等を挙げることができる。
前記界面活性剤は、単独でまたは2種以上を混合して使用することができる。
Furthermore, as surfactants other than the above, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as n-nonylphenyl ether; nonionic surfactants such as polyoxyethylene dilaurate and polyoxyethylene dialkyl esters such as polyoxyethylene distearate, and commercially available products under the trade name, for example, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 57, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).
The surfactants can be used alone or in admixture of two or more.
界面活性剤の配合量は、〔A〕重合体100重量部に対して、好ましくは5重量部以下、さらに好ましくは2重量部以下である。界面活性剤の配合量が5重量部を超えると、塗布時に膜荒れを生じやすくなる傾向がある。
前記接着助剤は、スペーサーと基体との密着性をさらに改善する作用を有する成分であり、官能性シランカップリング剤が好ましい。
The blending amount of the surfactant is preferably 5 parts by weight or less, more preferably 2 parts by weight or less with respect to 100 parts by weight of the polymer [A]. When the compounding amount of the surfactant exceeds 5 parts by weight, there is a tendency that film roughening tends to occur during coating.
The adhesion assistant is a component having an effect of further improving the adhesion between the spacer and the substrate, and a functional silane coupling agent is preferable.
前記官能性シランカップリング剤としては、例えば、カルボキシル基、メタクリロイル基、ビニル基、イソシアネート基、エポキシ基の如き反応性官能基を有する化合物を挙げることができる。より具体的には、トリメトキシシリル安息香酸、γ−メタクリロイルオキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、ビニルトリメトキシシラン、γ−イソシアナートプロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン等を挙げることができる。
これらの接着助剤は、単独でまたは2種以上を混合して使用することができる。
接着助剤の配合量は、〔A〕重合体100重量部に対して、好ましくは20重量部以下、さらに好ましくは10重量部以下である。接着助剤の配合量が20重量部を超えると、現像残りが生じやすくなる傾向がある。
Examples of the functional silane coupling agent include compounds having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, and an epoxy group. More specifically, trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.
These adhesion assistants can be used alone or in admixture of two or more.
The blending amount of the adhesion assistant is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, with respect to 100 parts by weight of the [A] polymer. When the blending amount of the adhesion assistant exceeds 20 parts by weight, there is a tendency that a development residue tends to occur.
前記保存安定剤としては、例えば、硫黄、キノン類、ヒドロキノン類、ポリオキシ化合物、アミン、ニトロニトロソ化合物等を挙げることができ、より具体的には、4−メトキシフェノール、N−ニトロソ−N−フェニルヒドロキシルアミンアルミニウム等を挙げることができる。
これらの保存安定剤は、単独でまたは2種以上を混合して使用することができる。
保存安定剤の配合量は、〔A〕重合体100重量部に対して、好ましくは3重量部以下、さらに好ましくは0.001〜0.5重量部である。保存安定剤の配合量が3重量部を超えると、感度が低下してパターン形状が損なわれるおそれがある。
前記耐熱性向上剤としては、例えば、N−(アルコキシメチル)グリコールウリル化合物、N−(アルコキシメチル)メラミン化合物挙げることができる。
Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N-phenyl. Examples include hydroxylamine aluminum.
These storage stabilizers can be used alone or in admixture of two or more.
The blending amount of the storage stabilizer is preferably 3 parts by weight or less, more preferably 0.001 to 0.5 parts by weight, with respect to 100 parts by weight of the [A] polymer. When the amount of the storage stabilizer exceeds 3 parts by weight, the sensitivity may be lowered and the pattern shape may be impaired.
Examples of the heat resistance improver include N- (alkoxymethyl) glycoluril compounds and N- (alkoxymethyl) melamine compounds.
前記N−(アルコキシメチル)グリコールウリル化合物としては、例えば、N,N,N,N−テトラ(メトキシメチル)グリコールウリル、N,N,N,N−テトラ(エトキシメチル)グリコールウリル、N,N,N,N−テトラ(n−プロポキシメチル)グリコールウリル、N,N,N,N−テトラ(i−プロポキシメチル)グリコールウリル、N,N,N,N−テトラ(n−ブトキシメチル)グリコールウリル、N,N,N,N−テトラ(t−ブトキシメチル)グリコールウリル等を挙げることができる。 Examples of the N- (alkoxymethyl) glycoluril compound include N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl) glycoluril, N, N , N, N-tetra (n-propoxymethyl) glycoluril, N, N, N, N-tetra (i-propoxymethyl) glycoluril, N, N, N, N-tetra (n-butoxymethyl) glycoluril , N, N, N, N-tetra (t-butoxymethyl) glycoluril and the like.
これらのN−(アルコキシメチル)グリコールウリル化合物のうち、特にN,N,N,N−テトラ(メトキシメチル)グリコールウリルが好ましい。
また、前記N−(アルコキシメチル)メラミン化合物としては、例えば、N,N,N,N,N,N−ヘキサ(メトキシメチル)メラミン、N,N,N,N,N,N−ヘキサ(エトキシメチル)メラミン、N,N,N,N,N,N−ヘキサ(n−プロポキシメチル)メラミン、N,N,N,N,N,N−ヘキサ(i−プロポキシメチル)メラミン、N,N,N,N,N,N−ヘキサ(n−ブトキシメチル)メラミン、N,N,N,N,N,N−ヘキサ(t−ブトキシメチル)メラミン等を挙げることができる。
Of these N- (alkoxymethyl) glycoluril compounds, N, N, N, N-tetra (methoxymethyl) glycoluril is particularly preferred.
Examples of the N- (alkoxymethyl) melamine compound include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N, N-hexa (ethoxy). Methyl) melamine, N, N, N, N, N, N-hexa (n-propoxymethyl) melamine, N, N, N, N, N, N-hexa (i-propoxymethyl) melamine, N, N, Examples thereof include N, N, N, N-hexa (n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) melamine and the like.
これらのN−(アルコキシメチル)メラミン化合物のうち、特にN,N,N,N,N,N−ヘキサ(メトキシメチル)メラミンが好ましい。その市販品としては、商品名で、例えば、ニカラックN−2702、同MW−30M(以上 三和ケミカル(株)製)等を挙げることができる。
前記耐熱性向上剤は、単独でまたは2種以上を混合して使用することができる。
Of these N- (alkoxymethyl) melamine compounds, N, N, N, N, N, N-hexa (methoxymethyl) melamine is particularly preferable. Examples of the commercially available products include Nicarak N-2702 and MW-30M (manufactured by Sanwa Chemical Co., Ltd.).
The heat resistance improvers can be used alone or in admixture of two or more.
耐熱性向上剤の配合量は、〔A〕重合体100重量部に対して、好ましくは30重量部以下、さらに好ましくは20重量部以下である。耐熱性向上剤の配合量が30重量部を超えると、感放射線性樹脂組成物の保存安定性が低下する傾向がある。
本発明の感放射線性樹脂組成物は、適当な溶剤に溶解した組成物溶液として使用に供することが好ましい。
The blending amount of the heat resistance improver is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, with respect to 100 parts by weight of the [A] polymer. When the blending amount of the heat resistance improver exceeds 30 parts by weight, the storage stability of the radiation sensitive resin composition tends to be lowered.
The radiation-sensitive resin composition of the present invention is preferably used as a composition solution dissolved in an appropriate solvent.
前記溶剤としては、感放射線性樹脂組成物を構成する各成分を均一に溶解し、各成分と反応せず、適度の揮発性を有するものが用いられる。各成分の溶解能、各成分との反応性および塗膜形成の容易性の観点から、アルコール、エチレングリコールモノアルキルエーテルアセテート、ジエチレングリコールモノアルキルエーテルアセテート、ジエチレングリコールアルキルエーテル、プロピレングリコールモノアルキルエーテルアセテート、ジプロピレングリコールアルキルエーテル、アルコキシプロピオン酸アルキル、酢酸エステル等が好ましく、特に、ベンジルアルコール、2−フェニルエタノール、3−フェニル−1−プロパノール、エチレングリコールモノ−n−ブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールエチルメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、ジプロピレングリコールジメチルエーテル、酢酸3−メトキシブチル、酢酸2−メトキシエチル等が好ましい。
前記溶剤は、単独でまたは2種以上を混合して使用することができる。
As the solvent, a solvent that dissolves each component constituting the radiation-sensitive resin composition uniformly, does not react with each component, and has appropriate volatility is used. From the viewpoints of solubility of each component, reactivity with each component, and ease of film formation, alcohol, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, Propylene glycol alkyl ether, alkoxypropionate alkyl, acetic acid ester and the like are preferable, and in particular, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether Le, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol dimethyl ether, 3-methoxybutyl acetate, 2-methoxyethyl acetate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.
本発明においては、さらに、前記溶剤と共に、高沸点溶剤を併用することもできる。
前記高沸点溶剤としては、例えば、N−メチルホルムアミド、N,N−ジメチルホルムアミド、N−メチルホルムアニリド、N−メチルアセトアミド、N,N−ジメチルアセトアミド、N−メチルピロリドン、ジメチルスルホキシド、ベンジルエチルエーテル、ジ−n−ヘキシルエーテル、アセトニルアセトン、イソホロン、カプロン酸、カプリル酸、1−オクタノール、1−ノナノール、ベンジルアルコール、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、マレイン酸ジエチル、γ−ブチロラクトン、炭酸エチレン、炭酸プロピレン、エチレングリコールモノフェニルエーテルアセテート等を挙げることができる。
In the present invention, a high boiling point solvent may be used in combination with the solvent.
Examples of the high boiling point solvent include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, Examples thereof include ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate.
これらの高沸点溶剤は、単独でまたは2種以上を混合して使用することができる。
また、前記のように調製された組成物溶液は、孔径0.5μm程度のミリポアフィルタ等を用いてろ過して、使用に供することもできる。
本発明の感放射線性樹脂組成物は、特に、液晶表示素子用スペーサーの形成に極めて好適に使用することができる。
These high boiling point solvents can be used alone or in admixture of two or more.
In addition, the composition solution prepared as described above can be filtered for use with a Millipore filter or the like having a pore diameter of about 0.5 μm.
Especially the radiation sensitive resin composition of this invention can be used very suitably for formation of the spacer for liquid crystal display elements.
スペーサーの形成方法
次に、本発明の感放射線性樹脂組成物を用いて本発明のスペーサーを形成する方法について説明する。
Method of forming spacers Next, a method of forming a spacer of the present invention will be described with reference to radiation-sensitive resin composition of the present invention.
本発明のスペーサーの形成方法は、少なくとも以下の工程を以下に記載の順序で含む。
(イ)本発明の感放射線性樹脂組成物の被膜を基板上に形成する工程、
(ロ)該被膜の少なくとも一部に露光する工程、
(ハ)露光後の該被膜を現像する工程、および
(ニ)現像後の該被膜を加熱する工程。
The method for forming a spacer of the present invention includes at least the following steps in the order described below.
(A) forming a film of the radiation sensitive resin composition of the present invention on a substrate;
(B) exposing at least a part of the coating;
(C) a step of developing the coated film after exposure, and (d) a step of heating the coated film after development.
以下、これらの各工程について順次説明する。 Hereinafter, each of these steps will be described sequentially.
−(イ)工程−
透明基板の一面に透明導電膜を形成し、該透明導電膜の上に、感放射線性樹脂組成物を、好ましくは組成物溶液として塗布したのち、塗布面を加熱(プレベーク)することにより、被膜を形成する。
スペーサーの形成に用いられる透明基板としては、例えば、ガラス基板、樹脂基板等を挙げることができる。より具体的には、例えばソーダライムガラス、無アルカリガラスの如きガラス基板;ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエーテルスルホン、ポリカーボネート、ポリイミド等のプラスチックからなる樹脂基板を挙げることができる。
-(I) Process-
A transparent conductive film is formed on one surface of a transparent substrate, and a radiation-sensitive resin composition is applied onto the transparent conductive film, preferably as a composition solution, and then the coated surface is heated (prebaked) to form a coating film. Form.
Examples of the transparent substrate used for forming the spacer include a glass substrate and a resin substrate. More specifically, examples include glass substrates such as soda lime glass and alkali-free glass; resin substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide.
透明基板の一面に設けられる透明導電膜としては、酸化スズ(SnO2)からなるNESA膜(米国PPG社登録商標)、酸化インジウム−酸化スズ(In2O3−SnO2)からなるITO膜等を用いることができる。
組成物溶液の塗布方法としては、例えば、スプレー法、ロールコート法、回転塗布法(スピンコート法)、スリットダイ塗布法、バー塗布法、インクジェット塗布法等の適宜の方法を採用することができるが、特に、スピンコート法、スリットダイ塗布法が好ましい。
また、プレベークの条件は、各成分の種類、配合割合などによっても異なるが、好ましくは70〜120℃で1〜15分間程度である。
Examples of the transparent conductive film provided on one surface of the transparent substrate include a NESA film (registered trademark of US PPG) made of tin oxide (SnO 2 ), an ITO film made of indium oxide-tin oxide (In 2 O 3 —SnO 2 ), etc. Can be used.
As a coating method of the composition solution, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet coating method can be employed. However, the spin coating method and the slit die coating method are particularly preferable.
Moreover, although the conditions of prebaking differ also with the kind of each component, a mixture ratio, etc., Preferably it is about 1 to 15 minutes at 70-120 degreeC.
−(ロ)工程−
次いで、形成された被膜の少なくとも一部に露光する。この場合、被膜の一部に露光する際には、好ましくは、所定のパターンを有するフォトマスクを介して露光する。
露光に使用される放射線としては、例えば、可視光線、紫外線、遠紫外線、電子線、X線等を使用できるが、波長が190〜450nmの範囲にある放射線が好ましく、特に365nmの紫外線を含む放射線が好ましい。
露光量は、露光される放射線の波長365nmにおける強度を、照度計(OAI model 356 、OAI Optical Associates Inc. 製)により測定した値として、好ましくは100〜10,000J/m2、より好ましくは1,200J/m2以下である。
-(B) Process-
Next, at least a part of the formed film is exposed. In this case, when a part of the film is exposed, it is preferably exposed through a photomask having a predetermined pattern.
As the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be used. However, radiation having a wavelength in the range of 190 to 450 nm is preferable, and particularly radiation containing 365 nm ultraviolet light. Is preferred.
The exposure dose is preferably 100 to 10,000 J / m 2 , more preferably 1 as a value obtained by measuring the intensity of the exposed radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.). , 200 J / m 2 or less.
−(ハ)工程−
次いで、露光後の被膜を現像することにより、不要な部分を除去して、所定のパターンを形成する。
現像に使用される現像液としては、アルカリ現像液が好ましく、その例としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニアの如き無機アルカリ;エチルアミン、n−プロピルアミンの如き脂肪族1級アミン;ジエチルアミン、ジ−n−プロピルアミンの如き脂肪族2級アミン;トリメチルアミン、メチルジエチルアミン、ジメチルエチルアミン、トリエチルアミンの如き脂肪族3級アミン;ピロール、ピペリジン、N−メチルピペリジン、N−メチルピロリジン、1,8−ジアザビシクロ[5.4.0]−7−ウンデセン、1,5−ジアザビシクロ[4.3.0]−5−ノネンの如き脂環族3級アミン;ピリジン、コリジン、ルチジン、キノリンの如き芳香族3級アミン;エタノールジメチルアミン、メチルジエタノールアミン、トリエタノールアミンの如きアルカノールアミン;テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシドの如き4級アンモニウム塩等のアルカリ性化合物の水溶液を挙げることができる。
-(C) Process-
Subsequently, the exposed film is developed to remove unnecessary portions and form a predetermined pattern.
The developer used for development is preferably an alkali developer, and examples thereof include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; ethylamine, n- Aliphatic primary amines such as propylamine; Aliphatic secondary amines such as diethylamine and di-n-propylamine; Aliphatic tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; pyrrole, piperidine and N-methyl Alicyclic tertiary amines such as piperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene; pyridine , Aromatic tertiary amines such as collidine, lutidine, quinoline; Examples include aqueous solutions of alkaline compounds such as ethanoldimethylamine, methyldiethanolamine, alkanolamines such as triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.
また、前記アルカリ性化合物の水溶液には、メタノール、エタノール等の水溶性有機溶媒や界面活性剤を適当量添加して使用することもできる。
現像方法としては、例えば液盛り法、ディッピング法、シャワー法等のいずれでもよく、現像時間は、好ましくは10〜180秒間程度である。
現像後、例えば流水洗浄を30〜90秒間行ったのち、例えば圧縮空気や圧縮窒素で風乾させることによって、所望のパターンが形成される。
In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the aqueous solution of the alkaline compound.
As the developing method, for example, any of a liquid filling method, a dipping method, a shower method and the like may be used, and the developing time is preferably about 10 to 180 seconds.
After development, for example, after washing with running water for 30 to 90 seconds, a desired pattern is formed by, for example, air drying with compressed air or compressed nitrogen.
−(二)工程−
次いで、得られたパターンを、例えばホットプレート、オーブン等の加熱装置により、所定温度、例えば100〜160℃で、所定時間、例えばホットプレート上では5〜30分間、オーブン中では30〜180分間、加熱(ポストベーク)をすることにより、所定のスペーサーを得ることができる。
スペーサーの形成に使用される従来の感放射線性樹脂組成物は、180〜200℃程度以上の温度で加熱処理を行わないと、得られるスペーサーが十分な性能を発揮できなかったが、本発明の感放射線性樹脂組成物では、加熱温度を従来より低温とすることができ、その結果、樹脂基板の黄変や変形をきたすことなく、圧縮強度、液晶配向時のラビング耐性、透明基板との密着性等の諸性能に優れるスペーサーを形成することができる。
-(2) Process-
Next, the obtained pattern is heated at a predetermined temperature, for example, 100 to 160 ° C., for a predetermined time, for example, 5 to 30 minutes on the hot plate, for 30 to 180 minutes in the oven, by a heating device such as a hot plate or oven. A predetermined spacer can be obtained by heating (post-baking).
The conventional radiation-sensitive resin composition used for the formation of the spacer cannot obtain sufficient performance unless the heat treatment is performed at a temperature of about 180 to 200 ° C. or higher. In the radiation-sensitive resin composition, the heating temperature can be made lower than before, and as a result, without causing yellowing or deformation of the resin substrate, compressive strength, rubbing resistance during liquid crystal alignment, adhesion to the transparent substrate It is possible to form a spacer excellent in various properties such as properties.
液晶表示素子
本発明の液晶表示素子は、前記のようにして形成された本発明のスペーサーを具備する。
本発明の液晶素子の構造としては、特に限定されるものではないが、例えば、図1に示すように、透明基板上にカラーフィルター層とスペーサーを形成し、液晶層を介して配置される2つの配向膜、対向する透明電極、対向する透明基板等を有する構造を挙げることができる。また図1に示すように、必要に応じて、偏光板や、カラーフィルター層上に保護膜を形成してもよい。
また、図2に示すように、透明基板上にカラーフィルター層とスペーサーを形成し、配向膜および液晶層を介して、薄膜トランジスター(TFT)アレイと対向させることによって、TN−TFT型の液晶表示素子とすることもできる。この場合も、必要に応じて、偏光板や、カラーフィルター層上に保護膜を形成してもよい。
Liquid crystal display element The liquid crystal display element of the present invention comprises the spacer of the present invention formed as described above.
The structure of the liquid crystal element of the present invention is not particularly limited. For example, as shown in FIG. 1, a color filter layer and a spacer are formed on a transparent substrate, and the liquid crystal element 2 is disposed via the liquid crystal layer. A structure having two alignment films, opposing transparent electrodes, opposing transparent substrates, and the like can be given. Moreover, as shown in FIG. 1, you may form a protective film on a polarizing plate or a color filter layer as needed.
In addition, as shown in FIG. 2, a color filter layer and a spacer are formed on a transparent substrate, and are opposed to a thin film transistor (TFT) array through an alignment film and a liquid crystal layer, whereby a TN-TFT type liquid crystal display. It can also be an element. Also in this case, a protective film may be formed on the polarizing plate or the color filter layer as necessary.
以下、実施例を挙げて、本発明の実施の形態をさらに具体的に説明する。ここで、部および%は重量基準である。 Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. Here, parts and% are based on weight.
合成例1
冷却管、撹拌機を備えたフラスコに、2,2’−アゾビス(2,4−ジメチルバレロニトリル)5部、酢酸3−メトキシブチル250部を仕込み、引き続いてメタクリル酸20部、3−(メタクリロイルオキシメチル)−3−エチルオキセタン30部、スチレン8部、メタクリル酸6−ヒドロキシヘキシルエステル25部、メタクリル酸テトラヒドロフラン−2−イル17部を仕込んで、窒素置換したのち、緩やかに攪拌しつつ、溶液の温度を70℃に上昇させ、この温度を4時間保持して重合することにより、固形分濃度30.9%の共重合体〔α−1〕溶液を得た。
得られた共重合体〔α−1〕について、MwをGPC(ゲルパーミエイションクロマトグラフィー) HLC−8020(商品名、東ソー(株)製)を用いて測定したところ、15,500であった。
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts of 3-methoxybutyl acetate, followed by 20 parts of methacrylic acid and 3- (methacryloyl). (Oxymethyl) -3-
For the obtained copolymer [α-1], Mw was measured by using GPC (Gel Permeation Chromatography) HLC-8020 (trade name, manufactured by Tosoh Corporation), and was found to be 15,500. .
次いで、前記共重合体〔α−1〕溶液に、2−メタクリロイルオキシエチルイソシアネート(商品名カレンズMOI、昭和電工(株)製)14部、4−メトキシフェノール0.08部を添加したのち、60℃で1時間攪拌して反応させた。2−メタクリロイルオキシエチルイソシアネート由来のイソシアネート基と共重合体〔α−1〕の水酸基の反応の進行は、IR(赤外線吸収)スペクトルにより確認した。固形分濃度32.5%の〔A〕重合体溶液を得た。この〔A〕重合体を、重合体(A−1)とする。 Subsequently, 14 parts of 2-methacryloyloxyethyl isocyanate (trade name Karenz MOI, manufactured by Showa Denko KK) and 0.08 part of 4-methoxyphenol were added to the copolymer [α-1] solution, and then 60 parts. The reaction was stirred for 1 hour at ° C. The progress of the reaction between the isocyanate group derived from 2-methacryloyloxyethyl isocyanate and the hydroxyl group of the copolymer [α-1] was confirmed by IR (infrared absorption) spectrum. A [A] polymer solution having a solid content concentration of 32.5% was obtained. Let this [A] polymer be a polymer (A-1).
合成例2
前記共重合体〔α−1〕溶液350部に、2−アクリロイルオキシエチルイソシアネート(商品名カレンズAOI、昭和電工(株)製)14部、4−メトキシフェノール0.08部を添加したのち、60℃で2時間攪拌して反応させることにより、固形分濃度33.2%の〔A〕重合体溶液を得た。この〔A〕重合体を、重合体(A−2)とする。
Synthesis example 2
After adding 14 parts of 2-acryloyloxyethyl isocyanate (trade name Karenz AOI, Showa Denko KK) and 0.08 part of 4-methoxyphenol to 350 parts of the copolymer [α-1] solution, 60 parts are obtained. By stirring and reacting at 2 ° C. for 2 hours, a [A] polymer solution having a solid content concentration of 33.2% was obtained. Let this [A] polymer be a polymer (A-2).
合成例3
冷却管、撹拌機を備えたフラスコに、2,2’−アゾビス(2,4−ジメチルバレロニトリル)7.5部、プロピレングリコールモノメチルエーテルアセテート100部、酢酸3−メトキシブチル100部を仕込み、引き続いてメタクリル酸18部、3−(メタクリロイルオキシメチル)−2−トリフロロメチルオキセタン30部、スチレン5部、ブタジエン5部、メタクリル酸2−(6−ヒドロキシ−ヘキサノイルオキシ)エチルエステルおよびメタクリル酸2−ヒドロキシエチルエステル混合物(商品名PLACCEL FM1D(ダイセル化学工業(株)製)25部、メタクリル酸テトラヒドロフラン−2−イル17部を仕込んで、窒素置換したのち、緩やかに攪拌しつつ、溶液の温度を70℃に上昇させ、この温度を3時間保持して重合することにより、固形分濃度31.7%の共重合体〔α−2〕溶液を得た。
得られた共重合体〔α−2〕について、GPCを用いて測定したところ、Mwは14,800であった。
Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 7.5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile), 100 parts of propylene glycol monomethyl ether acetate and 100 parts of 3-methoxybutyl acetate, and subsequently. 18 parts of methacrylic acid, 30 parts of 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 5 parts of styrene, 5 parts of butadiene, 2- (6-hydroxy-hexanoyloxy) ethyl methacrylate and methacrylic acid 2 -Hydroxyethyl ester mixture (trade name PLACEL FM1D (manufactured by Daicel Chemical Industries, Ltd.) 25 parts, tetrahydrofuran-2-yl methacrylate 17 parts were charged, and after nitrogen substitution, the temperature of the solution was adjusted while gently stirring. By raising the temperature to 70 ° C. and polymerizing while maintaining this temperature for 3 hours, Solid content concentration 31.7 percent of the copolymer [alpha-2] to obtain a solution.
When the obtained copolymer [α-2] was measured using GPC, Mw was 14,800.
次いで、前記共重合体〔α−2〕溶液に、合成例1と同様にして、2−メタクリロイルオキシエチルイソシアネートを反応させた。合成例1と同様にして、IRスペクトルによりイソシアネート基と共重合体の反応を確認した。固形分濃度33.9%の〔A〕重合体溶液を得た。この〔A〕重合体を、重合体(A−3)とする。 Subsequently, 2-methacryloyloxyethyl isocyanate was reacted with the copolymer [α-2] solution in the same manner as in Synthesis Example 1. In the same manner as in Synthesis Example 1, the reaction between the isocyanate group and the copolymer was confirmed by IR spectrum. An [A] polymer solution having a solid content concentration of 33.9% was obtained. Let this [A] polymer be a polymer (A-3).
合成例4
前記共重合体〔α−2〕溶液300部に、合成例2と同様にして、2−アクリロイルオキシエチルイソシアネートを反応させ、固形分濃度33.6%の〔A〕重合体溶液を得た。この〔A〕重合体を、重合体(A−4) とする。
Synthesis example 4
In the same manner as in Synthesis Example 2, 300 parts of the copolymer [α-2] solution was reacted with 2-acryloyloxyethyl isocyanate to obtain an [A] polymer solution having a solid content concentration of 33.6%. This [A] polymer is referred to as polymer (A-4).
合成例5
冷却管、撹拌機を備えたフラスコに、2,2’−アゾビス(2,4−ジメチルバレロニトリル)5部、プロピレングリコールモノメチルエーテルアセテートに250部を仕込み、引き続いてメタクリル酸18部、3−(メタクリロイルオキシメチル)−2−フェニルオキセタン30部、スチレン5部、ブタジエン5部、メタクリル酸2−(3−ヒドロキシ−2,2−ジメチル−プロポキシカルボニルオキシ)−エチルエステルおよびメタクリル酸2−ヒドロキシエチルエステル混合物(商品名 HEMAC1(ダイセル化学工業(株)製)25部、メタクリル酸テトラヒドロフラン−2−イル17部を仕込んで、窒素置換したのち、緩やかに攪拌しつつ、溶液の温度を70℃に上昇させ、この温度を4時間保持して重合することにより、固形分濃度30.6%の共重合体〔α−3〕溶液を得た。
得られた共重合体〔α−3〕について、GPCを用いて測定したところ、Mwは15,300であった。
Synthesis example 5
A flask equipped with a condenser and a stirrer was charged with 5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts of propylene glycol monomethyl ether acetate, followed by 18 parts of methacrylic acid, 3- ( (Methacryloyloxymethyl) -2-
When the obtained copolymer [α-3] was measured using GPC, Mw was 15,300.
次いで、前記共重合体〔α−3〕溶液に、合成例1と同様にして、2−メタクリロイルオキシエチルイソシアネートを反応させた。合成例1と同様にして、IRスペクトルによりイソシアネート基と共重合体の反応を確認した。固形分濃度32.7%の〔A〕重合体溶液を得た。この〔A〕重合体を、重合体(A−5)とする。 Subsequently, 2-methacryloyloxyethyl isocyanate was reacted with the copolymer [α-3] solution in the same manner as in Synthesis Example 1. In the same manner as in Synthesis Example 1, the reaction between the isocyanate group and the copolymer was confirmed by IR spectrum. An [A] polymer solution having a solid content concentration of 32.7% was obtained. Let this [A] polymer be a polymer (A-5).
合成例6
前記共重合体〔α−3〕溶液350部に、合成例2と同様にして、2−アクリロイルオキシエチルイソシアネートを反応させ、固形分濃度33.0%の〔A〕重合体溶液を得た。この〔A〕重合体を、重合体(A−6) とする。
Synthesis Example 6
In the same manner as in Synthesis Example 2, 2-acryloyloxyethyl isocyanate was reacted with 350 parts of the copolymer [α-3] solution to obtain an [A] polymer solution having a solid content concentration of 33.0%. This [A] polymer is referred to as polymer (A-6).
合成例7
冷却管、撹拌機を備えたフラスコに、2,2’−アゾビス(2,4−ジメチルバレロニトリル)7.5部、プロピレングリコールモノメチルエーテルアセテート100部を仕込み、酢酸3−メトキシブチル100部、引き続いてメタクリル酸18部、3−(メタクリロイルオキシメチル)−3−エチルオキセタン10部、スチレン5部、ブタジエン5部、メタクリル酸3−ヒドロキシメチル−アダマンタン−1−イルメチルエステル25部、メタクリル酸テトラヒドロフラン−2−イル37部を仕込んで、窒素置換したのち、緩やかに攪拌しつつ、溶液の温度を70℃に上昇させ、この温度を3時間保持して重合することにより、固形分濃度31.5%の共重合体〔α−4〕溶液を得た。
得られた共重合体〔α−4〕について、GPCを用いて測定したところ、Mwは16,600であった。
Synthesis example 7
A flask equipped with a condenser and a stirrer was charged with 7.5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 100 parts of propylene glycol monomethyl ether acetate, followed by 100 parts of 3-methoxybutyl acetate, and subsequently. 18 parts of methacrylic acid, 10 parts of 3- (methacryloyloxymethyl) -3-ethyloxetane, 5 parts of styrene, 5 parts of butadiene, 25 parts of 3-hydroxymethyl-adamantan-1-ylmethyl methacrylate, tetrahydrofuran-methacrylic acid- After charging 37 parts of 2-yl and substituting with nitrogen, the temperature of the solution was raised to 70 ° C. while gently stirring, and this temperature was maintained for 3 hours for polymerization to obtain a solid content concentration of 31.5%. A copolymer [α-4] solution was obtained.
When the obtained copolymer [α-4] was measured using GPC, Mw was 16,600.
次いで、前記共重合体〔α−4〕溶液に、合成例1と同様にして、2−メタクリロイルオキシエチルイソシアネートを反応させた。合成例1と同様にして、IRスペクトルによりイソシアネート基と共重合体の反応を確認した。固形分濃度33.7%の〔A〕重合体溶液を得た。この〔A〕重合体を、重合体(A−7)とする。 Subsequently, 2-methacryloyloxyethyl isocyanate was reacted with the copolymer [α-4] solution in the same manner as in Synthesis Example 1. In the same manner as in Synthesis Example 1, the reaction between the isocyanate group and the copolymer was confirmed by IR spectrum. An [A] polymer solution having a solid content concentration of 33.7% was obtained. This [A] polymer is referred to as a polymer (A-7).
合成例8
冷却管、撹拌機を備えたフラスコに、2,2’−アゾビス(2,4−ジメチルバレロニトリル)5部、プロピレングリコールモノメチルエーテルアセテート250部を仕込み、引き続いてメタクリル酸18部、メタクリル酸トリシクロ[ 5.2.1.02.6] デカン−8−イル10部、スチレン5部、ブタジエン5部、メタクリル酸2−ヒドロキシエチルエステル25部、メタクリル酸テトラヒドロフラン−2−イル37部を仕込んで、窒素置換したのち、緩やかに攪拌しつつ、溶液の温度を70℃に上昇させ、この温度を4時間保持して重合することにより、固形分濃度29.5%の共重合体〔α−5〕溶液を得た。
得られた共重合体〔α−5〕について、GPCを用いて測定したところ、Mwは17,000であった。
Synthesis example 8
A flask equipped with a condenser and a stirrer was charged with 5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts of propylene glycol monomethyl ether acetate, followed by 18 parts of methacrylic acid, tricyclomethacrylate [ 5.2.1.0 2.6 ] 10 parts decan-8-yl, 5 parts styrene, 5 parts butadiene, 25 parts methacrylic acid 2-hydroxyethyl ester, 37 parts tetrahydrofuran-2-yl methacrylate, After substituting with nitrogen, the temperature of the solution was raised to 70 ° C. while gently stirring, and polymerization was carried out while maintaining this temperature for 4 hours, whereby a copolymer with a solid content concentration of 29.5% [α-5] A solution was obtained.
When the obtained copolymer [α-5] was measured using GPC, Mw was 17,000.
次いで、前記共重合体〔α−5〕溶液に、合成例1と同様にして、2−メタクリロイルオキシエチルイソシアネートを反応させた。合成例1と同様にして、IRスペクトルによりイソシアネート基と共重合体の反応を確認した。固形分濃度32.0%の〔A〕重合体溶液を得た。この〔A〕重合体を、重合体(A−8)とする。 Subsequently, 2-methacryloyloxyethyl isocyanate was reacted with the copolymer [α-5] solution in the same manner as in Synthesis Example 1. In the same manner as in Synthesis Example 1, the reaction between the isocyanate group and the copolymer was confirmed by IR spectrum. A [A] polymer solution having a solid content concentration of 32.0% was obtained. Let this [A] polymer be a polymer (A-8).
実施例1
組成物溶液の調製
〔A〕成分として、合成例1で得た〔A〕重合体溶液を重合体(A−1) として100部、〔B〕成分として、ジペンタエリスリトールヘキサアクリレート(商品名KAYARAD DPHA、日本化薬(株)製)80部、〔C〕成分として、1−〔9−エチル−6−(2−メチルベンゾイル)−9.H.−カルバゾール−3−イル〕−エタン−1−オンオキシム−O−アセタート(商品名CGI−242、チバ・スペシャルティー・ケミカルズ社製)5部、2−(4−メチルベンゾイル)−2−(ジメチルアミノ)−1−(4−モルフォリノフェニル)−ブタン−1−オン(商品名イルガキュア379、チバ・スペシャルティー・ケミカルズ社製)10部、接着助剤として、γ−グリシドキシプロピルトリメトキシシラン5部、界面活性剤として、FTX−218(商品名、(株)ネオス製)0.5部、保存安定剤として、4−メトキシフェノール0.5部を混合し、固形分濃度が30%になるようにプロピレングリコールモノメチルエーテルアセテートに溶解したのち、孔径0.5μmのミリポアフィルタでろ過して、組成物溶液を調製した。
Example 1
Preparation of Composition Solution As component [A], 100 parts of polymer solution [A] obtained in Synthesis Example 1 was used as polymer (A-1), and dipentaerythritol hexaacrylate (trade name KAYARAD as component [B]. DPHA, manufactured by Nippon Kayaku Co., Ltd.) 80 parts, [C] component, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate (trade name CGI-242, manufactured by Ciba Specialty Chemicals), 2- (4-methylbenzoyl) -2- (dimethylamino) ) -1- (4-morpholinophenyl) -butan-1-one (trade name Irgacure 379, manufactured by Ciba Specialty Chemicals), γ-glycidoxypropyltrimethoxysilane 5 as an adhesion aid Part, 0.5 parts FTX-218 (trade name, manufactured by Neos Co., Ltd.) as a surfactant and 0.5 parts 4-methoxyphenol as a storage stabilizer are mixed to a solid content concentration of 30%. Thus, it melt | dissolved in propylene glycol monomethyl ether acetate, Then, it filtered with the Millipore filter with the hole diameter of 0.5 micrometer, and prepared the composition solution.
スペーサーの形成
無アルカリガラス基板上にスピンナーを用いて、前記組成物溶液を塗布したのち、90℃のホットプレート上で3分間プレベークして、膜厚4.0μmの被膜を形成した。
次いで、得られた被膜に、15μm丸の残しパターンのフォトマスクを介して、365nmにおける強度が250W/m2の紫外線で、所定の露光量で露光した。その後、水酸化カリウム0.05重量%水溶液により、25℃で60秒間現像したのち、純水で1分間洗浄し、さらに220℃のオーブン中で60分間加熱することにより、高さ3.5μmのスペーサーを形成した。
Formation of Spacer The composition solution was applied on a non-alkali glass substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 3 minutes to form a film having a thickness of 4.0 μm.
Next, the obtained film was exposed with ultraviolet rays having an intensity at 365 nm of 250 W / m 2 through a photomask having a 15 μm round left pattern, at a predetermined exposure amount. Then, after developing with a 0.05 wt% aqueous solution of potassium hydroxide at 25 ° C. for 60 seconds, washing with pure water for 1 minute, and further heating in an oven at 220 ° C. for 60 minutes, a height of 3.5 μm A spacer was formed.
次いで、下記の要領で各種評価を行った。評価結果を、表2に示す。 Next, various evaluations were performed in the following manner. The evaluation results are shown in Table 2.
(1)剥離液耐性の評価
得られたスペーサーに対して剥離液TS−204(三洋化成製)に50℃で30分浸漬し、さらに210℃15分加熱後に膜厚変化を測定した。加熱後の膜厚×100/初期膜厚により評価を行った。
(2)感度の評価
露光量を変量とした以外は前記スペーサーの形成と同様にして、スペーサーを形成したとき、現像後の残膜率(現像後の膜厚×100/初期膜厚。以下同様。)が90%以上になる露光量を感度とした。この露光量が1,200J/m2以下のとき、感度が良好といえる。
(3)解像度の評価
露光量を変量とした以外は前記スペーサーの形成と同様にして、スペーサーを形成したとき、現像後の残膜率が90%以上となる露光量により解像される最小のパターンサイズにより評価した。
(4)断面形状の評価
得られたスペーサーの断面形状を走査型電子顕微鏡にて観察して、図3に示すA〜Dのいずれに該当するかにより評価した。このとき、AあるいはBのように、パターンエッジが順テーパーあるいは垂直状である場合は、断面形状が良好といえる。これに対して、Cに示すように、感度が不十分で残膜率が低く、断面寸法がAおよびBに比較して小さくなり、底面が平面の半凸レンズ状である場合は、断面形状が不良であり、またDに示すように、逆テーパ状(断面形状で、膜表面の辺が基板側の辺よりも長い逆三角形状)である場合も、後のラビング処理時にパターンが剥がれるおそれが非常に大きくなることから、断面形状が不良とした。
(5)圧縮特性の評価
得られたスペーサーについて、微小圧縮試験機(商品名FISCHER SCOPE H100C、(株)フィッシャー・インストルメンツ製)を用い、直径50μmの平面圧子により、負荷速度および徐荷速度をともに2.6mN /秒として、50mNまでの荷重を負荷して5秒間保持したのち除荷して、負荷時の荷重−変形量曲線および徐荷時の荷重−変形量曲線を作成した。このとき、図4に示すように、負荷時の荷重50mNでの変形量と荷重5mNでの変形量との差をL1とし、除荷時の荷重50mNでの変形量と荷重5mNでの変形量との差をL2として、下記式により、弾性回復率を算出した。
弾性回復率(%)=L2×100/L1
また、L1が大きければ、柔軟性があると言える。
(6)ラビング耐性の評価
スペーサーを形成した基板に、液晶配向剤としてAL3046(商品名、JSR(株)製)を液晶配向膜塗布用印刷機により塗布したのち、180℃で1時間乾燥して、膜厚0.05μmの液晶配向剤の塗膜を形成した。
その後、この塗膜に、ポリアミド製の布を巻き付けたロールを有するラビングマシーンにより、ロールの回転数500rpm、ステージの移動速度1cm/秒として、ラビング処理を行った。このとき、パターンの削れや剥がれの有無を評価した。
(7)密着性の評価
フォトマスクを使用しなかった以外は前記スペーサーの形成と同様にして、硬化膜を形成したのち、JIS K−5400(1900)8.5の付着性試験のうち、8.5・2の碁盤目テープ法により評価した。このとき、100個の碁盤目のうち残った碁盤目の数を表3に示す。
(8)耐熱性の評価
フォトマスクを使用しなかった以外は前記スペーサーの形成と同様にして硬化膜を形成したのち、240℃のオーブン中で60分間加熱し、加熱前後の膜厚を測定して、残膜率(加熱後の膜厚×100/初期膜厚)により評価した。
(1) Evaluation of stripping solution resistance The resulting spacer was immersed in stripping solution TS-204 (manufactured by Sanyo Chemical Co., Ltd.) at 50 ° C. for 30 minutes, and further heated at 210 ° C. for 15 minutes, and the change in film thickness was measured. Evaluation was carried out by film thickness after heating × 100 / initial film thickness.
(2) Evaluation of sensitivity When the spacer is formed in the same manner as the formation of the spacer except that the exposure amount is variable, the residual film ratio after development (film thickness after development × 100 / initial film thickness. The same applies hereinafter. The exposure amount at which 90) is 90% or more was defined as sensitivity. When this exposure amount is 1,200 J / m 2 or less, it can be said that the sensitivity is good.
(3) Evaluation of resolution The minimum resolution that can be resolved by the exposure amount at which the residual film ratio after development is 90% or more when the spacer is formed in the same manner as the formation of the spacer except that the exposure amount is variable. Evaluation was based on the pattern size.
(4) Evaluation of cross-sectional shape The cross-sectional shape of the obtained spacer was observed with a scanning electron microscope and evaluated according to which of A to D shown in FIG. At this time, when the pattern edge is forward tapered or vertical like A or B, it can be said that the cross-sectional shape is good. On the other hand, as shown in C, when the sensitivity is insufficient, the remaining film rate is low, the cross-sectional dimension is small compared to A and B, and the bottom surface is a semi-convex lens shape with a flat surface, the cross-sectional shape is Also, as shown in D, the pattern may be peeled off during the subsequent rubbing process even in the case of an inversely tapered shape (in the cross-sectional shape, an inverted triangular shape in which the side of the film surface is longer than the side on the substrate side). Since it became very large, the cross-sectional shape was regarded as defective.
(5) Evaluation of compression characteristics About the obtained spacer, using a micro-compression tester (trade name: FISCHER SCOPE H100C, manufactured by Fisher Instruments Co., Ltd.), a flat indenter with a diameter of 50 μm was used to adjust the load speed and unloading speed. Both were set to 2.6 mN / sec, a load up to 50 mN was applied and held for 5 seconds, then unloaded, and a load-deformation curve and a load-deformation curve during slow loading were prepared. At this time, as shown in FIG. 4, the difference between the deformation amount at the load of 50 mN and the deformation amount at the load of 5 mN is L1, and the deformation amount at the load of 50 mN and the deformation amount at the load of 5 mN at unloading. The elastic recovery rate was calculated by the following formula, with the difference between L2 and L2.
Elastic recovery rate (%) = L2 × 100 / L1
Moreover, if L1 is large, it can be said that there is flexibility.
(6) Evaluation of rubbing resistance AL3046 (trade name, manufactured by JSR Co., Ltd.) as a liquid crystal aligning agent was applied to a substrate on which a spacer was formed by a printing machine for applying a liquid crystal alignment film, and then dried at 180 ° C. for 1 hour. A film of a liquid crystal aligning agent having a thickness of 0.05 μm was formed.
Thereafter, the coating film was subjected to a rubbing treatment with a rubbing machine having a roll around which a polyamide cloth was wound, with a roll rotation speed of 500 rpm and a stage moving speed of 1 cm / sec. At this time, the presence or absence of pattern shaving or peeling was evaluated.
(7) Evaluation of adhesion After forming a cured film in the same manner as the formation of the spacer except that no photomask was used, 8 of the adhesion tests of JIS K-5400 (1900) 8.5 Evaluation was performed by the cross-cut tape method of. At this time, the number of remaining grids out of 100 grids is shown in Table 3.
(8) Evaluation of heat resistance A cured film was formed in the same manner as the spacer formation except that no photomask was used, and then heated in an oven at 240 ° C for 60 minutes, and the film thickness before and after heating was measured. The remaining film ratio (film thickness after heating × 100 / initial film thickness) was evaluated.
実施例2〜17、比較例1〜6
実施例1において、表1に示す各成分を、接着助剤として、γ−グリシドキシプロピルトリメトキシシラン5部、界面活性剤として、FTX−218を0.5部、保存安定剤として、4−メトキフェノール0.5部と混合し、固形分濃度が30%になるようにプロピレングリコールモノメチルエーテルアセテートに溶解したのち、孔径0.5μmのミリポアフィルタでろ過して、組成物溶液を調製した。その後、実施例1と同様にして、スペーサーを形成して、実施例1と同様にして評価した。評価結果を、表2に示す。
Examples 2-17, Comparative Examples 1-6
In Example 1, each component shown in Table 1 was used as an adhesion assistant, 5 parts of γ-glycidoxypropyltrimethoxysilane, as a surfactant, 0.5 part of FTX-218, and as a storage stabilizer, 4 parts. -It mixed with 0.5 parts of methoxyphenol, dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 30%, and then filtered through a Millipore filter having a pore size of 0.5 µm to prepare a composition solution. Thereafter, spacers were formed in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
表1において、重合体以外の各成分は、下記のとおりである。 In Table 1, each component other than the polymer is as follows.
〔B〕成分
B−1:ジペンタエリストールヘキサアクリレート(商品名KAYARAD DPHA) B−2:多官能ウレタンアクリレート系化合物を含有する市販品(商品名KAYARAD DPHA−40H)
〔C〕成分
C−1:1−〔9−エチル−6−(2−メチルベンゾイル)−9.H.−カルバゾール−3−イル〕−エタン−1−オンオキシム−O−アセタート(商品名CGI−242、チバ・スペシャルティー・ケミカルズ社製)
C−2:2−メチル−1−(4−メチルチオフェニル)−2−モルホリノプロパン−1−オン(商品名イルガキュア907、チバ・スペシャルティー・ケミカルズ社製)
C−3:2−(4−メチルベンゾイル)−2−(ジメチルアミノ)−1−(4−モルフォリノフェニル)−ブタン−1−オン(商品名イルガキュア379、チバ・スペシャルティー・ケミカルズ社製)
C−4:2,2’−ビス(2−クロロフェニル)−4,4’,5,5’−テトラフェニル−1,2’−ビイミダゾール
C−5:4,4’−ビス(ジエチルアミノ)ベンゾフェノン
C−6:2−メルカプトベンゾチアゾール
[B] Component B-1: Dipentaerystol hexaacrylate (trade name KAYARAD DPHA) B-2: A commercial product containing a polyfunctional urethane acrylate-based compound (trade name KAYARAD DPHA-40H)
[C] component C-1: 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate (trade name CGI-242, manufactured by Ciba Specialty Chemicals)
C-2: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals)
C-3: 2- (4-methylbenzoyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (trade name Irgacure 379, manufactured by Ciba Specialty Chemicals)
C-4: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole C-5: 4,4′-bis (diethylamino) benzophenone C-6: 2-mercaptobenzothiazole
Claims (8)
(a2)下記式(1)〜(4)のそれぞれで表される水酸基含有不飽和化合物よりなる群から選ばれる少なくとも1つの化合物、(a3)下記式(5)または(6)で示されるオキセタニル基含有不飽和化合物、および(a4)(a1)及び(a2)及び(a3)以外の他の不飽和化合物の共重合体に、下記式(7)で表されるイソシアネート化合物を反応させて得られる重合体。
(A1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride,
(A2) at least one compound selected from the group consisting of hydroxyl group-containing unsaturated compounds represented by the following formulas (1) to (4), (a3) oxetanyl represented by the following formula (5) or (6) It is obtained by reacting an isocyanate compound represented by the following formula (7) with a copolymer of a group-containing unsaturated compound and an unsaturated compound other than (a4) (a1) and (a2) and (a3). Polymer.
(a2)上記式(1)〜(4)のそれぞれで表される水酸基含有不飽和化合物よりなる群から選ばれる少なくとも1つの化合物、(a3)下記式(5)または(6)で示されるオキセタニル基含有不飽和化合物、および(a4)(a1)及び(a2)及び(a3)以外の他の不飽和化合物の共重合体に、上記式(7)で表されるイソシアネート化合物を反応させることを特徴とする請求項1に記載の重合体の製造方法。 (A1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride,
(A2) at least one compound selected from the group consisting of hydroxyl group-containing unsaturated compounds represented by the above formulas (1) to (4), (a3) oxetanyl represented by the following formula (5) or (6) Reacting the isocyanate compound represented by the above formula (7) with a copolymer of a group-containing unsaturated compound and an unsaturated compound other than (a4) (a1) and (a2) and (a3). The method for producing a polymer according to claim 1, wherein
(イ)請求項3または4に記載の感放射線性樹脂組成物の被膜を基板上に形成する工程、
(ロ)該被膜の少なくとも一部に露光する工程、
(ハ)露光後の該被膜を現像する工程、および
(ニ)現像後の該被膜を加熱する工程。 A method for forming a spacer for a liquid crystal display element, comprising at least the following steps in the order described below.
(A) forming a film of the radiation sensitive resin composition according to claim 3 or 4 on a substrate;
(B) exposing at least a part of the coating;
(C) a step of developing the coated film after exposure, and (d) a step of heating the coated film after development.
A liquid crystal display device comprising the spacer according to claim 6.
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