JP6048670B2 - Radiation sensitive resin composition - Google Patents
Radiation sensitive resin composition Download PDFInfo
- Publication number
- JP6048670B2 JP6048670B2 JP2013067054A JP2013067054A JP6048670B2 JP 6048670 B2 JP6048670 B2 JP 6048670B2 JP 2013067054 A JP2013067054 A JP 2013067054A JP 2013067054 A JP2013067054 A JP 2013067054A JP 6048670 B2 JP6048670 B2 JP 6048670B2
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- meth
- mass
- resin composition
- radiation
- Prior art date
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- 230000005855 radiation Effects 0.000 title claims description 77
- 239000011342 resin composition Substances 0.000 title claims description 46
- -1 silane compound Chemical class 0.000 claims description 96
- 150000001875 compounds Chemical class 0.000 claims description 82
- 229920000642 polymer Polymers 0.000 claims description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 39
- 239000000758 substrate Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 32
- 238000000576 coating method Methods 0.000 claims description 31
- 125000006850 spacer group Chemical group 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 27
- 239000003505 polymerization initiator Substances 0.000 claims description 22
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 19
- 239000011229 interlayer Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 229910000077 silane Inorganic materials 0.000 claims description 12
- 238000011161 development Methods 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000003566 oxetanyl group Chemical group 0.000 claims description 7
- 125000000466 oxiranyl group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 206010047571 Visual impairment Diseases 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- VVMSDAAZTROUPZ-UHFFFAOYSA-N (3-ethyloxetan-2-yl)methyl prop-2-enoate Chemical compound CCC1COC1COC(=O)C=C VVMSDAAZTROUPZ-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims 1
- 239000000243 solution Substances 0.000 description 45
- 239000000203 mixture Substances 0.000 description 25
- 239000004973 liquid crystal related substance Substances 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 17
- 229920001577 copolymer Polymers 0.000 description 16
- 229920001296 polysiloxane Polymers 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 238000011084 recovery Methods 0.000 description 10
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 210000002858 crystal cell Anatomy 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 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 5
- 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 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000012024 dehydrating agents Substances 0.000 description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 4
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 4
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 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 3
- 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 3
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 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 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 3
- 150000008062 acetophenones Chemical class 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 238000004528 spin coating Methods 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
- 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
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-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
- 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 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 2
- LBNDGEZENJUBCO-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethyl]butanedioic acid Chemical compound CC(=C)C(=O)OCCC(C(O)=O)CC(O)=O LBNDGEZENJUBCO-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
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 2
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 2
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 2
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 2
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 2
- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PBHPFFDRTUWVIT-UHFFFAOYSA-N oxetan-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CCO1 PBHPFFDRTUWVIT-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- CSVRUJBOWHSVMA-UHFFFAOYSA-N oxolan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCO1 CSVRUJBOWHSVMA-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006335 response to radiation Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- BINKQJJWJHNOSQ-UHFFFAOYSA-N tetrabenzyl silicate Chemical compound C=1C=CC=CC=1CO[Si](OCC=1C=CC=CC=1)(OCC=1C=CC=CC=1)OCC1=CC=CC=C1 BINKQJJWJHNOSQ-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ADLSSRLDGACTEX-UHFFFAOYSA-N tetraphenyl silicate Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 ADLSSRLDGACTEX-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- GIHPVQDFBJMUAO-UHFFFAOYSA-N tributoxy(ethyl)silane Chemical compound CCCCO[Si](CC)(OCCCC)OCCCC GIHPVQDFBJMUAO-UHFFFAOYSA-N 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は、感放射線性樹脂組成物に関する。詳しくは表示素子のスペーサー又は層間絶縁膜に好適に適用することのできる感放射線性樹脂組成物に関する。 The present invention relates to a radiation sensitive resin composition. In detail, it is related with the radiation sensitive resin composition which can be applied suitably for the spacer or interlayer insulation film of a display element.
液晶表示素子に代表される表示素子は、種々の部材を組み合わせて構成されている。本発明はそのうちのスペーサー及び層間絶縁膜に適した材料に関する。
表示素子には、従来から、2枚の透明基板間の間隔を一定に保つため、所定の粒径を有するスペーサー粒子が使用されていた。これらスペーサー粒子は、ガラス基板等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粒子が存在すると、スペーサー粒子の写り込み現象を生じ、あるいは入射光が散乱を受けて液晶表示素子のコントラストが低下するという問題があった。そこで、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紫外線を露光したのち現像して、所定形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。
A display element typified by a liquid crystal display element is configured by combining various members. The present invention relates to a material suitable for the spacer and the interlayer insulating film.
Conventionally, spacer particles having a predetermined particle size have been used for display elements in order to keep the distance between two transparent substrates constant. Since these spacer particles are randomly distributed on a transparent substrate such as a glass substrate, if the spacer particles are present in the pixel formation region, the spacer particles are reflected, or the incident light is scattered and the liquid crystal display element. There was a problem that the contrast of the image was lowered. Therefore, a method of forming the spacer by photolithography has been adopted. In this method, a radiation-sensitive resin composition is applied onto a substrate, exposed to ultraviolet rays through a predetermined mask, and then developed to form a spacer having a predetermined shape. Since the spacer can be formed only at the place, the problem as described above is basically solved.
ところで、液晶テレビジョン用の大型基板を用いた液晶パネルの製造においては、いわゆるODF(One Drop Fill)方式が実施されている。ODF方式は、一方の基板上の数カ所に所定量の液晶を滴下しておき、ここに対向基板を押し付けて液晶を押し広げることにより、一対の基板間に液晶が挟持されてなる液晶セルを構成する方法である。この方法によると、従来の液晶注入方式に比べて、工程時間が大幅に短縮される。しかし、液晶滴下量の誤差、基板面何の僅かの圧力差等が原因となって、液晶セルの製造不良を来たす場合がある。このような製造不良を低減するためには、液晶セル製造時の加圧及び除荷に対して、総変異量と弾性回復特性のバランスに優れるスペーサーが必要である。
さらに、タッチパネル式の入力手段を搭載した表示素子(例えばスマートフォン、ウィンドウズ(登録商標)8対応端末等)では、従来の液晶パネルと比較して、より高精細な画像が求められる、特にスマートフォンにおいては、小さな画面上にドットの細かい高精細画像を表示するために、一画素の大きさがより小さくなり、これに付随してスペーサーのサイズも制限されることとなる。これに加えてタッチパネル式では、指またはタッチペンによって画面上に大きな負荷が印可されるため、小さいサイズでありながら、加圧時の圧縮変異量と除荷時の弾性回復特性とのバランスが高度に調整された、圧縮特性に優れるスペーサーが要求されているのである。
By the way, in the manufacture of a liquid crystal panel using a large substrate for a liquid crystal television, a so-called ODF (One Drop Fill) method is carried out. The ODF method forms a liquid crystal cell in which liquid crystal is sandwiched between a pair of substrates by dropping a predetermined amount of liquid crystal at several locations on one substrate and pressing the opposite substrate here to spread the liquid crystal. It is a method to do. According to this method, the process time is significantly reduced as compared with the conventional liquid crystal injection method. However, liquid crystal cell manufacturing defects may occur due to errors in the amount of liquid crystal dripping, slight pressure differences on the substrate surface, and the like. In order to reduce such manufacturing defects, a spacer having an excellent balance between the total amount of mutation and the elastic recovery characteristic is necessary for pressurization and unloading at the time of manufacturing the liquid crystal cell.
Furthermore, a display element (for example, a smartphone, a Windows (registered trademark) 8 compatible terminal, or the like) equipped with a touch panel type input means requires a higher-definition image compared to a conventional liquid crystal panel, particularly in a smartphone. In order to display a high-definition image with fine dots on a small screen, the size of one pixel becomes smaller, and the size of the spacer is limited accordingly. In addition to this, the touch panel type applies a large load on the screen with a finger or a touch pen, so the balance between the amount of compression variation during pressurization and the elastic recovery characteristic during unloading is high, despite the small size. There is a demand for spacers that are adjusted and have excellent compression characteristics.
一方で、表示素子においては、多層配線の層間の電気的絶縁を確保するための層間絶縁膜が使用されている。この層間絶縁膜もフォトリソグラフィーにより形成される。
層間絶縁膜には、透明性、耐光性、電気絶縁性等の種々の特性が要求されている。近年の表示素子の高精細化、動画固定技術の高度化等に伴って、より高い透明性が要求されている。また、モバイル用途、車載用途等の屋外使用を前提とした表示素子が普及してきたことにより、より一層の耐光性が求められるようになってきた。さらに、テレビジョン用途においては、表示素子の長時間視聴が常態化しているため、焼き付きを起こさない電気特性(高い電圧保持率)が求められている。
On the other hand, in the display element, an interlayer insulating film is used to ensure electrical insulation between the layers of the multilayer wiring. This interlayer insulating film is also formed by photolithography.
The interlayer insulating film is required to have various characteristics such as transparency, light resistance, and electrical insulation. In recent years, higher transparency has been demanded as display elements have been improved in definition and moving image fixing technology has been advanced. Further, with the widespread use of display elements based on outdoor use such as mobile use and in-vehicle use, further light resistance has been demanded. Furthermore, in television applications, since long-time viewing of display elements has become normal, electrical characteristics (high voltage holding ratio) that do not cause burn-in are required.
本発明は、上記のような現状を改善しようとしてなされたものである。
本発明の目的は、表示素子のスペーサー又は層間絶縁膜に好適に適用することのできる感放射線性樹脂組成物を提供することにある。該組成物は、これを表示素子のスペーサー用途又は層間絶縁膜用途に適用した場合、現在及び近い将来における要求性能の過酷化に適応する硬化膜を与えることができるものである。
The present invention has been made in an attempt to improve the current situation as described above.
The objective of this invention is providing the radiation sensitive resin composition which can be applied suitably for the spacer or interlayer insulation film of a display element. When the composition is applied to a display element spacer application or an interlayer insulating film application, the composition can provide a cured film that can be adapted to severe demand performance in the present and near future.
本発明によれば、本発明の上記課題は、
[A](A1)カルボキシル基を有する構造単位、
(A2)オキシラニル基及びオキセタニル基よりなる群から選ばれる少なくとも1種を有する構造単位、並びに
(A3)下記式(1)で表される構造単位
を有する重合体、
[B]重合性不飽和化合物、
[C]感放射線性重合開始剤、並びに
[D]下記式(2)で表される加水分解性シラン化合物の加水分解縮合物
を含有しそして上記[D]成分の含有割合が、[A]重合体100質量部に対して0.1〜50質量部である、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。
According to the present invention, the above problem of the present invention is as follows.
[A] (A1) a structural unit having a carboxyl group,
(A2) a structural unit having at least one selected from the group consisting of an oxiranyl group and an oxetanyl group, and (A3) a polymer having a structural unit represented by the following formula (1),
[B] polymerizable unsaturated compound,
[C] a radiation-sensitive polymerization initiator, and [D] a hydrolysis condensate of a hydrolyzable silane compound represented by the following formula (2), and the content ratio of the above [D] component is [A] This is achieved by a radiation-sensitive resin composition, which is 0.1 to 50 parts by mass with respect to 100 parts by mass of the polymer.
(式(1)中、Rは水素原子又はメチル基であり、R1及びR2は、それぞれ独立に、炭素数1〜6のアルキル基、炭素数1〜6のフルオロアルキル基又は炭素数6〜20のアリール基であり、hは1〜6の整数であり、iは0又は1である。) (In formula (1), R is a hydrogen atom or a methyl group, and R 1 and R 2 are each independently an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, or 6 carbon atoms. -20 aryl group, h is an integer of 1-6, i is 0 or 1.)
(式(2)中、R3は水素原子又はメチル基であり、R4及びR5は、それぞれ独立に、炭素数1〜6のアルキル基又は炭素数6〜20のアリール基であり、jは1〜6の整数であり、kは0又は1であり、mは0〜2の整数である。) (In Formula (2), R 3 is a hydrogen atom or a methyl group, R 4 and R 5 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms, j Is an integer from 1 to 6, k is 0 or 1, and m is an integer from 0 to 2.)
本発明の感放射線性樹脂組成物は、これを表示素子のスペーサーの形成に適用した場合には、高感度であり、解像度に優れるとともに、圧縮強度と復元力とのバランスに優れる硬化膜を与えることができ;
表示素子の層間絶縁膜の形成に適用した場合には、高感度であるとともに、透明性、耐光性及び電圧保持率に優れる硬化膜を与えることができる。
The radiation-sensitive resin composition of the present invention, when applied to the formation of a display element spacer, provides a cured film that is highly sensitive, excellent in resolution, and excellent in balance between compressive strength and restoring force. It is possible;
When applied to the formation of an interlayer insulating film of a display element, a cured film having high sensitivity and excellent transparency, light resistance, and voltage holding ratio can be provided.
本発明の感放射線性樹脂組成物は、上記のとおり、[A]重合体、[B]重合性不飽和化合物、[C]感放射線性重合開始剤及び[D]成分を含有する。これら以外に、[E]接着助剤、[F]界面活性剤、[G]重合禁止剤等を含有していてもよい。 As described above, the radiation-sensitive resin composition of the present invention contains a [A] polymer, a [B] polymerizable unsaturated compound, a [C] radiation-sensitive polymerization initiator, and a [D] component. In addition to these, [E] an adhesion assistant, [F] a surfactant, [G] a polymerization inhibitor may be contained.
<[A]重合体>
本発明における[A]重合体は、
(A1)カルボキシル基を有する構造単位(以下、「構造単位(A1)」という。)、
(A2)オキシラニル基及びオキセタニル基よりなる群から選ばれる少なくとも1種を有する構造単位(以下、「構造単位(A2)」という。)、並びに
(A3)下記式(1)で表される構造単位(以下、「構造単位(A3)」という。)
を有する重合体である。[A]重合体は、(A4)上記(A1)〜(A3)以外の構造単位(以下、「構造単位(A4)」という。)を有していてもよい。
上記式(1)におけるR1及びR2のアルキル基は直鎖状、分岐状及び環状のいずれでもよい。これらの具体例としては、R1及びR2それぞれ独立に、例えばメチル基、エチル基、n−プロピル基、iso−プロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基等を挙げることができる。R1及びR2のフルオロアルキル基は直鎖状、分岐状及び環状のいずれでもよい。これらの具体例としては、R1及びR2それぞれ独立に、例えばトリフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、パーフルオロイソプロピル基、パーフルオロシクロヘキシル基等を挙げることができる。R1及びR2のアリール基としては、炭素数が6〜14の単環式、二環式又は三環式のアリール基であることが好ましい。これらの具体例としては、R1及びR2それぞれ独立に、例えばフェニル基、ナフチル基、アントリル基、フェナントリル基等を挙げることができ、これらうちのフェニル基又はナフチル基であることが好ましく、特にフェニル基が好ましい。
上記式(1)におけるhとしては、2〜6の整数であることが好ましく、特には3又は4であることが好ましい。
<[A] polymer>
[A] polymer in the present invention,
(A1) a structural unit having a carboxyl group (hereinafter referred to as “structural unit (A1)”),
(A2) a structural unit having at least one selected from the group consisting of an oxiranyl group and an oxetanyl group (hereinafter referred to as “structural unit (A2)”), and (A3) a structural unit represented by the following formula (1) (Hereinafter referred to as “structural unit (A3)”.)
It is a polymer having [A] The polymer may have (A4) structural units other than the above (A1) to (A3) (hereinafter referred to as “structural unit (A4)”).
The alkyl group represented by R 1 and R 2 in the above formula (1) may be linear, branched or cyclic. Specific examples of these include R 1 and R 2 independently, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group. Hexyl group, cyclohexyl group and the like. The fluoroalkyl group for R 1 and R 2 may be linear, branched or cyclic. Specific examples of these include, independently, R 1 and R 2 such as a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, and a perfluorocyclohexyl group. The aryl group for R 1 and R 2 is preferably a monocyclic, bicyclic or tricyclic aryl group having 6 to 14 carbon atoms. Specific examples of these include, independently, R 1 and R 2 , for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, etc. Among them, a phenyl group or a naphthyl group is preferable, A phenyl group is preferred.
H in the above formula (1) is preferably an integer of 2 to 6, and particularly preferably 3 or 4.
[A]重合体における各構造単位の好ましい含有割合は、[A]重合体の全体を基準として、それぞれ、以下のとおりである。
構造単位(A1):好ましくは5〜60質量%、より好ましくは7〜50質量%、さらに好ましくは8〜40質量%
構造単位(A2):好ましくは0.5〜70質量%、より好ましくは1〜60質量%、さらに好ましくは3〜50質量%
構造単位(A3):好ましくは1〜50質量%、より好ましくは5〜40質量%、さらに好ましくは10〜30質量%
構造単位(A4):好ましくは80質量%以下、より好ましくは20〜70質量%、さらに好ましくは30〜70質量%
各構造単位の含有割合が上記の範囲にある[A]重合体を用いることにより、良好な塗布性及び高い弾性回復力が損なわれることなく高い解像度が達成されるから、小さいサイズのパターンであっても特性のバランスが高度に調整された硬化膜を与えることができることとなる。
上記構造単位(A1)は、(a1)不飽和カルボン酸及び不飽和カルボン酸無水物よりなる群から選択される少なくとも1種(以下、「化合物(a1)」という。)に由来する構造単位であることが、
上記構造単位(A2)は、(a2)オキシラニル基を有する不飽和化合物及びオキセタニル基を有する不飽和化合物よりなる群から選ばれる少なくとも1種(以下、「化合物(a2)」という。)に由来する構造単位であることが、
上記構造単位(A3)は、(a3)下記式(1−1)で表される化合物(以下、「化合物(a3)」という。)に由来する構造単位であることが、それぞれ好ましい。
[A] The preferable content rate of each structural unit in a polymer is as follows on the basis of the whole of [A] polymer, respectively.
Structural unit (A1): preferably 5 to 60% by mass, more preferably 7 to 50% by mass, still more preferably 8 to 40% by mass
Structural unit (A2): preferably 0.5 to 70% by mass, more preferably 1 to 60% by mass, still more preferably 3 to 50% by mass
Structural unit (A3): preferably 1 to 50% by mass, more preferably 5 to 40% by mass, still more preferably 10 to 30% by mass
Structural unit (A4): preferably 80% by mass or less, more preferably 20 to 70% by mass, and still more preferably 30 to 70% by mass.
By using the [A] polymer in which the content ratio of each structural unit is in the above range, high resolution can be achieved without impairing good coatability and high elastic recovery force. However, a cured film having a highly balanced property can be provided.
The structural unit (A1) is a structural unit derived from (a1) at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter referred to as “compound (a1)”). There is
The structural unit (A2) is derived from at least one selected from the group consisting of (a2) an unsaturated compound having an oxiranyl group and an unsaturated compound having an oxetanyl group (hereinafter referred to as “compound (a2)”). It must be a structural unit
The structural unit (A3) is preferably a structural unit derived from (a3) a compound represented by the following formula (1-1) (hereinafter referred to as “compound (a3)”).
(式(1−1)中、R、R1、R2、h及びiは、それぞれ、上記式(1)におけるのと同じ意味である。) (In the formula (1-1), R, R 1 , R 2 , h and i have the same meanings as in the formula (1)).
上記構造単位(A4)は、上記の化合物(a1)〜(a3)以外の不飽和化合物(以下、「化合物(a4)」という。)に由来する構造単位であることが好ましい。
上記化合物(a1)としては、例えばモノカルボン酸、ジカルボン酸、ジカルボン酸の無水物等を挙げることができる。上記モノカルボン酸としては、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等を;
上記ジカルボン酸としては、例えばマレイン酸、フマル酸、シトラコン酸等を;
上記ジカルボン酸の無水物としては、上記したジカルボン酸の無水物等を、それぞれ挙げることができる。これらのうち、共重合反応性、得られる共重合体の現像液に対する溶解性の点から、アクリル酸、メタクリル酸、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又は無水マレイン酸が好ましい。
化合物(a1)は、単独で又は2種以上を混合して使用することができる。
The structural unit (A4) is preferably a structural unit derived from an unsaturated compound other than the compounds (a1) to (a3) (hereinafter referred to as “compound (a4)”).
Examples of the compound (a1) include monocarboxylic acids, dicarboxylic acids, dicarboxylic acid anhydrides, and the like. Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and 2-methacryloyloxyethyl hexahydro. Phthalic acid etc .;
Examples of the dicarboxylic acid include maleic acid, fumaric acid, citraconic acid and the like;
Examples of the dicarboxylic acid anhydrides include the dicarboxylic acid anhydrides described above. Among these, acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, or maleic anhydride is used from the viewpoint of copolymerization reactivity and solubility of the resulting copolymer in a developer. preferable.
A compound (a1) can be used individually or in mixture of 2 or more types.
上記化合物(a2)としては、オキシラニル基を有する不飽和化合物として、例えば(メタ)アクリル酸オキシラニル(シクロ)アルキルエステル、α−アルキルアクリル酸オキシラニル(シクロ)アルキルエステル、不飽和結合を有するグリシジルエーテル化合物等を;
オキセタニル基を有する不飽和化合物として、例えばオキセタニル基を有する(メタ)アクリル酸エステル等を、それぞれ挙げることができる。これらの具体例としては、(メタ)アクリル酸オキシラニル(シクロ)アルキルエステルとして、例えば(メタ)アクリル酸グリシジル、(メタ)アクリル酸2−メチルグリシジル、4−ヒドロキシブチル(メタ)アクリレートグリシジルエーテル、(メタ)アクリル酸3,4−エポキシブチル、(メタ)アクリル酸6,7−エポキシヘプチル、(メタ)アクリル酸3,4−エポキシシクロヘキシル、(メタ)アクリル酸3,4−エポキシシクロヘキシルメチル等を;
α−アルキルアクリル酸オキシラニル(シクロ)アルキルエステルとして、例えば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等を;
不飽和結合を有するグリシジルエーテル化合物として、例えば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等を;
オキセタニル基を有する(メタ)アクリル酸エステルとして、例えば3−((メタ)アクリロイルオキシメチル)オキセタン、3−((メタ)アクリロイルオキシメチル)−3−エチルオキセタン、3−((メタ)アクリロイルオキシメチル)−2−メチルオキセタン、3−((メタ)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−((メタ)アクリロイルオキシエチル)オキセタン、3−メチル−3−(メタ)アクリロイルオキシメチルオキセタン、3−エチル−3−(メタ)アクリロイルオキシメチルオキセタン等を、それぞれ挙げることができる。これらのうち特に、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−エポキシシクロヘキシル、メタクリル酸3,4−エポキシシクロヘキシルメチル、3−メタクリロイルオキシメチル−3−エチルオキセタン、3−メチル−3−メタクリロイルオキシメチルオキセタン又は3−エチル−3−メタクリロイルオキシメチルオキセタンが、重合性の点から好ましい。
As the compound (a2), as an unsaturated compound having an oxiranyl group, for example, (meth) acrylic acid oxiranyl (cyclo) alkyl ester, α-alkylacrylic acid oxiranyl (cyclo) alkyl ester, glycidyl ether compound having an unsaturated bond Etc .;
Examples of the unsaturated compound having an oxetanyl group include (meth) acrylic acid ester having an oxetanyl group. Specific examples thereof include (meth) acrylic acid oxiranyl (cyclo) alkyl ester such as (meth) acrylic acid glycidyl, (meth) acrylic acid 2-methylglycidyl, 4-hydroxybutyl (meth) acrylate glycidyl ether, ( 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like;
Examples of α-alkylacrylic acid oxiranyl (cyclo) alkyl esters include 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 .;
Examples of the glycidyl ether compound having an unsaturated bond include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like;
Examples of (meth) acrylic acid ester having an oxetanyl group include 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, and 3-((meth) acryloyloxymethyl. ) -2-methyloxetane, 3-((meth) acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3-((meth) acryloyloxyethyl) oxetane, 3-methyl-3- (meth) acryloyloxy Examples thereof include methyl oxetane and 3-ethyl-3- (meth) acryloyloxymethyl oxetane. Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methyl- 3-Methacryloyloxymethyl oxetane or 3-ethyl-3-methacryloyloxymethyl oxetane is preferred from the viewpoint of polymerizability.
化合物(a2)は、単独で又は2種以上を混合して使用することができる。
上記化合物(a3)としては、例えば3−(メタ)アクリロイルオキシプロピルメチルジメトキシシラン、3−(メタ)アクリロイルオキシプロピルエチルジメトキシシラン、3−(メタ)アクリロイルオキシプロピルトリメトキシシラン、3−(メタ)アクリロイルオキシプロピルトリエトキシシラン等を挙げることができる。
化合物(a3)は、単独で又は2種以上を混合して使用することができる。
A compound (a2) can be used individually or in mixture of 2 or more types.
Examples of the compound (a3) include 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, and 3- (meth). Examples include acryloyloxypropyltriethoxysilane.
A compound (a3) can be used individually or in mixture of 2 or more types.
上記化合物(a4)としては、例えば(メタ)アクリル酸アルキルエステル、(メタ)アクリル酸シクロアルキルエステル、(メタ)アクリル酸アリールエステル、(メタ)アクリル酸アラルキルエステル、不飽和ジカルボン酸ジアルキルエステル、含酸素複素5員環又は含酸素複素6員環を有する(メタ)アクリル酸エステル、ビニル芳香族化合物、共役ジエン化合物及びその他の不飽和化合物を挙げることができる。これらの具体例としては、(メタ)アクリル酸アルキルエステルとして、例えばアクリル酸メチル、(メタ)アクリル酸n−プロピル、(メタ)アクリル酸i−プロピル、(メタ)アクリル酸n−ブチル、(メタ)アクリル酸sec−ブチル、(メタ)アクリル酸t−ブチル等を;
(メタ)アクリル酸シクロアルキルエステルとして、例えば(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸2−メチルシクロヘキシル、(メタ)アクリル酸トリシクロ[5.2.1.02,6]デカン−8−イル、(メタ)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、(メタ)アクリル酸イソボロニル等を;
(メタ)アクリル酸アリールエステルとして、例えばアクリル酸フェニル等を;
(メタ)アクリル酸アラルキルエステルとして、例えば(メタ)アクリル酸ベンジル等を;
不飽和ジカルボン酸ジアルキルエステルとして、例えばマレイン酸ジエチル、フマル酸ジエチル等を;
含酸素複素5員環又は含酸素複素6員環を有する(メタ)アクリル酸エステルとして、例えば(メタ)アクリル酸テトラヒドロフラン−2−イル、(メタ)アクリル酸テトラヒドロピラン−2−イル、(メタ)アクリル酸2−メチルテトラヒドロピラン−2−イル等を;
ビニル芳香族化合物として、例えばスチレン、α−メチルスチレン等を;
共役ジエン化合物として、例えば1,3−ブタジエン、イソプレン等を;
その他の不飽和化合物として、例えば(メタ)アクリル酸2−ヒドロキシエチル、アクリロニトリル、メタクリロニトリル、アクリルアミド、メタクリルアミド等を、それぞれ挙げることができる。これらの化合物(a2−3)のうち、共重合反応性の点から、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。
化合物(a4)は、単独で又は2種以上を混合して使用することができる。
Examples of the compound (a4) include (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid aryl ester, (meth) acrylic acid aralkyl ester, unsaturated dicarboxylic acid dialkyl ester, Mention may be made of (meth) acrylic acid esters, vinyl aromatic compounds, conjugated diene compounds and other unsaturated compounds having an oxygen hetero 5-membered ring or an oxygen-containing hetero 6-membered ring. Specific examples of these include (meth) acrylic acid alkyl esters such as methyl acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Sec-butyl acrylate, t-butyl (meth) acrylate, etc .;
Examples of the (meth) acrylic acid cycloalkyl ester include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 2,6 ] decane-8- (meth) acrylate. Yl, 2- (tricyclo [5.2.1.0 2,6 ] decan-8-yloxy) ethyl (meth) acrylate, isobornyl (meth) acrylate, and the like;
Examples of (meth) acrylic acid aryl esters include phenyl acrylate and the like;
Examples of (meth) acrylic acid aralkyl esters include benzyl (meth) acrylate and the like;
As unsaturated dicarboxylic acid dialkyl ester, for example, diethyl maleate, diethyl fumarate and the like;
Examples of the (meth) acrylic acid ester having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring include, for example, (meth) acrylic acid tetrahydrofuran-2-yl, (meth) acrylic acid tetrahydropyran-2-yl, (meth) 2-methyltetrahydropyran-2-yl acrylate, etc .;
Examples of vinyl aromatic compounds include styrene and α-methylstyrene;
Examples of the conjugated diene compound include 1,3-butadiene, isoprene and the like;
Examples of other unsaturated compounds include 2-hydroxyethyl (meth) acrylate, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide. Among these compounds (a2-3), from the viewpoint of copolymerization reactivity, n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, 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.
A compound (a4) can be used individually or in mixture of 2 or more types.
本発明における[A]重合体は、上記のような不飽和化合物を、各構造単位が上記した範囲内で所望の割合となるように混合してなる混合物を、好ましくは適当な溶媒中において、好ましくは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。
上記重合に用いられる溶媒としては、例えば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、ジエチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、エチレングリコールモノブチ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アセテート、ジプロピレングリコールモノメチルエーテルアセテート、酢酸3−メトキシブチル、シクロヘキサノールアセテート、ベンジルアルコール、3−メトキシブタノール等を挙げることができる。これらの溶媒は、単独で又は2種以上を混合して使用することができる。
上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)等のアゾ化合物を挙げることができる。これらのラジカル重合開始剤は、単独で又は2種以上を混合して使用することができる。
[A]重合体につき、ゲルパーミエーションクロマトグラフィ(GPC)によって測定したポリスチレン換算の重量平均分子量(以下、「Mw」という。)は、好ましくは2,000〜100,000であり、より好ましくは5,000〜50,000である。この範囲のMwを有する[A]重合体を使用することにより、良好な塗布性及び高い弾性回復力が損なわれることなく高い解像度が達成されるから、小さいサイズのパターンであっても特性のバランスが高度に調整された硬化膜を与えることができることとなる。
The [A] polymer in the present invention is a mixture obtained by mixing the unsaturated compound as described above so that each structural unit has a desired ratio within the above range, preferably in a suitable solvent. Preferably, it can be produced by polymerization in the presence of a radical polymerization initiator.
Examples of the solvent used for the polymerization include diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether. Examples include acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, 3-methoxybutanol and the like. These solvents can be used alone or in admixture of two or more.
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), 2,2 Examples include azo compounds such as' -azobis (4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators can be used alone or in admixture of two or more.
[A] The polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) of the polymer measured by gel permeation chromatography (GPC) is preferably 2,000 to 100,000, more preferably 5. , 50,000 to 50,000. By using the [A] polymer having Mw in this range, high resolution can be achieved without impairing good coatability and high elastic recovery force, so that even a small size pattern has a balanced property Can give a highly adjusted cured film.
<[B]重合性不飽和化合物>
本発明における[B]重合性不飽和化合物は、後述する(C)感放射線性重合開始剤の存在下において放射線を照射することにより重合する不飽和化合物である。このような重合性不飽和単量体としては、特に限定されるものではないが、例えば、単官能、2官能又は3官能以上の(メタ)アクリル酸エステルが、重合性が良好であり、且つ形成されるスペーサー及び層間絶縁膜の強度が向上する点から好ましい。
上記単官能(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(メタ)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)アクリレート、(2−(メタ)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、ω―カルボキシポリカプロラクトンモノ(メタ)アクリレート等を挙げることができる。これらの市販品としては、商品名で、例えば、アロニックスM−101、同M−111、同M−114、同M−5300(以上、東亞合成(株)製);KAYARADTC−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)等を挙げることができる。
上記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(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、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)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、1,9−ノナンジオールジ(メタ)アクリレート等を挙げることができる。これらの市販品としては、商品名で、例えばアロニックスM−210、同M−240、同M−6200(以上、東亞合成(株)製)、KAYARADHDDA、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)、ライトアクリレート1,9−NDA(共栄社化学(株)製等を挙げることができる。
<[B] polymerizable unsaturated compound>
[B] The polymerizable unsaturated compound in the present invention is an unsaturated compound that is polymerized by irradiation with radiation in the presence of a radiation-sensitive polymerization initiator (C) described later. Such a polymerizable unsaturated monomer is not particularly limited, and for example, a monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid ester has good polymerizability, and This is preferable because the strength of the formed spacer and interlayer insulating film is improved.
Examples of the monofunctional (meth) acrylic acid ester include 2-hydroxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, (2- (meth) acryloyloxyethyl) (2-hydroxypropyl) phthalate, ω -Carboxypolycaprolactone mono (meth) acrylate and the like. As these commercial items, for example, Aronix M-101, M-111, M-114, M-5300 (above, manufactured by Toagosei Co., Ltd.); KAYARA DTC-110S, TC- 120S (above, Nippon Kayaku Co., Ltd.); Biscoat 158, 2311 (above, Osaka Organic Chemical Industry Co., Ltd.) and the like.
Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol diacrylate, and tetraethylene glycol di (meth) acrylate. 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and the like. As these commercially available products, for example, Aronix M-210, M-240, M-6200 (above, manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (or more). , Nippon Kayaku Co., Ltd.), Biscoat 260, 312, 335HP (Osaka Organic Chemical Co., Ltd.), Light Acrylate 1,9-NDA (Kyoeisha Chemical Co., Ltd.), etc. it can.
上記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(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート;ジペンタエリスリトールペンタ(メタ)アクリレートとジペンタエリスリトールヘキサ(メタ)アクリレートとの混合物;エチレンオキサイド変性ジペンタエリスリトールヘキサ(メタ)アクリレート、トリ(2−(メタ)アクリロイルオキシエチル)フォスフェート、コハク酸変性ペンタエリスリトールトリ(メタ)アクリレート、コハク酸変性ジペンタエリスリトールペンタ(メタ)アクリレート;
直鎖アルキレン基及び脂環式構造を有し且つ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且つ3個、4個又は5個の(メタ)ア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。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、東亞合成(株)製)、KAYARADTMPTA、同DPHA、同DPCA−20、同DPCA−30、同DPCA−60、同DPCA−120、同DPEA−12(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)、KAYARADDPHA−40H(日本化薬(株)製)等を挙げることができる。
Examples of the trifunctional or higher functional (meth) acrylic acid ester include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate; mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; ethylene oxide modified dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxy Ethyl) phosphate, succinic acid modified pentaerythritol tri (meth) acrylate, succinic acid modified dipentaerythritol penta (meth) acrylate;
A compound having a straight-chain alkylene group and an alicyclic structure and having two or more isocyanate groups, and 3, 4, or 5 (meth) acryloyloxy having one or more hydroxyl groups in the molecule Examples thereof include polyfunctional urethane acrylate compounds obtained by reacting a group-containing compound. As a commercial item of trifunctional or higher functional (meth) acrylic acid ester, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M-8030 are trade names. , M-8060, TO-1450 (above, manufactured by Toagosei Co., Ltd.), KAYARADTMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPEA-12 (Nippon Kayaku Co., Ltd.), Biscoat 295, 300, 360, GPT, 3PA, 400 (above Osaka Organic Chemical Co., Ltd.) and polyfunctional urethane acrylate compounds Examples of commercially available products include New Frontier R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.), KAYARADDPHA-40H (Nippon Kayaku Co., Ltd.), etc. Can.
これらのうち、特に、ω―カルボキシポリカプロラクトンモノアクリレート、1,9−ノナンジオールジメタクリレート、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;
ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートとの混合物;
エチレンオキサイド変性ジペンタエリスリトールヘキサアクリレート、多官能ウレタンアクリレート系化合物、コハク酸変性ペンタエリスリトールトリアクリレート、コハク酸変性ジペンタエリスリトールペンタアクリレートを含有する市販品等が好ましい。
上記のような[B]重合性不飽和化合物は、単独で又は2種以上を混合して使用することができる。
本発明の感放射線性樹脂組成物における[B]重合性不飽和単量体の使用割合は、[A]重合体100質量部に対して、好ましくは30〜250質量部であり、さらに好ましくは50〜200質量部である。[B]重合性不飽和単量体の使用割合を上記の範囲とすることにより、現像残差の問題を生じることなく、弾性回復率に優れる硬化膜を、高い解像度で形成することができることとなり、好ましい。
Among these, ω-carboxypolycaprolactone monoacrylate, 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate ;
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate;
Commercially available products containing ethylene oxide-modified dipentaerythritol hexaacrylate, polyfunctional urethane acrylate compounds, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, and the like are preferable.
[B] The polymerizable unsaturated compounds as described above can be used alone or in admixture of two or more.
The proportion of the [B] polymerizable unsaturated monomer used in the radiation sensitive resin composition of the present invention is preferably 30 to 250 parts by mass, more preferably 100 parts by mass of the [A] polymer. It is 50-200 mass parts. [B] By setting the use ratio of the polymerizable unsaturated monomer within the above range, a cured film having an excellent elastic recovery rate can be formed with high resolution without causing a problem of development residual. ,preferable.
<[C]感放射線性重合開始剤>
本発明における[C]感放射線性重合開始剤は、放射線に感応して[B]重合性不飽和化合物の重合を開始しうる活性種を生じる成分である。このような[C]感放射線性重合開始剤としては、例えばO−アシルオキシム化合物、アセトフェノン化合物、ビイミダゾール化合物、ベンゾフェノン化合物等を挙げることができる。
上記O−アシルオキシム化合物の具体例としては、エタノン−1−〔9−エチル−6−(2−メチルベンゾイル)−9H−カルバゾール−3−イル〕−1−(O−アセチルオキシム)、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−アセテート、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−ベンゾエート、1−〔9−n−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−ベンゾエート、エタノン−1−[9−エチル−6−(2−メチル−4−テトラヒドロフラニルベンゾイル)−9.H.−カルバゾール−3−イル]−1−(O−アセチルオキシム)、エタノン−1−〔9−エチル−6−(2−メチル−4−テトラヒドロピラニルベンゾイル)−9.H.−カルバゾール−3−イル〕−1−(O−アセチルオキシム)、エタノン−1−〔9−エチル−6−(2−メチル−5−テトラヒドロフラニルベンゾイル)−9.H.−カルバゾール−3−イル〕−1−(O−アセチルオキシム)、エタノン−1−〔9−エチル−6−{2−メチル−4−(2,2−ジメチル−1,3−ジオキソラニル)メトキシベンゾイル}−9.H.−カルバゾール−3−イル〕−1−(O−アセチルオキシム)等を挙げることができ、これらのうち、エタノン−1−〔9−エチル−6−(2−メチルベンゾイル)−9H−カルバゾール−3−イル〕−1−(O−アセチルオキシム)、エタノン−1−〔9−エチル−6−(2−メチル−4−テトラヒドロフラニルメトキシベンゾイル)−9.H.−カルバゾール−3−イル〕−1−(O−アセチルオキシム)又はエタノン−1−〔9−エチル−6−{2−メチル−4−(2,2−ジメチル−1,3−ジオキソラニル)メトキシベンゾイル}−9.H.−カルバゾール−3−イル〕−1−(O−アセチルオキシム)を使用することが好ましい。
上記アセトフェノン化合物としては、例えばα−アミノケトン化合物、α−ヒドロキシケトン化合物を挙げることができる。
<[C] Radiation sensitive polymerization initiator>
The [C] radiation-sensitive polymerization initiator in the present invention is a component that generates an active species that can initiate polymerization of the [B] polymerizable unsaturated compound in response to radiation. Examples of such [C] radiation-sensitive polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and benzophenone compounds.
Specific examples of the O-acyloxime compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 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-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like. Among these, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) is preferably used.
Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.
上記α−アミノケトン化合物の具体例としては、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−ジメチルアミノ−2−(4−メチルベンジル)−1−(4−モルフォリン−4−イル−フェニル)−ブタン−1−オン、2−メチル−1−(4−メチルチオフェニル)−2−モルフォリノプロパン−1−オン等を;
上記α−ヒドロキシケトン化合物の具体例としては、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、それぞれ挙げることができる。これらのアセトフェノン化合物のうちα−アミノケトン化合物が好ましく、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−オン又は2−ジメチルアミノ−2−(4−メチルベンジル)−1−(4−モルフォリン−4−イル−フェニル)−ブタン−1−オンを使用することが特に好ましい。
上記ビイミダゾール化合物の具体例としては、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−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’−ビイミダゾール等を挙げることができ、これらのうち、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’−ビイミダゾール又は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’−ビイミダゾールを使用することが好ましい。なお、[C]感放射線性重合開始剤としてビイミダゾール化合物を使用する場合、ジアルキルアミノ基を有する脂肪族又は芳香族化合物(アミノ系増感剤)及びチオール化合物から選択される少なくとも1種を併用してもよい。
Specific examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1. -(4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and the like;
Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane- Examples thereof include 1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, and the like. Of these acetophenone compounds, α-aminoketone compounds are preferred, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-dimethylamino-2- (4-methylbenzyl) It is particularly preferred to use -1- (4-morpholin-4-yl-phenyl) -butan-1-one.
Specific examples of the biimidazole compound include, for example, 2,2′-bis (2-chlorophenyl) -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 and the like can be mentioned, and among these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-te Raphenyl-1,2′-biimidazole or 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole is preferred, In particular, it is preferable to use 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole. [C] When a biimidazole compound is used as a radiation-sensitive polymerization initiator, at least one selected from an aliphatic or aromatic compound (amino sensitizer) having a dialkylamino group and a thiol compound is used in combination. May be.
本発明の感放射線性樹脂組成物における[C]感放射線性重合開始剤の使用割合としては、[A]重合体100質量部に対して、好ましくは1〜60質量部であり、より好ましくは2〜50質量部であり、さらに好ましくは5〜40質量部である。
本発明の感放射線性樹脂組成物に含有される[C]感放射線性重合開始剤としては、O−アシルオキシム化合物及びアセトフェノン化合物よりなる群から選択される少なくとも1種を含有することが好ましく、O−アシルオキシム化合物及びアセトフェノン化合物よりなる群から選択される少なくとも1種並びにビイミダゾール化合物を含有することがより好ましい。[C]感放射線性重合開始剤におけるO−アシルオキシム化合物及びアセトフェノン化合物の割合としては、これらの合計量が[C]感放射線性重合開始剤の全量に対して好ましくは40質量%以上となる割合であり、より好ましくは45質量%以上となる割合であり、特に好ましくは50質量%以上となる割合である。このような組成の[C]感放射線性重合開始剤を使用することにより、良好な塗布性及び高い弾性回復力が損なわれることなく高い解像度が達成されるから、小さいサイズのパターンであっても特性のバランスが高度に調整された硬化膜を与えることができることとなる。
The use ratio of the [C] radiation sensitive polymerization initiator in the radiation sensitive resin composition of the present invention is preferably 1 to 60 parts by mass, more preferably 100 parts by mass of the [A] polymer. It is 2-50 mass parts, More preferably, it is 5-40 mass parts.
[C] The radiation-sensitive polymerization initiator contained in the radiation-sensitive resin composition of the present invention preferably contains at least one selected from the group consisting of an O-acyloxime compound and an acetophenone compound, More preferably, it contains at least one selected from the group consisting of O-acyloxime compounds and acetophenone compounds and a biimidazole compound. [C] As a ratio of the O-acyloxime compound and the acetophenone compound in the radiation-sensitive polymerization initiator, the total amount thereof is preferably 40% by mass or more based on the total amount of the [C] radiation-sensitive polymerization initiator. The ratio is more preferably 45% by mass or more, and particularly preferably 50% by mass or more. By using the [C] radiation-sensitive polymerization initiator having such a composition, high resolution can be achieved without impairing good coatability and high elastic recovery force. A cured film having a highly balanced property can be provided.
<[D]成分>
本発明における[D]成分は、上記式(2)で表される加水分解性シラン化合物の加水分解縮合物である。ここで、「加水分解縮合物」とは、上記式(2)におけるSi−OR5結合が加水分解してシラノール基を形成し、さらに該シラノール基の2個が脱水縮合してSi−O−Si結合を形成した生成物をいう。このとき、Si−OR5結合及びシラノール基のうちの片方又は双方が残存していたとしても、分子内に少なくとも1つのSi−O−Si結合が存在すれば、上記「加水分解縮合物」に該当するものである。
上記式(2)におけるR4及びR5のアルキル基は直鎖状、分岐状及び環状のいずれでもよい。これらの具体例としては、R4及びR5それぞれ独立に、例えばメチル基、エチル基、n−プロピル基、iso−プロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基等を挙げることができる。R4及びR5のフルオロアルキル基は直鎖状、分岐状及び環状のいずれでもよい。これらの具体例としては、R1及びR2それぞれ独立に、例えばトリフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、パーフルオロイソプロピル基、パーフルオロシクロヘキシル基等を挙げることができる。R4及びR5のアリール基としては、炭素数が6〜14の単環式、二環式又は三環式のアリール基であることが好ましい。これらの具体例としては、R4及びR5それぞれ独立に、例えばフェニル基、ナフチル基、アントリル基、フェナントリル基等を挙げることができ、これらうちのフェニル基又はナフチル基であることが好ましく、特にフェニル基が好ましい。
<[D] component>
[D] component in this invention is a hydrolysis-condensation product of the hydrolysable silane compound represented by the said Formula (2). Here, the “hydrolysis condensate” means that the Si—OR 5 bond in the above formula (2) is hydrolyzed to form a silanol group, and two of the silanol groups are dehydrated and condensed to form Si—O—. It refers to the product that has formed Si bonds. At this time, even if one or both of the Si—OR 5 bond and the silanol group remain, if at least one Si—O—Si bond is present in the molecule, the above “hydrolysis condensate” Applicable.
The alkyl group of R 4 and R 5 in the above formula (2) may be linear, branched or cyclic. Specific examples thereof include R 4 and R 5 independently, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group. Hexyl group, cyclohexyl group and the like. The fluoroalkyl group of R 4 and R 5 may be linear, branched or cyclic. Specific examples of these include, independently, R 1 and R 2 such as a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, and a perfluorocyclohexyl group. The aryl group of R 4 and R 5 is preferably a monocyclic, bicyclic or tricyclic aryl group having 6 to 14 carbon atoms. Specific examples of these include, independently, R 4 and R 5 , for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and the like. Among these, a phenyl group or a naphthyl group is preferable. A phenyl group is preferred.
上記式(2)におけるjとしては、2〜6の整数であることが好ましく、特には3又は4であることが好ましい。
上記式(2)で表される加水分解性シラン化合物としては、式(2)において、k=1、m=1の化合物;k=1、m=0の化合物;k=0、m=2の化合物;k=0、m=1の化合物;及びk=0、m=0の化合物よりなる群から選択される少なくとも1種を使用することが好ましい。
上記式(2)においてk=1、m=1の化合物としては、例えば上記化合物(a3)に該当する化合物のうちの、3−(メタ)アクリロイルオキシプロピルメチルジメトキシシラン、3−(メタ)アクリロイルオキシプロピルエチルジメトキシシラン等を;
k=1、m=0の化合物としては、例えば上記化合物(a3)に該当する化合物のうちの、3−(メタ)アクリロイルオキシプロピルトリメトキシシラン、3−(メタ)アクリロイルオキシプロピルトリエトキシシラン等を;
k=0、m=2の化合物の化合物としては、例えばジメチルジメトキシシラン、ジブチルジメトキシシラン、ジフェニルジメトキシシラン等を;
k=0、m=1の化合物としては、例えばメチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリ−iso−プロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリ−iso−プロポキシシラン、エチルトリブトキシシラン、ブチルトリメトキシシラン、デシルトリメトキシシラン、トリフルオロプロピルトリメトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン等を;
k=0、m=0の化合物としては、例えばテトラメトキシシラン、テトラエトキシシラン、テトラブトキシシラン、テトラフェノキシシラン、テトラベンジロキシシラン、テトラ−n−プロポキシシラン、テトラ−iso−プロポキシシラン等を、それぞれ挙げることができる。
J in the formula (2) is preferably an integer of 2 to 6, and particularly preferably 3 or 4.
Examples of the hydrolyzable silane compound represented by the above formula (2) include a compound of k = 1, m = 1 in the formula (2); a compound of k = 1, m = 0; k = 0, m = 2. It is preferable to use at least one selected from the group consisting of: a compound of k = 0, m = 1; and a compound of k = 0, m = 0.
In the above formula (2), examples of the compound having k = 1 and m = 1 include 3- (meth) acryloyloxypropylmethyldimethoxysilane and 3- (meth) acryloyl among the compounds corresponding to the compound (a3). Oxypropylethyldimethoxysilane and the like;
Examples of the compound with k = 1 and m = 0 include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, etc., among the compounds corresponding to the compound (a3). ;
Examples of the compound of the compound of k = 0 and m = 2 include dimethyldimethoxysilane, dibutyldimethoxysilane, diphenyldimethoxysilane and the like;
Examples of the compound with k = 0 and m = 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltri-iso-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-iso-propoxy. Silane, ethyltributoxysilane, butyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, etc .;
As a compound of k = 0, m = 0, for example, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, etc. Each can be mentioned.
上記式(2)で表される加水分解性シラン化合物としては、上記のうちのk=1、m=1の化合物;k=1、m=0の化合物;及びk=0、m=1の化合物よりなる群から選択される1種以上を0.1モル%以上含むことが好ましく、50モル%以上含むことがより好ましく、これらのみからなるものであることがさらに好ましい。上記式(2)で表される加水分解性シラン化合物として特に好ましくは、上記のうちのk=1、m=1の化合物;k=1、m=0の化合物;及びk=0、m=1の化合物のみからなり、且つk=1、m=1の化合物及びk=1、m=0の化合物よりなる群から選択される1種以上を5〜20モル%含む場合であり、後者を10〜20モル%含む場合がとりわけ好ましい。
[D]成分につき、ゲルパーミエーションクロマトグラフィ(GPC)によって測定したポリスチレン換算の重量平均分子量(以下、「Mw」という。)は、好ましくは200〜10,000であり、より好ましくは500〜7,000である。この範囲のMwを有する[D]成分を使用することにより、良好な塗布性及び高い弾性回復力が損なわれることなく高い解像度が達成されるから、小さいサイズのパターンであっても特性のバランスが高度に調整された硬化膜を与えることができることとなる。
Examples of the hydrolyzable silane compound represented by the above formula (2) include compounds of k = 1 and m = 1, compounds of k = 1 and m = 0, and those of k = 0 and m = 1. One or more selected from the group consisting of compounds is preferably contained in an amount of 0.1 mol% or more, more preferably 50 mol% or more, and even more preferably only of these. The hydrolyzable silane compound represented by the formula (2) is particularly preferably a compound of k = 1 and m = 1 of the above; a compound of k = 1 and m = 0; and k = 0, m = 1 to 5 mol% of one or more selected from the group consisting of a compound of k = 1 and m = 1 and a compound of k = 1 and m = 0. The case where it contains 10-20 mol% is especially preferable.
For the component [D], the weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC) is preferably 200 to 10,000, more preferably 500 to 7, 000. By using the [D] component having Mw in this range, high resolution can be achieved without impairing good coating properties and high elastic recovery force, so that the balance of characteristics can be achieved even with a small size pattern. A highly adjusted cured film can be provided.
上記式(2)で表される加水分解性シラン化合物の加水分解縮合は、公知の方法に従って行うことでき、例えば適当な有機溶媒中で、好ましくは適当な触媒の存在下に、加水分解性シラン化合物の全量に対して好ましくは0.1〜3倍モルの水を添加することによって行うことができる。ここで使用される触媒としては、酸、塩基、金属アルコキシド等を挙げることができる。上記酸の具体例としては、例えば塩酸、硫酸、硝酸、蟻酸、シュウ酸、酢酸、トリフルオロ酢酸、トリフルオロメタンスルホン酸、リン酸等のほか、酸性イオン交換樹脂、各種ルイス酸等を挙げることができる。上記塩基としては、例えば有機塩基、金属のアルコキシド、塩基性イオン交換樹脂、金属の水酸化物、金属の炭酸塩、金属のカルボン酸塩、各種ルイス酸等を挙げることができ、これらの具体例としては、上記有機塩基として、例えばアンモニア、1級アミン類、2級アミン類、3級アミン類、ピリジン等を;
上記金属の水酸化物として、例えば水酸化ナトリウム等を;
上記金属の炭酸塩として、例えば炭酸カリウム等を;
上記金属のカルボン酸塩として、例えば酢酸ナトリウム等を、それぞれ挙げることができる。上記金属のアルコキシドとして、例えばジルコニウムアルコキシド、チタニウムアルコキシド、アルミニウムアルコキシド(例えばテトラ−i−プロポキシアルミニウム等)等を挙げることができる。
触媒の使用割合は、加水分解性シラン化合物の合計1モルに対して、10−5〜0.2モルとすることが好ましく、10−5〜0.2モルとすることがより好ましい。反応温度は60〜90℃とすることが好ましく、反応時間は3〜9時間とすることが好ましい。
Hydrolysis condensation of the hydrolyzable silane compound represented by the above formula (2) can be carried out according to a known method, for example, hydrolyzable silane in an appropriate organic solvent, preferably in the presence of an appropriate catalyst. It can carry out by adding preferably 0.1-3 times mole water of the compound with respect to the whole quantity. Examples of the catalyst used here include acids, bases, metal alkoxides and the like. Specific examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resins, various Lewis acids, and the like. it can. Examples of the base include organic bases, metal alkoxides, basic ion exchange resins, metal hydroxides, metal carbonates, metal carboxylates, various Lewis acids, and specific examples thereof. As the organic base, for example, ammonia, primary amines, secondary amines, tertiary amines, pyridine and the like;
Examples of the metal hydroxide include sodium hydroxide;
Examples of the metal carbonate include potassium carbonate;
Examples of the metal carboxylate include sodium acetate. Examples of the metal alkoxide include zirconium alkoxide, titanium alkoxide, aluminum alkoxide (for example, tetra-i-propoxyaluminum) and the like.
The use ratio of the catalyst is preferably 10 −5 to 0.2 mol, and more preferably 10 −5 to 0.2 mol, with respect to 1 mol of the total hydrolyzable silane compound. The reaction temperature is preferably 60 to 90 ° C., and the reaction time is preferably 3 to 9 hours.
上記の説明から明らかなように、上記式(2)で表される加水分解性シラン化合物は、[A]重合体の原料として使用される化合物(a3)を包含する。また、[A]重合体を合成した後の重合混合物は、これに対して格別の精製操作を行うことなく、本発明の感放射線性樹脂組成物の調製に供することが便宜である。この場合、[A]重合体の合成時に使用した化合物(a3)が重合系内に存在する水分と反応して生成した加水分解縮合物は、本発明における[D]成分として考慮してよい。 As is clear from the above description, the hydrolyzable silane compound represented by the formula (2) includes the compound (a3) used as a raw material for the [A] polymer. Moreover, it is convenient to use for the preparation of the radiation sensitive resin composition of this invention, without performing a special refinement | purification operation with respect to the polymerization mixture after synthesize | combining a [A] polymer. In this case, the hydrolysis condensate generated by the reaction of the compound (a3) used in the synthesis of the [A] polymer with the water present in the polymerization system may be considered as the [D] component in the present invention.
本発明における[D]成分として特に好ましくは、[A]重合体の合成時に使用した化合物(a3)と同一の化合物の加水分解縮合物を使用することである。この場合の[D]成分は、下記(3)で表される構造を含むシロキサン化合物である。 As the [D] component in the present invention, it is particularly preferable to use a hydrolysis condensate of the same compound as the compound (a3) used in the synthesis of the [A] polymer. In this case, the component [D] is a siloxane compound having a structure represented by the following (3).
(式(3)中、R3及びjは、それぞれ、上記式(2)におけるのと同じ意味である。)
上記式(3)における大カッコは、この構造単位が繰り返し単位であることを示す。上記式(3)のケイ素原子から上に伸びる結合手は、式(2)中の係数mの値に応じて、酸素原子を介して他のケイ素原子と結合していてもよく(m=0の場合)、あるいはR4と結合していてもよい(m=1の場合)。
(In the formula (3), R 3 and j have the same meaning as in the above formula (2).)
The brackets in the above formula (3) indicate that this structural unit is a repeating unit. The bond extending upward from the silicon atom in the formula (3) may be bonded to another silicon atom via an oxygen atom according to the value of the coefficient m in the formula (2) (m = 0). Or may be bonded to R 4 (when m = 1).
本発明の感放射線性樹脂組成物における[D]成分の使用割合は、上記[A]重合体の100質量部に対して0.1〜50質量部であり、好ましくは1〜40質量部である。[D]成分の使用割合を上記の範囲とすることにより、良好な塗布性及び高い弾性回復力が損なわれることなく高い解像度が達成されるから、小さいサイズのパターンであっても特性のバランスが高度に調整された硬化膜を与えることができることとなる。
The ratio of [D] component in radiation-sensitive resin composition of the present invention, the [A] Ri 0.1 to 50 parts by mass der with respect to 100 parts by weight of the polymer, the good Mashiku 1-40 Part by mass. By setting the use ratio of the component [D] within the above range, high resolution can be achieved without impairing good coatability and high elastic recovery force. A highly adjusted cured film can be provided.
<その他の成分>
本発明の感放射線性樹脂組成物は、上記の[A]重合体、[B]重合性不飽和化合物、[C]感放射線性重合開始剤及び[D]成分を含有する。これら以外に、[E]接着助剤、[F]界面活性剤、[G]重合禁止剤等を含有していてもよい。
上記[E]接着助剤は、形成されるスペーサーと基板との接着性をさらに向上するために使用することができる。このような[E]接着助剤としては、上記化合物(a3)と同じものを使用することができるほか、トリメトキシシリル安息香酸、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−イソシアネ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、γ−グリシドキシプロピルアルキルジアルコキシシラン、γ−クロロプロピルトリアルコキシシラン、γ−メルカプトプロピルトリアルコキシシラン、β−(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等を使用することができる。本発明の感放射線性樹脂組成物における[E]接着助剤の使用割合は、[A]重合体100質量部に対して、好ましくは20質量部以下であり、より好ましくは1〜10質量部である。[E]接着助剤の含有割合を上記の範囲とすることにより、形成される硬化膜と基板との密着性が効果的に改善される。
上記[F]界面活性剤としては、例えばフッ素系界面活性剤、シリコーン系界面活性剤等を挙げることができる。本発明の感放射線性樹脂組成物における[F]界面活性剤の使用割合は、[A]重合体100質量部に対して、好ましくは1質量部以下であり、より好ましくは0.01〜0.6質量部である。
<Other ingredients>
The radiation sensitive resin composition of the present invention contains the above [A] polymer, [B] polymerizable unsaturated compound, [C] radiation sensitive polymerization initiator and [D] component. In addition to these, [E] an adhesion assistant, [F] a surfactant, [G] a polymerization inhibitor may be contained.
The [E] adhesion aid can be used to further improve the adhesion between the formed spacer and the substrate. As such [E] adhesion aid, the same compounds as the above compound (a3) can be used, and trimethoxysilylbenzoic acid, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxy. Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane or the like can be used. The use ratio of the [E] adhesion assistant in the radiation sensitive resin composition of the present invention is preferably 20 parts by mass or less, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the [A] polymer. It is. [E] By making the content rate of an adhesion assistant into said range, the adhesiveness of the cured film formed and a board | substrate is improved effectively.
Examples of the [F] surfactant include a fluorine-based surfactant and a silicone-based surfactant. The ratio of the [F] surfactant used in the radiation-sensitive resin composition of the present invention is preferably 1 part by mass or less, more preferably 0.01 to 0 with respect to 100 parts by mass of the [A] polymer. .6 parts by mass.
上記[G]重合禁止剤は、露光若しくは加熱によって発生したラジカルを捕捉し、又は酸化によって生成した過酸化物を分解することにより、[A]重合体の分子の開裂を抑制する成分である。本発明の感放射線性樹脂組成物が[G]重合禁止剤を含有することにより、形成される硬化膜中の重合体分子の解裂劣化が抑制されるから、硬化膜の例えば耐光性等を向上させることができる。
このような[G]重合禁止剤としては、例えばヒンダードフェノール化合物、ヒンダードアミン化合物、アルキルホスファイト化合物、チオエーテル化合物等を挙げることができるが、これらのうちのヒンダードフェノール化合物を好ましく使用することができる。
[G] The polymerization inhibitor is a component that suppresses the cleavage of [A] polymer molecules by capturing radicals generated by exposure or heating, or by decomposing a peroxide generated by oxidation. Since the radiation-sensitive resin composition of the present invention contains a [G] polymerization inhibitor, the degradation degradation of polymer molecules in the formed cured film is suppressed. Can be improved.
Examples of such a [G] polymerization inhibitor include hindered phenol compounds, hindered amine compounds, alkyl phosphite compounds, thioether compounds, and the like. Of these, hindered phenol compounds are preferably used. it can.
上記ヒンダードフェノール化合物としては、例えばペンタエリスリトールテトラキス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート]、チオジエチレンビス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート]、オクタデシル−3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート、トリス−(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)−イソシアヌレイト、1,3,5−トリメチル−2,4,6−トリス(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)ベンゼン、N,N’−ヘキサン−1,6−ジイルビス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニルプロピオンアミド)、3,3’,3’,5’,5’−ヘキサ−tert−ブチル−a,a’,a’−(メシチレン−2,4,6−トリイル)トリ−p−クレゾール、4,6−ビス(オクチルチオメチル)−o−クレゾール、4,6−ビス(ドデシルチオメチル)−o−クレゾール、エチレンビス(オキシエチレン)ビス[3−(5−tert−ブチル−4−ヒドロキシ−m−トリル)プロピオネート、ヘキサメチレンビス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート]、1,3,5−トリス[(4−tert−ブチル−3−ヒドロキシ−2,6−キシリル)メチル]−1,3,5−トリアジン−2,4,6(1H,3H,5H)−トリオン、2,6−ジ−tert−ブチル−4−(4,6−ビス(オクチルチオ)−1,3,5−トリアジン−2−イルアミン)フェノール等を挙げることができる。
これらの市販品としては、例えばアデカスタブAO−20、同AO−30、同AO−40、同AO−50、同AO−60、同AO−70、同AO−80、同AO−330(以上、(株)ADEKA製)、sumilizerGM、同GS、同MDP−S、同BBM−S、同WX−R、同GA−80(以上、住友化学(株)製)、IRGANOX1010、同1035、同1076、同1098、同1135、同1330、同1726、同1425WL、同1520L、同245、同259、同3114、同565、IRGAMOD295(以上、BASF社製)、ヨシノックスBHT、同BB、同2246G、同425、同250、同930、同SS、同TT、同917、同314(以上、(株)エーピーアイコーポレーション製)等を挙げることができる。
Examples of the hindered phenol compound include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert-butyl). -4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (3,5-di-tert-butyl-4-hydroxybenzyl)- Isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N′-hexane-1,6-diylbis [ 3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 3,3 ′, 3 ′, ', 5'-hexa-tert-butyl-a, a', a '-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate, hexamethylenebis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3 5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine-2 -B Amines) phenol and the like can be mentioned.
As these commercially available products, for example, ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, AO-330 (above, (Manufactured by ADEKA), sumilizer GM, GS, MDP-S, BBM-S, WX-R, GA-80 (above, manufactured by Sumitomo Chemical Co., Ltd.), IRGANOX 1010, 1035, 1076, Same 1098, Same 1135, Same 1330, Same 1726, Same 1425 WL, Same 1520L, Same 245, Same 259, Same 3114, Same 565, IRGAMOD295 (above, manufactured by BASF), Yoshinox BHT, Same BB, Same 2246G, Same 425 , 250, 930, SS, TT, 917, 314 (above, manufactured by API Corporation), etc. It is possible.
本発明における[G]重合禁止剤としては、上記のうちのペンタエリスリトールテトラキス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート]及びトリス−(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)−イソシアヌレイトよりなる群から選択される1種以上を使用することが好ましい。
[G]重合禁止剤の含有割合は、[A]重合体100質量部に対して、10質量部以下とすることが好ましく、0.1〜5質量部とすることがより好ましい。この範囲の含有割合とすることにより、本発明の多の効果を阻害することなく、硬化膜の開裂劣化を効果的に抑制することができることとなる。
As the [G] polymerization inhibitor in the present invention, among the above, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and tris- (3,5-di- It is preferable to use one or more selected from the group consisting of tert-butyl-4-hydroxybenzyl) -isocyanurate.
[G] The content of the polymerization inhibitor is preferably 10 parts by mass or less, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the [A] polymer. By setting the content ratio in this range, the degradation degradation of the cured film can be effectively suppressed without inhibiting many effects of the present invention.
<感放射線性樹脂組成物の調製>
本発明の感放射線性樹脂組成物は、上記の[A]重合体、[B]重合性不飽和化合物、[C]感放射線性重合開始剤及び[D]成分並びに任意的に添加されるその他の成分を所定の割合でそれぞれ均一に混合することによって調製される。この感放射線性樹脂組成物は、好ましくは適当な溶媒に溶解されて溶液状態で用いられる。
本発明の感放射線性樹脂組成物の調製に用いられる溶媒としては、[A]重合体、[B]重合性不飽和化合物、[C]感放射線性重合開始剤及び[D]成分並びに任意的に添加されるその他の成分を均一に溶解し、各成分と反応しないものが用いられる。このような溶媒としては、上述した[A]重合体を製造するために使用できる溶媒として例示したものと同様のものを挙げることができる。これらの溶媒は、1種のみを単独で使用することができ、2種以上を混合して使用してもよい。
本発明の感放射線性樹脂組成物を溶液状態として調製する場合、固形分濃度(組成物溶液中に占める溶媒以外の成分、すなわち上記の[A]重合体、[B]重合性不飽和化合物、[C]感放射線性重合開始剤及び[D]成分並びに任意的に添加されるその他の成分の合計量の割合)は、使用目的や所望の膜厚の値等に応じて任意の濃度(例えば5〜50質量%)に設定することができる。さらに好ましい固形分濃度は、基板上への塗膜の形成方法により異なる。塗布方法としてスピンコート法を採用する場合の固形分濃度は、20〜50質量%であることがさらに好ましく、特に30〜40質量%であることが好ましい。スリット塗布法を採用する場合の固形分濃度は、10〜35質量%であることがさらに好ましく、特に15〜30質量%であることが好ましい。
このようにして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濾過した後、使用に供してもよい。
<Preparation of radiation-sensitive resin composition>
The radiation-sensitive resin composition of the present invention includes the above-mentioned [A] polymer, [B] polymerizable unsaturated compound, [C] radiation-sensitive polymerization initiator and [D] component, and other optionally added. The components are uniformly mixed at a predetermined ratio. This radiation-sensitive resin composition is preferably used in a solution state after being dissolved in an appropriate solvent.
Solvents used in the preparation of the radiation sensitive resin composition of the present invention include [A] polymer, [B] polymerizable unsaturated compound, [C] radiation sensitive polymerization initiator and [D] component, and optional. The other components added to are uniformly dissolved and do not react with each component. As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture the above-mentioned [A] polymer can be mentioned. These solvents can be used alone or in a combination of two or more.
When preparing the radiation-sensitive resin composition of the present invention in a solution state, the solid content concentration (components other than the solvent in the composition solution, that is, the above-mentioned [A] polymer, [B] polymerizable unsaturated compound, [C] The ratio of the total amount of the radiation-sensitive polymerization initiator, the [D] component, and other components optionally added) can be any concentration (for example, depending on the purpose of use, the desired film thickness value, etc.) 5 to 50% by mass). A more preferable solid content concentration varies depending on a method of forming a coating film on a substrate. When the spin coating method is employed as the coating method, the solid content concentration is more preferably 20 to 50% by mass, and particularly preferably 30 to 40% by mass. The solid concentration in the case of employing the slit coating method is more preferably 10 to 35% by mass, and particularly preferably 15 to 30% by mass.
The composition solution thus prepared may be used after being filtered using a Millipore filter having a pore size of about 0.5 μm.
<スペーサー及び層間絶縁膜の形成方法>
次に、本発明の感放射線性樹脂組成物を用いてスペーサーを形成する方法について説明する。
本発明におけるスペーサー又は層間絶縁膜の形成方法は、少なくとも下記の工程(1)〜(4)を下記に記載の順で含むことを特徴とするものである。
(1)本発明の感放射線性樹脂組成物を基板上に塗布して塗膜を形成する工程、
(2)該塗膜の少なくとも一部に露光する工程、
(3)露光後の塗膜を現像する工程、及び
(4)現像後の塗膜を加熱する工程。
<Method for forming spacer and interlayer insulating film>
Next, a method for forming a spacer using the radiation sensitive resin composition of the present invention will be described.
The method of forming a spacer or an interlayer insulating film in the present invention is characterized by including at least the following steps (1) to (4) in the order described below.
(1) A step of applying a radiation sensitive resin composition of the present invention on a substrate to form a coating film,
(2) a step of exposing at least a part of the coating film;
(3) The process of developing the coating film after exposure, and (4) The process of heating the coating film after image development.
以下、これらの各工程について順次説明する。
(1)本発明の感放射線性樹脂組成物を基板上に塗布して塗膜を形成する工程
先ず、基板上に本発明の感放射線性樹脂組成物を塗布して塗膜を形成する。
TN(TwistedNematic)モード、STN(Super Twisted Nematic)モード、VA(Vertical Alignment)モード等の、基板面に対して垂直方向に発生させた電界を利用する液晶表示素子に用いられるスペーサーを形成する場合には、素子の構成要素及び保護膜が形成された基板上にさらに透明導電膜を形成し、該透明導電膜上に本発明の感放射線性樹脂組成物を塗布する。一方、基板面に対して水平方向に発生させた電界を利用するIPS(In−PlaneSwitching)モードの液晶表示素子に用いられるスペーサーを形成する場合には、素子の構成要素及び保護膜が形成された基板上に、本発明の感放射線性樹脂組成物を塗布する。
上記いずれの場合においても基板は好ましくは透明基板であり、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、ソーダライムガラス、無アルカリガラス等のガラス基板;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、ポリイミド等の合成樹脂からなる樹脂基板を挙げることができる。上記透明導電膜としては、酸化スズ(SnO2)からなるNESA膜(米国PPG社の登録商標)、酸化インジウム−酸化スズ(In2O3−SnO2)からなるITO膜等を挙げることができる。
感放射線性樹脂組成物を塗布する方法は特に限定されず、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)、スリット塗布法、バー塗布法、インクジェット法等の適宜の方法を採用することができる。
塗布後、好ましくはプレベークが行われる。プレベークの条件は、それぞれ、本発明の感放射線性樹脂組成物に含有される成分の種類、使用割合等によって適宜に設定されるべきである。プレベークは、例えば70〜100℃において、例えば1〜15分程度の条件で行うことができる。
このようにして形成された塗膜の膜厚は、好ましくは0.1〜8μmである。スペーサーを形成する場合の塗膜の膜厚は、より好ましくは1〜6μmであり;
層間絶縁膜を形成する場合の塗膜の膜厚は、より好ましくは0.1〜6μmであり、さらに好ましくは1〜4μmである。
Hereinafter, each of these steps will be described sequentially.
(1) The process of apply | coating the radiation sensitive resin composition of this invention on a board | substrate, and forming a coating film First, the radiation sensitive resin composition of this invention is apply | coated on a board | substrate, and a coating film is formed.
When forming spacers used in liquid crystal display elements that use an electric field generated in a direction perpendicular to the substrate surface, such as TN (Twisted Nematic) mode, STN (Super Twisted Nematic) mode, VA (Vertical Alignment) mode, etc. In the method, a transparent conductive film is further formed on a substrate on which a component of the element and a protective film are formed, and the radiation-sensitive resin composition of the present invention is applied on the transparent conductive film. On the other hand, in the case of forming a spacer used in an IPS (In-Plane Switching) mode liquid crystal display element using an electric field generated in the horizontal direction with respect to the substrate surface, the element components and the protective film are formed. On the board | substrate, the radiation sensitive resin composition of this invention is apply | coated.
In any of the above cases, the substrate is preferably a transparent substrate, and examples thereof 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 synthetic resins such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide. Examples of the transparent conductive film include a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO 2 ), an ITO film made of indium oxide-tin oxide (In 2 O 3 —SnO 2 ), and the like. .
The method for applying the radiation sensitive resin composition is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit coating method, a bar coating method, an ink jet method or the like is adopted. can do.
After application, pre-baking is preferably performed. The prebaking conditions should be appropriately set depending on the types of components contained in the radiation-sensitive resin composition of the present invention, the usage ratio, and the like. Prebaking can be performed, for example, at 70 to 100 ° C. under conditions of, for example, about 1 to 15 minutes.
The film thickness of the coating film thus formed is preferably 0.1 to 8 μm. The thickness of the coating film when forming the spacer is more preferably 1 to 6 μm;
The film thickness of the coating film in the case of forming the interlayer insulating film is more preferably 0.1 to 6 μm, and further preferably 1 to 4 μm.
(2)該塗膜の少なくとも一部に露光する工程
次いで、形成された塗膜の少なくとも一部に放射線を照射する。このとき、塗膜の一部にのみ照射する際には、例えば所定のパターンを有するフォトマスクを介して照射する方法等によることができる。
照射に使用される放射線としては、可視光線、紫外線、遠紫外線等を挙げることができる。このうち波長が250〜550nm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。
放射線照射量(露光量)は、照射される放射線の波長365nmにおける強度を照度計(OAImodel 356、OpticalAssociates Inc.製)により測定した値として、好ましくは100〜5,000J/m2、より好ましくは200〜3,000J/m2である。
本発明の感放射線性樹脂組成物は、従来知られている組成物と比較して放射線感度が高く、上記放射線照射量が1,000J/m2以下、好ましくは800J/m2以下であっても所望の膜厚、良好な形状、優れた密着性及び高い硬度のスペーサー又は層間絶縁膜を得ることができる。
(2) Step of exposing at least a part of the coating film Next, radiation is applied to at least a part of the formed coating film. At this time, when irradiating only a part of the coating film, for example, a method of irradiating through a photomask having a predetermined pattern can be used.
Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 250 to 550 nm is preferable, and radiation including ultraviolet light having a wavelength of 365 nm is particularly preferable.
The radiation irradiation amount (exposure amount) is preferably 100 to 5,000 J / m 2 , more preferably as a value obtained by measuring the intensity of the irradiated radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by Optical Associates Inc.). 200 to 3,000 J / m 2 .
The radiation-sensitive resin composition of the present invention has high radiation sensitivity compared to conventionally known compositions, and the radiation dose is 1,000 J / m 2 or less, preferably 800 J / m 2 or less. In addition, a spacer or an interlayer insulating film having a desired film thickness, a good shape, excellent adhesion, and high hardness can be obtained.
(3)露光後の塗膜を現像する工程
次に、放射線照射後の塗膜を現像することにより、不要な部分(非露光部分)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、例えば水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム等の無機アルカリ性化合物;
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等の4級アンモニウム塩等の有機アルカリ性化合物の水溶液を使用することができる。上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及び界面活性剤よりなる群から選択される少なくとも1種を適当量添加して使用してもよい。
現像方法としては、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、10〜180秒間程度とすることが好ましい。現像温度は、常温でよい。
現像処理に続いて、好ましくは例えば流水洗浄を30〜90秒間行った後、圧縮空気や圧縮窒素で風乾することによって所望のパターンを得ることができる。
(3) Step of developing the coated film after exposure Next, by developing the coated film after irradiation, unnecessary portions (non-exposed portions) are removed to form a predetermined pattern.
Examples of the developer used for development include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, and sodium carbonate;
An aqueous solution of an organic alkaline compound such as a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used. An appropriate amount of at least one selected from the group consisting of a water-soluble organic solvent such as methanol and ethanol and a surfactant may be added to the aqueous solution of the alkaline compound.
As a developing method, any of a liquid piling method, a dipping method, a shower method and the like may be used, and the developing time is preferably about 10 to 180 seconds. The development temperature may be room temperature.
Subsequent to the development processing, for example, after washing with running water for 30 to 90 seconds, a desired pattern can be obtained by air drying with compressed air or compressed nitrogen.
(4)現像後の塗膜を加熱する工程
次いで、得られたパターン状塗膜を、ホットプレート、オーブン等の適当な加熱装置により、所定温度、例えば100〜250℃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)することにより、所望のパターンを有する硬化膜を得ることができる。
上記の硬化膜は、これを表示素子用のスペーサーに適用した場合には、圧縮強度と復元力とのバランスに優れ;
表示素子用の層間絶縁膜に適用した場合には、透明性、耐光性及び電圧保持率に優れるものである。
(4) Step of heating the coated film after development Next, the obtained patterned coating film is heated at a predetermined temperature, for example, 100 to 250 ° C., for a predetermined time, for example, with a suitable heating device such as a hot plate or oven. A cured film having a desired pattern can be obtained by heating (post-baking) on the plate for 5 to 30 minutes and in the oven for 30 to 180 minutes.
The cured film has an excellent balance between compressive strength and restoring force when applied to a spacer for a display element;
When applied to an interlayer insulating film for a display element, it is excellent in transparency, light resistance and voltage holding ratio.
<[A]重合体の合成>
合成例A1
冷却管及び攪拌機を備えたフラスコに、2,2―アゾビスイソブチロニトリル5質量部及び酢酸3−メトキシブチル250質量部を仕込み、さらにメタクリル酸18質量部、メタクリル酸トリシクロ[5.2.1.02.6]デカン−8−イル25質量部、スチレン5部、3−メタクリロキシプロピルトリエトキシシラン30質量部及びメタクリル酸グリシジル22質量部を仕込んで窒素置換した後、緩やかに撹拌しつつ、溶液の温度を80℃に上昇した。この温度を5時間保持して重合することにより、共重合体(A−1)を28.8質量%含有する溶液を得た。この共重合体(A−1)の重量平均分子量Mwは12,000であった。
<[A] Synthesis of polymer>
Synthesis example A1
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate, and further 18 parts by mass of methacrylic acid and tricyclomethacrylate [5.2. 1.0 2.6 ] 25 parts by mass of decan-8-yl, 5 parts of styrene, 30 parts by mass of 3-methacryloxypropyltriethoxysilane and 22 parts by mass of glycidyl methacrylate were substituted with nitrogen, and then gently stirred. While increasing the temperature of the solution to 80 ° C. By polymerizing while maintaining this temperature for 5 hours, a solution containing 28.8% by mass of the copolymer (A-1) was obtained. The weight average molecular weight Mw of this copolymer (A-1) was 12,000.
合成例A2
冷却管及び攪拌機を備えたフラスコに、2,2―アゾビスイソブチロニトリル5質量部及び酢酸3−メトキシブチル250質量部を仕込み、さらにメタクリル酸18質量部、メタクリル酸トリシクロ[5.2.1.02.6]デカン−8−イル25質量部、スチレン5部、3−アクリロキシプロピルトリメトキシシラン20質量部及び3−エチル−3−メタクリロイルオキシメチルオキセタン32質量部を仕込んで窒素置換した後、緩やかに撹拌しつつ、溶液の温度を80℃に上昇した。この温度を5時間保持して重合することにより共重合体(A−2)を28.8質量%含有する溶液を得た。この共重合体(A−2)のMwは12,000であった。
Synthesis example A2
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate, and further 18 parts by mass of methacrylic acid and tricyclomethacrylate [5.2. 1.0 2.6 ] Charge 25 parts by mass of decan-8-yl, 5 parts of styrene, 20 parts by mass of 3-acryloxypropyltrimethoxysilane, and 32 parts by mass of 3-ethyl-3-methacryloyloxymethyloxetane to replace with nitrogen. Then, the temperature of the solution was raised to 80 ° C. while gently stirring. A solution containing 28.8% by mass of the copolymer (A-2) was obtained by polymerization at this temperature for 5 hours. Mw of this copolymer (A-2) was 12,000.
合成例A3
冷却管及び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質量部及びジエチレングリコールメチルエチルエーテル250質量部を仕込み、さらにメタクリル酸18質量部、メタクリル酸トリシクロ[5.2.1.02.6]デカン−8イル32質量部、3−メタクリロキシプロピルメチルジエトキシシラン20質量部及びメタクリル酸グリシジル30質量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℃に上昇した。この温度を5時間保持して重合することにより、共重合体(A−3)を31.0質量%含有する溶液を得た。この共重合体(A−3)のMwは11,000であった。
Synthesis example A3
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts by mass of diethylene glycol methyl ethyl ether, and further 18 parts by mass of methacrylic acid, tricyclomethacrylate. [5.2.1.0 2.6 ] 32 parts by mass of decane-8yl, 20 parts by mass of 3-methacryloxypropylmethyldiethoxysilane and 30 parts by mass of glycidyl methacrylate were substituted with nitrogen, and then gently stirred. However, the temperature of the solution was raised to 70 ° C. By polymerizing while maintaining this temperature for 5 hours, a solution containing 31.0% by mass of the copolymer (A-3) was obtained. Mw of this copolymer (A-3) was 11,000.
比較合成例a1
冷却管及び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質量部及びプロピレングリコールモノメチルエーテルアセテート200質量部を仕込んだ。引き続きスチレン20質量部、メタクリル酸18質量部、メタクリル酸トリシクロ[5.2.1.02.6]デカン−8−イル32質量部及びメタクリル酸グリシジル30質量部を仕込んで窒素置換した後、ゆるやかに攪拌を始めた。溶液の温度を70℃に上昇し、この温度を5時間保持して重合することにより、共重合体(a−1)を33.0質量%含有する溶液を得た。この共重合体(a−1)のMwは24,000であった。
Comparative synthesis example a1
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 20 parts by mass of styrene, 18 parts by mass of methacrylic acid, 32 parts by mass of tricyclo [5.2.1.0 2.6 ] decane-8-yl and 30 parts by mass of glycidyl methacrylate were charged and substituted with nitrogen. Stirring started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a solution containing 33.0% by mass of the copolymer (a-1). Mw of this copolymer (a-1) was 24,000.
<(D)成分の合成>
合成例D1
撹拌機を備えた容器内に、プロピレングリコールモノメチルエーテル24質量部を仕込み、続いてメチルトリメトキシシラン40質量部、フェニルトリメトキシシラン40質量部及びテトラエトキシシラン20質量部を仕込んで溶液温度が60℃になるまで加熱した。溶液温度が60℃に到達した後、リン酸0.1質量部及びイオン交換水19質量部を加えて溶液温度が75℃になるまで加熱し、この温度を2時間保持した。次いで、溶液温度を45℃に冷却し、脱水剤としてオルト蟻酸メチル28質量部を加えて1時間攪拌した。その後さらに溶液温度を40℃に冷却した後、この温度を保ちながらエバポレーションしてイオン交換水及び加水分解縮合で発生したメタノールを除去することにより、ポリシロキサン(D−1)を得た。このポリシロキサン(D−1)のMwは2,000であり、重量平均分子量Mwと数平均分子量Mnとの比Mw/Mnで表される分散度は2.0であった。
<Synthesis of component (D)>
Synthesis example D1
In a container equipped with a stirrer, 24 parts by mass of propylene glycol monomethyl ether was charged, followed by 40 parts by mass of methyltrimethoxysilane, 40 parts by mass of phenyltrimethoxysilane, and 20 parts by mass of tetraethoxysilane, and the solution temperature was 60. Heated to ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were added and heated until the solution temperature reached 75 ° C., and this temperature was maintained for 2 hours. Next, the solution temperature was cooled to 45 ° C., 28 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Then, after further cooling the solution temperature to 40 ° C., evaporation was performed while maintaining this temperature to remove ion-exchanged water and methanol generated by hydrolysis and condensation, thereby obtaining polysiloxane (D-1). Mw of this polysiloxane (D-1) was 2,000, and the degree of dispersion represented by the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn was 2.0.
合成例D2
撹拌機を備えた容器内に、プロピレングリコールモノメチルエーテル24質量部を仕込み、続いて3−メタクリロキシプロピルトリメトキシシラン90質量部、フェニルトリメトキシシラン15質量部を仕込んで溶液温度が60℃になるまで加熱した。溶液温度が60℃に到達した後、リン酸0.1質量部及びイオン交換水19質量部を加えて溶液温度が75℃になるまで加熱し、この温度を2時間保持した。次いで、溶液温度を45℃に冷却し、脱水剤としてオルト蟻酸メチル28質量部を加えて1時間攪拌した。その後さらに溶液温度を40℃に冷却した後、この温度を保ちながらエバポレーションしてイオン交換水及び加水分解縮合で発生したメタノールを除去することにより、ポリシロキサン(D−2)を得た。このポリシロキサン(D−2)のMwは1,500であり、Mw/Mnは2.0であった。
Synthesis example D2
In a vessel equipped with a stirrer, 24 parts by mass of propylene glycol monomethyl ether is charged, and subsequently 90 parts by mass of 3-methacryloxypropyltrimethoxysilane and 15 parts by mass of phenyltrimethoxysilane are charged, so that the solution temperature becomes 60 ° C. Until heated. After the solution temperature reached 60 ° C., 0.1 part by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were added and heated until the solution temperature reached 75 ° C., and this temperature was maintained for 2 hours. Next, the solution temperature was cooled to 45 ° C., 28 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Thereafter, the solution temperature was further cooled to 40 ° C. and then evaporated while maintaining this temperature to remove ion-exchanged water and methanol generated by hydrolysis and condensation to obtain polysiloxane (D-2). Mw of this polysiloxane (D-2) was 1,500, and Mw / Mn was 2.0.
合成例D3
撹拌機を備えた容器内に、プロピレングリコールモノメチルエーテル24質量部を仕込み、続いて3−メタクリロキシプロピルメチルジエトキシシラン100質量部を仕込んで溶液温度が60℃になるまで加熱した。溶液温度が60℃に到達した後、リン酸0.1質量部及びイオン交換水19質量部を加えて溶液温度が75℃になるまで加熱してこの温度を2時間保持した。次いで、溶液温度を45℃に冷却し、脱水剤としてオルト蟻酸メチル28質量部を加えて1時間攪拌した。その後さらに溶液温度を40℃に冷却し、この温度を保ちながらエバポレーションしてイオン交換水及び加水分解縮合で発生したメタノールを除去することにより、ポリシロキサン(D−3)を得た。このポリシロキサン(D−3)のMwは1,000であり、Mw/Mnは2.0であった。
Synthesis example D3
In a container equipped with a stirrer, 24 parts by mass of propylene glycol monomethyl ether was charged, and subsequently 100 parts by mass of 3-methacryloxypropylmethyldiethoxysilane was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were added and heated until the solution temperature reached 75 ° C., and this temperature was maintained for 2 hours. Next, the solution temperature was cooled to 45 ° C., 28 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Thereafter, the solution temperature was further cooled to 40 ° C., and evaporation was performed while maintaining this temperature to remove ion-exchanged water and methanol generated by hydrolysis and condensation to obtain polysiloxane (D-3). Mw of this polysiloxane (D-3) was 1,000, and Mw / Mn was 2.0.
合成例D4
撹拌機を備えた容器内に、プロピレングリコールモノメチルエーテル24質量部を仕込み、続いて3−メタクリロキシプロピルトリエトキシシラン100質量部を仕込んで溶液温度が60℃になるまで加熱した。溶液温度が60℃に到達した後、リン酸0.1質量部及びイオン交換水19質量部を仕込んで溶液温度が75℃になるまで加熱し、この温度を2時間保持した。次いで、溶液温度を45℃に冷却し、脱水剤としてオルト蟻酸メチル28質量部を加えて1時間攪拌した。その後さらに溶液温度を40℃に冷却し、この温度を保ちながらエバポレーションしてイオン交換水及び加水分解縮合で発生したメタノールを除去することにより、ポリシロキサン(D−4)を得た。このポリシロキサン(D−4)のMwは800であり、Mw/Mnは2.0であった。
Synthesis example D4
In a container equipped with a stirrer, 24 parts by mass of propylene glycol monomethyl ether was charged, and subsequently 100 parts by mass of 3-methacryloxypropyltriethoxysilane was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.1 part by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were charged and heated until the solution temperature reached 75 ° C., and this temperature was maintained for 2 hours. Next, the solution temperature was cooled to 45 ° C., 28 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Thereafter, the solution temperature was further cooled to 40 ° C., and evaporation was performed while maintaining this temperature to remove ion-exchanged water and methanol generated by hydrolysis and condensation to obtain polysiloxane (D-4). Mw of this polysiloxane (D-4) was 800, and Mw / Mn was 2.0.
合成例D5
撹拌機を備えた容器内に、プロピレングリコールモノメチルエーテル24質量部を仕込み、続いて3−アクリロキシプロピルトリメトキシシラン50質量部及びフェニルトリメトキシシラン50質量部を仕込んで溶液温度が60℃になるまで加熱した。溶液温度が60℃に到達した後、リン酸0.1質量部及びイオン交換水19質量部を仕込んで溶液温度が75℃になるまで加熱し、この温度を2時間保持した。次いで、溶液温度を45℃に冷却し、脱水剤としてオルト蟻酸メチル28質量部を加えて1時間攪拌した。その後さらに溶液温度を40℃に冷却し、この温度を保ちながらエバポレーションしてイオン交換水及び加水分解縮合で発生したメタノールを除去することにより、ポリシロキサン(D−5)を得た。このポリシロキサン(D−5)のMwは600であり、Mw/Mnは2.0であった。
Synthesis example D5
In a vessel equipped with a stirrer, 24 parts by mass of propylene glycol monomethyl ether is charged, and subsequently 50 parts by mass of 3-acryloxypropyltrimethoxysilane and 50 parts by mass of phenyltrimethoxysilane are added to bring the solution temperature to 60 ° C. Until heated. After the solution temperature reached 60 ° C., 0.1 part by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were charged and heated until the solution temperature reached 75 ° C., and this temperature was maintained for 2 hours. Next, the solution temperature was cooled to 45 ° C., 28 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Thereafter, the solution temperature was further cooled to 40 ° C., and evaporation was carried out while maintaining this temperature to remove ion-exchanged water and methanol generated by hydrolysis and condensation to obtain polysiloxane (D-5). Mw of this polysiloxane (D-5) was 600, and Mw / Mn was 2.0.
<[A]重合体及び[D]成分の1ポット合成>
合成例AD1
冷却管及び撹拌機を備えたフラスコに、2,2―アゾビスイソブチロニトリル5質量部及び酢酸3−メトキシブチル250質量部を仕込み、さらにメタクリル酸18質量部、メタクリル酸トリシクロ[5.2.1.02.6]デカン−8−イル25質量部、スチレン5部、3−メタクリロキシプロピルトリエトキシシラン30質量部及びメタクリル酸グリシジル22質量部を仕込んで窒素置換した後、緩やかに撹拌しつつ、溶液の温度を80℃に上昇した。この温度を5時間保持して重合し、共重合体(A−6)を含有する溶液を得た。
次いで、上記で得られた共重合体溶液に、3−メタクリロキシプロピルトリエトキシシラン5質量部を滴下し、80℃において2時間重合することにより、共重合体(A−6)及びポリシロキサン(D−6)を含有する溶液を得た。
この溶液中の共重合体(A−6)とポリシロキサン(D−6)の質量比は100:5であった。共重合体(A−6)のMwは8,000であり、ポリシロキサン(D−6)のMwは800であった。
<One-pot synthesis of [A] polymer and [D] component>
Synthesis example AD1
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate, and further 18 parts by mass of methacrylic acid, tricyclomethacrylate [5.2. 1.0 2.6 ] 25 parts by mass of decan-8-yl, 5 parts of styrene, 30 parts by mass of 3-methacryloxypropyltriethoxysilane and 22 parts by mass of glycidyl methacrylate were substituted with nitrogen, and then gently stirred. However, the temperature of the solution was raised to 80 ° C. This temperature was maintained for 5 hours for polymerization to obtain a solution containing the copolymer (A-6).
Next, 5 parts by mass of 3-methacryloxypropyltriethoxysilane was dropped into the copolymer solution obtained above and polymerized at 80 ° C. for 2 hours, whereby the copolymer (A-6) and polysiloxane ( A solution containing D-6) was obtained.
The mass ratio of the copolymer (A-6) and polysiloxane (D-6) in this solution was 100: 5. Mw of the copolymer (A-6) was 8,000, and Mw of the polysiloxane (D-6) was 800.
<感放射線性樹脂組成物の調製及び評価>
実施例及び比較例で用いた各成分の詳細を以下に示す。
[B]重合性不飽和化合物
B−1:ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートとの混合物(KAYARAD DPHA、日本化薬(株)製)
B−2:コハク酸変性ペンタエリスリトールトリアクリレート(アロニックスTO−756、東亞合成(株)製)
B−3:トリメチロールプロパントリアクリレート
B−4:ビスコート802(トリペンタエリスリトールオクタアクリレートとトリペンタエリスリトールヘプタアクリレートとの混合物、大阪有機化学工業(株)製)
B−5:コハク酸変性ジペンタエリスリトールペンタアクリレート(アロニックスM−520、東亞合成(株)製)
[C]感放射線性重合開始剤
C−1:2−メチル−1−(4−メチルチオフェニル)−2−モルフォリノプロパン−1−オン(イルガキュア907、BASF社製)
C−2:エタノン−1−[9−エチル−6−(2−メチルベンゾイル)−9H−カルバゾール−3−イル]−1−(O−アセチルオキシム)(イルガキュアOXE02、BASF社製)
C−3:1,2−オクタンジオン−1−[4−(フェニルチオ)−2−(O−ベンゾイルオキシム)](イルガキュアOXE01、BASF社製)
C−4:2−(ジメチルアミノ)−2−[(4−メチルフェニル)メチル]−1−[4−(4−モルホリニル)フェニル]−1−ブタノン(イルガキュア379EG、BASF社製)
[E]接着助剤
E−1:γ−グリシドキシプロピルトリメトキシシラン
<Preparation and Evaluation of Radiation Sensitive Resin Composition>
The detail of each component used by the Example and the comparative example is shown below.
[B] Polymerizable unsaturated compound B-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
B-2: Succinic acid-modified pentaerythritol triacrylate (Aronix TO-756, manufactured by Toagosei Co., Ltd.)
B-3: Trimethylolpropane triacrylate B-4: Biscoat 802 (mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
B-5: Succinic acid-modified dipentaerythritol pentaacrylate (Aronix M-520, manufactured by Toagosei Co., Ltd.)
[C] Radiation sensitive polymerization initiator C-1: 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907, manufactured by BASF)
C-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02, manufactured by BASF)
C-3: 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (Irgacure OXE01, manufactured by BASF)
C-4: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (Irgacure 379EG, manufactured by BASF)
[E] Adhesion aid E-1: γ-glycidoxypropyltrimethoxysilane
[感放射線性樹脂組成物の調製]
実施例1
[A]重合体として上記合成例A1で得た共重合体(A−1)を含有する溶液を固形分換算で100質量部、[B]重合性不飽和化合物として(B−1)100質量部、[C]感放射線性重合開始剤として(C−3)5質量部及び[D]成分として上記合成例D1で得たポリシロキサン(D−1)10質量部並びに接着助剤として(E−1)5質量部混合し、固形分濃度が30質量%と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を加えた後、孔径0.5μmのミリポアフィルタでろ過することにより、感放射線性樹脂組成物を調製した。
[Preparation of radiation-sensitive resin composition]
Example 1
[A] A solution containing the copolymer (A-1) obtained in Synthesis Example A1 as a polymer is 100 parts by mass in terms of solid content, and [B] (B-1) is 100 parts by mass as a polymerizable unsaturated compound. Part, [C] 5 parts by weight of (C-3) radiation-sensitive polymerization initiator, 10 parts by weight of polysiloxane (D-1) obtained in Synthesis Example D1 as [D] component, and (E -1) After mixing 5 parts by mass and adding propylene glycol monomethyl ether acetate so that the solid content concentration is 30% by mass, the mixture is filtered through a Millipore filter having a pore size of 0.5 μm to obtain a radiation sensitive resin composition. Prepared.
実施例2〜10並びに比較例1及び2
[A]〜[D]成分として表1に記載した種類及び量のものを使用したほかは上記実施例1と同様に実施して、感放射線性樹脂組成物をそれぞれ得た。ここで、表1には記載されてないが、各組成物には実施例1同様に、[A]重合体100質量部に対して、5質量部の接着助剤(E−1)も添加した。
Examples 2 to 10 and Comparative Examples 1 and 2
A radiation-sensitive resin composition was obtained in the same manner as in Example 1 except that the components [A] to [D] having the types and amounts described in Table 1 were used. Here, although not described in Table 1, 5 parts by mass of an adhesion assistant (E-1) is also added to each composition, as in Example 1, with respect to 100 parts by mass of [A] polymer. did.
実施例11及び12
[A]重合体及び[D]成分として、上記合成例AD1で得た共重合体(A−6)及びポリシロキサン(D−6)を含有する溶液を、[A]重合体換算で100質量部用い、
[B]重合性不飽和化合物及び[C]感放射線性重合開始剤として、表1に記載した種類及び量のものを使用したほかは上記実施例1と同様に実施して、感放射線性樹脂組成物をそれぞれ得た。ここで、表1には記載されてないが、各組成物には実施例1同様に、[A]重合体100質量部に対して、5質量部の接着助剤(E−1)も添加した。
Examples 11 and 12
As a [A] polymer and a [D] component, the solution containing the copolymer (A-6) and polysiloxane (D-6) obtained by the said synthesis example AD1 is 100 mass in conversion of [A] polymer. Part use,
[B] The radiation-sensitive resin was carried out in the same manner as in Example 1 except that the polymerizable unsaturated compound and [C] the radiation-sensitive polymerization initiator used were of the types and amounts listed in Table 1. Each composition was obtained. Here, although not described in Table 1, 5 parts by mass of an adhesion assistant (E-1) is also added to each composition, as in Example 1, with respect to 100 parts by mass of [A] polymer. did.
[感放射線性樹脂組成物の評価]
上記で調製した各感放射線性樹脂組成物の評価を以下のように実施した。評価結果は表2に示した。
評価項目のうち、解像度、感度及び圧縮性能は表示素子のスペーサーとしての適用を意図したものであり、
透過率、耐光性及び電圧保持率は表示素子の層間絶縁膜としての適用を意図したものである。
(1)解像度及び感度
無アルカリガラス基板上に、各感放射線性樹脂組成物溶液をスピンナーにより塗布した後、100℃のホットプレート上で2分間プレベークすることにより膜厚4.0μmの塗膜を形成した。次いで、得られた塗膜に直径8〜20μmの範囲の異なる大きさ(1μm刻み)の複数の丸状残しパターンを有するフォトマスクを介し、高圧水銀ランプを用いて露光量を200〜1,000J/m2の範囲で100J/m2刻みで変量して放射線照射を行った。その後、23℃の0.05質量%水酸化カリウム水溶液を現像液として、現像圧1kgf/cm2、ノズル径1mmで吐出することによりシャワー現像を行い、次いで純水洗浄を1分間行った。さらにオーブン中で230℃において30分間ポストベークすることにより、パターン状塗膜を形成した。
i)解像度
上記において、露光量700J/m2において形成される最小のパターンサイズを解像度(μm)とした。露光量700J/m2において、12μm以下のサイズのパターンが形成されていれば、解像度が良好であると判断できる。
[Evaluation of radiation-sensitive resin composition]
Evaluation of each radiation sensitive resin composition prepared above was implemented as follows. The evaluation results are shown in Table 2.
Among the evaluation items, resolution, sensitivity, and compression performance are intended to be used as spacers for display elements.
The transmittance, light resistance and voltage holding ratio are intended for application as an interlayer insulating film of a display element.
(1) Resolution and sensitivity After coating each radiation-sensitive resin composition solution on an alkali-free glass substrate with a spinner, pre-baking on a hot plate at 100 ° C. for 2 minutes forms a coating film having a thickness of 4.0 μm. Formed. Next, the obtained coating film is exposed to an exposure amount of 200 to 1,000 J using a high-pressure mercury lamp through a photomask having a plurality of circular residual patterns having different sizes (in increments of 1 μm) in a diameter range of 8 to 20 μm. Irradiation was performed with a variable amount in increments of 100 J / m 2 in the range of / m 2 . Thereafter, shower development was performed by discharging a 0.05 mass% potassium hydroxide aqueous solution at 23 ° C. with a developing pressure of 1 kgf / cm 2 and a nozzle diameter of 1 mm, and then cleaning with pure water was performed for 1 minute. Furthermore, a patterned coating film was formed by post-baking in an oven at 230 ° C. for 30 minutes.
i) Resolution In the above, the minimum pattern size formed at an exposure amount of 700 J / m 2 was defined as resolution (μm). If a pattern having a size of 12 μm or less is formed at an exposure amount of 700 J / m 2 , it can be determined that the resolution is good.
ii)感度
上記において形成された直径20μmの丸状残しパターンに着目し、該丸状残しパターンの現像前と現像後の高さを、非接触表面・層断面形状計測システム((株)菱化システム製、型名「Vertscan」)を用いて測定した。この値と下記式から残膜率(%)を求めた。
残膜率(%)=(現像後高さ/現像前高さ)×100
この残膜率が80%以上となる最小の露光量を感度(J/m2)とした。露光量が700J/m2以下の場合、感度が良好であると判断できる。
ii) Sensitivity Focusing on the 20 μm diameter circular residual pattern formed above, the non-contact surface / layer cross-sectional shape measurement system (Ryoka Corporation) can measure the height of the circular residual pattern before and after development. Measurement was made using a system name “Vertscan”. The residual film ratio (%) was determined from this value and the following formula.
Residual film ratio (%) = (height after development / height before development) × 100
The minimum exposure amount at which the remaining film ratio was 80% or more was defined as sensitivity (J / m 2 ). When the exposure amount is 700 J / m 2 or less, it can be determined that the sensitivity is good.
(2)圧縮性能
上記「解像度及び感度」におけるのと同様にして、残膜率が80%以上となる最小露光量で、基板上に直径15μmの丸状残しパターンを形成した。このパターンを微小圧縮試験機(フィッシャースコープH100C、フィッシャーインストルメンツ社製)で50μm角状の平面圧子を用い、40mNの荷重により圧縮試験を行い、荷重に対する圧縮変位量(μm)を測定した。また、40mNの荷重時の変位量と、40mNの荷重を取り除いた時の変位量と、から回復率(%)を算出した。この回復率が90%以上であり、かつ40mNの荷重時の圧縮変位量が0.15μm以上の場合、圧縮性能が良好であると判断できる。
(3)透明性(光透過率)
露光時にフォトマスクを使用せず、露光量を800J/m2とした以外は、上記「解像度及び感度」におけるのと同様にして、無アルカリガラス基板上に硬化膜を形成した。得られた硬化膜について、分光光度計(150−20型ダブルビーム、(株)日立製作所製)を用いて波長400nmにおける光透過率(%)を測定した。この光透過率が90%以上のとき、透明性が良好であると判断できる。
(4)耐光性
上記透明性の評価と同様にして、無アルカリガラス基板上に硬化膜を形成した。得られた硬化膜について、UV照射装置(UVX−02516S1JS01、ウシオ電機(株)製、ランプ;UVL−4001M3−N1)にて、500kJ/m2のUV光(波長365nm)を照射し、照射前後の残膜率を求めることにより評価した。この残膜率が95%以上の場合、耐光性(%)が良好であると判断できる。
(5)電圧保持率
本評価における基板としては、表面に、ナトリウムイオンの溶出を防止するSiO2膜及び所定形状のITO(インジウム−酸化錫合金)電極がこの順に積層されたソーダガラス基板を用いた。この基板のITO電極側の面に、各感放射線性樹脂組成物をスピンコートした後、90℃のクリーンオーブン内で10分間プレベークを行って、膜厚2.0μmの塗膜を形成した。次いで、フォトマスクを介さずに、該塗膜に露光量500J/m2にて露光した。その後、この基板を23℃の0.04質量%の水酸化カリウム水溶液からなる現像液に1分間浸漬して現像した後、超純水で洗浄して風乾し、さらに230℃で30分間ポストベークを行うことにより、基板上に硬化膜を形成した。
上記で得た硬化膜付き基板と、所定形状のITO電極のみが形成された基板とを一対として用い、該一対の基板につき、0.8mmのガラスビーズを混合したシール剤で外周部を貼り合わせた後、セルギャップ内にメルク社製液晶(MLC6608)を注入して、液晶セルを製造した。
この液晶セルを60℃の恒温層内に静置した状態で、該液晶セルの電圧保持率を液晶電圧保持率測定システム(VHR−1A型、(株)東陽テクニカ製)により測定した。このときの印加電圧は5.5Vの方形波であり、測定周波数は60Hzである。ここで電圧保持率とは、(電圧印可解除後16.7ミリ秒後の液晶セルの電位差/電圧解除時(0ミリ秒の時点)に印加されていた電圧)の値である。この電圧保持率が90%以下である液晶セルは、印加された電圧を16.7ミリ秒の間、所定レベルに保持することができず、従って液晶の配向が不十分であるから、残像等の「焼き付き」を起こすおそれが高い。
(2) Compression performance In the same manner as in “Resolution and sensitivity” above, a circular residual pattern having a diameter of 15 μm was formed on the substrate with the minimum exposure amount at which the residual film ratio was 80% or more. This pattern was subjected to a compression test with a load of 40 mN using a 50 μm square planar indenter with a micro compression tester (Fischerscope H100C, manufactured by Fisher Instruments), and the amount of compressive displacement (μm) relative to the load was measured. Further, the recovery rate (%) was calculated from the amount of displacement when a load of 40 mN was applied and the amount of displacement when a load of 40 mN was removed. When this recovery rate is 90% or more and the amount of compressive displacement at a load of 40 mN is 0.15 μm or more, it can be determined that the compression performance is good.
(3) Transparency (light transmittance)
A cured film was formed on an alkali-free glass substrate in the same manner as in the “resolution and sensitivity” except that a photomask was not used during exposure and the exposure amount was 800 J / m 2 . About the obtained cured film, the light transmittance (%) in wavelength 400nm was measured using the spectrophotometer (150-20 type double beam, Hitachi, Ltd. product). When this light transmittance is 90% or more, it can be determined that the transparency is good.
(4) Light resistance A cured film was formed on an alkali-free glass substrate in the same manner as in the evaluation of transparency. The obtained cured film was irradiated with UV light (wavelength 365 nm) of 500 kJ / m 2 with a UV irradiation apparatus (UVX-02516S1JS01, manufactured by Ushio Electric Co., Ltd., lamp; UVL-4001M3-N1). Evaluation was made by obtaining the remaining film ratio. When the remaining film ratio is 95% or more, it can be determined that the light resistance (%) is good.
(5) Voltage holding ratio As a substrate in this evaluation, a soda glass substrate in which a SiO 2 film for preventing elution of sodium ions and an ITO (indium-tin oxide alloy) electrode having a predetermined shape are laminated on the surface in this order is used. It was. Each radiation sensitive resin composition was spin coated on the surface of the substrate on the ITO electrode side, and then pre-baked in a clean oven at 90 ° C. for 10 minutes to form a coating film having a thickness of 2.0 μm. Next, the coating film was exposed at an exposure amount of 500 J / m 2 without using a photomask. Thereafter, this substrate was developed by being immersed in a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, washed with ultrapure water, air-dried, and further post-baked at 230 ° C. for 30 minutes. A cured film was formed on the substrate.
Using the cured film-provided substrate obtained above and a substrate on which only the ITO electrode of a predetermined shape is formed as a pair, the outer peripheral portion is bonded to the pair of substrates with a sealing agent mixed with 0.8 mm glass beads. Thereafter, a liquid crystal cell manufactured by Merck (MLC6608) was injected into the cell gap to produce a liquid crystal cell.
In the state which left this liquid crystal cell in a 60 degreeC thermostat, the voltage holding rate of this liquid crystal cell was measured with the liquid crystal voltage holding rate measuring system (VHR-1A type, Toyo Technica Co., Ltd. make). The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of (potential difference of liquid crystal cell after 16.7 milliseconds after voltage application is released / voltage applied at the time of voltage release (time of 0 milliseconds)). A liquid crystal cell having a voltage holding ratio of 90% or less cannot hold the applied voltage at a predetermined level for 16.7 milliseconds, and therefore the orientation of the liquid crystal is insufficient, so that an afterimage, etc. There is a high risk of causing “burn-in”.
Claims (9)
(A2)オキシラニル基及びオキセタニル基よりなる群から選ばれる少なくとも1種を有する構造単位、並びに
(A3)下記式(1)で表される構造単位
を有する重合体、
[B]重合性不飽和化合物、
[C]感放射線性重合開始剤、並びに
[D]下記式(2)で表される加水分解性シラン化合物の加水分解縮合物
を含有しそして上記[D]成分の含有割合が、[A]重合体100質量部に対して0.1〜50質量部である、ことを特徴とする、感放射線性樹脂組成物。
(A2) a structural unit having at least one selected from the group consisting of an oxiranyl group and an oxetanyl group, and (A3) a polymer having a structural unit represented by the following formula (1),
[B] polymerizable unsaturated compound,
[C] a radiation-sensitive polymerization initiator, and [D] a hydrolysis condensate of a hydrolyzable silane compound represented by the following formula (2), and the content ratio of the above [D] component is [A] The radiation sensitive resin composition characterized by being 0.1-50 mass parts with respect to 100 mass parts of polymers .
構造単位(A2)が(メタ)アクリル酸グリシジル、(メタ)アクリル酸3,4−エポキシシクロヘキシルメチル、4−ヒドロキシブチル(メタ)アクリレートグリシジルエーテル及び3−(メタ)アクリロイルオキシメチル−3−エチルオキセタンからなる群より選択される少なくとも1種の化合物に由来する構造単位である、請求項1〜2のいずれか一項に記載の感放射線性樹脂組成物。 The structural unit (A1) in the [A] polymer is a structural unit derived from at least one compound selected from the group consisting of (meth) acrylic acid and unsaturated carboxylic acid anhydride,
The structural unit (A2) is glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether and 3- (meth) acryloyloxymethyl-3-ethyloxetane The radiation sensitive resin composition as described in any one of Claims 1-2 which is a structural unit derived from the at least 1 sort (s) of compound selected from the group which consists of.
(1)請求項1〜4のいずれか一項に記載の感放射線性樹脂組成物を基板上に塗布して塗膜を形成する工程、
(2)該塗膜の少なくとも一部に露光する工程、
(3)露光後の塗膜を現像する工程、及び
(4)現像後の塗膜を加熱する工程。 A method for forming a cured film, wherein at least the following steps are passed in the order described below.
(1) The process of apply | coating the radiation sensitive resin composition as described in any one of Claims 1-4 on a board | substrate, and forming a coating film,
(2) a step of exposing at least a part of the coating film;
(3) The process of developing the coating film after exposure, and (4) The process of heating the coating film after image development.
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