TWI413861B - Negative photo sensitive resin composition, interlayer insulating film and forming method thereof - Google Patents
Negative photo sensitive resin composition, interlayer insulating film and forming method thereof Download PDFInfo
- Publication number
- TWI413861B TWI413861B TW100106488A TW100106488A TWI413861B TW I413861 B TWI413861 B TW I413861B TW 100106488 A TW100106488 A TW 100106488A TW 100106488 A TW100106488 A TW 100106488A TW I413861 B TWI413861 B TW I413861B
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- Taiwan
- Prior art keywords
- group
- carbon atoms
- resin composition
- negative
- photosensitive resin
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 53
- 239000011229 interlayer Substances 0.000 title claims description 42
- 238000000034 method Methods 0.000 title claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 48
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000005193 alkenylcarbonyloxy group Chemical group 0.000 claims abstract description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 4
- 125000003566 oxetanyl group Chemical group 0.000 claims abstract description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 21
- 239000003999 initiator Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- 239000005864 Sulphur Chemical group 0.000 abstract 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 abstract 1
- 125000005389 trialkylsiloxy group Chemical group 0.000 abstract 1
- 239000010408 film Substances 0.000 description 83
- -1 trimethoxydecyl group Chemical group 0.000 description 53
- 239000002904 solvent Substances 0.000 description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 239000004973 liquid crystal related substance Substances 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- 238000002845 discoloration Methods 0.000 description 7
- 239000007870 radical polymerization initiator Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229940042596 viscoat Drugs 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 6
- 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 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 5
- 239000012965 benzophenone Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 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 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- 229940022663 acetate Drugs 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229920006243 acrylic copolymer Polymers 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 2
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- RVGLEPQPVDUSOJ-UHFFFAOYSA-N 2-Methyl-3-hydroxypropanoate Chemical compound COC(=O)CCO RVGLEPQPVDUSOJ-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GQPVFBDWIUVLHG-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(CO)COC(=O)C(C)=C GQPVFBDWIUVLHG-UHFFFAOYSA-N 0.000 description 2
- CQHKDHVZYZUZMJ-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-prop-2-enoyloxypropyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CO)COC(=O)C=C CQHKDHVZYZUZMJ-UHFFFAOYSA-N 0.000 description 2
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 2
- 235000018417 cysteine Nutrition 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
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- PCDHSSHKDZYLLI-UHFFFAOYSA-N butan-1-one Chemical compound CCC[C]=O PCDHSSHKDZYLLI-UHFFFAOYSA-N 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- VFGRALUHHHDIQI-UHFFFAOYSA-N butyl 2-hydroxyacetate Chemical compound CCCCOC(=O)CO VFGRALUHHHDIQI-UHFFFAOYSA-N 0.000 description 1
- BMOACRKLCOIODC-UHFFFAOYSA-N butyl 3-butoxypropanoate Chemical compound CCCCOCCC(=O)OCCCC BMOACRKLCOIODC-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- GCFAUZGWPDYAJN-UHFFFAOYSA-N cyclohexyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OC1CCCCC1 GCFAUZGWPDYAJN-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical compound [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 1
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- 238000007607 die coating method Methods 0.000 description 1
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- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
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- GFUIDHWFLMPAGY-UHFFFAOYSA-N ethyl 2-hydroxy-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)O GFUIDHWFLMPAGY-UHFFFAOYSA-N 0.000 description 1
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 1
- GIRSHSVIZQASRJ-UHFFFAOYSA-N ethyl 3-butoxypropanoate Chemical compound CCCCOCCC(=O)OCC GIRSHSVIZQASRJ-UHFFFAOYSA-N 0.000 description 1
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- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
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- 238000010304 firing Methods 0.000 description 1
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- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 238000003384 imaging method Methods 0.000 description 1
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- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- AAXKMXAEFVWFDC-UHFFFAOYSA-N naphthalene;prop-2-enoic acid Chemical compound OC(=O)C=C.C1=CC=CC2=CC=CC=C21 AAXKMXAEFVWFDC-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- VWBWQOUWDOULQN-UHFFFAOYSA-N nmp n-methylpyrrolidone Chemical compound CN1CCCC1=O.CN1CCCC1=O VWBWQOUWDOULQN-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 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
- OJNNAJJFLWBPRS-UHFFFAOYSA-N phenyl-[(2,4,6-trimethylphenyl)methyl]-[(2,4,6-trimethylphenyl)methylidene]phosphanium Chemical compound CC1=C(C=P(C2=CC=CC=C2)=CC2=C(C=C(C=C2C)C)C)C(=CC(=C1)C)C OJNNAJJFLWBPRS-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- MPQUSGMFRFJXDF-UHFFFAOYSA-N prop-2-enoic acid;toluene Chemical compound OC(=O)C=C.CC1=CC=CC=C1 MPQUSGMFRFJXDF-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- OJTDGPLHRSZIAV-UHFFFAOYSA-N propane-1,2-diol Chemical compound CC(O)CO.CC(O)CO OJTDGPLHRSZIAV-UHFFFAOYSA-N 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- HJIYVZIALQOKQI-UHFFFAOYSA-N propyl 3-butoxypropanoate Chemical compound CCCCOCCC(=O)OCCC HJIYVZIALQOKQI-UHFFFAOYSA-N 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 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
- 239000010409 thin film Substances 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical compound BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 125000004360 trifluorophenyl group Chemical group 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-O trimethylammonium Chemical compound C[NH+](C)C GETQZCLCWQTVFV-UHFFFAOYSA-O 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- GIIXTFIYICRGMZ-UHFFFAOYSA-N tris(2,3-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(P(C=2C(=C(C)C=CC=2)C)C=2C(=C(C)C=CC=2)C)=C1C GIIXTFIYICRGMZ-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F277/00—Macromolecular compounds obtained by polymerising monomers on to polymers of carbocyclic or heterocyclic monomers as defined respectively in group C08F32/00 or in group C08F34/00
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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
-
- 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
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
- G03F7/405—Treatment with inorganic or organometallic reagents after imagewise removal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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Abstract
Description
本發明是有關於一種負片型感光性樹脂組成物、層間絕緣膜及其形成方法。The present invention relates to a negative-type photosensitive resin composition, an interlayer insulating film, and a method of forming the same.
薄膜電晶體(thin film transistor,以下記作「TFT」)型液晶顯示元件、磁頭元件、積體電路元件及固體攝像管元件等電子零件中,通常為了使配置為層狀的配線之間絕緣而設置有層間絕緣膜(參照專利文獻1)。作為上述層間絕緣膜的材料,較佳為用以獲得必需圖案形狀的步驟數少,而且具有充分的平坦性的材料,因此廣泛使用負片型感光性樹脂組成物(參照專利文獻2)。In an electronic component such as a thin film transistor (hereinafter referred to as a "TFT") liquid crystal display device, a magnetic head device, an integrated circuit device, and a solid-state image sensor device, in order to insulate between wirings arranged in a layer shape, An interlayer insulating film is provided (see Patent Document 1). The material of the interlayer insulating film is preferably a material having a small number of steps for obtaining a necessary pattern shape and having sufficient flatness. Therefore, a negative-type photosensitive resin composition is widely used (see Patent Document 2).
[先前技術文獻][Previous Technical Literature]
[專利文獻][Patent Literature]
專利文獻1:日本專利特開2000-10089號公報Patent Document 1: Japanese Patent Laid-Open No. 2000-10089
專利文獻2:日本專利第3650985號公報Patent Document 2: Japanese Patent No. 3650985
上述電子零件中,TFT型液晶顯示元件是經過在層間絕緣膜上形成透明電極膜,進而於該透明電極膜上形成液晶配向膜的步驟而製造。此時,該層間絕緣膜由於在透明電極膜的形成步驟中暴露於高溫條件下,故需要對該高溫條件的充分耐性。In the above electronic component, the TFT liquid crystal display device is produced by forming a transparent electrode film on the interlayer insulating film and forming a liquid crystal alignment film on the transparent electrode film. At this time, since the interlayer insulating film is exposed to high temperature conditions in the step of forming the transparent electrode film, sufficient resistance to the high temperature condition is required.
另外,近年來,TFT型液晶顯示元件中,於大畫面化、高亮度化、高精細化、及高速響應化等多種技術動向下,液晶顯示元件的結構亦隨之複雜化。因此,關於所使用的層間絕緣膜,於低介電常數、高透光率(>80%,λ=400 nm)等方面,要求與先前任何時候相比均更高的性能,並且於液晶顯示元件的結構上亦有可厚膜化至50 μm左右等特殊要求。In addition, in the TFT-type liquid crystal display device, the structure of the liquid crystal display element is complicated by various technologies such as large screen, high luminance, high definition, and high-speed response. Therefore, regarding the interlayer insulating film to be used, in terms of low dielectric constant, high light transmittance (>80%, λ=400 nm), etc., higher performance is required than before, and liquid crystal display is required. The structure of the component also has special requirements such as thick filming to about 50 μm.
但是,先前的層間絕緣膜形成時通常使用的負片型感光性樹脂組成物中,同時達成厚膜化與高透光率化及高解析度極其困難,故強烈要求開發出可形成兼具上述特性的層間絕緣膜的負片型感光性樹脂組成物。However, in the negative-type photosensitive resin composition which is usually used in the formation of the interlayer insulating film, it is extremely difficult to achieve thick film formation, high light transmittance, and high resolution at the same time, and it is strongly required to develop a combination of the above characteristics. A negative-type photosensitive resin composition of the interlayer insulating film.
本發明是鑒於上述情況而成,目的在於提供一種可形成即便厚膜化,解析度、透明性、耐熱性、耐熱變色性及耐溶劑性等諸多特性亦充分優異的層間絕緣膜的負片型感光性樹脂組成物。另外,本發明的目的在於提供一種由上述負片型感光性樹脂組成物所形成的層間絕緣膜及其形成方法。In view of the above, it is an object of the present invention to provide a negative-type photosensitive film capable of forming an interlayer insulating film which is sufficiently excellent in various properties such as resolution, transparency, heat resistance, heat discoloration resistance, and solvent resistance even when thickened. Resin composition. Further, an object of the present invention is to provide an interlayer insulating film formed of the above-described negative-type photosensitive resin composition and a method of forming the same.
本發明提供一種負片型感光性樹脂組成物,其包含:包含下述通式(1)所表示的重複單元的(A)環狀烯烴樹脂、(B)多官能性丙烯酸單體、及(C)光聚合起始劑。式(1)中R1 、R2 、R3 及R4 分別獨立地表示選自氫原子、碳數1~15的烷基、碳數2~20的烯基、碳數5~15的環烷基、碳數6~20的芳基或碳數1~20的烷氧基,或者水解性矽烷基、碳數2~20的烷氧基羰基、碳數4~20的三烷基矽烷氧基羰基、碳數2~20的烷基羰氧基、碳數3~20的烯基羰氧基及氧雜環丁基中的取代基,可直接或者經由氧原子、氮原子或硫原子而相互連結。The present invention provides a negative-type photosensitive resin composition comprising (A) a cyclic olefin resin comprising a repeating unit represented by the following formula (1), (B) a polyfunctional acrylic monomer, and (C) ) Photopolymerization initiator. In the formula (1), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and a ring having 5 to 15 carbon atoms. An alkyl group, an aryl group having 6 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, or a hydrolyzable alkylene group, an alkoxycarbonyl group having 2 to 20 carbon atoms, or a trialkyldecaneoxy group having 4 to 20 carbon atoms. The substituent in the carbonyl group, the alkylcarbonyloxy group having 2 to 20 carbon atoms, the alkenylcarbonyloxy group having 3 to 20 carbon atoms or the oxetanyl group may be directly or via an oxygen atom, a nitrogen atom or a sulfur atom. Connected to each other.
[化1][Chemical 1]
具備上述構成的負片型感光性樹脂組成物可形成即便厚膜化,解析度、透明性、耐熱性、耐熱變色性及耐溶劑性等諸多特性亦充分優異的層間絕緣膜。The negative-type photosensitive resin composition having the above-described configuration can form an interlayer insulating film which is sufficiently excellent in various properties such as resolution, transparency, heat resistance, heat discoloration resistance, and solvent resistance, even if it is thick.
(A)環狀烯烴樹脂較佳為包含由上述通式(1)所表示,且R1 、R2 、R3 及R4 為氫原子的結構單元。The cyclic olefin resin (A) preferably contains a structural unit represented by the above formula (1), and R 1 , R 2 , R 3 and R 4 are a hydrogen atom.
另外,(A)環狀烯烴樹脂較佳為包含由上述通式(1)所表示,且R1 、R2 、R3 及R4 中的任一者為碳數2~20的烷基羰氧基的結構單元。Further, the (A) cyclic olefin resin preferably contains an alkylcarbonyl group represented by the above formula (1), and any one of R 1 , R 2 , R 3 and R 4 is a carbon number of 2 to 20 carbon atoms. A structural unit of an oxy group.
本發明提供一種負片型感光性樹脂組成物,其用於層間絕緣膜的形成方法,該形成方法包括對由該負片型感光性樹脂組成物所形成的膜的至少一部分照射波長400 nm以下的紫外線的步驟。The present invention provides a negative-type photosensitive resin composition for forming an interlayer insulating film, which comprises irradiating at least a part of a film formed of the negative-type photosensitive resin composition with ultraviolet rays having a wavelength of 400 nm or less A step of.
另外,本發明的負片型感光性樹脂組成物較佳為更包含(D)鹼可溶性樹脂。Further, the negative-type photosensitive resin composition of the present invention preferably further contains (D) an alkali-soluble resin.
本發明提供一種由上述負片型感光性樹脂組成物所形成的層間絕緣膜。The present invention provides an interlayer insulating film formed of the negative-type photosensitive resin composition described above.
本發明提供一種層間絕緣膜的形成方法,其包括以下步驟:對由上述負片型感光性樹脂組成物所形成的膜的至少一部分照射光;將照射光後的上述膜進行顯影;以及將顯影後的上述膜煅燒而形成層間絕緣膜。The present invention provides a method of forming an interlayer insulating film, comprising the steps of: irradiating at least a portion of a film formed of the negative-type photosensitive resin composition; developing the film after irradiation; and developing The above film is calcined to form an interlayer insulating film.
[發明的效果][Effects of the Invention]
依據本發明,可提供一種可形成即便厚膜化,解析度、透明性、耐熱性、耐熱變色性及耐溶劑性等諸多特性亦充分優異的層間絕緣膜的負片型感光性樹脂組成物。According to the present invention, it is possible to provide a negative-type photosensitive resin composition which can form an interlayer insulating film which is sufficiently excellent in various properties such as resolution, transparency, heat resistance, heat-resistant discoloration property, and solvent resistance, even if it is thick.
以下,對本發明的較佳實施形態進行詳細說明。Hereinafter, preferred embodiments of the present invention will be described in detail.
本實施形態的負片型感光性樹脂組成物包含(A)環狀烯烴樹脂、(B)多官能性丙烯酸單體、及(C)光聚合起始劑。以下對各成分進行詳細說明。The negative-type photosensitive resin composition of the present embodiment contains (A) a cyclic olefin resin, (B) a polyfunctional acrylic monomer, and (C) a photopolymerization initiator. Each component will be described in detail below.
-(A)環狀烯烴樹脂-- (A) cyclic olefin resin -
本實施形態的(A)環狀烯烴樹脂是具有由下述通式(1)所表示的重複單元的聚合物。The (A) cyclic olefin resin of the present embodiment is a polymer having a repeating unit represented by the following general formula (1).
[化2][Chemical 2]
上述R1 、R2 、R3 及R4 分別獨立地表示選自氫原子、碳數1~15的烷基、碳數2~20的烯基、碳數5~15的環烷基、碳數6~20的芳基或碳數1~20的烷氧基,或者水解性矽烷基、碳數2~20的烷氧基羰基、碳數4~20的三烷基矽烷氧基羰基、碳數2~20的烷基羰氧基、碳數3~20的烯基羰氧基及氧雜環丁基中的取代基,可直接或者經由氧原子、氮原子或硫原子而相互連結。R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 5 to 15 carbon atoms, or carbon. An aryl group of 6 to 20 or an alkoxy group having 1 to 20 carbon atoms, or a hydrolyzable alkylene group, an alkoxycarbonyl group having 2 to 20 carbon atoms, a trialkyldecyloxycarbonyl group having 4 to 20 carbon atoms, or carbon The alkylcarbonyloxy group having 2 to 20 carbon atoms, the alkenylcarbonyloxy group having 3 to 20 carbon atoms, and the substituent in the oxetanyl group may be bonded to each other directly or via an oxygen atom, a nitrogen atom or a sulfur atom.
更佳為R1 、R2 、R3 及R4 分別獨立地為選自氫原子、碳數1~15的烷基、碳數2~20的烯基、碳數6~15的芳基、或者碳數6~20的烷氧基以及碳數2~20的烷基羰氧基中的取代基。藉由設為上述構成,獲得於各種溶劑中的溶解性提高的效果。More preferably, each of R 1 , R 2 , R 3 and R 4 is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 15 carbon atoms. Or a substituent in an alkoxy group having 6 to 20 carbon atoms and an alkylcarbonyloxy group having 2 to 20 carbon atoms. According to the above configuration, the effect of improving the solubility in various solvents is obtained.
其中,水解性矽烷基具體可列舉三甲氧基矽烷基、甲基二甲氧基矽烷基。Specific examples of the hydrolyzable alkylene group include a trimethoxydecyl group and a methyldimethoxydecyl group.
碳數2~20的烷基羰氧基具體可列舉:甲酯、第三丁酯、2-乙基己酯、苄酯、環戊酯、環己酯及烯丙酯。該些烷基羰氧基中,就耐熱性方面而言,特佳為使用甲酯及苄酯等。Specific examples of the alkylcarbonyloxy group having 2 to 20 carbon atoms include a methyl ester, a third butyl ester, a 2-ethylhexyl ester, a benzyl ester, a cyclopentyl ester, a cyclohexyl ester, and an allyl ester. Among the alkylcarbonyloxy groups, a methyl ester, a benzyl ester or the like is particularly preferably used in terms of heat resistance.
本實施形態中使用的(A)環狀烯烴樹脂較佳為以環狀烯烴中的式(1)的結構單元的總量為基準,包含1莫耳百分比(mol%)以上的由上述通式(1)所表示且R1 、R2 、R3 及R4 為氫原子的結構單元,更佳為包含10 mol%以上。於該比例為1 mol%以上的情況,存在所得負片型感光性樹脂組成物的耐熱性提高的傾向。另外,上述比例較佳為60 mol%以下,更佳為50 mol%以下。於上述比例為60 mol%以下的情況,存在於用以製備負片型感光性樹脂組成物的溶劑中的可溶性提高的傾向。The (A) cyclic olefin resin used in the present embodiment preferably contains the above formula by 1 mol% or more based on the total amount of the structural unit of the formula (1) in the cyclic olefin. (1) The structural unit represented by R 1 , R 2 , R 3 and R 4 is a hydrogen atom, and more preferably contains 10 mol% or more. When the ratio is 1 mol% or more, the heat resistance of the obtained negative-type photosensitive resin composition tends to be improved. Further, the above ratio is preferably 60 mol% or less, more preferably 50 mol% or less. When the ratio is 60 mol% or less, the solubility in the solvent for preparing the negative-type photosensitive resin composition tends to increase.
本實施形態中使用的(A)環狀烯烴樹脂較佳為以環狀烯烴中的式(1)的結構單元的總量為基準,包含1 mol%以上的由上述通式(1)所表示且R1 、R2 、R3 及R4 中的任一者為碳數2~20的烷基羰氧基的結構單元,更佳為包含10 mol%以上。於該比例為1 mol%以上的情況,存在獲得於用以製備負片型感光性樹脂組成物的溶劑中的可溶性提高的效果的傾向。上述比例較佳為60 mol%以下,更佳為50 mol%以下。於上述比例為60 mol%以下的情況,存在獲得所得負片型感光性樹脂組成物的耐熱性提高的效果的傾向。The (A) cyclic olefin resin used in the present embodiment is preferably represented by the above formula (1), based on the total amount of the structural unit of the formula (1) in the cyclic olefin, and containing 1 mol% or more. Further, any one of R 1 , R 2 , R 3 and R 4 is a structural unit of an alkylcarbonyloxy group having 2 to 20 carbon atoms, more preferably 10 mol% or more. When the ratio is 1 mol% or more, there is a tendency that the solubility in the solvent for preparing the negative-type photosensitive resin composition is improved. The above ratio is preferably 60 mol% or less, more preferably 50 mol% or less. When the ratio is 60 mol% or less, the effect of improving the heat resistance of the obtained negative-type photosensitive resin composition tends to be obtained.
上述(A)環狀烯烴樹脂可藉由將下述通式(2)所表示的單體於溶劑中,在金屬觸媒的存在下進行加成共聚合而製造。The above (A) cyclic olefin resin can be produced by subjecting a monomer represented by the following formula (2) to a solvent in the presence of a metal catalyst.
[化3][Chemical 3]
(A)環狀烯烴樹脂的製造時使用的溶劑例如可列舉:戊烷(pentane)、己烷(hexane)及庚烷(heptane)等脂肪族烴,環己烷(cyclohexane)等脂環族烴,苯(benzene)、甲苯(toluene)及二甲苯(xylene)等芳香族烴,二氯甲烷(dichloromethane)、氯仿(chloroform)及氯苯(chlorobenzene)等鹵化烴,硝基甲烷(nitromethane)、硝基苯(nitrobenzene)及乙腈(acetonitrile)等含氮系烴,以及二乙醚(diethyl ether)、二噁烷(dioxane)及四氫呋喃(tetrahydrofuran)等醚類。該些溶劑可單獨使用1種,或者將2種以上混合使用。(A) Examples of the solvent used in the production of the cyclic olefin resin include aliphatic hydrocarbons such as pentane, hexane, and heptane, and alicyclic hydrocarbons such as cyclohexane. , aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as dichloromethane, chloroform, and chlorobenzene, nitromethane, and nitrate Nitrogen-containing hydrocarbons such as nitrobenzene and acetonitrile, and ethers such as diethyl ether, dioxane, and tetrahydrofuran. These solvents may be used alone or in combination of two or more.
(A)環狀烯烴樹脂的聚合時使用的觸媒(E)較佳為於選自元素週期表第8族元素、第9族元素及第10族元素中的一種過渡金屬上至少配位有環戊二烯基(cyclopentadienyl)系配位子的錯合物。具體例可列舉鐵(Fe)、鈷(Co)、鎳(Ni)、釕(Ru)、銠(Rh)、鈀(Pd)、及鉑(Pt)。該些金屬中,就提高觸媒的聚合活性的觀點而言較佳的元素為鈷、鎳、鈀、及鉑,特佳為使用鈀。(A) The catalyst (E) used in the polymerization of the cyclic olefin resin is preferably at least coordinated to a transition metal selected from the group consisting of Group 8, element 9, and Group 10 elements of the periodic table. A cyclopentadienyl complex of a ligand. Specific examples thereof include iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), and platinum (Pt). Among these metals, preferred ones are cobalt, nickel, palladium, and platinum from the viewpoint of improving the polymerization activity of the catalyst, and palladium is particularly preferably used.
(A)環狀烯烴樹脂的聚合時使用的助觸媒(F)較佳為促進形成觸媒(E)的錯合物的配位子的解離的助觸媒。例如可列舉將以下所例示的非配位性陰離子與陽離子組合而成的離子性化合物。The promoter (F) used in the polymerization of the cyclic olefin resin (A) is preferably a promoter which promotes dissociation of the ligand forming the complex of the catalyst (E). For example, an ionic compound obtained by combining a non-coordinating anion and a cation exemplified below can be mentioned.
非配位性陰離子例如可列舉:四(苯基)硼酸鹽(tetra(phenyl)borate)、四(氟苯基)硼酸鹽、四(二氟苯基)硼酸鹽、四(三氟苯基)硼酸鹽、四(四氟苯基)硼酸鹽、四(五氟苯基)硼酸鹽、四(四氟甲基苯基)硼酸鹽、四(甲苯基)硼酸鹽(tetra(tolyl)borate)、四(二甲苯基)硼酸鹽tetra(xylyl)borate)、(三苯基,五氟苯基)硼酸鹽、[三(五氟苯基),苯基]硼酸鹽及十三氫化-7,8-二碳代十一硼酸鹽(tridecahydride-7,8-dicarbaundecaborate)。Examples of the non-coordinating anion include tetra(phenyl)borate, tetrakis(fluorophenyl)borate, tetrakis(difluorophenyl)borate, and tetrakis(trifluorophenyl). Borate, tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(tetrafluoromethylphenyl)borate, tetra(tolyl)borate, Tetrakis(xylyl)borate, (triphenyl, pentafluorophenyl) borate, [tris(pentafluorophenyl), phenyl]borate and tridecahydro-7,8 -Tridecahydride-7, 8-dicarbaundecaborate.
上述陽離子可列舉:碳鎓(carbonium)陽離子、氧鎓(oxonium)陽離子、銨(ammonium)陽離子、鏻(phosphonium)陽離子、環庚三烯基(cycloheptyltrienyl)陽離子及具有過渡金屬的二茂鐵(ferrocenium)陽離子等。Examples of the above cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a transition metal ferrocene (ferrocenium). ) cations and the like.
碳鎓陽離子的具體例可列舉三苯基碳鎓陽離子及三取代苯基碳鎓陽離子等三取代碳鎓陽離子。三取代苯基碳鎓陽離子的具體例可列舉三(甲基苯基)碳鎓陽離子及三(二甲基苯基)碳鎓陽離子。Specific examples of the carbonium cation include a trisubstituted carbonium cation such as a triphenylcarbonium cation and a trisubstituted phenylcarbenium cation. Specific examples of the trisubstituted phenylcarbenium cation include a tri(methylphenyl)carbonium cation and a tris(dimethylphenyl)carbonium cation.
銨陽離子的具體例可列舉:三甲基銨(trimethyl ammonium)陽離子、三乙基銨陽離子、三丙基銨陽離子、三丁基銨陽離子及三(正丁基)銨陽離子等三烷基銨陽離子,N,N-二乙基苯銨(N,N-diethyl anilinium)陽離子及N,N-2,4,6-五甲基苯銨陽離子等N,N-二烷基苯銨陽離子,以及二(異丙基)銨陽離子及二環己基銨陽離子等二烷基銨陽離子。Specific examples of the ammonium cation include trialkyl ammonium cations such as trimethyl ammonium cation, triethyl ammonium cation, tripropyl ammonium cation, tributyl ammonium cation, and tri(n-butyl) ammonium cation. , N,N-diethyl anilinium cations and N,N-dialkylanilinium cations such as N,N-2,4,6-pentamethylanilinium cation, and a dialkylammonium cation such as an (isopropyl)ammonium cation or a dicyclohexylammonium cation.
鏻陽離子的具體例可列舉:三苯基鏻(triphenylphosphonium)陽離子、三(甲基苯基)鏻陽離子及三(二甲基苯基)鏻陽離子等三芳基鏻陽離子。Specific examples of the phosphonium cation include a triphenylphosphonium cation, a tris(methylphenyl)phosphonium cation, and a triarylsulfonium cation such as a tris(dimethylphenyl)phosphonium cation.
上述離子性化合物例如為三苯甲基四(五氟苯基)硼酸鹽(trityl tetra(pentafluorophenyl)borate)、三苯基碳鎓四(氟苯基)硼酸鹽(triphenylcarbonium tetra(fluorophenyl)borate)、N,N-二甲基苯銨四(五氟苯基)硼酸鹽(N,N-dimethylanilinium tetra(pentafluorophenyl)borate)及1,1'-二甲基二茂鐵四(五氟苯基)硼酸鹽(1,1'-dimethylferrocenium tetra(pentafluorophenyl)borate)。The above ionic compound is, for example, trityl tetra(pentafluorophenyl)borate, triphenylcarbonium tetra(fluorophenyl)borate, N,N-dimethylanilinium tetra(pentafluorophenyl)borate and 1,1'-dimethylferrocene tetrakis(pentafluorophenyl)borate 1,1'-dimethylferrocenium tetra(pentafluorophenyl)borate.
本實施形態中,觸媒(E)與助觸媒(F)的比例由於根據各種條件而有所不同,故無法一概而定,但通常較佳為以觸媒E/助觸媒F(莫耳比)計為1/0.1~1/10000,更佳為1/0.5~1/5000,進而更佳為1/1~1/2000。In the present embodiment, the ratio of the catalyst (E) to the promoter (F) varies depending on various conditions, and therefore cannot be determined in a general manner. However, it is generally preferred to use the catalyst E/catalyst F (Mo The ear ratio is 1/0.1 to 1/10000, more preferably 1/0.5 to 1/5000, and still more preferably 1/1 to 1/2000.
本實施形態的(A)環狀烯烴樹脂的聚苯乙烯換算重量平均分子量(以下稱為「Mw」)較佳為2×103 至2×105 ,更佳為2×104 至1.8×105 。若Mw小於2×103 ,則所得被膜存在耐熱性及表面硬度下降的傾向。另一方面,若Mw超過2×105 ,則存在顯影性、於感光性樹脂組成物製備用溶劑中的溶解性下降的傾向。The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the (A) cyclic olefin resin of the present embodiment is preferably 2 × 10 3 to 2 × 10 5 , more preferably 2 × 10 4 to 1.8 ×. 10 5 . When Mw is less than 2 × 10 3 , the obtained film tends to have heat resistance and surface hardness. On the other hand, when the Mw exceeds 2 × 10 5 , the developability and the solubility in the solvent for preparing the photosensitive resin composition tend to decrease.
-(B)多官能性丙烯酸單體-- (B) Polyfunctional acrylic monomer -
本實施形態的(B)多官能性丙烯酸單體是使用二官能以上的多官能(甲基)丙烯酸酯。具體可列舉:二季戊四醇六丙烯酸酯(dipentaerythritol hexaacrylate)、二季戊四醇六甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇五甲基丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇二丙烯酸酯、季戊四醇二甲基丙烯酸酯、四羥甲基丙烷四丙烯酸酯(tetramethylolpropane tetraacrylate)、四羥甲基丙烷四甲基丙烯酸酯、四羥甲基甲烷四丙烯酸酯、四羥甲基甲烷四甲基丙烯酸酯、三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、1,3,5-三丙烯醯基六氫-均三嗪(1,3,5-triacryloyl hexahydro-s-triazine)、1,3,5-三甲基丙烯醯基六氫-均三嗪、三(羥基乙基丙烯醯基)三聚異氰酸酯(tris(hydroxyethylacryloyl)isocyanurate)、三(羥基乙基甲基丙烯醯基)三聚異氰酸酯、三丙烯醯基縮甲醛(triacryloyl formal)、三甲基丙烯醯基縮甲醛、1,6-己二醇丙烯酸酯(1,6-hexanediol acrylate)、1,6-己二醇甲基丙烯酸酯、新戊二醇二丙烯酸酯(neopentyl glycol diacrylate)、新戊二醇二甲基丙烯酸酯、乙二醇二丙烯酸酯(ethylene glycol diacrylate)、乙二醇二甲基丙烯酸酯、2-羥基丙二醇二丙烯酸酯(2-hydroxy propanediol diacrylate)、2-羥基丙二醇二甲基丙烯酸酯、二乙二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯、異丙二醇二丙烯酸酯、異丙二醇二甲基丙烯酸酯、三乙二醇二丙烯酸酯、三乙二醇二甲基丙烯酸酯、N,N'-雙(丙烯醯基)半胱胺酸(N,N'-bis(acryloyl)cysteine)、N,N'-雙(甲基丙烯醯基)半胱胺酸、硫代雙乙醇二丙烯酸酯(thiodiglycol diacrylate)、硫代雙乙醇二甲基丙烯酸酯、雙酚A二丙烯酸酯(bisphenol A diacrylate)、雙酚A二甲基丙烯酸酯、雙酚F二丙烯酸酯、雙酚F二甲基丙烯酸酯、雙酚S二丙烯酸酯、雙酚S二甲基丙烯酸酯、雙苯氧基乙醇茀二丙烯酸酯(bisphenoxy ethanol fluorene diacrylate)、雙苯氧基乙醇茀二甲基丙烯酸酯、二烯丙醚雙酚A(diallylether bisphenol A)、鄰二烯丙基雙酚A、順丁烯二酸二烯丙酯(diallyl maleate)及偏苯三甲酸三烯丙酯(triallyl trimellitate)。藉由使用二官能以上的多官能(甲基)丙烯酸酯,而獲得機械強度增加的效果。In the (B) polyfunctional acrylic monomer of the present embodiment, a difunctional or higher polyfunctional (meth) acrylate is used. Specific examples thereof include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and pentaerythritol. Acrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylol Methane tetraacrylate, tetramethylol methane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,3,5-tripropylene decyl hexahydro- Triazine (1,3,5-triacryloyl hexahydro-s-triazine), 1,3,5-trimethylpropenyl hexahydro-s-triazine, tris(hydroxyethylpropenyl)trimeric isocyanate (tris) (hydroxyethylacryloyl)isocyanurate), tris(hydroxyethylmethacryloyl)trimeric isocyanate, triacryloyl formal, trimethyl propylene phthalate Formaldehyde, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol Dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 2-hydroxy propanediol diacrylate, 2-hydroxypropanediol dimethacrylate Ester, diethylene glycol diacrylate, diethylene glycol dimethacrylate, isopropyl glycol diacrylate, isopropyl glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate Ester, N, N'-bis(acryloyl)cysteine, N,N'-bis(methacryloyl)cysteine, thio Thiodiglycol diacrylate, thiodiethanol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate, bisphenol S dimethacrylate, bisphenoxy Bisphenoxy ethanol fluorene diacrylate, bisphenoxyethanol oxime dimethacrylate, diallyl bisphenol A, o-diallyl bisphenol A, maleic acid Diallyl maleate and triallyl trimellitate. The effect of increasing the mechanical strength is obtained by using a difunctional or higher polyfunctional (meth) acrylate.
上述多官能性丙烯酸單體可作為市售品而容易獲取,例如可列舉:Kyarad T-1420、Kyarad DPHA、Kyarad DPHA-2C、Kyarad D-310、Kyarad D-330、Kyarad DPCA-20、Kyarad DPCA-30、Kyarad DPCA-60、Kyarad DPCA-120、Kyarad DN-0075、Kyarad DN-2475、Kyarad R-526、Kyarad NPGDA、Kyarad PEG400DA、Kyarad MANDA、Kyarad R-167、Kyarad HX-220、Kyarad HX620、Kyarad R-551、Kyarad R-712、Kyarad R-604、Kyarad R-684、Kyarad GPO-303、Kyarad TMPTA、Kyarad THE-330、Kyarad TPA-320、Kyarad TPA-330、Kyarad PET-30、Kyarad RP-1040(以上由日本化藥(股)製造);Aronix M-210、Aronix M-240、Aronix M-6200、Aronix M-305、Aronix M-309、Aronix M-400、Aronix M-402、Aronix M-405、Aronix M-450、Aronix M-7100、Aronix M-8030、Aronix M-8060、Aronix M-1310、Aronix M-1600、Aronix M-1960、Aronix M-8100、Aronix M-8530、Aronix M-8560、Aronix M-9050(以上由東亞合成(股)製造);Viscoat 295、Viscoat 300、Viscoat 360、Viscoat GPT、Viscoat 3PA、Viscoat 400、Viscoat 260、Viscoat 312及Viscoat 335HP(以上由大阪有機化學工業(股)製造)。另外,該些多官能性丙烯酸單體可單獨使用1種,或者將2種以上組合使用。The above polyfunctional acrylic monomer can be easily obtained as a commercially available product, and examples thereof include Kyarad T-1420, Kyarad DPHA, Kyarad DPHA-2C, Kyarad D-310, Kyarad D-330, Kyarad DPCA-20, and Kyarad DPCA. -30, Kyarad DPCA-60, Kyarad DPCA-120, Kyarad DN-0075, Kyarad DN-2475, Kyarad R-526, Kyarad NPGDA, Kyarad PEG400DA, Kyarad MANDA, Kyarad R-167, Kyarad HX-220, Kyarad HX620, Kyarad R-551, Kyarad R-712, Kyarad R-604, Kyarad R-684, Kyarad GPO-303, Kyarad TMPTA, Kyarad THE-330, Kyarad TPA-320, Kyarad TPA-330, Kyarad PET-30, Kyarad RP -1040 (above manufactured by Nippon Kayaku Co., Ltd.); Aronix M-210, Aronix M-240, Aronix M-6200, Aronix M-305, Aronix M-309, Aronix M-400, Aronix M-402, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix M-1310, Aronix M-1600, Aronix M-1960, Aronix M-8100, Aronix M-8530, Aronix M-8560, Aronix M-9050 (manufactured by Toagosei Co., Ltd.); Viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 3PA, Viscoat 400, Viscoat 260, Viscoat 312 and Viscoat 335HP (above manufactured by Osaka Organic Chemical Industry Co., Ltd.). In addition, these polyfunctional acrylic monomers may be used alone or in combination of two or more.
該些多官能性丙烯酸單體中,就於顯影液中的溶解性及透明性而言,特佳為二季戊四醇六丙烯酸酯、二季戊四醇六甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇五甲基丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇二丙烯酸酯及季戊四醇二甲基丙烯酸酯。Among these polyfunctional acrylic monomers, in terms of solubility and transparency in the developer, it is particularly preferably dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Methacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, and pentaerythritol dimethacrylate.
-(C)光聚合起始劑--(C) Photopolymerization initiator -
本實施形態的(C)光聚合起始劑可列舉感光性自由基聚合起始劑。該感光性自由基聚合起始劑例如可列舉:苯偶醯(benzil)及雙乙醯(diacetyl)等α-二酮(α-diketone)類,安息香(benzoin)等醇酮(acyloin)類,安息香甲醚(benzoin methylether)、安息香乙醚及安息香異丙醚等醇酮醚(acyloin ether)類,噻吨酮(thioxanthone)、2,4-二乙基噻吨酮、噻吨酮-4-磺酸,二苯甲酮(benzophenone)、4,4'-雙(二甲基胺基)二苯甲酮及4,4'-雙(二乙基胺基)二苯甲酮等二苯甲酮類,苯乙酮(acetophenone)、對二甲基胺基苯乙酮(p-dimethylamino acetophenone)、α,α'-二甲氧基乙醯氧基二苯甲酮(α,α'-dimethoxy acetoxy benzophenone)、2,2'-二甲氧基-2-苯基苯乙酮、對甲氧基苯乙酮、2-甲基(4-(甲基硫基)苯基)-2-嗎啉基-1-丙酮(2-methyl(4-(methylthio)phenyl)-2-morpholino-1-propanone)及2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁-1-酮等苯乙酮類,蒽醌(anthraquinone)及1,4-萘醌(1,4-naphthoquinone)等醌(quinone)類,苯甲醯甲基氯(phenacyl chloride)、三溴甲基苯基碸(tribromomethyl phenyl sulfone)及三(三氯甲基)-均三嗪(tris(trichloromethyl)-s-triazine)等鹵化物,2,4,6-三甲基苯甲醯基二苯基氧化膦(2,4,6-trimethyl benzoyl diphenyl phosphine oxide)、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基氧化膦及雙(2,4,6-三甲基苯甲醯基)苯基氧化膦等醯基氧化膦、及過氧化二第三丁基(di-t-butyl peroxide)等過氧化物等。藉由使用感光性自由基聚合起始劑,獲得負片型感光性樹脂組成物對光的感度提高的效果。The (C) photopolymerization initiator of the present embodiment includes a photosensitive radical polymerization initiator. Examples of the photosensitive radical polymerization initiator include α-diketones such as benzil and diacetyl, and acyloins such as benzoin. Acylin methylether, benzoin ether and acyloin ether, thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonate Acid, benzophenone, 4,4'-bis(dimethylamino)benzophenone, and benzophenone such as 4,4'-bis(diethylamino)benzophenone Class, acetophenone, p-dimethylamino acetophenone, α,α'-dimethoxyethoxy benzophenone (α,α'-dimethoxy acetoxy) Benzophenone), 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl(4-(methylthio)phenyl)-2-morpholine 2-methyl(4-(methylthio)phenyl)-2-morpholino-1-propanone) and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl) ) - acetophenones such as butan-1-one, quinones such as anthraquinone and 1,4-naphthoquinone, phenacyl ch Loride), tribromomethyl phenyl sulfone and tris(trichloromethyl)-s-triazine, etc., 2,4,6-trimethyl 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentyl Peroxides such as phosphine oxide and bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, and peroxides such as di-t-butyl peroxide Wait. By using a photosensitive radical polymerization initiator, the effect of improving the sensitivity of the negative-type photosensitive resin composition is obtained.
作為該些感光性自由基聚合起始劑的市售品,例如可列舉:Irgacure-184、Irgacure-369、Irgacure-500、Irgacure-651、Irgacure-907、Irgacure-1700、Irgacure-819、Irgacure-124、Irgacure-1000、Irgacure-2959、Irgacure-149、Irgacure-1800、Irgacure-1850、Irgacure-OXE-01、Darocur-1173、Darocur-1116、Darocur-2959、Darocur-1664、Darocur-4043(以上由Ciba Specialty Chemicals公司製造);Kayacure-DETX、Kayacure-MBP、Kayacure-DMBI、Kayacure-EPA、Kayacure-OA(以上由日本化藥(股)製造);Lucirintpo(BASF Co.LTD製造);Vicure-10、Vicure-55(以上由STAUFFER Co.LTD製造);Trigonal P1(AKZO Co.LTD製造);Sandoray 1000(SANDOZ Co.LTD製造);DEAP(APJOHN Co.LTD製造);Quantacure-PDO、Quantacure-ITX及Quantacure-EPD(以上由WARDBLEKINSOP Co.LTD製造)。另外,藉由將該些感光性自由基聚合起始劑與感光增感劑併用,亦可獲得由氧引起的失活少的高感度的負片型感光性樹脂組成物。Commercial products of such photosensitive radical polymerization initiators include, for example, Irgacure-184, Irgacure-369, Irgacure-500, Irgacure-651, Irgacure-907, Irgacure-1700, Irgacure-819, Irgacure- 124, Irgacure-1000, Irgacure-2959, Irgacure-149, Irgacure-1800, Irgacure-1850, Irgacure-OXE-01, Darocur-1173, Darocur-1116, Darocur-2959, Darocur-1664, Darocur-4043 (above Ciba Specialty Chemicals, Inc.; Kayacure-DETX, Kayacure-MBP, Kayacure-DMBI, Kayacure-EPA, Kayacure-OA (manufactured by Nippon Kayaku Co., Ltd.); Lucirintpo (manufactured by BASF Co., Ltd.); Vicure-10 , Vicure-55 (above manufactured by STAUFFER Co. LTD); Trigonal P1 (manufactured by AKZO Co. LTD); Sandoray 1000 (manufactured by SANDOZ Co. LTD); DEAP (manufactured by APJOHN Co. LTD); Quantacure-PDO, Quantacure-ITX And Quantacure-EPD (above manufactured by WARDBLEKINSOP Co. LTD). In addition, by using these photosensitive radical polymerization initiators together with a photosensitizing agent, it is possible to obtain a high-sensitivity negative-plate type photosensitive resin composition which is less deactivated by oxygen.
上述感光性自由基聚合起始劑中,就於感光性樹脂組成物製備液中的溶解性、曝光後的透明性而言,特佳為α,α'-二甲氧基乙醯氧基二苯甲酮、2-甲基(4-(甲基硫基)苯基)-2-嗎啉基-1-丙酮及2-甲基(4-(甲基硫基)苯基)-2-嗎啉基-1-丙酮。Among the above-mentioned photosensitive radical polymerization initiators, α, α'-dimethoxyacetoxy group is particularly preferable in terms of solubility in a photosensitive resin composition preparation liquid and transparency after exposure. Benzophenone, 2-methyl(4-(methylthio)phenyl)-2-morpholinyl-1-propanone and 2-methyl(4-(methylthio)phenyl)-2- Morpholinyl-1-propanone.
-(D)鹼可溶性樹脂--(D) alkali soluble resin -
本實施形態的鹼可溶性樹脂是線狀有機高分子聚合物,可自分子(較佳為以丙烯酸系共聚物、苯乙烯系共聚物為主鏈的分子)中具有至少1個促進鹼可溶性的基團(例如羧基、磷酸基及磺酸基等)的鹼可溶性樹脂中適當選擇。其中,尤佳為可溶於有機溶劑中且可利用弱鹼水溶液進行顯影的樹脂。The alkali-soluble resin of the present embodiment is a linear organic high molecular polymer, and has at least one base which promotes alkali solubility from a molecule (preferably a molecule mainly composed of an acrylic copolymer or a styrene copolymer). An alkali-soluble resin of a group (for example, a carboxyl group, a phosphate group, a sulfonic acid group, etc.) is suitably selected. Among them, a resin which is soluble in an organic solvent and can be developed with a weak aqueous alkali solution is particularly preferred.
製造鹼可溶性樹脂時,例如可應用藉由公知的自由基聚合法的方法。利用自由基聚合法來製造鹼可溶性樹脂時的溫度、壓力、自由基聚合起始劑的種類及量,以及溶劑的種類等聚合條件對本領域技術人員而言可容易設定,亦可以實驗的方式設定條件。When the alkali-soluble resin is produced, for example, a method by a known radical polymerization method can be applied. The polymerization conditions such as the temperature, the pressure, the type and amount of the radical polymerization initiator, and the kind of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, or can be experimentally set. condition.
上述線狀有機高分子聚合物較佳為側鏈具有羧酸的聚合物。例如可列舉:日本專利特開昭59-44615號、日本專利特公昭54-34327號、日本專利特公昭58-12577號、日本專利特公昭54-25957號、日本專利特開昭59-53836號及日本專利特開昭59-71048號的各公報中記載的甲基丙烯酸共聚物、丙烯酸共聚物、衣康酸共聚物、丁烯酸共聚物、順丁烯二酸共聚物、部分酯化順丁烯二酸共聚物、使側鏈具有羧酸的酸性纖維素衍生物及具有羥基的聚合物上加成有酸酐的高分子聚合物等,進而亦可列舉側鏈具有(甲基)丙烯醯基的高分子聚合物作為較佳聚合物。The linear organic high molecular polymer is preferably a polymer having a carboxylic acid in its side chain. For example, Japanese Patent Laid-Open No. Sho 59-44615, Japanese Patent Publication No. Sho 54-34327, Japanese Patent Publication No. Sho 58-12577, Japanese Patent Publication No. Sho 54-25957, Japanese Patent Laid-Open No. 59-53836 The methacrylic acid copolymer, the acrylic copolymer, the itaconic acid copolymer, the butenoic acid copolymer, the maleic acid copolymer, and the partially esterified cis-form described in each of the publications of JP-A-59-71048 a butenedioic acid copolymer, an acidic cellulose derivative having a carboxylic acid in a side chain, a polymer having an acid anhydride added to a polymer having a hydroxyl group, and the like, and further having a (meth) propylene fluorene in a side chain. The base polymer is a preferred polymer.
該些聚合物中,特佳為包含(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物及(甲基)丙烯酸苄酯/(甲基)丙烯酸/其他單體的多元共聚物。除此以外,亦可列舉使甲基丙烯酸2-羥基乙酯共聚合而成的聚合物等作為有用的聚合物。該聚合物可以任意的量混合使用。Among these polymers, a multicomponent copolymer comprising a benzyl (meth)acrylate/(meth)acrylic copolymer and a benzyl (meth)acrylate/(meth)acrylic acid/other monomer is particularly preferred. In addition, a polymer obtained by copolymerizing 2-hydroxyethyl methacrylate or the like may be mentioned as a useful polymer. The polymer can be used in admixture in any amount.
除上述以外,可列舉:日本專利特開平7-140654號公報中記載的(甲基)丙烯酸2-羥基丙酯/聚苯乙烯巨單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物、丙烯酸2-羥基-3-苯氧基丙酯/聚甲基丙烯酸甲酯巨單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物、甲基丙烯酸2-羥基乙酯/聚苯乙烯巨單體/甲基丙烯酸甲酯/甲基丙烯酸共聚物及甲基丙烯酸2-羥基乙酯/聚苯乙烯巨單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物等。In addition to the above, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, acrylic acid, as described in JP-A-7-140654 2-Hydroxy-3-phenoxypropyl ester/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/ Methyl methacrylate/methacrylic acid copolymer and 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer.
關於(D)鹼可溶性樹脂的具體結構單元,特佳為(甲基)丙烯酸與可與其共聚合的其他單體的共聚物。可與上述(甲基)丙烯酸共聚合的其他單體可列舉(甲基)丙烯酸烷基酯、(甲基)丙烯酸芳酯及乙烯基化合物等。其中,烷基及芳基的氫原子亦可由取代基取代。Regarding the specific structural unit of the (D) alkali-soluble resin, a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith is particularly preferred. Examples of the other monomer copolymerizable with the above (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, and a vinyl compound. Among them, the hydrogen atom of the alkyl group and the aryl group may be substituted by a substituent.
上述(甲基)丙烯酸烷基酯及(甲基)丙烯酸芳基酯的具體例可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸苯酯、丙烯酸苄酯、丙烯酸甲苯酯、丙烯酸萘酯及丙烯酸環己酯。Specific examples of the alkyl (meth)acrylate and the aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. Butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl acrylate , toluene acrylate, naphthalene acrylate and cyclohexyl acrylate.
另外,上述乙烯基化合物例如可列舉:苯乙烯、α-甲基苯乙烯、乙烯基甲苯、甲基丙烯酸縮水甘油酯、丙烯腈、乙酸乙烯酯、N-乙烯基吡咯啶酮(N-vinyl pyrrolidone)、甲基丙烯酸四氫糠酯(tetrahydrofurfuryl methacrylate)、聚苯乙烯巨單體、聚甲基丙烯酸甲酯巨單體、CH2 =CR5 R6 [其中,R5 表示氫原子或碳數1~5的烷基,R6 表示碳數6~10的芳香族烴環]及CH2 =C(R5 )(COOR7 )[其中,R5 表示氫原子或碳數1~5的烷基,R7 表示碳數1~8的烷基或碳數6~12的芳烷基]。該些可共聚合的其他單體可單獨使用1種,或者將2種以上組合使用。Further, examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, and N-vinyl pyrrolidone (N-vinyl pyrrolidone). ), tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH 2 =CR 5 R 6 [wherein R 5 represents a hydrogen atom or a carbon number of 1 ~5 alkyl, R 6 represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms] and CH 2 =C(R 5 )(COOR 7 ) [wherein R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R 7 represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. These other monomers which can be copolymerized may be used alone or in combination of two or more.
較佳的可共聚合的其他單體是選自CH2 =CR5 R6 、CH2 =C(R5 )(COOR7 )、(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯及苯乙烯中的至少1種,特佳為CH2 =CR5 R6 及/或CH2 =C(R5 )(COOR7 )。Preferred other copolymerizable monomers are selected from the group consisting of CH 2 =CR 5 R 6 , CH 2 =C(R 5 )(COOR 7 ), phenyl (meth)acrylate, benzyl (meth)acrylate, and At least one of styrene is particularly preferably CH 2 =CR 5 R 6 and/or CH 2 =C(R 5 )(COOR 7 ).
-負片型感光性樹脂組成物的製備-- Preparation of Negative Film Type Photosensitive Resin Composition -
本實施形態的負片型感光性樹脂組成物是藉由將上述(A)環狀烯烴樹脂、(B)多官能性丙烯酸單體及(C)光聚合起始劑的各成分混合而製備。上述負片型感光性樹脂組成物適宜溶解於適當的溶劑中而以溶液狀態使用。例如可藉由將(A)環狀烯烴樹脂、(B)多官能性丙烯酸單體、(C)光聚合起始劑、及視需要的其他調配劑以預定比例混合,而製備溶液狀態的負片型感光性樹脂組成物。The negative-type photosensitive resin composition of the present embodiment is prepared by mixing the components of the above (A) cyclic olefin resin, (B) polyfunctional acrylic monomer, and (C) photopolymerization initiator. The negative-type photosensitive resin composition is suitably dissolved in a suitable solvent and used in a solution state. For example, a negative film in a solution state can be prepared by mixing (A) a cyclic olefin resin, (B) a polyfunctional acrylic monomer, (C) a photopolymerization initiator, and optionally other formulation agents in a predetermined ratio. A photosensitive resin composition.
本實施形態的負片型感光性樹脂組成物是以相對於(A)環狀烯烴樹脂10重量份,較佳為10重量份~150重量份、更佳為40重量份~120重量份的比例含有(B)多官能性丙烯酸單體。於(B)多官能性丙烯酸單體小於10重量份的情況,存在無法獲得充分的感光性的傾向。另一方面,於超過150重量份的情況,存在斷裂強度下降的傾向。另外,以較佳為1重量份~40重量份、更佳為3重量份~35重量份的比例含有(C)光聚合起始劑。於(C)光聚合起始劑小於1重量份的情況,存在無法獲得耐熱性、表面硬度及耐藥品性的傾向。另一方面,於超過40重量份的情況,存在透明性下降的傾向。The negative-type photosensitive resin composition of the present embodiment is contained in an amount of 10 parts by weight to 150 parts by weight, more preferably 40 parts by weight to 120 parts by weight, based on 10 parts by weight of the (A) cyclic olefin resin. (B) A polyfunctional acrylic monomer. When the (B) polyfunctional acrylic monomer is less than 10 parts by weight, sufficient photosensitivity may not be obtained. On the other hand, in the case of more than 150 parts by weight, the breaking strength tends to decrease. Further, (C) a photopolymerization initiator is contained in a proportion of preferably from 1 part by weight to 40 parts by weight, more preferably from 3 parts by weight to 35 parts by weight. When the (C) photopolymerization initiator is less than 1 part by weight, heat resistance, surface hardness, and chemical resistance tend not to be obtained. On the other hand, in the case of more than 40 parts by weight, the transparency tends to decrease.
本實施形態的負片型感光性樹脂組成物的製備時使用的溶劑是使用溶解(A)環狀烯烴樹脂、(B)多官能性丙烯酸單體及(C)光聚合起始劑的各成分且不與各成分反應的溶劑。具體可列舉:甲醇及乙醇等醇類,四氫呋喃等醚類,乙二醇單甲醚及乙二醇單乙醚等二醇醚類,甲基溶纖劑乙酸酯及乙基溶纖劑乙酸酯等乙二醇烷基醚乙酸酯類,二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇二甲醚、二乙二醇乙基甲醚及二乙二醇二乙醚等二乙二醇類,丙二醇甲醚、丙二醇乙醚、丙二醇丙醚及丙二醇丁醚等丙二醇單烷基醚類,丙二醇甲醚乙酸酯、丙二醇乙醚乙酸酯、丙二醇丙醚乙酸酯及丙二醇丁醚乙酸酯等丙二醇烷基醚乙酸酯類,丙二醇甲醚丙酸酯、丙二醇乙醚丙酸酯、丙二醇丙醚丙酸酯及丙二醇丁醚丙酸酯等丙二醇烷基醚乙酸酯類,甲苯及二甲苯等芳香族烴類,甲基乙基酮、環己酮及4-羥基-4-甲基-2-戊酮等酮類,以及乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、羥基乙酸甲酯、羥基乙酸乙酯、羥基乙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3-羥基丙酸甲酯、3-羥基丙酸乙酯、3-羥基丙酸丙酯、3-羥基丙酸甲酯、3-丁氧基丙酸乙酯、3-丁氧基丙酸丙酯及3-丁氧基丙酸丁酯等酯類。The solvent used in the preparation of the negative-type photosensitive resin composition of the present embodiment is a component obtained by dissolving (A) a cyclic olefin resin, (B) a polyfunctional acrylic monomer, and (C) a photopolymerization initiator. A solvent that does not react with each component. Specific examples thereof include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, methyl cellosolve acetate and ethyl cellosolve acetate. Glycol alkyl ether acetate such as ester, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether and diethylene glycol diethyl ether Propylene glycol monoalkyl ethers such as diethylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol Propylene glycol alkyl ether acetate such as butyl ether acetate, propylene glycol alkyl ether propionate such as propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate, toluene And aromatic hydrocarbons such as xylene, ketones such as methyl ethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone, and methyl acetate, ethyl acetate, propyl acetate, acetic acid Butyl ester, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, hydroxyl Methyl acetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropane Esters such as propyl acrylate, methyl 3-hydroxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate.
該些溶劑中,就溶解性、與各成分的反應性及塗膜的形成容易度而言,較佳為使用丙二醇烷基醚乙酸酯類、丙二醇烷基醚乙酸酯類及芳香族烴類。Among these solvents, propylene glycol alkyl ether acetates, propylene glycol alkyl ether acetates, and aromatic hydrocarbons are preferably used in terms of solubility, reactivity with each component, and ease of formation of a coating film.
進而亦可將高沸點溶劑與上述溶劑併用。可併用的高沸點溶劑例如可列舉:N-甲基甲醯胺(N-methyl formamide)、N,N-二甲基甲醯胺(N,N-dimethyl formamide)、N-甲基甲醯苯胺(N-methyl formanilide)、N-甲基乙醯胺(N-methyl acetamide)、N,N-二甲基乙醯胺(N,N-dimethyl acetamide)、N-甲基吡咯啶酮(N-methyl pyrrolidone)、二甲基亞碸(dimethyl sulfoxide)、苄基乙醚、二己醚、丙酮基丙酮(acetonyl acetone)、異佛爾酮(isophorone)、己酸(caproic acid)、辛酸(caprylic acid)、1-辛醇(1-octanol)、1-壬醇(1-nonanol)、苄醇(benzyl alcohol)、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、順丁烯二酸二乙酯、γ-丁內酯(γ-butyrolactone)、碳酸乙二酯、碳酸丙二酯及苯基溶纖劑乙酸酯。本實施形態的負片型感光性樹脂組成物可於不損及本發明目的的範圍內,視需要含有上述以外的其他成分。Further, a high boiling point solvent may be used in combination with the above solvent. Examples of the high-boiling solvent which can be used in combination include N-methyl formamide, N, N-dimethyl formamide, and N-methylformamide. (N-methyl formanilide), N-methyl acetamide, N, N-dimethyl acetamide, N-methylpyrrolidone (N- Methyl pyrrolidone), dimethyl sulfoxide, benzyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid , 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate , γ-butyrolactone, ethylene carbonate, propylene carbonate and phenyl cellosolve acetate. The negative-type photosensitive resin composition of the present embodiment may contain other components than the above, as needed, within the range not impairing the object of the present invention.
以上述方式製備的負片型感光性樹脂組成物可使用孔徑0.2 μm~0.5 μm左右的微孔過濾器等進行過濾後,供於使用。The negative-type photosensitive resin composition prepared in the above manner can be used by filtration using a micropore filter having a pore diameter of about 0.2 μm to 0.5 μm.
-層間絕緣膜的形成方法-- Method of forming interlayer insulating film -
本實施形態的層間絕緣膜的形成方法至少包括下述步驟。(1)將上述負片型感光性樹脂組成物的膜形成於基板上的步驟;(2)對上述膜的至少一部分照射光(以下存在「曝光」的情況)的步驟;(3)將曝光後的上述膜進行顯影的步驟;以及4)將顯影後的上述膜煅燒(以下存在「烘烤」的情況)而形成層間絕緣膜的步驟。The method of forming the interlayer insulating film of the present embodiment includes at least the following steps. (1) a step of forming a film of the negative-type photosensitive resin composition on a substrate; (2) a step of irradiating at least a part of the film with light (in the case where "exposure" is present); (3) after exposing a step of developing the film; and 4) a step of forming the interlayer insulating film by firing the developed film (hereinafter, "baking").
其中,本實施形態所謂的「光」,是指包括紫外線、遠紫外線、X射線、電子束、分子束、γ射線、同步加速器光及質子束等的光。Here, the term "light" as used in the present embodiment means light including ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, gamma rays, synchrotron light, and proton beams.
以下,對該些步驟進行詳細說明。Hereinafter, these steps will be described in detail.
-(1)步驟-- (1) Step -
於(1)步驟中,將負片型感光性樹脂組成物較佳為製成液狀組成物,於基板表面上形成膜,藉由進行預烘烤而去除溶劑,形成負片型感光性樹脂組成物的膜。In the step (1), the negative-type photosensitive resin composition is preferably formed into a liquid composition, a film is formed on the surface of the substrate, and the solvent is removed by prebaking to form a negative-type photosensitive resin composition. Membrane.
可使用的基板的種類可列舉玻璃基板、矽晶圓以及於該些基板的表面形成有各種金屬的基板等。組成物溶液的膜形成方法並無特別限定,較佳為藉由塗佈的方法。塗佈方法可採用噴射法、輥塗法、旋轉塗佈法、狹縫式模塗法、棒塗法及噴墨法等適當的方法。Examples of the type of the substrate that can be used include a glass substrate, a germanium wafer, and a substrate on which various metals are formed on the surfaces of the substrates. The film formation method of the composition solution is not particularly limited, and a method of coating is preferred. The coating method may be an appropriate method such as a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, or an inkjet method.
預烘烤的條件根據負片型感光性樹脂組成物的構成成分的種類及使用比例等而有所不同,例如可設為60℃~130℃下30秒~15分鐘。所形成的上述膜的膜厚較佳為以預烘烤後的值計為5 μm~20 μm。The pre-baking conditions vary depending on the type and use ratio of the constituent components of the negative-type photosensitive resin composition, and can be, for example, 30 to 15 minutes at 60 to 130 °C. The film thickness of the film formed is preferably from 5 μm to 20 μm in terms of prebaking.
-(2)步驟-- (2) Step -
於(2)步驟中,對所形成的上述膜的至少一部分進行曝光。於此情況,當僅對上述膜的一部分進行曝光時,通常是經由具有預定形狀的圖案的光罩而進行曝光。In the step (2), at least a portion of the formed film is exposed. In this case, when only a part of the above film is exposed, exposure is usually performed via a photomask having a pattern of a predetermined shape.
曝光時使用的光例如可列舉:i線(波長365 nm)等紫外線、KrF準分子雷射及ArF準分子雷射等遠紫外線、同步加速器光等X射線、以及電子束等荷電粒子束。該些光中,較佳為紫外線,更佳為波長400 nm以下的紫外線,進而更佳為包含i線的紫外線。曝光量較佳為設為50 J/m2 ~10000 J/m2 左右。Examples of the light used for the exposure include ultraviolet rays such as i-line (wavelength 365 nm), far ultraviolet rays such as KrF excimer lasers and ArF excimer lasers, X-rays such as synchrotron light, and charged particle beams such as electron beams. Among these lights, ultraviolet rays are preferable, ultraviolet rays having a wavelength of 400 nm or less are more preferable, and ultraviolet rays containing i-lines are more preferable. The exposure amount is preferably set to about 50 J/m 2 to 10000 J/m 2 .
-(3)步驟-- (3) Step -
於(3)步驟中,藉由將曝光後的上述膜進行顯影,去除未曝光部而形成預定形狀的圖案。In the step (3), the exposed film is developed to remove the unexposed portion to form a pattern having a predetermined shape.
顯影時使用的顯影液較佳為:氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨、乙胺、正丙胺、二乙胺、二乙基胺基乙醇、二正丙胺、三乙胺、甲基二乙胺、二甲基乙醇胺、三乙醇胺、四甲基氫氧化銨、四乙基氫氧化銨、吡咯(pyrrole)、哌啶(piperidine)、1,8-二氮雜雙環[5,4,0]-7-十一烯(1,8-diazabicyclo[5,4,0]-7-undecene)及1,5-二氮雜雙環[4,3,0]-5-壬烯(1,5-diazabicyclo[4,3,0]-5-nonene)等鹼性化合物的水溶液。上述鹼性化合物的水溶液中可適量添加甲醇及乙醇等水溶性有機溶劑、以及界面活性劑。The developing solution used for development is preferably: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, and N-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperididine, 1,8- Diazabicyclo[5,4,0]-7-undecene (1,8-diazabicyclo[5,4,0]-7-undecene) and 1,5-diazabicyclo[4,3,0 An aqueous solution of a basic compound such as -5-decene (1,5-diazabicyclo[4,3,0]-5-nonene). A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous solution of the basic compound in an appropriate amount.
另外,本實施形態中,於負片型感光性樹脂組成物不含填充材料或顏料等不溶性成分的情況,亦可使用溶解構成成分的各種有機溶劑作為顯影液。In the present embodiment, when the negative-type photosensitive resin composition does not contain an insoluble component such as a filler or a pigment, various organic solvents in which the constituent components are dissolved may be used as the developer.
顯影方法可採用液池法、浸漬法、搖動浸漬法及噴淋法等適當方法。The development method may be a suitable method such as a liquid pool method, a dipping method, a shaking dipping method, or a shower method.
顯影時間根據負片型感光性樹脂組成物的調配組成而有所不同,例如可設為30秒~300秒。此外,自先前以來用於形成層間絕緣膜的負片型感光性樹脂組成物由於若顯影時間自最佳條件超出20秒以上,則所形成的圖案產生剝落等不良情況,故必需嚴格控制顯影時間,但於本發明的負片型感光性樹脂組成物的情況,即便自最佳顯影時間的超出時間為30秒以上,亦可形成良好的圖案,製品良率提高。The development time varies depending on the compounding composition of the negative-type photosensitive resin composition, and can be, for example, 30 seconds to 300 seconds. In addition, since the negative-type photosensitive resin composition for forming the interlayer insulating film has been used for more than 20 seconds from the optimum conditions, the formed pattern is defective in peeling, and the development time must be strictly controlled. However, in the case of the negative-type photosensitive resin composition of the present invention, even if the excess time from the optimum development time is 30 seconds or more, a favorable pattern can be formed and the product yield can be improved.
-(4)步驟-- (4) Step -
於(4)步驟中,將顯影後的上述膜視需要進行後曝光,然後利用加熱板及烘箱等加熱裝置進行烘烤,藉此使上述膜硬化而形成層間絕緣膜。後曝光時使用的光例如可列舉:i線(波長365 nm)等紫外線、KrF準分子雷射及ArF準分子雷射等遠紫外線、同步加速器光等X射線、以及電子束等荷電粒子束。In the step (4), the developed film is post-exposed as needed, and then baked by a heating means such as a hot plate or an oven to cure the film to form an interlayer insulating film. Examples of the light used for the post-exposure include ultraviolet rays such as i-line (wavelength 365 nm), far-ultraviolet rays such as KrF excimer lasers and ArF excimer lasers, X-rays such as synchrotron light, and charged particle beams such as electron beams.
該些光中,較佳為紫外線,更佳為波長400 nm以下的紫外線,進而更佳為包含i線的紫外線。後曝光的曝光量較佳為設為50 J/m2 ~10000 J/m2 。烘烤條件根據負片型感光性樹脂組成物的構成成分的種類及使用比例、所需圖案形狀、以及所使用的加熱裝置等而有所不同,但於加熱板的情況,例如為150℃~240℃下10分鐘~30分鐘,於烘箱的情況,例如為150℃~240℃下30分鐘~90分鐘。另外,烘烤時,亦可採用進行2次以上加熱處理的階段烘烤法等。Among these lights, ultraviolet rays are preferable, ultraviolet rays having a wavelength of 400 nm or less are more preferable, and ultraviolet rays containing i-lines are more preferable. The exposure amount of the post-exposure is preferably set to 50 J/m 2 to 10000 J/m 2 . The baking conditions vary depending on the type and use ratio of the constituent components of the negative-type photosensitive resin composition, the desired pattern shape, and the heating device to be used, but in the case of a hot plate, for example, 150 ° C to 240 10 ° to 30 minutes at ° C, and in the case of an oven, for example, from 150 ° C to 240 ° C for 30 minutes to 90 minutes. Further, at the time of baking, a stage baking method in which heat treatment is performed twice or more may be employed.
如上所述,可將作為目標的層間絕緣膜形成於基板上。所得的層間絕緣膜即便厚膜化,解析度、透明性、耐熱性、耐熱變色性及耐溶劑性等諸多特性亦優異,例如可極其適宜用於包含TFT型液晶顯示元件的各種液晶顯示元件、磁頭元件、積體電路元件及固體攝像元件等電子零件等。另外,利用本實施形態的層間絕緣膜的形成方法,可以高製品良率簡便地形成具有優異特性的層間絕緣膜。As described above, the target interlayer insulating film can be formed on the substrate. The obtained interlayer insulating film is excellent in various properties such as resolution, transparency, heat resistance, heat discoloration resistance, and solvent resistance, and can be used, for example, in various liquid crystal display elements including TFT liquid crystal display elements. Electronic components such as magnetic head elements, integrated circuit elements, and solid-state imaging elements. Further, according to the method for forming an interlayer insulating film of the present embodiment, an interlayer insulating film having excellent characteristics can be easily formed with high product yield.
[實例][Example]
以下表示實例,對本發明進行更具體的說明,但本發明並不限定於該些實例。The invention is more specifically illustrated by the following examples, but the invention is not limited to the examples.
(實例1)(Example 1)
-負片型感光性樹脂組成物的製備-- Preparation of Negative Film Type Photosensitive Resin Composition -
將作為(B)多官能性丙烯酸單體的Aronix M-305(東亞合成(股)製造,商品名)10 g溶解於甲苯36.4 g中,接著向所得的溶液中添加使R1 、R2 及R4 為氫原子且R3 為甲酯基的單體與R1 、R2 、R3 及R4 為氫原子的單體以1:1(莫耳比)進行共聚合而成的(A)環狀烯烴樹脂1 g,及作為(C)光聚合起始劑的2-甲基-1-(4-甲基硫基苯基)-2-嗎啉基丙-1-酮(Ciba Specialty Chemicals公司製造,商品名:IRGACURE-907)0.6 g,然後利用孔徑0.5 μm的薄膜過濾器進行過濾,製備整體的固體成分濃度為30重量百分比(wt%)的溶液狀態的負片型感光性樹脂組成物(S-1)。10 g of Aronix M-305 (manufactured by Toagosei Co., Ltd., trade name) as (B) polyfunctional acrylic monomer was dissolved in 36.4 g of toluene, and then R 1 and R 2 were added to the obtained solution. A monomer in which R 4 is a hydrogen atom and R 3 is a methyl ester group and a monomer in which R 1 , R 2 , R 3 and R 4 are a hydrogen atom is copolymerized in a ratio of 1:1 (mole ratio) (A) 1 g of a cyclic olefin resin, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one as a (C) photopolymerization initiator (Ciba Specialty Manufactured by Chemicals, trade name: IRGACURE-907) 0.6 g, and then filtered using a membrane filter having a pore size of 0.5 μm to prepare a negative-type photosensitive resin having a solid content of 30% by weight (wt%) in a solution state. (S-1).
-層間絕緣膜的形成-- Formation of interlayer insulating film -
使用台式塗佈機將負片型感光性樹脂組成物(S-1)塗佈於玻璃基板上後,於80℃的防爆乾燥機內預烘烤10分鐘,形成塗膜。接著,對該塗膜,經由具有預定形狀的圖案的光罩,將波長365 nm的紫外線以累計曝光量成為100 mJ/cm2 的方式進行曝光。然後,使用2.38 wt%的四甲基氫氧化銨水溶液,於25℃下浸漬顯影5分鐘後,以純水清洗1分鐘,藉此去除不需要的部分,獲得圖案狀薄膜。The negative-type photosensitive resin composition (S-1) was applied onto a glass substrate using a table coater, and then prebaked in an explosion-proof dryer at 80 ° C for 10 minutes to form a coating film. Next, the coating film was exposed to ultraviolet light having a wavelength of 365 nm at a cumulative exposure amount of 100 mJ/cm 2 via a mask having a pattern having a predetermined shape. Then, using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, immersing and developing at 25 ° C for 5 minutes, and then washing with pure water for 1 minute, thereby removing unnecessary portions, and obtaining a patterned film.
接著,將所得的圖案狀薄膜於200℃的烘箱中烘烤30分鐘,使其硬化,藉此獲得具有特定圖案形狀的膜厚50 μm的層間絕緣膜。Next, the obtained patterned film was baked in an oven at 200 ° C for 30 minutes to be hardened, whereby an interlayer insulating film having a film thickness of 50 μm having a specific pattern shape was obtained.
-評價--Evaluation-
接著,以下述要領進行評價。將評價結果與層間絕緣膜的膜厚一併(以下同樣)示於表1中。Next, evaluation was performed in the following manner. The evaluation results are shown in Table 1 together with the film thickness of the interlayer insulating film (the same applies hereinafter).
-解析度的評價-- Evaluation of resolution -
對於所得的層間絕緣膜,使用直徑50 μm的遮罩圖案來評價解析度。將50 μm見方的孔圖案可解析的情況評價為良好(A),將50 μm見方的孔圖案無法解析的情況評價為不良(B)。For the obtained interlayer insulating film, a mask pattern having a diameter of 50 μm was used to evaluate the resolution. The case where the 50 μm square hole pattern was analyzed was evaluated as good (A), and the case where the 50 μm square hole pattern could not be analyzed was evaluated as defective (B).
-透明性的評價-- Evaluation of transparency -
對所得的層間絕緣膜的連續膜部分,使用雙光束分光光度計U-2900((股)日立製作所製造,商品名)來測定波長400 nm下的穿透率進行評價。當該穿透率超過90%時,可以說透明性良好(A)。The continuous film portion of the obtained interlayer insulating film was evaluated by measuring the transmittance at a wavelength of 400 nm using a two-beam spectrophotometer U-2900 (manufactured by Hitachi, Ltd., trade name). When the transmittance exceeds 90%, it can be said that the transparency is good (A).
-耐熱性的評價-- Evaluation of heat resistance -
將所得的層間絕緣膜於220℃的烘箱中加熱60分鐘,使用(股)Mitutoyo製造的數位式量錶來測定加熱前後的膜厚的變化率(%)[=(加熱前的膜厚-加熱後的膜厚)×100/加熱前的膜厚],進行評價。當該變化率為5%以內時,可以說耐熱性良好(A)。The obtained interlayer insulating film was heated in an oven at 220 ° C for 60 minutes, and the rate of change (%) of the film thickness before and after heating was measured using a digital scale manufactured by Mitutoyo [= (film thickness before heating - heating) The film thickness after the film) × 100 / film thickness before heating] was evaluated. When the rate of change is within 5%, it can be said that the heat resistance is good (A).
-耐熱變色性的評價-- Evaluation of heat-resistant discoloration -
對250℃的烘箱進行氮氣沖洗,將所得的層間絕緣膜於該烘箱中加熱60分鐘,然後對層間絕緣膜的連續膜部分,使用雙光束分光光度計U-2900(商品名,(股)日立製作所製造)來測定波長400 nm下的穿透率。根據加熱前後的穿透率的變化率(%)[=(加熱前的穿透率-加熱後的穿透率)×100/加熱前的穿透率]進行評價。當該變化率為5%以內時,可以說耐熱變色性良好(A)。Nitrogen rinsing was performed on an oven at 250 ° C, and the obtained interlayer insulating film was heated in the oven for 60 minutes, and then a continuous beam portion of the interlayer insulating film was used using a double beam spectrophotometer U-2900 (trade name, Hitachi Hitachi) Manufactured by the manufacturer to determine the transmittance at a wavelength of 400 nm. The rate of change (%) of the transmittance before and after heating [= (penetration before heating - transmittance after heating) × 100 / transmittance before heating] was evaluated. When the rate of change is within 5%, it can be said that the heat discoloration resistance is good (A).
-耐溶劑性的評價-- Evaluation of solvent resistance -
將形成有層間絕緣膜的玻璃基板於50℃的N-甲基吡咯啶酮中浸漬15分鐘,使用(股)Mitutoyo製造的數位式量錶來測定浸漬前後的層間絕緣膜的膜厚的變化率(%)[=(浸漬後的膜厚-浸漬前的膜厚)×100/浸漬前的膜厚],進行評價。當該變化率為±10%以內時,可以說耐溶劑性良好(A)。The glass substrate on which the interlayer insulating film was formed was immersed in N-methylpyrrolidone at 50 ° C for 15 minutes, and the change rate of the film thickness of the interlayer insulating film before and after the immersion was measured using a digital scale manufactured by Mitutoyo. (%) [= (film thickness after immersion - film thickness before immersion) × 100 / film thickness before immersion] was evaluated. When the rate of change is within ±10%, it can be said that the solvent resistance is good (A).
(實例2)(Example 2)
於實例1中,除了代替10 g的Aronix M-305而使用10 g的Aronix M-402(東亞合成(股)製造,商品名)以外,以與實例1相同之方式製備溶液狀態的負片型感光性樹脂組成物(S-2),獲得具有預定圖案形狀的膜厚40 μm的層間絕緣膜。將評價結果示於表1中。In the example 1, a negative-type photosensitive solution in a solution state was prepared in the same manner as in Example 1 except that 10 g of Aronix M-305 was used instead of 10 g of Aronix M-402 (manufactured by Toagosei Co., Ltd., trade name). The resin composition (S-2) obtained an interlayer insulating film having a film thickness of 40 μm having a predetermined pattern shape. The evaluation results are shown in Table 1.
實例1及實例2中任一層間絕緣膜均可確認,即便厚膜化,解析度、透明性、耐熱性、耐熱變色性及耐溶劑性亦優異。In any of the interlayer insulating films of Examples 1 and 2, it was confirmed that the film thickness was excellent, and the resolution, transparency, heat resistance, heat discoloration resistance, and solvent resistance were excellent.
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