SG189383A1 - Photosensitive resin composition and method for producing same - Google Patents
Photosensitive resin composition and method for producing same Download PDFInfo
- Publication number
- SG189383A1 SG189383A1 SG2013027719A SG2013027719A SG189383A1 SG 189383 A1 SG189383 A1 SG 189383A1 SG 2013027719 A SG2013027719 A SG 2013027719A SG 2013027719 A SG2013027719 A SG 2013027719A SG 189383 A1 SG189383 A1 SG 189383A1
- Authority
- SG
- Singapore
- Prior art keywords
- group
- resin composition
- general formula
- photosensitive resin
- polyorganosiloxane
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 139
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 99
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000003999 initiator Substances 0.000 claims abstract description 28
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 79
- 229910052799 carbon Inorganic materials 0.000 claims description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 74
- -1 methacryloyl group Chemical group 0.000 claims description 70
- 239000000203 mixture Substances 0.000 claims description 70
- 239000000758 substrate Substances 0.000 claims description 64
- 239000002904 solvent Substances 0.000 claims description 43
- 125000001424 substituent group Chemical group 0.000 claims description 40
- 125000001931 aliphatic group Chemical group 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 33
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 31
- 125000002723 alicyclic group Chemical group 0.000 claims description 29
- 125000004429 atom Chemical group 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 28
- 125000000962 organic group Chemical group 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 claims description 21
- 230000003247 decreasing effect Effects 0.000 claims description 20
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000005227 gel permeation chromatography Methods 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004611 light stabiliser Substances 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 6
- 125000003158 alcohol group Chemical group 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 5
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 238000000016 photochemical curing Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- VMXUWOKSQNHOCA-UKTHLTGXSA-N ranitidine Chemical compound [O-][N+](=O)\C=C(/NC)NCCSCC1=CC=C(CN(C)C)O1 VMXUWOKSQNHOCA-UKTHLTGXSA-N 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 2
- 150000004692 metal hydroxides Chemical class 0.000 claims 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 12
- 238000003384 imaging method Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000005476 soldering Methods 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- 238000001228 spectrum Methods 0.000 description 39
- 239000010408 film Substances 0.000 description 36
- 239000000047 product Substances 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- 229920005989 resin Polymers 0.000 description 23
- 239000000463 material Substances 0.000 description 21
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
- 239000000126 substance Substances 0.000 description 16
- 230000007423 decrease Effects 0.000 description 15
- 235000006708 antioxidants Nutrition 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 14
- 230000003287 optical effect Effects 0.000 description 14
- 230000035484 reaction time Effects 0.000 description 14
- 239000011521 glass Substances 0.000 description 13
- 238000005100 correlation spectroscopy Methods 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 230000035939 shock Effects 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 229920000426 Microplastic Polymers 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 8
- 230000002708 enhancing effect Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- 206010034972 Photosensitivity reaction Diseases 0.000 description 7
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 150000002923 oximes Chemical class 0.000 description 7
- 230000036211 photosensitivity Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005809 transesterification reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 4
- CMIAIUZBKPLIOP-YZLZLFLDSA-N methyl (1r,4ar,4br,10ar)-7-(2-hydroperoxypropan-2-yl)-4a-methyl-2,3,4,4b,5,6,10,10a-octahydro-1h-phenanthrene-1-carboxylate Chemical compound C1=C(C(C)(C)OO)CC[C@@H]2[C@]3(C)CCC[C@@H](C(=O)OC)[C@H]3CC=C21 CMIAIUZBKPLIOP-YZLZLFLDSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 4
- 125000005372 silanol group Chemical group 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 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
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
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- 230000007062 hydrolysis Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- FZTPAOAMKBXNSH-UHFFFAOYSA-N 3-trimethoxysilylpropyl acetate Chemical compound CO[Si](OC)(OC)CCCOC(C)=O FZTPAOAMKBXNSH-UHFFFAOYSA-N 0.000 description 2
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-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
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000005529 alkyleneoxy group Chemical group 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- KKCJXDUBNUSNTR-UHFFFAOYSA-N dicyclopentyl(dihydroxy)silane Chemical compound C1CCCC1[Si](O)(O)C1CCCC1 KKCJXDUBNUSNTR-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
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- 150000004677 hydrates Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-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
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000012487 rinsing solution Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
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- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- ZUNGGJHBMLMRFJ-UHFFFAOYSA-O ethoxy-hydroxy-oxophosphanium Chemical compound CCO[P+](O)=O ZUNGGJHBMLMRFJ-UHFFFAOYSA-O 0.000 description 1
- HOBHPFBUEAGWFH-UHFFFAOYSA-N ethyl 2,3-dioxo-3-phenylpropanoate Chemical compound CCOC(=O)C(=O)C(=O)C1=CC=CC=C1 HOBHPFBUEAGWFH-UHFFFAOYSA-N 0.000 description 1
- AYCOCJMEYVYNPM-UHFFFAOYSA-N ethyl 7-(dimethylamino)-2-oxochromene-3-carboxylate Chemical compound C1=C(N(C)C)C=C2OC(=O)C(C(=O)OCC)=CC2=C1 AYCOCJMEYVYNPM-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N methyl cyclohexan-4-ol Natural products CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- NWAHZAIDMVNENC-UHFFFAOYSA-N octahydro-1h-4,7-methanoinden-5-yl methacrylate Chemical compound C12CCCC2C2CC(OC(=O)C(=C)C)C1C2 NWAHZAIDMVNENC-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N para-hydroxytoluene Natural products CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- KCIKCCHXZMLVDE-UHFFFAOYSA-N silanediol Chemical compound O[SiH2]O KCIKCCHXZMLVDE-UHFFFAOYSA-N 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- UZIAQVMNAXPCJQ-UHFFFAOYSA-N triethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C(C)=C UZIAQVMNAXPCJQ-UHFFFAOYSA-N 0.000 description 1
- WDUXKFKVDQRWJN-UHFFFAOYSA-N triethoxysilylmethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C=C WDUXKFKVDQRWJN-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
-
- 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
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
- C08L43/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- 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
- G03F7/0017—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor for the production of embossing, cutting or similar devices; for the production of casting means
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
-
- 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
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
Abstract
Photosensitive Resin Composition and Method for Producing SameThe present invention provides: a photosensitivetransparent resin composition having excellent thermalshock resistance in the production of products with integrated electronic parts or of solid-state imaging elements that requires a reflow soldering process; and amicroplastic lens or an optical-element molded productfor liquid crystal polarizing plates that uses said photosensitive transparent resin composition. The photosensitive resin composition contains: 100 parts by mass of a polyorganosiloxane (a) having a polymerizablefunctional group and prepared according to a method ofmixing an alkoxysilane compound represented by the following general formula (1), RlaR2bSi(OR3)4-a-b (wherein R1, R2, R3, a, and b are as defined in the Description), with a catalyst and polymerizing the alkoxysilanecompound, wherein said polyorganosiloxane (a) includes a structure represented by the following general formula(2), (wherein X is as defined in theDescription), and the structure of said general formula(2) contains 5 to 60% of the Si atoms contained in said polyorganosiloxane (a); and 0.01 to 30 parts by mass of aphotopolymerization initiator (b).Figure 1
Description
EE
Photosensitive Resin Composition and Method for
Producing Same
TECHNICAI FIELD
[0001]
The present invention relates to a photosensitive resin composition useful as an electrical component in semiconductor devices, microplastic lenses, liquid crystal polarizing plates, optical waveguides and the like which are intended mainly for optical applications, and a resin insulating film used for an i5 electrical/electronic material of semiconductor devices, multilayer circuit boards and the like. More specifically, the present invention relates to a material for camera module plastic mini-lenses or camera module peripherals of cellular phones, monitor cameras and the like; a material for the formaticn of a microplastic lens for optical communication, a microplastic lens for solid imaging devices such as CCD or CMCS image sensor, an LED encapsulant, a photonic crystal for achieving high LED luminance, a thin-film transistor array in the display field, or a material for the antireflection film, a material for optical elements for a polarizing plate in a liquid crystal projector, and a material for the formation of a buffer ccat or an interlayer insulating film of an LSI chip.
[0002]
A plastic lens is easy to mold and inexpensive compared to glass, and therefore is widely used in a variety of optical products. As the material therefor, various transparent materials, for example, a thermoplastic plastic, such as polymethyl methacrylate or polystyrene; and a thermosetting plastic, such as polydiethylene glycol bis(allyl carbonate), are used.
However, as indicated in Patent Documents 1 and 2, most conventional materials merely have heat resistance of 260°C or less even when improved, and do not ensure resistance to a solder reflow heat at 260°C.
[0003]
In general, a siloxane polymer having a =8i-0-Si= structure has high heat resistance. Patent Document 3 discloses a polysiloxane having a molecular weight of 3,000 to 10,000, which is obtained by polymerizing a silanediol and an alkoxysilane by a two-stage process.
PATENT DCCUMENT
[0004]
Patent Document 1: Japanese Unexamined Patent
Publication {(Kokai) No. 08%-3113¢%
Patent Document 2: Kokail No. 2004-245867
Patent Document 3: International Publication No. 2008/123224, pamphlet
[0005]
An object of the present invention is to provide a photosensitive resin composition having excellent characteristics, such as thermal shock resistance high enough tc cause no cracking or peeling even when passed through a cold~heat cycle of ~40°C to 125°C after curing, which is useful for production cof products with integrated electronic parts or of sclid-state imaging elements that reguires a reflow soldering process, a resin usable for the composition, and a cured product using the composition.
MEANS TO SOLVE THE PROBLEMS
[0006]
The present inventors have studied how to improve a silcoxane-containing photosensitive resin so as to attain the above-described object, as a result, it has been found that, when only a specific silancl compound is condensation-polymerized and is added with a photopolymerization initiator, or when a specific silanol compound and a specific alkoxysilane compound are mixed and condensation-polymerized and a photopolymerization initiator is added thereto, a photosensitive resin excellent in the thermal shock resistance can be obtained. The present inventors have also invented a method for increasing the molecular weight of a polysiloxane. The present invention has been accomplished based on these findings, i.e., the present invention is as follows.
[0007]
[1] A photosensitive resin composition comprising: (a) 100 parts by mass of a polyorganosiloxane having a polymerizable functional group; and (b} from 0.01 to 30 parts by mass of a photopolymerization initiator; wherein the polyorganosiloxane is obtained by means of a method of mixing at least one alkoxysilane compound represented by following general formula (1):
R'aR%pS1 (OR?) goamp (1) {wherein R' is an ester bond—~containing organic group having a carbon number of 2 to 17, and at least one R' has an acryloyl group or a methacryloyl group; R? is, when a plurality of R®s are present, each is independently, an aliphatic group having a carbon number of 1 to 10, which may have a substituent; Rr? is, when a plurality of R®s are present, each is independently, a methyl group cr an ethyl group; a is an integer of I or 2; b is an integer of 0, 1 or 2; and a+b is 3 or less} and a catalyst to obtain a mixture, and polymerizing the mixture, wherein the polyorganosiloxane contains a structure represented by following general formula (2): =51-0-¥-Si= (2) {wherein X is an organic group having a carbon number of 1 to 15}, and wherein from 5 to 60% by number of Si atoms in the polyorgancsiloxane are contained in the structure represented by general formula (2). i0 [0008]
[2] The photosensitive resin composition according to [1], wherein the polyorganosiloxane is obtained by means of a method of mixing the at least one alkoxysilane compound represented by general formula (1}, at least one silanol compound represented by following general formula (3):
RIR’S1 (OH) » (3) {wherein each of R? and R® is an aliphatic, alicyclic or aromatic group having a carbon number of 3 te 10, which may have a substituent}? and a catalyst to obtain a mixture, and peclymerizing the mixture.
[0009]
[3] The photosensitive resin composition according to [1] or [2], wherein from 10 to 40% by number of Si atoms in the polyorgancosiloxane are contained in the structure represented by general formula (2).
[0010]
[4] A photosensitive resin composition comprising: (a) 100 parts by mass of a polyorganosiloxane; and (b) from 0.01 to 30 parts by mass of a photopolymerization initiator: wherein the polyorganosiloxane 1s obtained by means of a method of mixing at least one alkoxysilane compound represented by following general formula (1):
R'.R*,S1 (ORY) grap (1) {wherein R® is an ester bond-containing organic group having a carbon number of 2 to 17, and at
- 5 ro least one R' has an acryloyl group or a methacryloyl group; R? is, when a plurality of R%s are present, each is independently, an aliphatic group having a carbon number of 1 to 10, which may have a substituent; R® is, when a plurality of R’s are present, each is independently, hydrogen, a methyl group or an ethyl group; a is an integer of 1 or 2; b is an integer of 0, 1 or 2; and a+b is 3 or less} and a catalyst to obtain a mixture, and polymerizing the mixture, and 1c wherein the ratio of the peak area derived from a carboxylic acid of the ester bond and the peak area derived from an alcohol of the ester bond in the polyorganosiloxane by ‘H-NMR spectrum is decreased by 5 to 60% compared to the mixture of the alkoxysilane compound before polymerization.
[0011]
[5] The photosensitive resin compositicn according to [4], wherein the polyorgancsiloxane is cobtained by means of a method of mixing the at least one alkoxysilane compound represented by general formula (1), at least one silanol compound represented by following general formula (3):
RRS (OH) » (3) {wherein each of R? and R® is an aliphatic, alicyclic or aromatic group having a carbon number of 3 to 10, which may have a substituent} and a catalyst to obtain a mixture, and polymerizing the mixture.
[0012]
[6] The photosensitive resin composition according to [4] or {5}, wherein the ratio of the peak area derived from a carboxylic acid of the ester bond and the peak area derived from an alcohol of the ester bond in the 'H-
NMR spectrum of the polyorganosiloxane is decreased by 10 to 40% compared to the mixture of the alkoxysilane compound and the silanol compound before polymerization.
[0013]
[7] A photosensitive resin composition comprising:
{a} 100 parts by mass of a polyorganosiloxane; and (b} from 0.01 to 30 parts by mass of a photopolymerization initiator; wherein the polyorganosilcexane is obtained by means of a method of mixing at least one alkoxysilane compound represented by following general formula (1):
R'aR%,81 (OR?) 45m (1) {wherein R' is an ester bond-containing organic group having a carbon number of 2 to 17, and at 19 least one R' has an acryloyl group or a methacryloyl group; R? is, when a plurality of R?s are present, each is independently, an aliphatic group having a carbon number of 1 to 10, which may have a substituent; R’ is, when a plurality of R’s are present, each is independently, a methyl group or an ethyl group; a is an integer of 1 or 2; b 1s an integer of 0, 1 or 2; and atb is 3 or less}, at least cone silanol compound represented by following general formula {3):
RIR’S1 (OH) 5 (3) {wherein each of R! and R® is an aliphatic, alicyclic or aromatic group having a carbon number of 3 to 10, which may have a substituent} and a catalyst to obtain a mixture, and polymerizing the mixture, and wherein an area having a weight average molecular weight of 1,050 or more in terms of standard polystyrene as measured by gel permeation chromatography (GPC) is 70% or more of the whole GPC peak area.
[0014]
[8] The photosensitive resin composition according to any one of [1] to [7], wherein the alkoxysilane compound represented by general formula (1) is at least one alkoxysilane compound represented by following general formula (4):
HoC=C (R®) = (C=0) -0- (CH) ,—SiR’; (OR%}) 4 (4) {wherein R® is hydrogen or a methyl group; R’ is, when a plurality of R's are present, each is independently, an aliphatic group having a carbon number of 1 to 10, which may have a substituent; R® is, when a plurality of R%s are present, each is independently, a methyl group or an ethyl group; c¢ is an integer of 0, 1 or 2; d is an integer of 1, 2 or 3; ct+d is 3 or less; and nis from 1 to 14}.
[0015]
[9] The photosensitive resin composition according to any cne of [2], [3] and [5] to [8], wherein at least one of R* and R’ in general formula (3) is an alicyclic group having a carbon number of 3 to 10, which may have a substituent.
[0016] [10} The photosensitive resin composition according to any one of [1] to [2], further comprising (cc) from 0.1 to 1,000 parts by mass of an ethylenically unsaturated addition-polymerizable monomer per 100 parts by mass of the poelyorganosiloxane.
[0017]
[11] The photosensitive resin composition according to [10], wherein the ethylenically unsaturated addition- polymerizable monomer is a compound containing an alicyclic group.
[0018]
[12] The photosensitive resin composition according te any one of [1} to [11], further comprising at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, an adhesion ald, a polymerization inhibitor, a sensitizer, an antioxidant and a smoothness-imparting agent.
[0019]
[13] The photosensitive resin composition according te any one of [1] to [12], wherein the concentration of the alkali metal or alkaline earth metal in the photosensitive resin composition is from 0.1 to 500 ppm.
[0020]
[14] A production process of a polycrganosiloxane,
comprising the following steps of: i) producing (a) a polyorganosiloxane by mixing at least one alkoxysilane compound represented by following general formula (1}:
R'aR%,S1 (OR?) ap (1) {wherein R* is an ester bond-containing crganic group having a carbon number of 2 to 17, and at least one R' has an acryloyl group or a methacryloyl group; R* is, when a plurality of R?s are present, each is independently, an aliphatic grecup having a carbon number of 1 to 10, which may have a substituent; R’ is, when a plurality of Rs are present, each is independently, a methyl group or an ethyl group; a is an integer of 1 or 2; b is an integer of 0, 1 or 2; and a+b is 3 or less}, from 0.01 to 0.5 equivalents of walter per one equivalent of OR® contained in the alkoxysilane compound present in the reaction system, and a catalyst to obtain a mixture, and reacting the mixture at 20 to 130°C for 0.1 to 20 hours while remecving an alcchol produced by the reaction from the reaction system; and 11) washing the polyorganosiloxane with a solvent incapable of dissolving the polyorganosiloxane.
[0021]
[15] A production process of a pelyorganosiloxane, comprising the following steps of: i} producing {a) a polyorganosiloxane by mixing at least one alkoxysilane compound represented by following general formula (1):
R'aR%S1 (ORY) gegen (1) {wherein R' is an ester bond-containing organic group having a carbon number of 2 to 17, and at least one R' has an acryloyl group or a methacryloyl group: R® is, when a plurality of R’s are present, each is independently, an aliphatic group having a carbon number of 1 to 10, which may have a substituent: Rr’ is, when a plurality of R’s are present, each is independently, a methyl group or an ethyl group; a is an integer of 1 or
2; b 1s an integer of 0, 1 or 2; and ath is 3 or less}, at least one silanol compound represented by following general formula (3):
R'RS1 (OH), (3) {wherein each of R® and R® is an aliphatic, alicyclic or aromatic group having a carbon number of 3 to 10, which may have a substituent} and a catalyst to obtain a mixture, and reacting the mixture at 20 to 130°C for 0.1 to 20 hours while removing an alcohol produced by the reaction from the reaction system; and ii} washing the polyorganosiloxane with a solvent incapable of dissolving the polyorganosiloxane.,
[0022] {16] The production process according to [14] or
[15], wherein the catalyst is at least one compound selected from the group consisting of an alkali metal hydroxide and an alkaline earth metal hydroxide.
[0023]
[17] The production process according to any one of
[14] to [le], wherein the catalyst is Ba (OH), and/or a hydrate thereof.
[0024]
[18] The production process according to any one of
[14] to [17], wherein the amount of the catalyst is from 0.05 to 30 mol% based on a total number of moles of silicon (51).
[0025] {191 The production process according to any one of
[14] to [18], wherein the amount of the catalyst is from 340 0.1 to 10 mol% based on a total number of moles of silicon (Si).
[0026]
[20] The production preccess according tc any one of [14} to [19], wherein the solvent is an alcohol or an acetonitrile.
[0027]
[21] A cured product obtained by photocuring the photosensitive resin composition according to any one of
[1] te [13}, or a photosensitive resin composition comprising (a) a polyorganosiloxane obtained by the production process according to any one of [14] to {20} and (b) a photopolymerizaticon initiator.
[0028] [227 A method for preducing a melded article, comprising the following steps of: filling a shape-forming meld with the photosensitive rasin composition according to any one of [11 te [13}, or a photosensitive resin composition comprising (a) a polyorgancsiloxane obtained by the production process according to any one of [14] te [20] and (b) a photopolymerization initiator, pressing the opening of the mold against a substrate or another mold, exposing the photosensitive resin composition to light from the mold and/or substrate side to obtain a photocured product, separating the mold from the substrate, or separating the molds from both surfaces of the photocured product, and heating only the photocured product, or the photocured product with the substrate.
[0029] {231 A molded article cbtained by the method according to [22].
[00301]
[24] A polyorganosiloxane obtained by means of a method of mixing at least one alkoxysilane compound represented by following general formula (I):
R™ aR%,81 (OR) ¢-amp (1) {wherein R'' is an ester bond-containing organic group having a carbon number of 2 to 17; R? is, when a plurality of R?s are present, each is independently, an aliphatic group having a carbon number of 1 to 10, which may have a substituent; R* is, when a
~ 11 = plurality of R’s are present, each is independently, a methyl group or an ethyl group; a is an integer of 1 or 2; b is an integer of C, 1 or 2; and a+b is 3 or less}, at least one silanol compound represented by following general formula (3):
R'R*S1 (OH), (3) {wherein each of R' and R® is an aliphatic, alicyclic or aromatic group having a carbon number of 3 to 10, which may have a substituent} and a catalyst to obtain a mixture, and polymerizing the mixture, wherein the polyorgancsiloxane contains a structure represented by following general formula {2): =31-0-X-Si= (2) {wherein ¥X is an organic group having a carbon number of 1 to 15}, and wherein from 5 to 60% by number of Si atoms in the polyorganosiloxane are contained in the structure represented by general formula (2).
[0031]
[25] The polyorganosiloxane according to [24], wherein R'' in general formula (I) is a group having an acrylic acid ester and/or a methacrylic acid ester.
[0032]
According to the present invention, a resin or photosensitive resin composition, having excellent characteristics, such as thermal shock resistance high enough to cause no cracking or peeling even when passed through a cold-heat cycle, and being useful for the production of products with integrated electronic parts or of solid-state imaging elements that requires a reflow soldering process.
[0033] [Fig. 1] Fig. 1 shows a ‘H-NMR spectrum chart of the polyorgancsiloxane in an embodiment of the present invention. [Fig. 2] Fig. 2 shows a GPC chart of the polycrganosiloxane in an embodiment of the present invention. [Fig. 3] Fig. 3 shows a BC-NMR spectrum chart of the polyorganosiloxane in an embodiment of the present invention. [Fig. 41 Fig. 4 shows a ‘H-NMR spectrum chart of the polyorganosiloxane in another embodiment of the present invention. [Fig. 5) Fig. 5 shows a H-NMR spectrum chart of the polyorganosiloxane in still another embodiment of the present invention. [Fig. 6] Fig. 6 shows a GPC chart cof the pelyorganosiloxane in still another embodiment of the present invention. [Fig. 7] Fig. 7 shows an HH COSY spectrum of the polyorganosiloxane in an embodiment of the present invention. [Fig. 8] Fig. 8 shows a CH COSY spectrum of the polyorganosiloxane in an embodiment of the present invention.
[0034] <Photosensitive Resin Composition>
The photosensitive resin composition of the present invention comprises: (a) a polyorganocsiloxane which is obtained by means of a method of mixing a specific alkoxysilane compound and a catalyst to obtain a mixture, and polymerizing the mixture, and which contains a structure represented by following general formula (2): =51~0mX~Si= (2) {wherein X 1s an organic group having a carbon number of 1 to 15}; and
(b) a photopolymerization initiator.
[0035]
The alkoxysilane compound is at least one alkoxysilane compound represented by following general formula (1):
R'R%p81 (OR?) goamn (1) {wherein R' is an ester bond-containing organic group having a carbon number of 2 to 17, and at least one R' has an acryloyl group or a methacryloyl group; R? is, when a plurality of R’s are present, each is independently, an aliphatic, alicyclic or aromatic group having a carbon number of 1 to 10, which may have a substituent; R® is, when a plurality of R's are present, each is independently, a methyl group or an ethyl group; a is an integer of 1 or 2; b is an integer of 0, 1 or 2; and a+b is 3 or less).
[0036]
In view of stcrage stability, it is preferable to use, as the polyorgancsiloxane (a), a polyorganosiloxane cbtained by means cf a method of mixing at least one alkoxysilane compound represented by above general formula (1), a specific silanol compound and a catalyst to obtain a mixture, and polymerizing the mixture.
[0037]
In this case, the silanol compcund is at least one silanol compound represented by feollowing general formula (3):
R'R*S1 (OH); (3) {wherein each of R* and R® is an aliphatic, alicyclic or aromatic group having a carbon number of 3 te 10, which may have a substituent}.
[0038]
The alkoxysilane represented by above general formula (1) is preferably at least one alkoxysilane compound represented by following formula (5):
R= (C=0) -0-X-5iR'", (OR?) 4 (5) {wherein R? is an aliphatic, alicyclic or aromatic group having a carbon number of 1 to 15, which may have a substituent, and at least one R’ has an acrylic acid ester and/or a methacrylic acid ester; X is an aliphatic, alicyclic or aromatic group having a carbon number of 1 to 15, which may have a substituent; R' is, when a plurality of R's are present, each is independently, an aliphatic group having a carbon number of 1 to 10, which may have a substituent; R? is, when a plurality of R%s are present, each is independently, a methyl group or an ethyl group; ¢ is an integer of 0, 1 or 2; d is an integer of 1, 2 or 3; c+d is 3 or less; and n is from 1 to 14}, more preferably a compound having an acrylic acid ester and/or a methacrylic acid ester.
Among others, it is preferable in view of UV photosensitivity to use at least one alkoxysilane compound represented by following formula (4):
HzC=C (R®) = (C=0) ~0~ (CHz} n= SiR’: (OR%) 4 (4) {wherein R® is hydrogen or a methyl group; R’ is, when a plurality of R’s are present, each is independently, an aliphatic, alicyclic or aromatic group having a carben number of 1 to 10, which may have a substituent; R® is, when a plurality of R%s are present, each 1s independently, a methyl group or an ethyl group; c is an integer of 0, 1 or 2; d is an integer of 1, 2 or 3; c+td is 3 or less; and n is from 1 to 14}.
Examples of the alkoxysilane compound represented by above general formula (4) include 3- methacryloxypropyltrimethoxysilane, 3- methacryloxypropyltriethoxysilane, 3- methacryloxypropylmethyldimethoxysilane, 3- acryloxypropyltrimethoxysilane, 3- acryloxypropyltriethoxysilane, 2- methacryloxyethyltrimethoxysilane, 2- methacryloxyethyltriethoxysilane, 2- macryloxyethylmethyldimethoxysilane, 2- acryloxyethyltrimethoxysilane, 2- acryloxyethyltriethoxysilane,
J 15 — methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethylmethyldimethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane and the like. An ester bond~containing alkoxysilane without a polymerizable functional group, such as 3- acetoxypropyltrimethoxysilane, may be also used.
In the case of obtaining a polyorganosiloxane which is produced by means of a method of mixing at least one alkoxysilane compound represented by following general formula (I):
RY aR*pS1 (OR?) 4am (1) {wherein R'' is an ester bond-containing organic group having a carbon number of 2 to 17; R? is, when a plurality of R®s are present, each is independently, an aliphatic group having a carbon number of 1 to 10, which may have a substituent; R3 is, when a plurality of R’s are present, each is independently, a methyl group or an ethyl group; a is an integer of 1 or 2; b is an integer of 0, 1 or 2; and at+b is 3 or less}, at least one silancl compound represented by following general formula (3):
R*R°51 (OH); (3) {wherein each of R® and R’ is an aliphatic, alicyclic or aromatic group having a carbon number of 3 to 10, which may have a substituent} and a catalyst to obtain a mixture, and polymerizing the mixture, and which contains a structure represented by following general formula (2): =81-0~X~Si= (2) {wherein ¥X is an organic group having a carbon number of 1 te 15}, and which contains from 5 to 60% by number of Si atoms in the structure represented by above general formula (2), only an ester bond-containing alkoxysilane not having a polymerizable functional group, such as 3-acetoxypropyltrimethoxysilane, may be used as the at least one alkoxysilane compound represented by above general formula (I), other than the above-described alkoxysilane compound.
By using the above-described polycrganosiloxane, a resin excellent in thermal shock resistance can be obtained.
[0038]
As the catalyst, a compound that accelerates hydrolysis of an alkoxy group of the alkoxysilane compound and a condensation reaction between silanols produced by the hydrolysis or between an alkoxysilane and a silanol and also advances an ester hydrolysis reaction or a transesterification reaction during polymerization, can be used.
[0040]
As the catalyst used in the reaction of the alkoxysilane compound and the silanol compound, a compound that accelerates a dealccoholization condensation reaction of a silanol group of the silancl compound with an alkoxy group of the alkoxysilane compound and also advances an ester hydrolysis reaction or a transesterification reaction during polymerization, can be used.
[0041]
The catalyst may be either an acidic compound or a basic compound, and includes, for example, a metal alkoxide, an inorganic acid, an organic acid, an inorganic base, an organic base, and a phosphazene compound. Amcng others, an alkali metal hydroxide, an alkaline earth metal oxide, an ammonium compound or the 1ike is preferred, and specific examples thereof include
Ba (OH),, Ca (OH),, Mg (OH)., KOH, LiOH, NH;, NH4OH, NR,4{OH),
NR4sCl, NR4Br, NRyI and the like. In NR, (OH), NR4Cl, NR4BEr and NR;I, R is an aliphatic, alicyclic or aromatic group having a carbon number cof 1 to 10, which may have a substituent. The catalyst is more preferably an alkali metal hydroxide, an alkaline earth metal hydroxide or the
: iike, still more preferably an alkaline earth metal hydroxide, and specific examples thereof include Ba (OH),
Ca(OH),, Mg{OH}z, etc. Hydrates of Ba{OH),, Ca(OH), and
Mg (CH); may be also used, and in view of stability, and a reaction with good reproducibility because the reaction time can be shortened and the reaction time in an inhomogeneous state becomes short, it is more preferable to use Ba (QOH), -8H,0.
[0042]
The amount cof the catalyst added is preferably a concentration that allows for appropriate progress of a hydrolysis reaction by a hydrate water or the like contained in the catalyst or transesterification reaction or the like, and the amount of the catalyst is, for example, from 0.05 to 30 mol%, and in view of transparency and reaction controllability, preferably from 0.1 to 20 mol%, still more preferably from 0.1 to 10 mois, yet still more preferably from 0.2 to 10 mol%, pased on the number of moles of S5i atom charged. The number of moles of Si atom charged is a number of moles of Si atom calculated by adding up the alkoxysilane compound represented by above general formula (1), the silanol compound represented by above general formula (3} and other condensable silane compounds present in the reaction system, and the "mol%" expressing the catalyst amount indicates how many moles the catalyst is added based on the number of moles of Si atom.
[0043]
In the silanol compound represented by above general formula (3), in view of stability of the compound, R? and
R®> is preferably an aromatic or alicyclic group which is a bulky substituent. In view of light resistance and heat resistance, a compound where at least one of R! and R° is an alicyclic group having a carbon number of 3 to 10, which may have a substituent, is more preferred as the silanol compound. In addition, in view of excellent transparency, dicyclohexylsilanediol or
: + dicycleopentylsilanediol is still more preferred as the silanol compound.
[0044]
With respect to a mixing ratic of the alkoxysilane compound represented by above general formula (1) and the silanol compound represented by above general formula (3), the ratio of the alkoxysilane compound represented by above general formula (1) to 100 mol of the silancl compound represented by above general formula (3) is from 10 to 200 mol, preferably from 20 to 180 mol, more preferably from 30 fo 150 mol, still more preferably from 40 to 120 mel, and in view of molecular weight and UV photosensitivity of a resin to be obtained, most preferably from 60 to 100 mol.
[0045]
In the case where the alkoxysilane compound represented by above general formula (1) and the silanol compound represented by above general formula (3) are mixed, and reacted in the presence of a catalyst, the reaction temperature is from 20 to 130°C, preferably from 30 to 100°C, more preferably from 40 to 80°C, and the reaction time is from 0.1 to 20 hours, preferably from 0.2 to 10 hours, still more preferably from 0.3 to 5 hours. The atmosphere in the reaction vessel may be a nitrogen atmosphere or an air atmosphere. Water may or may not be positively added to the reaction system. Even in the case of not positively adding water to the reaction system, water in the hydrate compound of the catalyst or water in the silanol may be present in the reaction system. In the case of using only the alkoxysilane compound represented by above general formula (1), a minimum amount of water may be used, and the amount is preferably from 0.001 to 0.5 equivalents per one equivalent of an alkoxy group bonded to the Si atom of the alkoxysilane compound.
[0046]
For the purpose of, for example, decreasing the coefficient of thermal expansion of the cured product or adjusting the refractive index cof the cure product, a fine particle of silica, zirconia, titania or the like may be added to the reaction system.
[0047] <Reaction of Alkoxysilane Compound or Reaction between
Alkoxysilane Compound and Silanol Compound>
The alkoxysilane compound represented by above general formula (1) and water, or the alkoxysilane 1G compound represented by above general formula (1) and the silanol compound represented by above general formula (3) are mixed and reacted in the presence of a catalyst. The
H-NMR spectrum measurement of the reaction mixture is performed every certain time (for example, 15 minutes, 30 i5 minutes, 60 minutes), and the reaction is allowed to proceed while confirming the decrease ratio of the peak area on the side derived from a carboxylic acid cof the ester bond contained in the alkoxysilane compound represented by above general formula (1). For example, in the case of an ester bond "A-C(=0)-0-B", A is the side derived from a carboxylic acid of the ester bond, and B is the side derived from an alcohol of the ester bond.
Due to hydrolysis or solvolysis of the ester, the peak area of a certain proton derived from A in H-NMR decreases, and the decrease ratio of the peak area on the side derived from a carboxylic acid indicates how much the peak area of a certain proton derived from A is decreased based on another certain preton that undergoes no change during reaction.
[0048]
The decrease ratio is determined by comparison with
NMR spectrum of a raw material. For example, in the case of using HpC=C (Me) -(C=0)-0~(CHy) 3-51 (OMe)3 as the raw material, at the beginning of charging it te a reaction vessel, i.e., in the NMR spectrum of the raw material, a proton of =5i-CHy- appears near 0.6 ppm, a peak of a proton of HpC=C< appears near 5.5 ppm and near 6.0 ppm,
the peak areas thereof is 2:2 and the ratio thereof is 1.
On the other hand, an ester bond is formed by condensing a carboxylic acid and an alcohol, and in a polyorganosiloxane wherein the carboxylic acid moiety of the ester bond decreased, the peak area of HpC=C< corresponding to the carboxylic acid moiety of the ester bond is decreased compared to the peak area of =Si-CHg- corresponding to the alcohol moiety of the ester bond, and the ratio of the peak area of HpC=C< to the peak area of =3i-CHp- becomes 1 or less, whereby the percentage by which the carboxylic acid moiety of the ester bond decreased can be calculated.
As a specific example, when a polyorganosiloxane as shown in Fig. 1 is obtained, the sum of peak areas of two
HpC=C< is 1.997, the peak area of =S5i-CHy~ is 2.885 and in turn, the peak area ratio is 1.997/2.885, i.e., 0.69, revealing 31% reduction of the peak area derived from a carboxylic acid of the ester bond, in other words, the decrease in the carboxylic acid moiety of the ester bond by 31%, compared to the ratio at the beginning of charging the raw material to a reaction vessel, i.e., the peak area ratio of 1 of the raw material. In this case, the 'H-NMR spectrum is based on the peak of CHCl; taken at 7.24 ppm.
[0049]
The decrease in the peak area derived from a carboxylic acid of the ester bond of the alkoxysilane compound represented by above general formula (1) can be controlled by changing, for example, the catalyst amount, the time, the temperature, the pressure in the reaction vessel or the like. For example, the decreasing rate can be increased by changing the conditions, such as an increase in the catalyst amount, elongation cof time, rise in temperature or the like.
As a specific example, in the case of using an alkoxysilane having a methacrylic acid ester as the alkoxysilane represented by above general formula (1) and using Ba{OH): 'H:0 as the catalyst, when the catalyst is used in a usually-needed concentration of 0.1 mol% based on the total $i amount, the peak area derived from a carboxylic acid of the ester bond is not decreased even by setting the reaction temperature at 50°C and the reaction time to 2 hours. However, when the reaction is carried out by increasing the catalyst amount to 0.3 mol%, an corganosiloxane that the peak area derived from a carbozylic acid of the ester bond 1s decreased by about 30% can be synthesized. In this way, the peak area derived from a carboxylic acid of the ester bond can be decreased by a desired quantity by changing the catalyst amount, the temperature or the reaction time.
[0050]
A percentage by which the ester bond in the alkoxysilane compound represented by above general formula (1) decreases during the polymerization reaction is from 5 to 60%, preferably from 7 to 50%, more preferably from 10 to 40%, and most preferably from 15 to 35%, based on the amount of the alkoxysilane compound represented by above general formula (1) which is charged into an reaction system. The decrease in the percentage corresponds to the percentage by which the peak area derived from a carboxylic acid of the ester bond of the alkoxysilane compcund represented by above general formula (1) decreases.
[0051]
The decrease in the peak area of the carboxylic acid molety of the ester bond is considered to occur because due to, for example, the production of an alcohol (methanol or ethanol} by condensation of an alkoxy moiety of the alkoxysilane compound represented by above general formula (1) with a silanol moiety of the silanol represented by above general formula (3) as well as a slight amount of water and the presence cof a basic catalyst, a hydrolysis reaction, a transesterification reaction and the like of the ester bond proceeds, as shown by following reaction formula (6):
Chem. 1] xy 1201] rere xn 120, RY ~§— © + ROH —s— + R T (6) {wherein X is an organic group having a carbon number of 1 to 15, RY is an organic group having a carbon number of 0 to 15, the sum of carbon numbers of X and RY is from 1 to 16, and RY? is a methyl group, an ethyl group or hydrogen).
[0052]
By the hydrolysis reaction and transesterification reaction cf the ester bond, the moiety derived from a carboxylic acid disappears, and the moiety derived from an alcohol remains. Furthermore, it is believed that due to an alcohol exchange reaction or the like of the produced alcohol with an alkoxy group of the alkoxysilane compound represented by above general formula (1) and a silanol group of the silanol compound represented by above general formula (3), a crosslinking reaction represented by feollowing formula (7) takes place: [Chenm. 2]
ETE eb ee t I | 1 : (7) (wherein X is an organic group having a carbon number of 1 to 15, preferably an organic greup having a carbon number of 2 to 10, more preferably an organic group having a carbon number of 3 to 5 and in view of heat resistance and crack resistance, most preferably an organic group having a carbon number of 3, and RY is a methyl group, an ethyl group or hydrogen).
— 23 J
In other words, it is considered that a polyorganosiloxane (a) where the alkylene alcohol or phenylene alcohol produced resulting from disappearance of the ester moiety is partially or entirely crosslinked with an alkoxysilane compound represented by general formula (1), a silanol compound represented by general formula (3) or a polycondensation product of at least one kind of such a compound, is obtained.
[0054]
The crosslinking reaction enables increasing the molecular weight. In turn, the polyorgancsiloxane (a) having the structure represented by above general formula (2) can be obtained. By having the structure of above general formula (2}, an effect that the thermal shock resistance is excellent is provided. In above general formula (2), X may have an aromatic group in the main chain thereof, and is preferably an alkyl group or an aromatic group, which may be further substituted.
Specifically, -X-0- includes structures represented by following general formula (8): [Chem. 3]
EAC —)o- ~0nL Rg. 0 (8B) (wherein 1 is from 1 to 15, m is from 0 to 9, n is from 0 to 9, and n+m<9). In view of light resistance, an alkyl group is preferred as X, and in view of heat resistance, the carbon number of X is preferably from 2 to 10, more preferably from 3 to 5, and most preferably 3.
[0055]
It can also be confirmed, for example, by ‘H-NMR and
BCc-~NMR spectrum measurements that the polyorganosiloxane has the structure represented by above general formula (2).
[0056]
Specifically, in the case of using H,C=C (CH) (C=0)-
O- (CHz)2~S1 (OCH3)3 as the alkoxysilane compound represented by above general formula (1), the structure represented by above general formula (2) becomes =S1-0~CHy-CH,-CH;-Sis=, and in the ‘H-NMR spectrum, the peak of the underlined proton of the HyC=C(CHj)- (C=0}-0-CH;-CH;-CH,;-3i= structure which keeps from disappearance of the ester bond appears at 3.9-4.2 ppm, whereas the peak of the underlined proton of the =5i-0-CH,-CH,-CH,-S5i= structure appears near 3.4-3.9 ppm. Furthermore, in the **C-NMR spectrum, the peak of the underlined carbon of the HpC=C(CHj)- (C=0)-0~CH;~CHy~
CH,-Si= structure appears near 66.5 ppm, whereas the peak of the underlined carbon of the HO-CH,~CH;-CH-Si= structure produced by above reaction formula (6) appears near 62.0 ppm and the peak of the underlined carbon of the =8i-0-CH,-CH,-CH,-Si= structure produced by above reaction formula (7) appears near 64.5 ppm (here, the peak of CHCl; is set at 7.24 ppm in the 'H-NMR spectrum, the peak in the center of CDCl; is set at 77.0 ppm in the
C-NMR spectrum, and the PC-NMR spectrum is measurement in NNE mcde; see Figs. 1 and 3).
[0057]
These peaks can be identified by two-dimensional measurement of NMR spectrum. Fig. 7 1s an HH COSY spectrum, and Fig. 8 is a CH COSY spectrum. In general, the HH COSY spectrum allows a correlation to appear in the peaks of hydrogen atoms bonded respectively to two carbon atoms in an adjacent relationship, and the CH COSY spectrum allows a correlation to appear in the peaks of a carbon atom and a hydrogen atom which are bonded.
In the HH COSY spectrum shown in Fig. 7, it is seen that the peak at 3.4-3.9 ppm and the peak near 1.0 ppm have a relationship, and the peak near 1.0 ppm and the peak near 0.0 ppm have a relationship. It is also seen from the CH COSY spectrum shown in Fig. 8 that the peak at 64.5 ppm in C-NMR spectrum has a relationship with the peak at 3.4-3.9 ppm in ‘H-NMR spectrum. By
- 2h — comprehensively evaluating these results, respective peaks can be identified (here, when the peak in 'H NMR spectrum has its basis on the highest magnetic field side, the peak in COSY spectrum is corrected to 0 ppm, and the spectrum in COSY is completely shifted about 0.6 ppm to the high magnetic field side compared to the actual *H NMR spectrum).
[0058]
The abundance ratio of the structure represented by above general formula (2) can be calculated by the above identifications. specifically, assuming that the *’C NMR spectrum shown in Fig. 3 is obtained in the case of using
H,C=C (CH3) — (C=0) -0~ (CH) 3-31 (OCH3} 3 as the alkoxysilane compound represented by above general fcrmula (1), the peak area of the underlined carbon of the H;C=C{CHi)~ {C=0) ~0~CHz~CH,~CHy~Si= structure is 0.853, the peak area of the underlined carbon of the HO-CH,-CHz~CHx-Sis structure is 0.099, and the peak area of the underlined carbon of the =5i-0~CHy;~CH;~CHy-Si= structure is 0.415. In this connection, when the alkoxysilane compound represented by above general formula (1) and the silanol compound represented by above general formula (3) are charged at 50:50, the =5i-0-CH;-CH;-CH,-Si= structure is calculated as that 30% by number of 5i atoms contained in the polymer form the bond in the structure represented by above general formula (2).
[0059]
In addition, even when the charging ratio of the alkoxysilane compound or silanol compound is nol known, the Si atom content can be measured by a 2931 NMR spectrum using an internal standard, the ester structure content can be measured by a 'H NMR spectrum using an internal standard, the structures can be identified by a °C NMR spectrum (NNE mode}, an HH COSY spectrum and a CH COSY spectrum, and the content percentage of =5i-0-X-S8Si= can be calculated based on the identified structures.
—- 26 -~
[0060]
The NMR spectrum was measured by using JNM-GSX400.
The 'H NMR spectrum was measured at 400 MHz, and the °C
NMR spectrum was measured at 100 MHz.
[0061]
In view of crack resistance, easy handleability and photocurability, out of Si atoms contained in the polyorgancsiloxane, the percentage of the number of Si atoms forming the bond in the structure represented by above general formula (2) is from 5 tc 60%, preferably from 7 to 50%, more preferably from 10 to 40%, and most preferably from 15 to 35%.
[0062]
As the method for increasing the molecular weight while maintaining the equivalent of the crosslinking functional group of the polyorganosiloxane, a method of adding a boron compound or a method of adding a phosphorus compound and a peroxide may be also used.
[0063]
Low mclecular materials (for example, dimer, trimer and tetramer) may be also removed by washing the pelycrganosiloxane obtained in the reaction step with a solvent incapable of dissolving the polyorganosiloxane.
The solvent incapable of dissolving the polyorganosiloxane in the washing step includes, for example, water, an alcohol (such as methanol or ethanol}, an acetonitrile, etc.
[0064]
In the washing step, a sclvent incapable of dissolving a polyorganosiloxane is added toc the polyorgancsiloxane obtained in the reaction step, or the polyorgancsiloxane obtained in the reaction step is added tec a solvent incapable of dissolving the polyorganosiloxane, and is then stirred. Stirring a mixture of the polyorganosiloxane and the solvent is continued in inhomogeneous state and thereafter, the mixture is left standing still. After the mixture is separated into a polyorgancsiloxane layer and a solvent layer, the polyorganosiloxane layer is collected or the solvent layer 1s removed, whereby washing can be performed.
[0065]
The residual catalyst can be reduced by means of the washing step. In view of storage stability of the rolyorgancosiloxane resin and the resin composition, the amount of the residual catalyst in the resin composition is preferably from 0.1 to 500 ppm.
[0066] <Increase of Molecular Weight of Polyorganosiloxane>
The polyorganosiloxane (a) for use in the photosensitive resin composition of the present invention is obtained by means of a method of mixing the alkoxysilane compound represented by above general formula (1), the silanol compound represented by above general formula (3) and the catalyst to obtain a mixture, and polymerizing the mixture, wherein in the polyorganosiloxane, the area having a weight average molecular weight of 1,050 or more in terms of standard polystyrene as measured by gel permeation chromatography (GPC) is 70% or more of the whole GPC peak area.
[0067]
The method for evaluating the molecular weight (GPC measurement} is as follows.
A calibration curve is prepared by using HLC-8020 manufactured by Tosoh Corporation with a differential refractometer (RI) as the detector and series-connected
G5000HHR, G4000HHR, G3C00HHR and G2500HHR manufactured by
Tosoh Corporation as columns and using a polystyrene (TSK
Standards produced by Tosoh Corporation, molecular weight: 1,090,000; 706,000; 355,000; 190,000; 96,400; 37,900; 18,100; 9,100; 5,970; 2,630; 1,056; and 500) as the standard polystyrene under the condition of 40°C, and measurement is performed using THF as the solvent at a flow rate of 1 mL/min.
[0068]
The silanol compound, the alkoxysilane compound, the catalyst, the reaction conditions and the like are the same as those described above.
[0069]
Increase of the molecular weight is achieved by forming the structure represented by above general formula (2). Accordingly, the molecular weight may be controlled by controlling the structure represented by above general formula (2), i.e., the reactions represented by above reaction formulae (6) and (7).
[0070]
These reactions can be controlled by changing the reaction temperature, the reaction time, the reaction pressure, the catalyst amount, and the catalyst type.
[0071] <Production Process of Polyorganosiloxane>
The production process of (a) a polyorganosiloxane, comprises, in order: i) a step of producing a polyorganosiloxane by mixing the at least one alkoxysilane compound represented by above general formula (1) and a catalyst to obtain a mixture, and reacting the mixture at a temperature cf 20 to 130°C, preferably from 30 to 100°C, more preferably from 40 to 80°C, for a reaction time of 0.1 to 20 hours, preferably from 0.2 to 10 hours, more preferably from 0.3 to 5 heurs, while removing an alcohol produced by the reaction from the reaction system; and ii) a step of washing the polyorganosiloxane with a solvent incapable cf dissolving the polyorganosiloxane.
[0072]
Water may be added to the reaction system, but the amount of water added is preferably from 0.01 to 0.5 equivalents, more preferably from 0.05 to 0.45 equivalents, and in view of storage stability and reactivity due to the terminal alkoxy structure, still more preferably from 0.1 to 0.4 equivalents, per one equivalent of an alkoxy group bonded to the Si atom contained in the alkoxysilane compound present in the reaction system.
[0073]
The production process of (a) a pelyorganosiloxane, comprises, in order: i} a step of producing a polyorganosiloxane by mixing the at least one alkoxysilane compound represented by above general formula (1), the at least one silanol compound represented by above general formula (3) and a catalyst to obtain a mixture, and reacting the mixture at a temperature of 20 to 130°C, preferably from 30 to 100°C, mere preferably from 40 to 80°C, for a reaction time of 0.1 to 20 hours, preferably from 0.2 to 10 hours, more preferably from 0.3 to 5 hours, while removing an alcohol produced by the reaction from the reaction system; and ii) a step of washing the polyorgancsiloxane with a solvent incapable of dissolving the polyorganosiloxane.
[0074]
In the production process of the polyorganosiloxane (a), removal of the alcohol in the production step i) is preferably performed by reducing the pressure at a temperature of 30 to 80°C. That is, the production process of the polyorganosiloxane is characterized by performing the reaction while removing the produced alcohol to the cutside of the reaction system under atmospheric pressure when the reaction temperature is not less than the boiling point of the produced alcohol, or under reduced pressure when the reaction temperature is not more than the boiling point. Due to this removal, the amount of an alcohol in a reaction vessel is reduced, and high controllability of reaction results (i.e., breakage of an ester is retarded and thereby can be easily controlled).
[0075]
As the catalyst used for polymerization, a compound
_ 30 = that accelerates a dealcoholization condensation reaction of a silanol group of the silancl compound with an alkoxy group of the alkoxysilane compound, and advances an ester hydrolysis reaction or a transesterification reaction during polymerization, can be used. The catalyst may be either an acidic compound or a basic compound, and includes, for example, a metal alkoxide, an inorganic acid, an organic acid, an inorganic base, an organic base, and a phosphazene compound, etc. Among others, an alkali metal hydroxide, an alkaline earth metal hydroxide, an ammonium compound or the like is preferred, and specific examples thereof include Ba{OH)., Ca(OH),
Mg (OH) ,, KOH, LiOH, NHz, NH40H, NR;(OH), NR,C1l, NR4Br, NR,I, etc. In NRg{(OH), NR4Cl, NR4Br and NR,I, R is an aliphatic, alicyclic or aromatic group having a carbon number of 1 to 10, which may have a substituent. The catalyst is more preferably an alkali metal hydroxide, an alkaline earth metal hydroxide or the like, still more preferably an alkaline earth metal hydroxide, and specific examples thereof include Ba {QOH),, Ca(OH), Mg(OH)., etc. Hydrates of Ba(OH);, Ca(OH), and Mg{QH): may be alsc used, and in view of stability and reaction with good reproducibility because the reaction time, specifically the reaction time in an inhomogeneous state can be shortened, Ba (CH), :8H,0 is more preferably used.
[0076]
The amount of the catalyst added is preferably a concentration that allows for progressicn of a hydrolysis reaction by a hydrate water or the like contained in the catalyst or transesterification reaction or the like, and the concentration is, for example, from 0.05 to 30 molk, and in view of transparency and reaction controllability, preferably from 0.1 to 20 mol%, still more preferably from 0.1 to 10 mol%, yet still more preferably from 0.2 to 10 mol%, based on the number of moles of Si atom which is charged to a reaction system. The number of moles of
Si atom charged is a number of moles of Si atom calculated by adding up the alkoxysilane compound represented by above general formula (1), the silanol compound represented by above general formula (3) and other condensable silane compounds present in the reaction system, and the mol$% expressing the catalyst amount indicates how many moles the catalyst is added based on the number of moles of Si atom.
[0077]
In the case where the catalyst is precipitated 1C during reaction or during drying, only the obtained polyorgancsiloxane (a) is preferably dissolved with a solvent capable of dissolving the polyorganosiloxane and incapable of dissolving the catalyst, for example, when the catalyst is an alkali metal hydroxide or an alkaline earth metal hydroxide, such as Ba(OH)., with cyclohexane, toluene or the like, and then filtered, whereby the catalyst can be removed. In this case, the solvent added is gradually removed and then dried under reduced pressure and heating. The temperature at the drying is from 50 te 130°C, preferably from 80 to 130°C, the pressure is 20 hPa or less, preferably 15 hPa or less, and the drying time is 10 minutes or more, preferably 30 ninutes or more, more preferably 1 hour.
[0078]
By washing the resulting polyorganosiloxane (a) with a solvent incapable of dissolving the pelycrganosiloxane, low-molecular materials may be reduced. As the solvent, for example, methanol, ethanol, aceteonitrile, dimethylsulfoxide, water or the like can be used, as described above, depending on the molecular weight of the produced polyorgancsiloxane (a).
[0079]
The solubility of the low-molecular material differs depending on the solvent used and therefore, with respect to the number of washings, the washing can be performed a plurality of times until the low-molecular material is removed in a desired amount.
[0080]
With respect to the specific washing method, as described above, the solvent is added to the polyorganosiloxane (a}, or the polyorganosiloxane {a) is added to the solvent, to obtain a mixture, and the mixture 1s stirred, thereby dissolving the low molecular material in the solvent, and after stirring for a necessary time, the mixture is left standing still to cause separation into a polyorganosiloxane layer and a solvent layer. Thereafter, the solvent layer is removed or the polyorganosiloxane layer is collected, whereby a polyorganosiloxane in which the amount of the low- molecular material is reduced can be isclated.
[0081]
The polyorganosiloxane (a) after isolation is subjected to removal of the solvent and then dried under reduced pressure and heating condition, whereby a peclyorganosiloxane in which the amount of the low- molecular material is reduced is obtained.
[0082] <Photopolymerization Initiator Contained in
Photosensitive Resin Composition>
Preferred compounds as the photopolymerization initiator (bk) for use in the photosensitive resin composition of the present invention include the followings: {1) a benzophenone derivative: for example, benzophenone, methyl o-benzoylbenzoate, 4d-benzoyl-4'- methyl diphenyl ketone, dibenzyl ketone and fluorenone; (2) an acetophenone derivative: for example, 2,2'- diethoxyacetophenone, 2-hydroxy-Z2-methylpropiophenone, 2,2-dimethoxy-1, 2-diphenylethan~1l~one {(IRGACURE (registered trademark) 651, produced by BASF), l-hydroxycycliohexyl phenyl ketone {IRGACURE (registered trademark) 184, produced by BASF), Z-methyli-1-[4- (methylthio) phenyl] -2-morpholinopropan-1-one (IRGACURE {registered trademark) 907, produced by BASF),
I. 33 — 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)~benzyl]- phenyl}-Z-methylpropan~1l~one (IRGACURE (registered trademark} 127, produced by BASF) and methyl phenylglyoxylate; (3) a thioxanthone derivative: for example, thioxanthone, Z-methylthioxanthone, 2- isopropylithioxanthone and diethylthioxanthone; (4) a benzyl derivative: for example, benzyl, benzyl dimethyl ketal and benzyl-f-methoxyethyl acetal; {0083] {5) a benzoin derivative: for example, benzoin, benzoin methyl ether and 2~hydroxy-2-methyl-1 phenylpropan-l-one (DAROCURE (registered trademark) 1173, produced by BASF); (6) an oxime-based compound: for example, 1-phenyl- 1,2-butanedione-2- (O-methoxycarbonyl)oxime, l-phenyl-1,2- propanedione-2- (O-methoxycarbonyl) oxime, l-phenyi-1,2- propanedione~2- (O-ethoxycarbonyl) oxime, l-phenyi-1,2- propanedione-2- (O-benzoyl) oxime, 1,3~ diphenylpropanetrione-2~ (O~-ethoxycarbonyl) oxime, 1- phenyl-3-ethoxypropanetrione~2~ (C~benzoyl)oxime, 1,2- octanedione, 1-[4-(phenylthic)-2-(0-benzoyloxime) ] (IRGACURE (registered trademark) OXE-01, produced by
BASF), and ethanone, 1-[9-ethyl-6-{(2-methylibenzoyl)-9H- carbazol-3-yl]-, 1-{0O-acetyloxime) {IRGACURE (registered trademark) OXE02 produced by BASE); {7) an o-hydroxy ketone-based compound: for example, 2-hydroxy-2-methyl-1l-phenylpropan~l-one, 1-[4-(2- hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-l-propan-li-one and Z-hydroxy-i-{4-[4-(2-hydroxy-2-methylpropionyl) - benzyl]phenyl}-2-methylpropane;
[0084] (8) an o-aminocalkylphenone-based compound: for example, Z2-benzyl-2-dimethylamino~-1l-(4-morpholinophenyl)- butanone~1 (IRGACURE (registered trademark) 369 produced by BASF) and Z2-dimethylamino-2-(4-methylbenzyl)-1-(4-
—- 34 ~ morpholin-4-yl-phenyl)butan~l~one {(IRGACURE (registered trademark) 379 produced by BASF); (2) a phosphine oxide-based compound: for example, bis(2,4,6~trimethylbenzoyl) -phenylphosphine oxide {IRGACURE (registered trademark} 819 produced by BASF), bis (2, 6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide and 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide (Lucirin (registered trademark), TPO, produced by BASF); and {10} a titanocene compound: for example, bis(nb-2,4- cyclopentadien~l~yl)~bis (2, 6-difluoro-3-(1H-pyrrol-1- yliphenyl)titanium (IRGACURE (registered trademark) 784 produced by BASE).
In using the above photopolymerization initiators {b), one compound may be used alone, or a mixture cof two or mere thereof may be used.
[0085]
Among the above photopolymerization initiators (b), in view of photosensitivity and transparency, a benzoin derivative (5) and a phosphine oxide-based compound (9) are preferred. The amcunt of the photopolymerization initiater (b) added is from 0.01 to 30 parts by mass, preferably from 0.1 to 5 parts by mass, more preferably from 0.2 to 2 parts by mass, still more preferably from 0.3 to 1 part by mass, per 100 parts by mass of the polyorganosiloxane (a). The amount of the photopolymerization initiator (b) added is 0.01 parts by mass or more from the standpoint of obtaining a practical cured pattern, and 30 parts by mass or less in view of transparency.
[0086] <Ethylienically Unsaturated Addition-Polymerizable Monomer
Contained in Photosensitive Resin Composition»
The photosensitive resin composition of the present invention preferably further contains (c) an ethylenically unsaturated addition-polymerizable monomer (hereinafter, sometimes referred to as "monomer")., As the monomer added to the photosensitive resin composition, from the standpoint of enhancing the crack resistance, heat resistance and hardness, a compound containing an acryloyl group or a methacryloyl group can be used.
[0087]
Specific examples of the monomer which can be used are described below,
The monomer for enhancing the crack resistance includes a monomer having a polyalkylether chain or an oligoalkylether chain, as represented by following general formula (9):
HpC=C (R) = (C=0) =0= (PO) pp = (EO) += (C=0) =C (R) =CH, (9) {wherein R is hydrogen or a methyl group, PO is a propylene oxide group, EO is an ethylene oxide group, m' is a number of less than 30, n' is a number of less than 30, and when both PO and EO are present, PO and EO may exist in a random or block manner and m'+n' 1s a number of less than 60}.
[0088]
The monomer includes, for example, a polyethylene glycol diacrylate [number of ethylene glycol units: from 2 to 201, a polyethvlene glycol dimethacrylate [number of ethylene glycol units: from 2 to 20], a poly(l,2- propylene glycol)diacrylate [number of 1,2-propylene glycel units: from 2 to 20], and a peoly(l,2-propylene glycocl)dimethacryiate [number of 1,2-propylene glycol units: from 2 to 207.
[0089]
The monomer for enhancing the heat resistance is preferably a compcund having an alicyclic group, and includes, for example, an alicyclic group-containing menomer, as represented by following general formula (10):
HoC=C (R) = {C=0) —0-Y"'-X'-Y?-0- (C=0) -C (R} =CH; (10) {wherein R is hydrogen or a methyl group, each of Y* and Y° is an organic group having a carbon number of 1 to
20 and containing an ethylene oxide group and/or a propylene oxide group, and X' is a cyclohexyl group- containing substituent, as represented by following formula (11): [Chem. 41] } (11) bo and a polycyclic structure-~containing monomer, as represented by following general formula (12): [Chem. 5}
EI {12) {wherein each of Y¥' and X" is hydrogen or an organic group containing an alkyl group, an ethylene oxide group or a propylene oxide group, and at least one of Y' and X" is an acryloyloxy group, a methacryloyloxy group, an i5 acryloyloxymethyl group or a methacryloyloxymethyl group}.
[0090]
The monomers represented by above general formulae {10) and (12) inciude, for example, 1,4-cyclohexane diacrylate, 1,4-cyclohexane dimethacrylate, an ethoxylated (hydrogenated bisphenol A) diacrylate [number of ethylene glycol units: from 2 to 30}, an ethoxylated (hydrogenated bisphencl A) dimethacrylate [number of ethylene giycol units: from 2 to 30%, tricyclodecanedimethanol dimethacrylate, tricyclodecanedimethanol diacrylate, dicyclopentanyl acrylate, dicyclopentenylozxyethyl acrylate, dicyclopentenyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyloxyethyl methacrylate, etc.
The monomer for rising the refractive index includes a benzene ring-containing monomer, as represented by following general formula (13):
HoC=C (R) — (C=0) —0-Y'-X"'''=Y*-0- (C=0) -C(R) =CH, (13) {wherein R is hydrogen or a methyl group, each of Y! and Y? is an organic group having a carbon number of 1 to 90 and containing an ethylene oxide group and/or a propylene oxide group, and X''' is an aromatic group- containing substituent, as represented by following formula (14): {Chem. ©] }
[0092]
The monomer represented by above general formula (13} includes, for example, a bisphenol A diglycidyl ether-acrylic acid adduct, a bisphenol A diglycidyl ether-methacrylic acid adduct, an ethoxylated bisphenol A diacrylate [number of ethylene glycol units: from 2 to 30], and an ethoxylated bisphenol A dimethacrylate [number of ethylene glycel units: from 2 to 30].
[0093]
The monomer for enhancing the hardness and photosensitivity includes a monomer having three or more acrvloyl or methacryloyl groups, as represented by following general formula (15): (HpC=C (R) =~ (C=0) ~0=Y),~X"'""""' (15) {wherein R 1s hydrogen or a methyl group, ¥Y is an organic group having a carbon number of 1 to 90 and containing an ethylene oxide group and/or a propylene oxide group, X'''' is an n-valent organic group having a carbon number of 1 to 6, and n is 3 or 4}.
[0094]
The monomer represented by above general formula
(15) includes, for example, a pentaerythritcl acrylate, a pentaerythritol tetraacrylate, a trimethylolpropane triacrylate, an ethoxylated trimethylolpropane triacrylate [number of ethylene glycel units: from 2 to 20}, a trimethylolpropane trimethacrylate, a tri-2- hydroxyethylisccyanurate triacrylate, a tri-2- hydroxyethylisocyanurate trimethacrylate, ditrimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc. In addition, in using these monomers, 1f desired, one monomer may be used alone, or two or more thereof may be mixed and used.
[0095]
In view of crack resistance, heat resistance, refractive index and viscosity {(handleability), it is preferable to use an alicyclic group-containing monomer.
Specific examples of the alicyclic group-containing monomer include a tricyclodecanedimethanol dimethacrylate, a tricyclodecanedimethanol diacrylate, a dicyclopentanyloxy acrylate, a dicyclopentanyloxy methacrylate, hydrogenated bisphenol ethylene oxide-~ modified acrylate (number of ethylene oxide units: 10), a hydrogenated bisphenol ethylene oxide-modified methacrylate (number of ethylene oxide units: 10), etc.
[0096]
In view of higher crack resistance, it is more preferable to further use an alkyleneoxy group-containing moneomer in combination with the alicyclic group- containing monomer. Specific examples of the alkyleneoxy greup-containing monomer include a polyethylene glycol #400 acrylate {(m'=0, n'=9), a polyethylene glycol #600 acrylate (m'=0, n'=14), a polyethylene glycol #400 methacrylate (m'=0, n'=9), a polyethylene glycol #600 methacrylate (m'=0, n'=14) or the like, as represented by above general formula (9).
[0097]
The amount of the ethylenically unsaturated addition-polymerizable monomer (c¢} (i.e., one or more types of compounds selected from the group consisting of an acrylate and a methacrylate) added is from 0.1 to 1,000 parts by mass, preferably from 1 to 500 parts by mass, mere preferably from 2 te 200 parts by mass, and in view of heat resistance, most preferably from 5 to 100 parts by mass, per 100 parts by mass of the polyorganosiloxane (a).
[0098] <Cther Additives>
In order to provide a photosensitive resin composition having excellent characteristics in terms of light resistance of a molded article after curing, at least one compound selected from the group consisting of an ultraviolet absorber and a hindered amine-containing light stabilizer may be further added to the photosensitive resin composition of the present invention. In the case of adding such an additive, the amount thereof 1s, as the total amount of additives, preferably from 0.001 to 10C parts by mass, and in view of transparency and thermogravimetric loss, more preferably from 0.01 to 20 parts by mass, per 100 parts by mass of the polyorganosiloxane (a).
[0099]
In the case where the photosensitive resin composition contains an ultraviolet absorber or a hindered amine-containing light stabilizer, the amount added of the ultraviclet absorber or light stabilizer is preferably from 0.2 to 50 parts by mass, more preferably from 1 to 10 parts by mass, per 100 parts by mass of the polyorganosiloxane (a). When the amount added is 0.2 parts by mass or more, the ultraviolet absorber or light stabilizer is effective in enhancing the weather resistance and light resistance of the cured molded article, whereas when the amount added is 50 parts by mass or less, the light resistance and weather resistance can be enhanced while maintaining high transparency of the photosensitive resin composition to which the ultraviolet absorber or light stabilizer is added and the cured molded article thereof.
[0100]
An adhesion aid, such as silane coupling agent may be further added to the photosensitive resin composition of the present invention, in order to provide a photosensitive resin composition helding high adherence to an inorganic material substrate, such as glass and metal.
[0101]
In particular, in view of cost and harmful effect, 3-glycidoxypropyltrimethoxysilane (KBM-403, available from Shin-Etsu Chemical Co., Ltd.), 3- methacryloxypropyltrimethoxysilane (RKBM-503, available frem Shin-Etsu Chemical Ce., Ltd.), and 3- aminopropyltriethoxysilane (KBE-903, available from Shin-
Etsu Chemical Co., Ltd.) are preferred as the adhesion aid.
[0102]
In the case of incorporating a silane coupling agent into the photosensitive resin composition, the amount added of the silane coupling agent is preferably from 1 to 100 parts by mass, more preferably from 10 to 50 parts by mass, per 100 parts by mass of the polyorganocsiloxane (a). When the amount added is 1 part by mass or mere, a cured molded article having excellent adherence to an inorganic material substrate, such as glass and metal can be obtained.
[0103]
If desired, a sensitizer for enhancing photosensitivity may be added tc the photosensitive resin composition of the present invention.
The sensitizer includes, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis{4'- diethylaminobenzylidene)cyclopentanone, 2,6-bis{4'- diethylaminobenzylidene) cyclohexanone, 2,6-bis(4'-
dimethylaminobenzylidene)~4-methylcyclohexanone, 2, 6- bis{4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis{dimethylaminc) chalcone, 4,4'~ bis {diethylamino)chalccne, 2-{4'- dimethylaminocinnamylidene)indanecne, 2-(4'- dimethylaminobenzylidene) indancne, 2-(p-4'- dimethylaminopiphenyl)benzothiazole, 1,3-bis{é~ dimethylaminobenzylidene) acetone, 1,3-bis(4- diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis{(7- diethylaminccoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3- benzyloxycarbonyl-7~dimethylaminocoumarin, 3- methoxycarbonyl~7~diethylaminocoumarin, 3-ethoxycarbonyl-
T-diethylaminocoumarin, N-phenyl~N-~ethylethanolamine, N- phenyldiethanolamine, N-p-tolyldiethanolamine, N- phenylethanolamine, N,N-bis(2~hydroxyethyl)aniline, 4- morpholinobenzophenone, iscamyl 4-dimethylaminobenzoate, isoamyl 4~diethylaminobenzoate, benzotriazole, 2- mercaptobenzimidazole, 1-phenyl~5-mercapto-1,2,3,4- tetrazole, l-cyciohexyl-5-mercapto-1,2,3,4-tetrazole, 1- (tert-butyl) -5-mercapte-1,2,3,4~tetrazole, 2- mercaptobenzothiazole, 2-(p- dimethylaminostyryl)benzoxazole, 2-{p- dimethylaminostyryl)benzothiazole, 2-{p- dimethylaminostyryl)naphtho (1, 2-p) thiazole, 2-(p- dimethylaminobenzoyl} styrene, etc.
One of these compounds may be used alone, or a mixture cf two or more thereof may be used.
In the case of adding a sensitizer to the photosensitive resin composition, the amount added of the sensitizer depends on the amount of the other additive components, but is preferably from 0.1 to 10 parts by mass, more preferably from 1 to 5 parts by mass, per 100 parts by mass of the polyorganosiloxane (a).
[0104]
If desired, in order to enhance the viscosity stability or photosensitivity stability during storage, a polymerization inhibitor may be added to the photosensitive resin composition of the present invention.
The pelymerization inhibitor which can be used includes, for example, hydroquinone, N- nitrosodiphenylamnine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2- cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p- methylphencl, 5-nitroso-8-hydroxyguinoline, l-nitroso-2- naphthol, Z-nitroso-l-naphthel, 2-nitroso-5-(N-ethyl-N- sulfopropylamino)} phencl, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N=-phenylhydroxylamine ammonium salt, N-nitroso-N-{l-naphthyl)hydroxylamine ammonium salt, bis(4~hydroxy~3,5-di~tert-butyl)phenylmethane, etc.
In the case of adding a pelymerization inhibitor to the photosensitive resin composition, the amount added of the polymerization inhibitor is preferably from 0.001 to 5 parts by mass, more preferably from 0.01 to 1 part by mass, per 100 parts by mass of the polyorganosiloxane (a).
[0105]
If desired, in order to enhance the thermal stability in the presence of oxygen, an antioxidant may be added to the photosensitive resin composition of the present invention.
The antioxidant includes, for example, hindered phenolic antioxidant, phosphorus-based antioxidant, lactone antioxidant, vitamin E antioxidant, sulfur-based antioxidant, etc.
Specific examples of the antioxidant include, but are not limited to, triethylene glycol~bis[3-(3-tert- butyl-5-methyl-4-hydroxyphenyl) propionate] {IRGANOX (registered trademark} 245, produced by BASE), 1, 6-hexanediol-bis[3-(3,b-di-tert-butyl~4- -hydroxyphenyl) propionate] (IRGANOX (registered trademark)
259, produced by BASE), 2,4-bis-{n-cctylthio}-6&6-{4- hydroxy-3, 5-di-tert~butylaniline)-1,3,5-triazine {IRGANOX (registered trademark) 565, produced by BASF}, pentaerythrityl ‘tetrakis|[3-(3, 5~di~-tert-butyl-4- hydroxyphenyl) propionate) (IRGANOX (registered trademark) 1016, produced by BASF}, 2,2-thio-diethylenebis{3-(3,5- di-tert-butyl-4-hydroxyphenyl)propionate] (IRGANOX (registered trademark) 1035, produced by BASF), octadecyl-3-(3,5-di-tert-butyl-4-hydrozyphenyl)propionate {IRGANCX (registered trademark} 1076, produced by BASF),
N,N'-hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy- hydrocinnamamide) (IRGANOX (registered trademark) 1098, produced by BASF}, 3,b-di-tert-butyl-4- hydroxybenzylphosphonate-diethyl ester (IRGAMOD (registered trademark) 295, produced by BASE), 1,3,5-trimethyl-2,4,6-tris (3, 5-di-tert-butyl-4- hydroxybenzyl)benzene (IRGANOX (registered trademark) 1330, produced by BASF), tris-{(3,5-di-tert-butyl-4- hydroxybenzyl} -isocyanurate (IRGANOX (registered trademark) 3114, produced by BASF), cctylated diphenylamine {(IRGANOX (registered trademark) 5057, produced by BASF), Z,4-bis|(octylthic)methyl]~o-cresol (IRGANOX (registered trademark) 1520L, produced by BASF), isooctyl-3-(3, b-di-tert-hutyl-4-hydroxyphenyl) propionate {IRGANOX (registered trademark) 1135, produced by BASF), 2,4-bis(dodecylthiomethyl)-6-methylphenol (IRGANOX (registered trademark) 1726, produced by BASF), 2,5,7,8~tetramethyl~2~{4,8,12«trimethyltridecyl)chroman- 6-0l (IRGANOX (registered trademark) EZ01, produced by
BASF), 5,7-di-tert-butyl-3-(3,4- dimethyliphenyl)benzofuran~2 (3H) one (IRGANOX (registered trademark) HP-136, preduced by BASF}, tris(2Z,4-di-tert- butylphenyl) phosphite (IRGAFOS (registered trademark) 168, produced by BASE), tris[2-[[2,4,8,10-tetrakis(l,1- dimethylethyl)dibenzo([d, f]1[1, 3,2]dioxaphosphepin-6- yl]oxylethyl] amine (IRGAFCS (registered trademark) 12, produced by BASF), bis(2,4-di-tert-butyl-6-
methylphenyl)ethylphosphite (IRGAFOS {registered trademark) 38, produced by BASF), didodecyl 3, 3- thiobispropiconate (IRGANOX (registered trademark) PS§00, produced by BASF), dicctadecyl 3,3-thicbispropionate (IRGANOX (registered trademark) PS802, produced by BASF), 3,9-bis[2~[3~(3~tert-butyl-4-hydroxy-5- methylphenyl)propionyloxy]-1, 1-dimethylethyl}-2,4,8,10- tetraoxaspirol5 5]lundecane (SUMILIZER (registered trademark) GA-80, produced by Sumitomo Chemical), 2,2'- methylenebis (6~tert~butyl~4-methylphenol) (SUMILIZER (registered trademark} MDP-S, produced by
Sumitomo Chemical), 4,4'-butylidenebis(6-tert-butyl-3- methyiphenol) (SUMILIZER (registered trademark) BBM-S, produced by Sumitomo Chemical), 4,4'-thiobis(6-tert- butyl-3-methylphenol) (SUMILIZER (registered trademark)
WX-R, produced by Sumitomo Chemical), pentaerythrytyl tetrakis(3~lauryithiopropionate) (SUMILIZER (registered trademark) TP-D, produced by Sumitomo Chemical), 2- mercaptobenzimidazole {(SUMILIZER (registered trademark)
MB, produced by Sumitomo Chemical), biphenyl-4,4'-diyl bis[bis(2,4-di-tert-butyl-5-methylphenoxy)phosphine] {(GSY~P101, produced by Osaki Industry), etc.
One of these antioxidants may be used alone, or a mixture of two or more thereof may be used.
In the case of adding an antioxidant to the photosensitive resin composition, the amount added of the antioxidant is preferably from 0.001 to 30 parts by mass, more preferably from G.C0l1 to 10 parts by mass, per 100 parts by mass of the polyorgancsiloxane (a).
[0106]
If necessary, the photosensitive resin composition of the present invention can be appropriately blended with various additives, such as coating film smoothness- imparting agent and inorganic fine particle as long as the various additives do not inhibit various characteristics required of the photosensitive resin composition of the present invention.
- 45 -~
[0107] <Solvent> : A solvent can be added to the photosensitive resin composition of the present invention, so as to adjust the viscosity thereof. Suitable solvents include, for example, N,N~dimethylformamide, N-methyl-2-pyrrolidone (hereafter, sometimes referred to as "NMP"), N-~ethyl-2- pvrrolidone, tetrahydrofuran, N,N-dimethylacetamide (hereafter, sometimes referred to as "DMAc"), dimethyl suifoxide, hexamethylphospheoramide, pyridine, cyclopentanone, y-butyrolactone {hereinafter, sometimes referred to as "GBL"), a-acetyl-y-butyrolactone, tetramethylurea, 1,3~dimethyl-Z-imidazolinone, N- cyclchexyl-2-pyrrolidone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, anisole, ethyl acetate, ethyl lactate, butyl lactate, etc. One of these solvents may be used alone, or two or more thereof may be used in combination. Among these, N-methyl-2- pyrrolidone, y-butyrolactone and propylene glycol monomethyl ether acetate are preferred.
The sclvent may be appropriately added to the photosensitive resin composition depending on the coated film thickness and viscosity, but is preferably used in an amount of 0 to 200 parts by mass, per 100 parts by mass of the polyorgancsiloxane (a).
[0108] <Cured Product>
In an embodiment of the present invention, a cured product is obtained by photocuring the photosensitive resin composition of the present invention, or a photosensitive resin composition comprising the polyorganosiloxane (a) obtained by the above-described production process of a polyorganosiloxane, and the photopolilymerization initiator (bh).
-<Production Method of Molded Article>
The method for producing a molded article by using the photosensitive resin composition of the present invention is described below.
The molded article includes, for example, a microplastic lens or an optical element for a liquid crystal polarizing plate.
In the description of the present invention, a microplastic lens indicates a plastic fine lens having a diameter of generally several mm or less. A microlens array in which a number of microlenses each having a diameter of about tens of pum are arranged is used for enhancing light utilization efficiency in a CCD imaging element or an LCD projector, and a microlens having a diameter of about hundreds of pm is used in an optical communication connector, a cellular phone camera module or the like.
[0110]
The optical element for a liquid crystal polarizing plate is referred to as a structure on a polarized light filter (polarizing plate) that is one member of a liguid crystal projector or liguid crystal display. In a liguid crystal panel, generally, a palr of peclarized light filters (polarizing plates) is provided on the front and back of a transparent substrate for enclosing a liquid crystal, and allows polarized light only in a given oscillating direction to pass therethrough. The liquid crystal pclarizing plate can be produced, for example, by stretching a film and thereby orientating the composition thereof. A material having characteristics as a polarized light filter can be alsc produced by forming a specific structure with a pitch of 0.2 fo 0.3 pm on a substrate.
[0111]
The microplastic lens and the optical element for a liquid crystal polarizing plate differ only in the size and type, and the production methods for these two members are the same. Specifically, the production method of a molded article of the present invention comprises: 1) a step of filling a shape-forming mold with the photosensitive resin composition of the present invention, or a photosensitive resin composition comprising {a) a polyorganosiloxane obtained by the above-described production process and (b} a rhotopolymerization initiator; 2) a step of pressing the opening of the mold against a substrate or another mold; 3) a step of exposing the photosensitive resin composition to light from the mold and/or substrate side to obtain a photocured product; 4) a step of separating the mold from the substrate, or separating the molds from both surfaces of the photeocured product; and 5) a step of heating only the photocured product or the photocured product with the substrate.
[0112] 1) Step of filling a shape-forming mold with the photosensitive resin composition
A shape-forming mold is filled with the photosensitive resin composition through the opening of the shape-forming mold.
Alternatively, a shape-forming mold is filled with the photosensitive resin composition by dropping the photosensitive resin composition on a substrate or mold; and pressing a substrate or mold to the photosensitive resin composition make a stack of "substrate/photosensitive resin composition/mold" or "mold/photosensitive resin composition/mold".
[0113]
In the case of applying the photosensitive resin composition te the opening of the shape-forming mold, the photosensitive resin composition may be dropped in the opening by using a syringe or a dispenser.
—~ 48 -~
In the case of coating the photosensitive resin composition on the substrate side, the photosensitive resin compesition is dropped by using a syringe or dispenser, and then coated by a spin coater, a bar ceoater, a blade coater, a curtain coater, a screen printer or the like, or spray-coated by a spray coater or the like, to coat the composition on a substrate that is subjected, if desired, to coat the composition on a pretreated substrate, whereby a film of the photosensitive resin composition is formed.
[0114]
The thickness of the photosensitive resin composition is preferably from 0.01 to 10 mm, more preferably from 0.05% to 1 mm, still more preferably from 100 to 500 pum. When coating the photosensitive resin composition, the composition may be diluted with a solvent, such as NMP, but in this case, a step of removing the used solvent by heating is required.
Heating the photosensitive resin composition is carried out by arranging the photosensitive resin composition thin film-formed surface of the coated substrate to face upward. As for a heating apparatus, any known apparatus, such as oven, far-infrared ray furnace and hot plate may be used as long as heating can be carried out. The heating conditions are from 50 to 150°C, preferably from 100 to 140°C, and for 1 to 30 minutes, preferably from 5 to 10 minutes. Incidentally, even in the case where the photosensitive resin composition is not diluted with a solvent, from the standpoint of increasing the adherence of the photosensitive resin composition to the substrate, a step of heating substrate with the photosensitive resin composition may be optionally added, and the apparatus used here is preferably a hot plate.
[0115]
As a pretreatment of the substrate, a silane coupling agent may be also optionally coated on the substrate, sc as to impart adherence property to the substrate. In the case of coating a substrate with a silane coupling agent, the silane coupling agent is diluted with an organic solvent, such as NMP, and is coated by using a spin coater, a bar ccater, a blade coater, a curtain coater, a screen printer or the like, and thereafter, the solvent used is removed by heating.
The heating is carried out by using a known apparatus, such as an cven, far infrared furnace or hot plate.
Preferred chemical species of the silane coupling agent include, for example, 3-glycidoxypropyltrimethoxysilane (KBM-403, produced by Shin~Etsu Chemical), 3- methacryloxypropyltrimethoxysilane (KBM-~503, produced by
Shin-Etsu Chemical), 3-acryloxypropyltrimethoxysilane (KBM-5103, produced by Shin-Etsu Chemical), 3- aminopropyltriethoxysilane (KBE-903, produced by Shin-
Etsu Chemical), etc.
[0116]
The substrate which can be used includes, for example, a glass substrate, a quartz substrate, a silicon substrate, and a copper substrate, such as copper clad laminate. In the case where the shape-forming mold is made of a material impermeable to light, a glass substrate or a quartz substrate is preferred.
[0117] 2) Step of pressing the opening of the shape-forming mold against a substrate or another mold
The cpening of the shape-forming mold, for example, a microplastic lens mold or a mold for an optical element for a liquid crystal polarizing plate, is pressed against the thin-film formed surface of the substrate or another mold. At this time, a pressure may be applied, if desired. The shape-forming mold material includes rubber, glass, a resin, such as polydimethylsiloxane, and a metal, such as Ni, and among others, a transparent resin is preferred.
In the production method of a molded article of the present invention, in the case of pressing the opening of the mold against the substrate, a step of applying a silane coupling agent on the substrate is preferably added before a step of pressing the opening of the mold against the substrate, and the opening of the mold is preferably pressed against the silane coupling agent- applied surface of the substrate during the step of pressing the opening of the mold against the substrate,
[0119] 3) Step of exposing the photosensitive resin composition to light from the mold and/or substrate side to obtain a photocured product
In the state of sandwiching the photosensitive resin composition between a substrate and a shape-forming mold, the photosensitive resin composition is irradiated with an ultraviolet ray from the side of the shape-~forming mold or substrate which is formed of a material permeable to the exposure light.
If desired, the photosensitive resin composition may be irradiated with an ultraviolet ray from both sides of a laminate which is in the state of sandwiching the photosensitive resin composition between a substrate and a shape-forming mold or between a mold and a mold. In view of pattern resclution and handleability as the photocuring resin, the wavelength of the exposure light source is preferably i-line.
[0120] 4) Step of separating the mold from the substrate or separating the molds from both surfaces of the photosensitive resin composition
After curing the photosensitive resin composition with ultraviolet light, the shape~forming mold is separated from the substrate, or the molds on both surfaces of the photosensitive resin composition are separated.
- 51 ~ 5) Step of heating only the photocured product or the photocured product with the substrate (PEB treatment)
The remaining reactive groups are bonded by heating the photocured product at a temperature of 150 to 270°C for 5 seconds to 5 hours, whereby a molded article excellent in the heat resistance, for example, a microplastic lens or an optical element for a liquid crystal polarizing plate, can be cbtained. The heating may be performed by using a hot plate, an oven, or a temperature-programmed oven capable of setting a temperature program. The atmosphere gas during heating may be air, but it is preferable to use an inert gas, such as nitrogen and argon. Incidentally, this heating step is a step that can be optionally added so as to increase the hardness of the molded article, for example, a microplastic lens or an optical element for a liquid crystal polarizing plate.
[0122]
By performing the steps described above, the molded article of the present invention is obtained.
[0123] <Method for Forming Cured Relief Pattern and
Polyorganosiloxane Film>
An example of the method for forming a cured relief pattern by using the photosensitive resin composition of the present invention is described below. The production method of a cured relief pattern comprises: 1) a step of coating the photosensitive resin composition of the present invention or a photosensitive resin composition containing (a) a polyorganosiloxane obtained by the prcducticon process of a poiyorganosiloxane of the present invention and (b) a photopolymerization initiator to obtain a coated film, 2) a step of irradiating the coated film with an active ray to photocure the exposed area of the film, 3) a step of removing the uncured portion of the film by using a developer, and
4) a step of heating the cured portion with the substrate material.
[0124] 1) Step of ccating the photosensitive resin composition of the present inveniticn to obtain a ccated film
First, the photcsensitive resin composition of the present invention is coated on a silicon wafer, a ceramic substrate, an aluminum substrate or other various desired substrates. As for the coating apparatus or coating methed, a spin coater, a die coater, a spray coater, dipping, printing, a blade coater, roll coating and the like may be utilized. The substrate coated with the photosensitive resin composition is soft-baked at 80 to 200°C for a time of 10 seconds to 1 hour.
[0125] 2) Step of irradiating the coated film with an active ray to photocure the exposed area of the film
The coated film is irradiated with an actinic ray through a desired photomask by using an exposure projection apparatus, such as contact aligner, mirror projection and stepper. As the active ray, an X-ray, an electron beam, an ultraviolet ray, a visible light ray and the like may be utilized, but in the present invention, an active ray having a wavelength of 200 to 500 nm is preferably used. In view of pattern resolution and handleability, the light source wavelength is preferably a UV-i line (365 nm}, and a stepper is preferred as the exposure projection apparatus.
[0126]
After step 2), for the purpose of enhancing the photosensitivity or the like, a post-exposure baking (PEB) or a pre-~development baking may be performed, if desired, by optionally combining the temperature and the time (preferably a temperature of 40 to 200°C and a time of 10 seconds to 30 minutes).
[0127] 3) Step of removing the uncured portion of the film by
- ha a using a developer : This step can be carried out by a method, such as dipping method, puddling method and rotating spray method. As the developer, a good solvent for the photosensitive resin composition of the present invention may be used alone, or a geod solvent and a poor solvent may be appropriately mixed and used. The good solvent includes, for example, N-methyl-Z2-pyrrolidone, N-acetyl- 2~-pyrreclidene, N,N-dimethylacetamide, N,N- dimethylformamide, dimethyl sulfoxide, gamma- butyrolactone, oa-acetyl-gamma-butyrclactone, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, and methyl isobutyl ketone.
The poor solvent includes, for example, methanol, ethanol, isopropanol, and water.
[0128]
After the completion of development, washing is performed with a rinsing solution to remove the developer, whereby a coating film with a relief pattern is obtained. As the rinsing solution, distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether and the like may be used alone or as an appropriate mixture or may be used by stepwise combining these.
[0129] 4) Step of heating the cured portion with the substrate material ((final) heating step, PEB treatment)
The relief pattern obtained as above is converted to a cured relief pattern at 150 to 260°C. The heat curing may be performed by using a hot plate, an inert oven, a temperature-programmed oven capable of setting a temperature program, or the like. The atmosphere gas during heat curing may be alr, or an inert gas, such as nitrcocgen and argon may be used, if desired.
[0130]
The cured relief pattern obtained by the production
— 5 4 — method above is used as any one member selected from the group consisting of a surface protective film, an interlayer insulating film and an a-ray shielding film of a semiconductor device formed on a substrate, such as silicon wafer, and a support (partition wall) between a microsructure, such as microlens array and a package material thereof, and further subjected to other steps in the known manufacturing method of a semiconductor device, whereby a variety of semiconductor devices including an optical element, such as CMCS image sensor can be manufactured. An electronic component or semiconductor device having a coating film composed of a resin obtained by curing the photosensitive resin composition can also be produced.
[0131]
The present invention is explained in greater detail below by referring to Examples, but the scope of the present invention is not limited thereto. [Example 1]
Photosensitive Resin Composition:
A 2-L separable flask was charged with 1.37 mol (275 g) of dicyclopentylsilanedicl as the silanol compound, 1.37 mol (341 g) of (CH30)3-8i-(CHy)3~0~(C=0)~C(CH;)=CH, as the alkoxysilane compound and 0.00858 mol (1.63 g) of
Ba (OH), -H20 as the catalyst, and equipped with a Liebig condenser for removing the alcohol produced, and in this state, the mixture was gradually heated from room temperature to 50°C in an oil bath under reduced pressure of 500 hPa. Since the initiation of reaction, when the reaction solution became transparent (that is, the dicyclopentylsilanediol was dissolved), the pressure was reduced to 250 hPa. Methanol generated by keeping the stirring was cooled by the Liebig condenser and liquefied, and after confirming that the liquefied methanol began discharging to the outside of the system,
the reaction was further continued for 2 hours. The degree of vacuum was gradually raised to aveid occurrence of bumping at the same temperature as that in the pressure reduction, and while further removing the methanol at 8 to 15 hPa, the reaction was continued for 2 hours. Finally, the system was returned to the atmospheric pressure to terminate the removal of methanol. The obtained white cloudy viscous liquid was dissolved in cyclohexane and then filtered, and the solvent was removed by an evaporator. Subseguently, vacuum suction was performed at 80°C for 30 minutes.
After standing to cool, when the system was returned to room temperature, an operation of adding methanol to the system, stirring the mixture and removing the supernatant was repeated three times. Remains methanol from the obtained methancl-insoluble part was removed by using an evaporator at 60°C, and the residue was dried at 80°C for 1 hour and 30 minutes. The welght average molecular weight of the obtained polyorganosiloxane was 5,329. In the obtained polyorganosiloxane, 30% by number of Si atoms were contained in the structure represented by above general formula (2) {in the formula, X was -(CH;}z:-) (based on C-NMR spectrum). In the H-NMR spectrum, the peak derived from a carboxylic acid of the ester moiety was decreased by 31%, and in the GPC chart, the area having a weight average molecular weight of 1,050 or more was 83% of the whole GPC peak area (Figs. 1, 2 and 3).
[0132] 2 Parts by mass of radical photopolymerization initiator DAROCURE (registered trademark) 1173 (produced by BASF) was added per 100 parts by mass of the polyorganosiloxane to obtain a photosensitive resin composition.
[0133]
The decrease ratio of the peak derived from a carboxylic acid of the ester moiety was calculated by comparison between -C=CH; and Si-CHz- of (CH30}3;-8i-(CHz)s~
O~ (C=0) ~C {CH3) =CH, in the 'H-NMR spectrum.
[0134] [Example 2]
Photosensitive Resin Composition:
Synthesis of a polyorganosiloxane was carried out in the same manner as in Example 1, except that {(CH30);-5i- {CHy) 3-0~ (C=0) -CH=CH, was used in place of (CH:0)3~-5i- (CH) 3=0= (C=0) ~C {CH3) =CH (CH3) used in Example 1 and reacted for 75 minutes, and as the solvent for washing the obtained polyorgancsiloxane, acetonitrile was used in place of methanol. The weight average molecular weight of the obtained polyorganosiloxane was 1,582. In the obtained polyorganosiloxane, 27% by number of Si atoms were contained in the structure represented by above general formula (2), and X was =~ (CH:z)i~ (based on C-NMR spectrum). In the 'H-NMR spectrum, the peak derived from a carboxylic acid of the ester moiety was decreased by 29% (Fig. 4). 2 Parts by mass of radical photopolymerization initiator Lucirin (registered trademark) TPO (produced by BASF) was added per 100 parts by mass of the obtained polycrganosiloxane to obtain a photosensitive resin composition.
[0135]
The decrease ratio of the peak derived from a carboxylic acid of the ester moiety was calculated by comparison between -CH=CH, (the peaks near 5.80 ppm, 6.10 ppm and 6.37 ppm) and Si-CHy- (the peak near (.65 ppm) of (CH30) 3-Si- (CHp) 3-0- (C=0) -CH=CH, in the 'H~NMR spectrum.
[0136] [Example 3]
Photosensitive Resin Composition:
Synthesis was carried out in the same manner as in
Example 2, except for changing the reaction time of
Example 2 to 60 minutes. The weight average molecular weight of the obtained polyorgancsiloxane was 1,495. In the obtained polyorganosiloxane, 21% by number of Si atoms were contained in the structure represented by above general formula (2), and X was -{CH;)3;~ (based on
C-NMR spectrum). In the 'H-NMR spectrum, the peak derived from a carboxylic acid of the ester moiety was decreased by 22%.
[0137] [Example 4]
Photesensitive Resin Composition:
Synthesis was carried out in the same manner as in
Example 2, except for changing the reaction time of
Example 2 to 45 minutes. The weight average molecular welght of the obtained polyorganosiloxane was 1,380. In the obtained polyorganosiloxane, 12% by number of Si atoms were contained in the structure represented by above general formula (2), and X was = (CHz)s~. In the Iy-
NMR spectrum, the peak derived from a carboxylic acid of the ester moiety was decreased by 13%.
[0138] [Example 5]
Photosensitive Resin Composition:
Synthesis was carried out in the same manner as in
Example 2, except for changing the reaction time of
Example 2 to 30 minutes. The weight average molecular weight of the obtained polyorganosiloxane was 1,260. In the cbtained polycrganosiloxane, 9% by number of Si atoms were contained in the structure represented by above general formula (2), and X was -(CH,)3— (based on C-NMR spectrum). In the ‘H-NMR spectrum, the peak derived from a carboxylic acid of the ester molety was decreased by 9%.
[0139] {Example 6]
Photosensitive Resin Composition:
A photosensitive resin composition was obtained by carrying out the same processing as in Example 1, except that after cooling the photosensitive resin of Example 1 to room temperature, 5 mass% of A-600 (produced by Shin-
Nakamura Chemical) and 45 mass% of A-DCP (produced by
~ 58 —
Shin~-Nakamura Chemical} were added together with the radical photopolymerization initiator.
[0140] [Example 7]
Photosensitive Resin Composition:
A photosensitive resin composition was obtained by carrying out the same processing as in Example 2, except that after cooling the photosensitive resin of Example 2 to room temperature, 10 mass% of A~600 (produced by Shin-
Nakamura Chemical) and 5 mass% of A-DCP (produced by
Shin-Nakamura Chemical} were added together with the radical photopolymerization initiator.
[0141] [Example 8]
Photosensitive Resin Composition:
A 2-1. separable flask was charged with 0.2 mol (49.8 g) of (CH30)3-Si-(CHz)3;-0~(C=0)-CH=CH; as the alkoxysilane compound, 0.001 mol (0.19 g) of Ba (OH), HO as the catalyst and 0.18 mol {3.24 g) of water, and equipped with a Liebig condenser for removing the alcohol produced, and in this state, the mixture was gradually heated from room temperature to 50°C in an oil bath under reduced pressure of 250 hPa. Methanol generated by keeping the stirring was cooled by the Liebig condenser and liquefied, and after confirming that the liquefied methanol began discharging to the outside of the system, the reaction was further continued for 2 hours.
Thereafter, the reaction temperature was gradually raised to 80°C and the reaction was further allowed to proceed for 2 hours. Subsequently, the degree of vacuum was gradually raised to avoid occurrence of bumping, and while further removing the methanol at 8 to 15 hPa, the reaction was continued for 2 hours. Finally, the system was returned to the atmospheric pressure to terminate the removal of methancl. The obtained white cloudy viscous liquid was dissolved in cyclohexane and then filtered, and the solvent was removed by an evaporator.
~ 59 : Furthermere, vacuum suction was performed at 80°C for 30 minutes. After standing to cool, when the system was returned to room temperature, an operation of adding methanol, stirring the mixture and removing the supernatant was repeated three times. Remains methanol from the obtained methanol-inscluble part was removed by using an evaporator at 60°C, and the residue was dried at 80°C for 1 hour and 30 minutes. The weight average molecular weight of the obtained polyorganosiloxane was 5,256. In the obtained polyorganosiloxane, 14% by number of 5i atoms were contained in the structure represented by above general formula (2), and X was ~{CHz)s~) {based on C-NMR spectrum). In the "H-NMR spectrum, the peak derived from a carboxylic acid of the ester moiety was decreased by 16%.
[0142] [Comparative Example 1]
Photeosensitive Resin Composition:
A 30C-mlL separable flask was charged with 0.150 mol (30.0 g} of dicyclopentylsilanedicl as the silanol compound, 0.15 mol (37.2 g) of (CH30)}3-Si-{CHy)3-0~(C=0)-
C(CH3)=CH; as the alkoxysilane compound and 0.0003 mol (0.0945 g) of Ba(OH}); H:0 as the catalyst, and equipped with a Liebig condenser for removing the alcohol produced, and in this state, the mixture was gradually heated from room temperature to 50°C in an oil bath under reduced pressure cf 500 hPa. Since the initiation of reaction, when the reaction solution became transparent (that is, the dicyclopentylsilanediol was dissclved), the pressure was reduced to 250 hPa. Methanol generated by keeping the stirring was cooled by the Liebig condenser and liquefied, and after confirming that the liquefied methanol began discharging to the outside of the system, the reaction was further continued for 2 hours. The degree of vacuum was gradually raised to avoid occurrence of bumping at the same temperature as that in the
= 60 - pressure reduction, and while further removing the methanol at 8 to 15 hPa, the reaction was continued for 2 hours. Finally, the system was returned to the atmospheric pressure to terminate the removal of methanol. The obtained white cloudy viscous liquid was dissolved in cyclohexane and then filtered, and the solvent was removed by an evaporator. Subsequently, vacuum suction was carried out at 80°C for 30 minutes.
The weight average molecular weight of the obtained polyorganosiloxane was 1,002. In the obtained . polyorganosiloxane, 1% or less by number of Si atoms were contained in the structure represented by above general formula {2), and X was -(CH,)3- (based on C-NMR spectrum). In the 'H-NMR spectrum, the decrease ratio of the peak derived from a carboxylic acid of the ester moiety was 1% or less. 2 Parts by mass of radical photopolymerization initiator Lucirin {registered trademark) TPO (produced by BASF) was added per 100 parts by mass of the obtained polyorganosiloxane to obtain a photosensitive resin composition.
[0143] [Performance Comparison Result 1]
The performance cof a cured film obtained by sandwiching each of the resin compositions obtained in
Examples 1 to 8 and Comparative Example 1 hetween glass substrates, and under the condition of a diameter of 10 mm and a thickness of 500 pum, performing exposure of 3,000 mJ/cm® is shown in Table 1 below. In the evaluation of thermal shock(crack, peeling) resistance, a cold-heat cycle test (a test of alternately repeating standing for 15 minutes in an atmosphere of +125°C and standing for 15 minutes in an atmosphere of -40°C}) was carried out by using TSE-11 manufactured by ESPEC Corp., and the presence or absence of cracks generated in the resin deposited as a film on the glass substrate and the presence or absence of film peeling were inspected by eye. Ratings are:
A: no crack in the resin and ne film peeling even after 100 cold-heat cycles,
B: no crack in the resin and no film peeling after cold-heat cycles, but cracks and film peeling were observed after 100 cycles, and
C: cracks and film peeling were observed after 10 cold-heat cycles.
[0144] 10 [Table 1]
Example|Exanple|Example|Example 1 Z 3 4
Percentage of Si bonds 30 27 21 12 forming =5i-0-X-Si= bond (%)
Decrease ratio of peak area 31 29 22 13 derived from carboxylic acid in ‘H-NMR spectrum {%)
Thermal shock resistance* A 0B
Example|ExamplelExample{Example|Comparative 5 © 7 8 Example 1
Percentage of Si 30 27 14 <1 bonds forming =31-0-
X-Si= bond (%)
Decrease ratio of 31 29 16 <1 peak area derived from carboxylic acid in 'H~NMR spectrum (%)
Thermal shock A A Cc resistance* *Cold~heat cycle test: A indicates >100 cycles, B indicates from 10 to 100 cycles, and C indicates <10 cycles.
[0145] [Example 9]
Photosensitive Resin Composition:
Synthesis was carried out in the same manner as in
Example 1, except for changing the reaction temperature to 95°C, the reaction pressure to atmospheric pressure, the reaction time to 30 minutes, the drying temperature i 67 - to 130°C, and the drying time to 30 minutes, respectively in Example 1. The weight average molecular weight of the obtained polyorganosiloxane was 7,830. In the obtained polyorganosiloxane, 48% by number of Si atoms were contained in the structure represented by above general formula (2), and X was -{(CHp)s—. In the H-NMR spectrum, the peak derived from a carboxylic acid of the ester moiety was decreased by 54%, and in the GPC chart, the area having a weight average molecular weight of 1,050 or more was 89% (Figs. 5 and 6).
[0146] [Example 10}
Photosensitive Resin Composition:
A photosensitive resin composition was obtained by carrying out the same processing as in Example 1, except that after cooling the photosensitive resin of Example 1 to room temperature, 50 mass% of dicyclopentanyloxy acrylate (FA-513AS, produced by Hitachi Chemical) was added together with the radical photopolymerization initiator.
[0147] [Comparative Example 2]
Photosensitive Resin Composition:
A photosensitive resin composition was obtained by using a polyorganosiloxane synthesized according to the method described in Synthesis Example 1 of Patent
Document 3, by means of the same method as in Example 1.
[0148] [Performance Comparison Result 2}
The performance of a cured film obtained by sandwiching each cof the resin compositions obtained in
Examples 1, 6, 9 and 10 and Comparative Example 2 between glass substrates, and under the condition of a diameter of 10 mm and a thickness of 500 um, performing exposure of 3,000 md/cm® is shown in Table 2 below. In the evaluation of thermal shock (crack, peeling) resistance, a cold-heat cycle test (a test of alternately repeating
— £3 — standing for 15 minutes in an atmosphere of +125°C and standing for 15 minutes in an atmosphere of -40°C) was carried out, and the presence or absence of cracks generated in the resin deposited as a film on the glass substrate and the presence or absence of film peeling were inspected by eye. Ratings are:
A: no crack in the resin and no film peeling even after 100 cold-heat cycles, and
B: cracks in the resin and film peeling were observed after 100 cycles.
[0148] [Table 2]
Table 2
Peer nes 1 o 9 10 Example 2
Content percentage 83% 83% 89% 83% 67% of high molecular
Cl ee resistance® *Cold-heat cycle test: A indicates >100, and B indicates <100.
YY: The content percentage of high molecular weight indicates the area of portions having a weight average molecular weight of 1,050 or more in the chart by RI detector of GPC.
[0150] [Example 11]
Photosensitive Resin Composition:
A photosensitive resin composition was obtained by performing the same processing as in Example 7, except that 0.28 parts by mass of antioxidant IRGANOX (registered trademark) 245 (produced by BASF) and 0.11 parts by mass of antioxidant GSY-P101l (produced by Osaki Industry) were further added to the photosensitive resin composition of
Example 7.
A sample was produced by stripping off one glass a 64 — substrate from a cured film which was obtained by sandwiching each of the resin compositions obtained in
Examples 7 and 11 between glass substrates, and under the condition of a thickness of 500 pm, performing exposure of 3,000 mJ/cm?. The transmittance for light at a wavelength of 400 nm when the obtained sample was subjected to a heat treatment at 150°C for 13 hours in nitrogen or in a nitrogen atmosphere having an oxygen concentraticn of 7% (treatment in nitrcgen is designated as Al and that in an atmosphere with 7% of oxygen is designated as AZ), and the transmittance for light at 400 nm when the heat-treated sample above was further subjected to a heat treatment (B) in nitrogen at 260°C for 10 seconds three times, are shown in Table 3 below. The transmittance of the cured film was measured by using an ultraviolet-visible spectrophotometer V-550 manufactured by JASCO with reference to an untreated glass substrate,
It is seen that the photosensitive resin composition of
Example 10 where an antioxidant was added, is improved in the thermal stability in the presence of oxygen.
[0151] [Table 3]
Table 3
ET
Transmittance (%)i{Transmittance (%}
Heat treatment (A1) [| 9% | 91 float Trenton A
Heat treatment (A2) _ | 83 | 52
[0152]
According to the present invention, a photosensitive transparent resin composition having excellent thermal shock resistance in the production of products with integrated electronic parts or solid-state imaging - elements that requires a reflow soldering process at 260°C, can be obtained, and in turn, a plastic lens or an
—- B65 optical element for a liquid crystal polarizing plate for a projector, each requiring heat resistance, can be obtained.
Claims (1)
- CLAIMS [Claim 1} A photosensitive resin composition comprising: (a) 100 parts by mass of a poiyorganosiloxane having a polymerizable functional group; and (b) from 0.01 to 30 parts by mass of a photopelymerization initiator; wherein the polyorganosiloxane 1s obtained by means of a method of mixing at least one alkoxysilane compound represented by following general formula (1):R*.R%51 (OR?) grap (1) {wherein R' is an ester bond-containing crganic group having a carbon number of 2 to 17, and at least one R! has an acryloyl group or a methacryloyl group: R? is, when a plurality of R?’s are present, each is independently, an aliphatic group having a carbon number of 1 to 10, which may have a substituent; Rr? is, when a plurality of R’s are present, each 1s independently, a methyl group or an ethyl group; a is an integer of 1 or 2; b is an integer of 0, 1 or 2; and a+b is 3 or less} and a catalyst to obtain a mixture, and polymerizing the mixture, wherein the polyorgancsiloxane contains a structure represented by following general formula (2): =5i1-0-X-8i= (2) {wherein X is an organic group having a carbon number of 1 to 15}, and wherein from 5 to 60% by number of Si atoms in the polycrganosiloxane are contained in the structure represented by general formula (2).[Claim 2] The photosensitive resin composition according to claim 1, wherein the polyorgancsiloxane is obtained by means of a method of mixing the at least one alikoxysilane compound represented by general formula (1), at least one silanol compound represented by following general formula— a7 — R'R>S1 (OH), (3) {wherein each of R! and R®> is an aliphatic, alicyclic or aromatic group having a carbon number of 3 to 10, which may have a substituent} and a catalyst to obtain a mixture, and polymerizing the mixture. [Claim 3) The photosensitive resin composition according to claim 1 or 2, wherein from 10 to 40% by number of Si atoms in the pclyorganosiloxane are contained in the structure represented by general formula (2).[Claim 4] A photosensitive resin composition comprising: (a) 100 parts by mass of a polyorganosiloxane; and (b) from 0.01 to 30 parts by mass cof a photopoiymerization initiator; wherein the polyocrgancsiloxane is obtained by means of a method of mixing at least one alkoxysilane compound represented by following general formula (1): R*:R%:S1 (OR?) 4-aup (1) {wherein R! is an ester bond-contalining organic group having a carbon number of 2Z to 17, and at least one R* has an acryloyl group or a methacryloyl group; R® is, when a plurality of R?s are present, each is independently, an aliphatic group having a carbon number of 1 to 10, which may have a substituent; R> is, when a plurality of R’s are present, each is independently, hydrogen, a methyl group or an ethyl group; a is an integer of 1 or 2; b is an integer of GC, 1 or 2; and a+b is 3 or less} and a catalyst to obtain a mixture, and polymerizing the mixture, and wherein the ratio cof the peak area derived from a carboxylic acid of the ester bond and the peak area derived from an alcohol of the ester bond in the polyorganosiloxane by 'H~NMR spectrum is decreased by 5 to 60% compared to the mixture of the alkoxysilane compound before polymerization.[Claim 5]The photosensitive resin composition according to claim 4, wherein the polyorganosiloxane is obtained by means of a method of mixing the at least one alkoxysilane compound represented by general formula (1), at least one silanol compound represented by following general formula (3): R'R°S1i (OH) ; (3) {wherein each of R' and R® is an aliphatic, alicyclic or aromatic group having a carbon number of 3 to 10, which may have a substituent} and a catalyst to obtain a mixture, and polymerizing the mixture. [Claim ©] The photosensitive resin composition according to claim 4 or 5, wherein the ratic of the peak area derived from a carboxylic acid of the ester bond and the peak area derived from an alcohol of the ester bond in the *H- NMR spectrum of the polyorganosiloxane is decreased by 10 to 40% compared to the mixture of the alkoxysilane compcund and the silanol compound before polymerization.[Claim 7] A photosensitive resin composition comprising: (a) 100 parts by mass of a polyocrgancosiloxane; and (b) from 0.01 to 30 parts by mass cof a photopolymerization initiator; wherein the polvorganosiloxane is obtained by means of a method of mixing at least one alkoxysilane compound represented by following general formula (1): R'aR%S1 (ORY) 4-amp (1) {wherein R' is an ester bond-containing organic group having a carbon number of 2 to 17, and at least one R' has an acryloyl group or a methacryloyl group; R? is, when a plurality of R%s are present, each is independently, an aliphatic group having a carbon number of 1 to 10, which may have a substituent; R® is, when a plurality of Rs are present, each is independently, a methyl group or an ethyl group; a is an integer of 1 or 2: b is an integer of 0, 1 or 2; and atb is 3 or less},— HO — at least one silanol compound represented by following general formula (3): R'RSi (OH) (3) {wherein each of R? and R®> is an aliphatic, alicyclic or aromatic group having a carbon number of 3 to 10, which may have a substituent] and a catalyst to obtain a mixture, and polymerizing the mixture, and wherein an area having a weight average molecular weight of 1,050 or more in terms of standard polystyrene as measured by gel permeation chromatography (GPC) 1s 70% or more of the whole GPC peak area.[Claim 8] The photosensitive resin composition according to any one of claims 1 to 7, wherein the alkoxysilane compound represented by general formula {1) is at least one alkoxysilane compound represented by following general formula (4): HyC=C (R®) = (C=0) —0= (CH) n=SiR’. (OR%) 4 (4) {wherein R® is hydrogen or a methyl group; R’ is, when a plurality of R's are present, each is independently, an aliphatic group having a carbon number of 1 to 10, which may have a substituent; R® is, when a plurality of R%s are present, each is independently, a methyl group or an ethyl group; c¢ is an integer of 0, 1 or 2; d is an integer of 1, 2 or 3; ct+td is 3 or less; and n is from 1 to 14}. [Ciaim 9] The photosensitive resin composition according to any cone of claims 2, 3 and 5 to 8, wherein at least one of R* and R® in general formula (3) is an alicyclic group having a carbon number of 3 to 10, which may have a substituent.[Claim 10] The photosensitive resin composition according to any one of claims 1 to 9, further comprising (cc) from 0.1 to 1,000 parts by mass of an ethylenically unsaturated addition-pelymerizable monomer per 100 parts by mass of the polyorganosilozane.[Claim 11] The photosensitive resin composition according to claim 10, wherein the ethylenically unsaturated addition- polymerizable monomer is a compound containing an alicyclic group.[Claim 12] The photosensitive resin composition according to any one of claims 1 to 11, further comprising at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, an adhesion aid, a polymerization inhibitor, a sensitizer, an antioxidant and a smcothness-imparting agent.[Claim 13] The photosensitive resin composition according to any one of claims 1 to 12, wherein the concentration of the alkali metal or alkaline earth metal in the photosensitive resin composition is from 0.1 to 500 ppm.[Claim 14] A production process of a polyorganosiloxane, comprising the following steps of: i) producing {a) a polyorganosiloxane by mixing at least one alkoxysilane compound represented by following general formula (1):R*.R?%:S1 (OR) goamn (1) {wherein R! is an ester bond-containing organic group having a carbon number of 2 to 17, and at least one R' has an acryloyl group or a methacryloyl group; R? is, when a plurality of Rs are present, each is independently, an aliphatic group having a carbon number cf 1 to 10, which may have a substituent; Rr? is, when a plurality of R’s are present, each 1s independently, a methyl group or an ethyl group; a is an integer of 1 or 2; b is an integer of 0, 1 or 2; and a+b is 3 or less}, from 0.01 to 0.5 equivalents of water per one equivalent of OR? contained in the alkoxysilane compound present in the reaction system, and a catalyst to obtain a mixture,—- FT] and reacting the mixture at 20 to 130°C for 0.1 to 20 hours while removing an alcohcl produced by the reaction from the reaction system; and ii) washing the polyorganosiloxane with a solvent incapable of dissolving the polyorganosiloxane. [Claim 15) A production process of a polyorgancsiloxane, comprising the following steps of: 1) preducing (a) a polycrganosiloxane by mixing at least one alkoxysilane compound represented by following general formula (1): RYR%,S1 (OR?) 4-amb (1) {wherein R! is an ester bond-containing organic group having a carbon number of 2 to 17, and at least one R' has an acryloyl group or a methacryloyl group; R? is, when a plurality of R*s are present, each is independently, an aliphatic group having a carbon number of 1 to 10, which may have a substituent; R’ is, when a plurality of R’s are present, each is independently, a methyl group or an ethyl group; a is an integer of 1 or 2; b is an integer of 0, 1 or 2; and a+b is 3 or less}, at least one silanol compound represented by following general formula (3): R'R°S1 (OH), (3) {wherein each of R! and R° is an aliphatic, alicyclic or aromatic group having a carbon number of 3 to 10, which may have a substituent} and a catalyst to obtain a mixture, and reacting the mixture at 20 to 130°C for 0.1 to 20 hours while removing an alcohol produced by the reaction from the reaction system; and ii) washing the polyorganosiloxane with a solvent incapable of dissolving the polyorganosiloxane.[Claim 16] The production process according to claim 14 or 15, wherein the catalyst is at least one compound selected from the group consisting of an alkeli metal hydroxide and an aikaline earth metal hydroxide.[Claim 17] The production process according to any one of claims 14 to 16, wherein the catalyst is Ba (OH), and/or a hydrate therect.[Claim 18] The production process according to any one of claims 14 to 17, wherein the amount of the catalyst is from 0.05 to 30 mol% based on a total number of moles of silicon (Si). {Claim 19] The production process according tc any one of claims 14 to 18, wherein the amount of the catalyst is from 0.1 to 10 mol% based on a total number of moles of silicon (858i).[Claim 20] The production process according to any one of claims 14 to 19, wherein the solvent is an alcohol or an acetonitrile.[Claim 21] A cured product obtained by photocuring the photosensitive resin composition according to any one of claims 1 to 13, or a photosensitive resin composition comprising {a) a polyorganosiloxane obtained by the production process according to any one of claims 14 to 20 and (b) a photopolymerization initiator.[Claim 22] A method for producing a molded article, comprising the following steps of: filling a shape-forming mold with the photosensitive resin composition according to any one of claims 1 to 13, or a photosensitive resin composition comprising (a) a polyorganosiloxane obtained by the production process according to any one of claims 14 to 20 and (b) a photopolymerization initiator, pressing the opening of the mold against a substrate or another mold, exposing the photosensitive resin composition to light from the mold and/or substrate side to obtain a photocured product, separating the mold from the substrate, or separating the molds from both surfaces of the photocured product, and heating only the photocured product, or the photocured product with the substrate.[Claim 23] A molded article obtained by the method according to claim 22. {Claim 24] A polyorganosiloxane obtained by means of a method of mixing at least one alkoxysilane compound represented by fellowing general formula (I): RM aR*:S1 (OR?) g-gn (1) {wherein R'' is an ester bond-containing crganic group having a carbon number of 2 to 17; R? is, when a plurality of R’s are present, each is independently, an aliphatic group having a carbon number of 1 to 10, which may have a substituent; rR? is, when a plurality of R's are present, each is independently, a methyl group or an ethyl group; a is an integer of 1 or 2; b is an integer of 0, 1 or 2; and a+b is 3 or less], at least one silanol compound represented by following general formula (3): R'R’Si (OH) » (3) {wherein each of R'! and R®> is an aliphatic, alicyclic or aromatic group having a carbon number of 3 to 10, which may have a substituent} and a catalyst to obtain a mixture, and polymerizing the mixture, wherein the polyorgancsiloxane contains a structure represented by following general formula (2): =531-0-X-8i= (2) {wherein X is an organic group having a carbon number of 1 to 15}, and wherein from 5 to 60% by number of S5i atoms in the polyorgancosiloxane are contained in the structure oo 7 4 — represented by general formula (2).[Claim 25] The polyorganosiloxane according to claim 24, wherein R'' in general formula (I) is a group having an acrylic acid ester and/or a methacrylic acid ester.
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TWI801443B (en) * | 2017-10-27 | 2023-05-11 | 美商陶氏有機矽公司 | Curable polyorganosiloxane composition, cured body obtained by curing said compositions, and electronic device comprising the same |
JP2019104836A (en) * | 2017-12-13 | 2019-06-27 | 信越化学工業株式会社 | Organopolysiloxane compound and active energy ray-curable composition containing the same |
TWI698636B (en) * | 2018-12-18 | 2020-07-11 | 英業達股份有限公司 | Printing machine scraper automatic testing equipment |
KR102315376B1 (en) | 2021-03-16 | 2021-10-20 | 모멘티브퍼포먼스머티리얼스코리아 주식회사 | Silicone-based composition and cured product thereof |
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US6818721B2 (en) * | 2002-12-02 | 2004-11-16 | Rpo Pty Ltd. | Process for producing polysiloxanes and use of the same |
US7393469B2 (en) * | 2003-07-31 | 2008-07-01 | Ramazan Benrashid | High performance sol-gel spin-on glass materials |
JP2008239634A (en) * | 2005-07-12 | 2008-10-09 | Toagosei Co Ltd | Organic silicon resin having alcoholic hydroxy group, and method for producing the same |
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US20090088547A1 (en) * | 2006-10-17 | 2009-04-02 | Rpo Pty Limited | Process for producing polysiloxanes and use of the same |
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