JP7415653B2 - Curable resin composition, polymer optical waveguide, method for producing polymer optical waveguide - Google Patents
Curable resin composition, polymer optical waveguide, method for producing polymer optical waveguide Download PDFInfo
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- JP7415653B2 JP7415653B2 JP2020029860A JP2020029860A JP7415653B2 JP 7415653 B2 JP7415653 B2 JP 7415653B2 JP 2020029860 A JP2020029860 A JP 2020029860A JP 2020029860 A JP2020029860 A JP 2020029860A JP 7415653 B2 JP7415653 B2 JP 7415653B2
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- 229920000642 polymer Polymers 0.000 title claims description 63
- 239000011342 resin composition Substances 0.000 title claims description 62
- 230000003287 optical effect Effects 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 106
- 229910052731 fluorine Inorganic materials 0.000 claims description 78
- 239000011737 fluorine Substances 0.000 claims description 69
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 68
- 238000005253 cladding Methods 0.000 claims description 43
- 125000000524 functional group Chemical group 0.000 claims description 29
- 239000003505 polymerization initiator Substances 0.000 claims description 27
- 125000003118 aryl group Chemical class 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 20
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 20
- -1 methacryloyl group Chemical group 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 150000001491 aromatic compounds Chemical class 0.000 claims description 13
- 125000001153 fluoro group Chemical group F* 0.000 claims description 13
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 8
- 238000000206 photolithography Methods 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 5
- SNKGRZCNAUFJBB-UHFFFAOYSA-N 3-(2-phenylethynyl)benzene-1,2-diol Chemical class OC1=CC=CC(C#CC=2C=CC=CC=2)=C1O SNKGRZCNAUFJBB-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical class [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 claims description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 2
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 description 33
- 229920002313 fluoropolymer Polymers 0.000 description 18
- 239000004811 fluoropolymer Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 239000000470 constituent Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000004528 spin coating Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- ONUFSRWQCKNVSL-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4,5,6-pentafluorophenyl)benzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1C1=C(F)C(F)=C(F)C(F)=C1F ONUFSRWQCKNVSL-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- USPWUOFNOTUBAD-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(trifluoromethyl)benzene Chemical compound FC1=C(F)C(F)=C(C(F)(F)F)C(F)=C1F USPWUOFNOTUBAD-UHFFFAOYSA-N 0.000 description 2
- UVJSKKCWUVDYOA-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-[2,4,6-trifluoro-3,5-bis(2,3,4,5,6-pentafluorophenyl)phenyl]benzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1C1=C(F)C(C=2C(=C(F)C(F)=C(F)C=2F)F)=C(F)C(C=2C(=C(F)C(F)=C(F)C=2F)F)=C1F UVJSKKCWUVDYOA-UHFFFAOYSA-N 0.000 description 2
- RHNJVKIVSXGYBD-UHFFFAOYSA-N 10-prop-2-enoyloxydecyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCCOC(=O)C=C RHNJVKIVSXGYBD-UHFFFAOYSA-N 0.000 description 2
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UCWVSDQZAZJFEK-UHFFFAOYSA-N FC1=C(F)C(F)=C(F)C(F)=C1C(C(=C1C=2C(=C(F)C(F)=C(F)C=2F)F)F)=C(F)C(F)=C1C1=C(F)C(F)=C(F)C(F)=C1F Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1C(C(=C1C=2C(=C(F)C(F)=C(F)C=2F)F)F)=C(F)C(F)=C1C1=C(F)C(F)=C(F)C(F)=C1F UCWVSDQZAZJFEK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 2
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VERMEZLHWFHDLK-UHFFFAOYSA-N tetrahydroxybenzene Natural products OC1=CC=C(O)C(O)=C1O VERMEZLHWFHDLK-UHFFFAOYSA-N 0.000 description 2
- PRBBFHSSJFGXJS-UHFFFAOYSA-N (2,2-dimethyl-3-prop-2-enoyloxypropyl) prop-2-enoate;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O.C=CC(=O)OCC(C)(C)COC(=O)C=C PRBBFHSSJFGXJS-UHFFFAOYSA-N 0.000 description 1
- NIJWSVFNELSKMF-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=C(F)C(F)=C(F)C(F)=C1F NIJWSVFNELSKMF-UHFFFAOYSA-N 0.000 description 1
- RFOWDPMCXHVGET-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl) prop-2-enoate Chemical compound FC1=C(F)C(F)=C(OC(=O)C=C)C(F)=C1F RFOWDPMCXHVGET-UHFFFAOYSA-N 0.000 description 1
- DSESELHEBRQXBA-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=C(F)C(F)=C(F)C(F)=C1F DSESELHEBRQXBA-UHFFFAOYSA-N 0.000 description 1
- FSMJGUSJTKJBAD-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)methyl prop-2-enoate Chemical compound FC1=C(F)C(F)=C(COC(=O)C=C)C(F)=C1F FSMJGUSJTKJBAD-UHFFFAOYSA-N 0.000 description 1
- HIYIGPVBMDKPCR-UHFFFAOYSA-N 1,1-bis(ethenoxymethyl)cyclohexane Chemical compound C=COCC1(COC=C)CCCCC1 HIYIGPVBMDKPCR-UHFFFAOYSA-N 0.000 description 1
- VXDMAOXNTAQJSJ-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(1,2,2-trifluoroethenoxy)benzene Chemical compound FC(F)=C(F)OC1=C(F)C(F)=C(F)C(F)=C1F VXDMAOXNTAQJSJ-UHFFFAOYSA-N 0.000 description 1
- GZQZKLFXWPAMFW-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(1,2,2-trifluoroethenyl)benzene Chemical compound FC(F)=C(F)C1=C(F)C(F)=C(F)C(F)=C1F GZQZKLFXWPAMFW-UHFFFAOYSA-N 0.000 description 1
- BYKJIXWANUDHRW-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2-phenylethynyl)benzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1C#CC1=CC=CC=C1 BYKJIXWANUDHRW-UHFFFAOYSA-N 0.000 description 1
- PAMDUCVOZJIWOK-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-[2,3,4,5-tetrafluoro-6-(2-phenylethynyl)phenyl]benzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1C1=C(F)C(F)=C(F)C(F)=C1C#CC1=CC=CC=C1 PAMDUCVOZJIWOK-UHFFFAOYSA-N 0.000 description 1
- UWTFGHPTJQPZQP-UHFFFAOYSA-N 1,2,3,4-tetrafluoro-5,6-bis(trifluoromethyl)benzene Chemical group FC1=C(F)C(F)=C(C(F)(F)F)C(C(F)(F)F)=C1F UWTFGHPTJQPZQP-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- XDWRKTULOHXYGN-UHFFFAOYSA-N 1,3-bis(ethenoxy)-2,2-bis(ethenoxymethyl)propane Chemical compound C=COCC(COC=C)(COC=C)COC=C XDWRKTULOHXYGN-UHFFFAOYSA-N 0.000 description 1
- MWZJGRDWJVHRDV-UHFFFAOYSA-N 1,4-bis(ethenoxy)butane Chemical compound C=COCCCCOC=C MWZJGRDWJVHRDV-UHFFFAOYSA-N 0.000 description 1
- WGVVLKIKGKGXOT-UHFFFAOYSA-N 1,9-bis(ethenoxy)nonane Chemical compound C=COCCCCCCCCCOC=C WGVVLKIKGKGXOT-UHFFFAOYSA-N 0.000 description 1
- CZAVRNDQSIORTH-UHFFFAOYSA-N 1-ethenoxy-2,2-bis(ethenoxymethyl)butane Chemical compound C=COCC(CC)(COC=C)COC=C CZAVRNDQSIORTH-UHFFFAOYSA-N 0.000 description 1
- LVJZCPNIJXVIAT-UHFFFAOYSA-N 1-ethenyl-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(C=C)C(F)=C1F LVJZCPNIJXVIAT-UHFFFAOYSA-N 0.000 description 1
- PBEXVWXHXPEARD-UHFFFAOYSA-N 1-ethynyl-2,3,4,5,6-pentafluorobenzene Chemical group FC1=C(F)C(F)=C(C#C)C(F)=C1F PBEXVWXHXPEARD-UHFFFAOYSA-N 0.000 description 1
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 1
- YXWJGZQOGXGSSC-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzonitrile Chemical compound FC1=C(F)C(F)=C(C#N)C(F)=C1F YXWJGZQOGXGSSC-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- MGMSZKIPUNOMCS-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC=C MGMSZKIPUNOMCS-UHFFFAOYSA-N 0.000 description 1
- URQQDYIVGXOEDA-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethyl prop-2-enoate Chemical compound C=COCCOCCOC(=O)C=C URQQDYIVGXOEDA-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- YCPMSWJCWKUXRH-UHFFFAOYSA-N 2-[4-[9-[4-(2-prop-2-enoyloxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethyl prop-2-enoate Chemical compound C1=CC(OCCOC(=O)C=C)=CC=C1C1(C=2C=CC(OCCOC(=O)C=C)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YCPMSWJCWKUXRH-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YFLCRIVVBTUHKH-UHFFFAOYSA-N 3-[5-hydroxy-2-(2-phenylethynyl)phenyl]-4-(2-phenylethynyl)phenol Chemical group C=1C(O)=CC=C(C#CC=2C=CC=CC=2)C=1C1=CC(O)=CC=C1C#CC1=CC=CC=C1 YFLCRIVVBTUHKH-UHFFFAOYSA-N 0.000 description 1
- AODMJIOEGCBUQL-UHFFFAOYSA-N 3-ethynylphenol Chemical compound OC1=CC=CC(C#C)=C1 AODMJIOEGCBUQL-UHFFFAOYSA-N 0.000 description 1
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- NVUNTCDLAQYNFR-UHFFFAOYSA-N 4-(2-phenylethynyl)phenol Chemical compound C1=CC(O)=CC=C1C#CC1=CC=CC=C1 NVUNTCDLAQYNFR-UHFFFAOYSA-N 0.000 description 1
- QQZPJSLIXPKVHW-UHFFFAOYSA-N 4-(4-hydroxyphenyl)-2,3-bis(2-phenylethynyl)phenol Chemical group C1(=CC=CC=C1)C#CC=1C(=C(C=CC=1O)C1=CC=C(C=C1)O)C#CC1=CC=CC=C1 QQZPJSLIXPKVHW-UHFFFAOYSA-N 0.000 description 1
- SJABSRWDSPINPE-UHFFFAOYSA-N 4-[2,3-bis(4-hydroxyphenyl)phenyl]phenol Chemical compound C1=CC(O)=CC=C1C1=CC=CC(C=2C=CC(O)=CC=2)=C1C1=CC=C(O)C=C1 SJABSRWDSPINPE-UHFFFAOYSA-N 0.000 description 1
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- DGLBSXCHSLHTOP-UHFFFAOYSA-N 4-[4-hydroxy-2-(2-phenylethynyl)phenyl]-3-(2-phenylethynyl)phenol Chemical group C=1C(O)=CC=C(C=2C(=CC(O)=CC=2)C#CC=2C=CC=CC=2)C=1C#CC1=CC=CC=C1 DGLBSXCHSLHTOP-UHFFFAOYSA-N 0.000 description 1
- XRBNDLYHPCVYGC-UHFFFAOYSA-N 4-phenylbenzene-1,2,3-triol Chemical group OC1=C(O)C(O)=CC=C1C1=CC=CC=C1 XRBNDLYHPCVYGC-UHFFFAOYSA-N 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 238000001746 injection moulding Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
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- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- 238000000059 patterning Methods 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
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- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
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- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
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- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 238000001226 reprecipitation Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- 235000011121 sodium hydroxide Nutrition 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Optical Integrated Circuits (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、硬化性樹脂組成物、ポリマー光導波路、ポリマー光導波路の製造方法に関する。 The present invention relates to a curable resin composition, a polymer optical waveguide, and a method for producing a polymer optical waveguide.
通信機器の分野では、機器の小型化および通信の高速化に伴い、信号の伝送に樹脂製のポリマー光導波路を用いることへの期待が高まっている。樹脂材料としては、ノルボルネン樹脂や、シロキサン樹脂などが知られている。しかしこれらの樹脂は光通信に用いられる、例えば、1260~1360nm(O-band)、1530~1565nm(C-band)等の波長域で透明性に劣るなどの問題がある。また、これらの樹脂は耐熱性に劣るという問題もあった。
そこで最近では、透明性と耐熱性に優れた含フッ素ポリマーをポリマー光導波路材料として用いることが注目されている。
In the field of communication equipment, as devices become smaller and communication speeds increase, expectations are increasing for the use of resin polymer optical waveguides for signal transmission. Known resin materials include norbornene resin and siloxane resin. However, these resins have problems such as poor transparency in wavelength ranges used for optical communications, such as 1260 to 1360 nm (O-band) and 1530 to 1565 nm (C-band). Further, there was a problem that these resins had poor heat resistance.
Therefore, recently, attention has been paid to the use of fluorine-containing polymers, which have excellent transparency and heat resistance, as polymer optical waveguide materials.
ポリマー光導波路は、例えば下記手順で製造される。
(1)基材上に硬化性樹脂組成物を塗布し、光照射または熱で硬化させ、第一のクラッドを形成する。
(2)第一のクラッド上に硬化性樹脂組成物の塗膜を形成した後、該塗膜をフォトリソグラフィ法で加工してコアを形成する。
(3)第一のクラッドおよびコア上の一部または全部に硬化性樹脂組成物を塗布し、光照射または熱で硬化させ、第二のクラッドを形成する。
A polymer optical waveguide is manufactured, for example, by the following procedure.
(1) A curable resin composition is applied onto a base material and cured by light irradiation or heat to form a first cladding.
(2) After forming a coating film of a curable resin composition on the first cladding, the coating film is processed by photolithography to form a core.
(3) A curable resin composition is applied to part or all of the first cladding and core, and cured by light irradiation or heat to form a second cladding.
上記の場合、フォトリソグラフィ法により微細なコアを形成するため、第一のクラッドとコアとの界面で生じるコアの剥離が課題となっていた。第一のクラッドとの界面でのコアの剥離は、製造されたポリマー光導波路の断線等の問題を生じるため課題となる。 In the above case, since a fine core is formed by photolithography, peeling of the core at the interface between the first cladding and the core has been a problem. Peeling of the core at the interface with the first cladding poses a problem because it causes problems such as disconnection of the manufactured polymer optical waveguide.
特許文献1には、光導波路としてモノマーまたはオリゴマーが部分的にフッ素化された樹脂を用いることで光学特性が長時間維持される点が開示されているが、コアの剥離抑制に関しては開示も示唆もない。 Patent Document 1 discloses that optical properties are maintained for a long time by using a resin in which monomers or oligomers are partially fluorinated as an optical waveguide, but it also suggests disclosure regarding suppression of core peeling. Nor.
本発明は、これらを解決するため、クラッドとの界面でのコアの剥離を抑制することができる硬化性樹脂組成物を提供することを課題とする。 In order to solve these problems, it is an object of the present invention to provide a curable resin composition that can suppress peeling of the core at the interface with the cladding.
本発明の一態様に係る硬化性樹脂組成物は、含フッ素ポリマー(A)を100質量部、重合開始剤(B)を0.5~4質量部、及びイソシアヌレート骨格を有する化合物(C)を3~20質量部含有する。
前記含フッ素ポリマー(A)は、下記一般式(1)で表される含フッ素芳香族化合物(X)と、架橋性官能基及びフェノール性水酸基を有する化合物(Y-1)並びに架橋性官能基及びフッ素原子置換芳香環を有する化合物(Y-2)の少なくともいずれか一方と、フェノール性水酸基を3個以上有する化合物(Z)と、を含有する。
The curable resin composition according to one embodiment of the present invention contains 100 parts by mass of a fluorine-containing polymer (A), 0.5 to 4 parts by mass of a polymerization initiator (B), and a compound (C) having an isocyanurate skeleton. Contains 3 to 20 parts by mass.
The fluorine-containing polymer (A) comprises a fluorine-containing aromatic compound (X) represented by the following general formula (1), a compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group, and a crosslinkable functional group. and a compound (Y-2) having a fluorine atom-substituted aromatic ring, and a compound (Z) having three or more phenolic hydroxyl groups.
(式中、nは0~3の整数を表し、a、bはそれぞれ独立に0~3の整数を表し、Rf1及びRf2はそれぞれ独立に炭素数8以下の含フッ素アルキル基を表し、芳香環内のFはその芳香環の水素原子が全てフッ素原子で置換されていることを表す。) (In the formula, n represents an integer of 0 to 3, a and b each independently represent an integer of 0 to 3, Rf 1 and Rf 2 each independently represent a fluorine-containing alkyl group having 8 or less carbon atoms, F in an aromatic ring indicates that all hydrogen atoms in the aromatic ring are replaced with fluorine atoms.)
本発明によれば、硬化させてポリマー光導波路とした際に、クラッドとの界面でのコアの剥離を抑制できる硬化性樹脂組成物を提供できる。 According to the present invention, it is possible to provide a curable resin composition that can suppress peeling of the core at the interface with the cladding when it is cured to form a polymer optical waveguide.
以下、本発明の硬化性樹脂組成物について説明する。
[含フッ素ポリマー(A)]
本実施形態にかかる含フッ素ポリマー(A)は、後述する含フッ素芳香族化合物(X)と、架橋性官能基及びフェノール性水酸基を有する化合物(Y-1)並びに架橋性官能基及びフッ素原子置換芳香環を有する化合物(Y-2)の少なくともいずれか一方と、フェノール性水酸基を3個以上有する化合物(Z)と、を含有する。
The curable resin composition of the present invention will be explained below.
[Fluorine-containing polymer (A)]
The fluorine-containing polymer (A) according to the present embodiment includes a fluorine-containing aromatic compound (X) described below, a compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group, and a crosslinkable functional group and a fluorine atom substituted compound (Y-1). Contains at least one of the compounds (Y-2) having an aromatic ring and a compound (Z) having three or more phenolic hydroxyl groups.
含フッ素ポリマー(A)の数平均分子量は、1×103以上が好ましく、1.5×103以上がより好ましく、また、5×105以下が好ましく、1×105以下がより好ましい。この範囲の場合、硬化性樹脂組成物としての塗布特性が良好であり、得られた硬化膜は良好な耐熱性、機械特性、及び耐溶剤性等を有する。 The number average molecular weight of the fluorine-containing polymer (A) is preferably 1 x 10 3 or more, more preferably 1.5 x 10 3 or more, and preferably 5 x 10 5 or less, more preferably 1 x 10 5 or less. In the case of this range, the coating properties as a curable resin composition are good, and the obtained cured film has good heat resistance, mechanical properties, solvent resistance, etc.
[含フッ素芳香族化合物(X)]
含フッ素芳香族化合物(X)は、下記一般式(1)で表される化合物である。
[Fluorine-containing aromatic compound (X)]
The fluorine-containing aromatic compound (X) is a compound represented by the following general formula (1).
(一般式(1)中、nは0~3の整数を表し、a、bは各々独立して0~3の整数を表し、Rf1及びRf2はそれぞれ独立して炭素数8以下の含フッ素アルキル基を表し、芳香環内のFはその芳香環の水素原子が全てフッ素原子で置換されていることを表す。) (In general formula (1), n represents an integer of 0 to 3, a and b each independently represent an integer of 0 to 3, and Rf 1 and Rf 2 each independently represent a carbon number of 8 or less. Represents a fluorine alkyl group, and the F in the aromatic ring represents that all hydrogen atoms in the aromatic ring are substituted with fluorine atoms.)
一般式(1)中、Rf1及びRf2は炭素数8以下、好ましくは炭素数3以下の含フッ素アルキル基である。中でも、耐熱性の観点より、ペルフルオロアルキル基が好ましい。具体例としては、ペルフルオロメチル基、ペルフルオロエチル基、ペルフルオロプロピル基、ペルフルオロブチル基、ペルフルオロヘキシル基、ペルフルオロオクチル基が挙げられる。 In general formula (1), Rf 1 and Rf 2 are fluorine-containing alkyl groups having 8 or less carbon atoms, preferably 3 or less carbon atoms. Among these, perfluoroalkyl groups are preferred from the viewpoint of heat resistance. Specific examples include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluorohexyl group, and perfluorooctyl group.
Rf1及びRf2が多くなると製造が困難となるので、これらRf1及びRf2の数であるa及びbはそれぞれ独立に0~2が好ましく、0が最も好ましい。なお、a、bが2以上である場合、複数存在するRf1、Rf2の構造は同一でも異なっていてもよい。 If Rf 1 and Rf 2 increase, production becomes difficult, so a and b, which are the numbers of Rf 1 and Rf 2 , are each independently preferably from 0 to 2, and most preferably 0. Note that when a and b are 2 or more, the structures of a plurality of Rf 1 and Rf 2 may be the same or different.
一般式(1)中、nは0~3の整数であり、好ましくは1~3の整数である。含フッ素芳香族化合物(X)は、一般式(1)においてn=0の場合は、ペルフルオロベンゼン、ペルフルオロトルエン、ペルフルオロキシレン;n=1の場合は、ペルフルオロビフェニル;n=2の場合は、ペルフルオロテルフェニル;n=3の場合は、ペルフルオロ(1,3,5-トリフェニルベンゼン)、ペルフルオロ(1,2,4-トリフェニルベンゼン)が好ましく、特に、ペルフルオロトルエン、ペルフルオロ(1,3,5-トリフェニルベンゼン)、ペルフルオロ(1,2,4-トリフェニルベンゼン)、ペルフルオロビフェニルが好ましい。
含フッ素芳香族化合物(X)は単独で用いても、2種以上混合して用いてもよい。n=3の場合は、含フッ素ポリマー(A)に分岐構造が導入されるため硬化物の耐熱性を向上させることができる。得られる硬化物の誘電率と耐熱性のバランスに優れ、かつ硬化物の可とう性が高くなる点で、含フッ素芳香族化合物(X)としては、ペルフルオロビフェニルが最も好ましい。
In general formula (1), n is an integer from 0 to 3, preferably from 1 to 3. In the general formula (1), when n=0, the fluorine-containing aromatic compound (X) is perfluorobenzene, perfluorotoluene, perfluoroxylene; when n=1, perfluorobiphenyl; when n=2, perfluorobiphenyl; Terphenyl; When n=3, perfluoro(1,3,5-triphenylbenzene) and perfluoro(1,2,4-triphenylbenzene) are preferred, particularly perfluorotoluene and perfluoro(1,3,5-triphenylbenzene). -triphenylbenzene), perfluoro(1,2,4-triphenylbenzene), and perfluorobiphenyl are preferred.
The fluorine-containing aromatic compound (X) may be used alone or in combination of two or more. When n=3, a branched structure is introduced into the fluoropolymer (A), so that the heat resistance of the cured product can be improved. As the fluorine-containing aromatic compound (X), perfluorobiphenyl is most preferable because the obtained cured product has an excellent balance of dielectric constant and heat resistance, and the cured product has high flexibility.
[化合物(Y-1)]
化合物(Y-1)は、架橋性官能基及びフェノール性水酸基を有する化合物である。
具体的には、4-ヒドロキシスチレン、4-アセトキシスチレン等の反応性二重結合を有するフェノール類;3-エチニルフェノール、4-フェニルエチニルフェノール、4-(4-フルオロフェニル)エチニルフェノール等のエチニルフェノール類や、2,2’-ビス(フェニルエチニル)-5,5’-ジヒドロキシビフェニル、2,2’-ビス(フェニルエチニル)-4,4’-ジヒドロキシビフェニル等のビス(フェニルエチニル)ジヒドロキシビフェニル類;4,4’-ジヒドロキシトラン、3,3’-ジヒドロキシトラン等のジヒドロキシジフェニルアセチレン類が挙げられる。
これらは単独で用いても、2種以上を混合して用いてもよい。これらの中でも含フッ素芳香族化合物(X)との反応効率の観点から反応性二重結合を有するフェノール類が好ましく、4-アセトキシスチレンがより好ましい。
[Compound (Y-1)]
Compound (Y-1) is a compound having a crosslinkable functional group and a phenolic hydroxyl group.
Specifically, phenols having reactive double bonds such as 4-hydroxystyrene and 4-acetoxystyrene; ethynyls such as 3-ethynylphenol, 4-phenylethynylphenol, and 4-(4-fluorophenyl)ethynylphenol; Phenols and bis(phenylethynyl)dihydroxybiphenyl such as 2,2'-bis(phenylethynyl)-5,5'-dihydroxybiphenyl and 2,2'-bis(phenylethynyl)-4,4'-dihydroxybiphenyl. dihydroxydiphenylacetylenes such as 4,4'-dihydroxytran and 3,3'-dihydroxytran.
These may be used alone or in combination of two or more. Among these, phenols having a reactive double bond are preferred from the viewpoint of reaction efficiency with the fluorine-containing aromatic compound (X), and 4-acetoxystyrene is more preferred.
[化合物(Y-2)]
化合物(Y-2)は、架橋性官能基及びフッ素原子置換芳香環を有する化合物である。
具体的には、ペンタフルオロスチレン、ペンタフルオロベンジルアクリレート、ペンタフルオロベンジルメタクリレート、ペンタフルオロフェニルアクリレート、ペンタフルオロフェニルメタクリレート、ペルフルオロスチレン、ペンタフルオロフェニルトリフルオロビニルエーテル、3-(ペンタフルオロフェニル)ペンタフルオロプロペン-1等の反応性二重結合を有する含フッ素アリール類;ペンタフルオロベンゾニトリル等のシアノ基を有する含フッ素アリール類;ペンタフルオロフェニルアセチレン、ノナフルオロビフェニルアセチレン等の三重結合を有する含フッ素アリールアセチレン類;フェニルエチニルペンタフルオロベンゼン、フェニルエチニルノナフルオロビフェニル、デカフルオロトラン等の含フッ素ジアリールアセチレン類が挙げられる。
これらは単独で用いても2種以上を混合して用いてもよい。比較的低温で架橋反応が進行し、かつ得られる含フッ素ポリマー(A)の硬化物の耐熱性が高くなることから、反応性二重結合を有する含フッ素アリール類、三重結合を有する含フッ素アリールアセチレン類が好ましい。
[Compound (Y-2)]
Compound (Y-2) is a compound having a crosslinkable functional group and a fluorine atom-substituted aromatic ring.
Specifically, pentafluorostyrene, pentafluorobenzyl acrylate, pentafluorobenzyl methacrylate, pentafluorophenyl acrylate, pentafluorophenyl methacrylate, perfluorostyrene, pentafluorophenyl trifluorovinyl ether, 3-(pentafluorophenyl)pentafluoropropene- Fluorine-containing aryls having a reactive double bond such as 1; Fluorine-containing aryls having a cyano group such as pentafluorobenzonitrile; Fluorine-containing arylacetylenes having a triple bond such as pentafluorophenylacetylene, nonafluorobiphenylacetylene, etc. Examples include fluorine-containing diarylacetylenes such as phenylethynylpentafluorobenzene, phenylethynylnonafluorobiphenyl, and decafluorotolane.
These may be used alone or in combination of two or more. Since the crosslinking reaction proceeds at a relatively low temperature and the heat resistance of the resulting cured fluoropolymer (A) increases, fluorine-containing aryls having a reactive double bond and fluorine-containing aryls having a triple bond are used. Acetylenes are preferred.
前記化合物(Y-1)および化合物(Y-2)はいずれか一方のみ用いてもよく、両方用いてもよいが、後述する製造方法の観点から化合物(Y-1)を用いることが好ましい。
化合物(Y-1)および化合物(Y-2)は架橋性官能基を有することにより、硬化させた際に、低誘電率、低吸水率及び高耐熱性を同時に満足する硬化物が得られる。
The compound (Y-1) and the compound (Y-2) may be used alone or both, but it is preferable to use the compound (Y-1) from the viewpoint of the production method described below.
Since Compound (Y-1) and Compound (Y-2) have a crosslinkable functional group, when cured, a cured product can be obtained that satisfies low dielectric constant, low water absorption, and high heat resistance at the same time.
[フェノール性水酸基を3個以上有する化合物(Z)]
化合物(Z)は、フェノール性水酸基を3個以上有する化合物である。化合物(Z)におけるフェノール性水酸基の数は、3~6個が好ましく、3個または4個が特に好ましい。なお、化合物(Z)は架橋性官能基を有さないため、化合物(Y-1)とは明確に区別できる。
[Compound (Z) having 3 or more phenolic hydroxyl groups]
Compound (Z) is a compound having three or more phenolic hydroxyl groups. The number of phenolic hydroxyl groups in compound (Z) is preferably 3 to 6, particularly preferably 3 or 4. Note that since compound (Z) does not have a crosslinkable functional group, it can be clearly distinguished from compound (Y-1).
具体的には、トリヒドロキシベンゼン、トリヒドロキシビフェニル、トリヒドロキシナフタレン、1,1,1-トリス(4-ヒドロキシフェニル)エタン、トリス(4-ヒドロキシフェニル)ベンゼン、テトラヒドロキシベンゼン、テトラヒドロキシビフェニル、テトラヒドロキシビナフチル、テトラヒドロキシスピロインダン類が挙げられる。
得られる硬化膜の可とう性が高くなることから、化合物(Z)としてはフェノール性水酸基を3個有する化合物が好ましく、その中でも、得られる硬化物の誘電率が低くなることから、トリヒドロキシベンゼン、1,1,1-トリス(4-ヒドロキシフェニル)エタンがより好ましく、トリヒドロキシベンゼンがさらに好ましい。
Specifically, trihydroxybenzene, trihydroxybiphenyl, trihydroxynaphthalene, 1,1,1-tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)benzene, tetrahydroxybenzene, tetrahydroxybiphenyl, tetra Examples include hydroxybinaphthyl and tetrahydroxyspiroindanes.
As the compound (Z), a compound having three phenolic hydroxyl groups is preferable because the flexibility of the cured film obtained is high, and among these, trihydroxybenzene is preferable because the dielectric constant of the cured product obtained is low. , 1,1,1-tris(4-hydroxyphenyl)ethane are more preferred, and trihydroxybenzene is even more preferred.
フェノール性水酸基を3個以上有する化合物(Z)を用いることにより、ポリマー鎖に分岐構造を導入し、分子構造を三次元化する。そのことで、ポリマーの自由体積を増大させて低密度化、すなわち低誘電率化が達成できる。また、一般的に、芳香環を有する直鎖状ポリマーは芳香環のスタッキングによる分子の配向が起き易いが、本実施形態にかかる硬化性樹脂組成物では、分岐構造を導入することにより分子の配向が抑えられ、その結果、複屈折が小さくなる。 By using a compound (Z) having three or more phenolic hydroxyl groups, a branched structure is introduced into the polymer chain, making the molecular structure three-dimensional. By doing so, the free volume of the polymer can be increased to achieve a lower density, that is, a lower dielectric constant. Furthermore, in general, linear polymers having aromatic rings tend to have molecular orientation due to stacking of aromatic rings, but in the curable resin composition according to this embodiment, molecular orientation is achieved by introducing a branched structure. is suppressed, and as a result, birefringence is reduced.
[含フッ素ポリマー(A)の製造方法]
含フッ素ポリマー(A)は、下記(i)または(ii)の方法のいずれか又は両方で製造することができる。
(i)一般式(1)で示される含フッ素芳香族化合物(X)と、フェノール性水酸基を3個以上有する化合物(Z)と、架橋性官能基及びフェノール性水酸基を有する化合物(Y-1)と、を脱HF剤存在下に縮合反応させる方法。
(ii)一般式(1)で示される含フッ素芳香族化合物(X)と、フェノール性水酸基を3個以上有する化合物(Z)と、架橋性官能基及びフッ素原子置換芳香環を有する化合物(Y-2)と、を脱HF剤存在下に縮合反応させる方法。
[Method for producing fluoropolymer (A)]
The fluoropolymer (A) can be produced by either or both of the following methods (i) and (ii).
(i) A fluorine-containing aromatic compound (X) represented by the general formula (1), a compound (Z) having three or more phenolic hydroxyl groups, and a compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group. ) and a condensation reaction in the presence of an HF removing agent.
(ii) A fluorine-containing aromatic compound (X) represented by the general formula (1), a compound (Z) having three or more phenolic hydroxyl groups, and a compound (Y) having a crosslinkable functional group and a fluorine atom-substituted aromatic ring. -2) and a method of carrying out a condensation reaction in the presence of an HF removing agent.
なお、上記(i)及び(ii)の両方の方法により含フッ素ポリマー(A)を製造する場合は、含フッ素芳香族化合物(X)と、化合物(Z)と、化合物(Y-1)と、化合物(Y-2)と、を脱HF剤存在下に縮合反応させる。 In addition, when producing the fluorine-containing polymer (A) by both methods (i) and (ii) above, the fluorine-containing aromatic compound (X), the compound (Z), the compound (Y-1) and , and compound (Y-2) are subjected to a condensation reaction in the presence of an HF removing agent.
なお上記(i)又は(ii)の方法のいずれにおいても、縮合反応は一段階で全てを反応させてもよく、多段階に分けて反応させてもよい。また反応原料のうち特定の化合物を先に優先的に反応させた後に、引き続いて他の化合物を反応させてもよい。縮合反応を多段階に分けて行う場合に、途中で得られた中間生成物は、反応系から分離し精製した後に、後続の反応(縮合反応)に用いてもよい。反応の場において原料化合物は一括で投入されてもよく、連続的に投入されてもよく、間歇的に投入されてもよい。 In either method (i) or (ii) above, the condensation reaction may be carried out entirely in one step, or may be carried out in multiple steps. Alternatively, a specific compound among the reaction raw materials may be preferentially reacted first, and then other compounds may be reacted subsequently. When the condensation reaction is carried out in multiple stages, intermediate products obtained during the process may be used in the subsequent reaction (condensation reaction) after being separated from the reaction system and purified. In the reaction site, the raw material compounds may be added all at once, continuously, or intermittently.
脱HF剤としては、塩基性化合物が好ましく、特にアルカリ金属の、炭酸塩、炭酸水素塩又は水酸化物が好ましい。具体的には、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、水酸化ナトリウム、水酸化カリウムが挙げられる。 As the HF removing agent, basic compounds are preferred, and carbonates, hydrogen carbonates, or hydroxides of alkali metals are particularly preferred. Specific examples include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, and potassium hydroxide.
[重合開始剤(B)]
本実施形態の重合開始剤(B)は、重合反応が開始されれば特に限定されないが、ベンゾインアルキルエーテル誘導体、ベンゾフェノン誘導体、α-アミノアルキルフェノン系、オキシムエステル誘導体、チオキサントン誘導体、アントラキノン誘導体、アシルホスフィンオキサイド誘導体、グリオキシエステル誘導体、有機過酸化物系、トリハロメチルトリアジン誘導体、及びチタノセン誘導体からなる群から選択される1つ以上を含有することが好ましく、これらの中でも、オキシムエステル誘導体がラジカル生成効率の観点からより好ましい。
[Polymerization initiator (B)]
The polymerization initiator (B) of this embodiment is not particularly limited as long as it starts the polymerization reaction, but includes benzoin alkyl ether derivatives, benzophenone derivatives, α-aminoalkylphenone derivatives, oxime ester derivatives, thioxanthone derivatives, anthraquinone derivatives, acyl It is preferable to contain one or more selected from the group consisting of phosphine oxide derivatives, glyoxyester derivatives, organic peroxides, trihalomethyltriazine derivatives, and titanocene derivatives, and among these, oxime ester derivatives are more effective at generating radicals. More preferred from the viewpoint of efficiency.
オキシムエステル誘導体として好適な市販品としては、チバスペシャリティーケミカルズ社製のIRGACURE OXE01、IRGACURE OXE02および、IRGACURE OXE04が挙げられる。 Commercial products suitable as oxime ester derivatives include IRGACURE OXE01, IRGACURE OXE02, and IRGACURE OXE04 manufactured by Ciba Specialty Chemicals.
[イソシアヌレート骨格を有する化合物(C)]
本実施形態のイソシアヌレート骨格を有する化合物(C)はイソシアネートの三量体構造を有すれば特に限定されないが、以下の一般式(2)で表される化合物が好ましい。
[Compound (C) having an isocyanurate skeleton]
The compound (C) having an isocyanurate skeleton of the present embodiment is not particularly limited as long as it has an isocyanate trimer structure, but a compound represented by the following general formula (2) is preferable.
(一般式(2)中、R1~R3は各々独立して、水素原子、置換基を有していてもよい炭素数1~10のアルキル基、シクロアルキル基、アクリロイル基、メタクリロイル基、チオール基、エポキシ基、カルボキシ基を表し、前記置換基はシクロアルキル基、アクリロイル基、メタクリロイル基、チオール基、エポキシ基、カルボキシ基、-OCOCR4=CR5R6、-OCO-CH2CH(SH)-CH3、及び-OCO-CH2CH2-SHからなる群より選ばれる少なくとも1種であり、R4~R6は各々独立して、水素原子、ヒドロキシ基、炭素数1~10のアルキル基、又はチオール基を表す。) (In general formula (2), R 1 to R 3 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, a cycloalkyl group, an acryloyl group, a methacryloyl group, It represents a thiol group, an epoxy group, or a carboxy group, and the substituent group is a cycloalkyl group, an acryloyl group, a methacryloyl group, a thiol group, an epoxy group, a carboxy group, -OCOCR 4 =CR 5 R 6 , -OCO-CH 2 CH ( at least one member selected from the group consisting of SH)-CH 3 and -OCO-CH 2 CH 2 -SH, and R 4 to R 6 each independently represent a hydrogen atom, a hydroxy group, or a carbon number of 1 to 10 represents an alkyl group or a thiol group.)
これらの中でも、R1~R3は各々独立して、置換基として-OCOCR4=CR5R6を有する炭素数1~3のアルキル基が好ましく、かかる置換基によりアルキル基の末端が置換されていることがより好ましく、かかる置換基のR4~R6は水素原子またはメチル基がさらに好ましい。具体的には、アルキル基の末端が、-OCOCH=CH2、-OCOCH=CHCH3、-OCOCCH3=CH2で置換された炭素数1~3のアルキル基がさらに好ましい。
R1~R3は各々独立して、置換基として-OCO-CH2CH(SH)-CH3、-OCO-CH2CH2-SHを有する炭素数1~3のアルキル基も好ましく、これら置換基によりアルキル基の末端が置換されていることがより好ましい。
R1~R3は各々独立して、置換基としてエポキシ基を有する炭素数1~3のアルキル基も好ましく、アルキル基の末端がエポキシ基で置換された炭素数1~3のアルキル基がより好ましい。
Among these, R 1 to R 3 are each independently preferably an alkyl group having 1 to 3 carbon atoms and having -OCOCR 4 =CR 5 R 6 as a substituent, and the terminal of the alkyl group is substituted with such a substituent. It is more preferable that R 4 to R 6 of such substituents are a hydrogen atom or a methyl group. Specifically, an alkyl group having 1 to 3 carbon atoms in which the terminal end of the alkyl group is substituted with -OCOCH=CH 2 , -OCOCH=CHCH 3 , or -OCOCCH 3 =CH 2 is more preferable.
R 1 to R 3 are each independently preferably an alkyl group having 1 to 3 carbon atoms having -OCO-CH 2 CH (SH)-CH 3 or -OCO-CH 2 CH 2 -SH as a substituent; More preferably, the terminal of the alkyl group is substituted with a substituent.
R 1 to R 3 are each independently preferably an alkyl group having 1 to 3 carbon atoms and having an epoxy group as a substituent, and more preferably an alkyl group having 1 to 3 carbon atoms in which the terminal of the alkyl group is substituted with an epoxy group. preferable.
上記R1~R3は、クラッドとの界面でのコア剥離抑制の点からR1およびR2は同じ置換基が好ましく、R1~R3が全て同じ置換基であることが特に好ましい。 From the viewpoint of suppressing core separation at the interface with the cladding, R 1 to R 3 are preferably the same substituent, and it is particularly preferable that R 1 to R 3 are all the same substituent.
これらの中でも、化合物(C)として以下の式で表される化合物(2C-1)~化合物(2C-6)が特に好適に用いられる。 Among these, compounds (2C-1) to (2C-6) represented by the following formulas are particularly preferably used as compound (C).
上記の中でも、化合物(2C-5)と化合物(2C-1)がポリマー光導波路とした際のクラッドとの界面でのコアの剥離の抑制の点から好ましく、化合物(2C-1)がクラッドとの界面でのコア剥離の抑制が目視だけでなく顕微鏡による観察でも微小剥離やうねりが発生しない点からより好ましい。これは、含フッ素ポリマー(A)との反応性と共重合性により硬化物の分子量が大きくなることによって現像液によるコアの膨潤が抑制されること、また疎水性の含フッ素ポリマー(A)に添加することによってクラッドとの密着力が向上することから、コアの剥離が抑制されると推測される。 Among the above, compound (2C-5) and compound (2C-1) are preferable from the viewpoint of suppressing peeling of the core at the interface with the cladding when used as a polymer optical waveguide, and compound (2C-1) is preferable from the viewpoint of suppressing peeling of the core at the interface with the cladding. Suppression of core peeling at the interface is more preferable since minute peeling and waviness do not occur not only visually but also when observed under a microscope. This is because the molecular weight of the cured product increases due to its reactivity and copolymerizability with the fluoropolymer (A), which suppresses the swelling of the core by the developer, and also because the hydrophobic fluoropolymer (A) Since the adhesion with the cladding is improved by adding it, it is presumed that peeling of the core is suppressed.
[硬化性樹脂組成物]
本実施形態の硬化性樹脂組成物は、上記した、含フッ素ポリマー(A)と、重合開始剤(B)と、イソシアヌレート骨格を有する化合物(C)とを含む。
[Curable resin composition]
The curable resin composition of this embodiment includes the above-described fluorine-containing polymer (A), a polymerization initiator (B), and a compound having an isocyanurate skeleton (C).
含フッ素ポリマー(A)100質量部に対し、重合開始剤(B)は0.5~4質量部含有し、好ましくは後述するポリマー光導波路の光吸収特性の点から0.5~2質量部である。 The polymerization initiator (B) is contained in an amount of 0.5 to 4 parts by mass, preferably 0.5 to 2 parts by mass in view of the light absorption characteristics of the polymer optical waveguide described later, per 100 parts by mass of the fluorine-containing polymer (A). It is.
含フッ素ポリマー(A)100質量部に対し、イソシアヌレート骨格を有する化合物(C)は3~20質量部含有し、好ましくは光学特性や、後述するポリマー光導波路のコアの剥離の抑制の観点から5質量部以上であり、また、15質量部以下である。 The compound (C) having an isocyanurate skeleton is preferably contained in an amount of 3 to 20 parts by mass per 100 parts by mass of the fluorine-containing polymer (A), preferably from the viewpoint of optical properties and suppression of peeling of the core of the polymer optical waveguide described later. It is 5 parts by mass or more and 15 parts by mass or less.
[ポリマー光導波路]
本実施形態のポリマー光導波路は上記硬化性樹脂組成物を硬化させてなる。ポリマー光導波路は、コアとコアよりも屈折率が低いクラッドとで構成されることが好ましい。
コアおよびクラッドの構成材料である硬化性樹脂組成物について、コアの屈折率よりもクラッドの屈折率が低くなるように、含フッ素ポリマー(A)、重合開始剤(B)およびイソシアヌレート骨格を有する化合物(C)の混合比率を調整する方法や、後述する化合物(D)を適宜添加することによって調整する方法が挙げられる。
[Polymer optical waveguide]
The polymer optical waveguide of this embodiment is formed by curing the above-mentioned curable resin composition. Preferably, the polymer optical waveguide is composed of a core and a cladding having a lower refractive index than the core.
The curable resin composition that is the constituent material of the core and cladding has a fluorine-containing polymer (A), a polymerization initiator (B), and an isocyanurate skeleton so that the cladding has a lower refractive index than the core. Examples include a method of adjusting the mixing ratio of compound (C) and a method of adjusting by appropriately adding compound (D), which will be described later.
[コアの構成材料の好適例]
コアの構成材料としては、前記含フッ素ポリマー(A2)100質量部に対し、重合開始剤(B2)を0.5~4質量部と、イソシアヌレート骨格を有する化合物(C2)を3~20質量部含有する硬化性樹脂組成物が好ましく、含フッ素ポリマー(A2)100質量部に対し、重合開始剤(B2)を0.5~2質量部と、イソシアヌレート骨格を有する化合物(C2)を5~15質量部含有する硬化性樹脂組成物がより好ましい。
[Suitable examples of core constituent materials]
As constituent materials of the core, 0.5 to 4 parts by mass of a polymerization initiator (B2) and 3 to 20 parts by mass of a compound having an isocyanurate skeleton (C2) are used for 100 parts by mass of the fluorine-containing polymer (A2). A curable resin composition containing 0.5 to 2 parts by mass of the polymerization initiator (B2) and 5 parts by mass of the compound having an isocyanurate skeleton (C2) per 100 parts by mass of the fluoropolymer (A2) is preferable. A curable resin composition containing up to 15 parts by mass is more preferred.
[クラッドの構成材料の好適例]
クラッドの構成材料としては、前記含フッ素ポリマー(A1)又は(A3)100質量部に対し、重合開始剤(B1)又は(B3)を0.5~4質量部と、分子量が140~5000であり、架橋性官能基を有し、フッ素原子を有していない化合物(D1)又は(D3)を5~50質量部含有する硬化性樹脂組成物が好ましく、含フッ素ポリマー(A1)又は(A3)100質量部に対し、重合開始剤(B1)又は(B3)を0.5~2質量部と、分子量が140~5000であり、架橋性官能基を有し、フッ素原子を有していない化合物(D1)又は(D3)を5~50質量部含有する硬化性樹脂組成物がより好ましい。
[Suitable examples of cladding materials]
The constituent materials of the cladding include 0.5 to 4 parts by mass of a polymerization initiator (B1) or (B3) to 100 parts by mass of the fluorine-containing polymer (A1) or (A3), and a molecular weight of 140 to 5000. A curable resin composition containing 5 to 50 parts by mass of a compound (D1) or (D3) that has a crosslinkable functional group and does not have a fluorine atom is preferable, and a curable resin composition containing a fluorine-containing polymer (A1) or (A3) ) 100 parts by mass, 0.5 to 2 parts by mass of polymerization initiator (B1) or (B3), has a molecular weight of 140 to 5000, has a crosslinkable functional group, and does not have a fluorine atom. A curable resin composition containing 5 to 50 parts by mass of compound (D1) or (D3) is more preferred.
ここで、含フッ素ポリマー(A1)~(A3)はいずれも含フッ素ポリマー(A)と同義であり、コアを構成するものを含フッ素ポリマー(A2)、第一のクラッドを構成するものを含フッ素ポリマー(A1)、第二のクラッドを構成するものを含フッ素ポリマー(A3)と称する。これら含フッ素ポリマー(A1)~(A3)は、同じものを用いても、異なるものを用いてもよく、光の伝搬損失の観点から含フッ素ポリマー(A1)及び(A3)は同じであることが好ましい。また、重合開始剤(B1)~(B3)、化合物(C2)、並びに、化合物(D1)及び(D3)についても同様であり、また、同じものを用いても異なるものを用いてもよいが、光の伝搬損失の観点から、重合開始剤(B1)及び(B3)、化合物(D1)及び(D3)はそれぞれ同じであることが好ましい。 Here, fluoropolymers (A1) to (A3) are all synonymous with fluoropolymer (A), and the fluoropolymer (A2) is the one that makes up the core, and the fluoropolymer (A2) is the one that makes up the first cladding. The fluoropolymer (A1), which constitutes the second cladding, is referred to as a fluoropolymer (A3). These fluoropolymers (A1) to (A3) may be the same or different, and from the viewpoint of light propagation loss, fluoropolymers (A1) and (A3) must be the same. is preferred. The same applies to the polymerization initiators (B1) to (B3), the compound (C2), and the compounds (D1) and (D3), and the same or different ones may be used. From the viewpoint of light propagation loss, it is preferable that the polymerization initiators (B1) and (B3) and the compounds (D1) and (D3) are the same, respectively.
分子量が140~5000であり、架橋性官能基を有しフッ素原子を有していない化合物(D)としては、架橋性官能基を2個以上有することが好ましく、また、20個以下有することがより好ましく、8個以下有することが特に好ましい。架橋性官能基を2個以上有していると、分子間を架橋させることができるため、硬化膜における耐熱性を向上させ、硬化膜における加熱による膜厚減少を良好に抑えることができる。 The compound (D) having a molecular weight of 140 to 5000, having a crosslinkable functional group and having no fluorine atom, preferably has two or more crosslinkable functional groups, and preferably has 20 or less. More preferably, it is particularly preferable to have 8 or less. When it has two or more crosslinkable functional groups, it is possible to crosslink between molecules, thereby improving the heat resistance of the cured film and suppressing reduction in film thickness due to heating in the cured film.
架橋性官能基としては、ビニル基、アリル基、エチニル基、ビニルオキシ基、アリルオキシ基、アクリロイル基、アクリロイルオキシ基、メタクリロイル基、メタクリロイルオキシ基が挙げられる。これらのうちで、重合開始剤の存在下でなくても、光照射により反応を生じる点でアクリロイル基、アクリロイルオキシ基が好ましい。 Examples of the crosslinkable functional group include a vinyl group, an allyl group, an ethynyl group, a vinyloxy group, an allyloxy group, an acryloyl group, an acryloyloxy group, a methacryloyl group, and a methacryloyloxy group. Among these, acryloyl groups and acryloyloxy groups are preferred because they cause a reaction upon irradiation with light even in the absence of a polymerization initiator.
架橋性官能基を有しフッ素原子を有していない化合物(D)の具体例としては、ジペンタエリスリトールトリアクリレートトリウンデシレート、ジペンタエリスリトールペンタアクリレートモノウンデシレート、エトキシ化イソシアヌル酸トリアクリレート、ε-カプロラクトン変性トリス-(2-アクリロキシエチル)イソシアヌレート、ジペンタエリスリトールポリアクリレート、9,9-ビス[4-(2-アクリロイルオキシエトキシ)フェニル]フルオレン、ポリエチレングリコールジアクリレート、ポリエチレングリコールジメタクリレート、ポリプロピレングリコールジアクリレート、ポリプロピレングリコールジメタクリレート、エトキシ化ビスフェノールAジアクリレート、エトキシ化ビスフェノールAジメタクリレート、プロポキシ化ビスフェノールAジアクリレート、プロポキシ化ビスフェノールAジメタクリレート、1,10-デカンジオールジアクリレート、1,6-ヘキサンジオールジアクリレート、1,6-ヘキサンジオールジメタクリレート、1,4-ブタンジオールジメタクリレート、1,3-ブタンジオールジメタクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジアクリレート、1,9-ノナンジオールジアクリレート、1,9-ノナンジオールジメタクリレート、ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジメタクリレート、ペンタエリスリトールトリアクリレート、トリメチロールプロパントリアクリレート、エトキシ化トリメチロールプロパントリアクリレート、プロポキシ化トリメチロールプロパントリアクリレート、トリアリルシアヌレート、トリアリルイソシアヌレート、トリメタアリルイソシアヌレート、1,4-ブタンジオールジビニルエーテル、1,9-ノナンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、トリエチレングリコールジビニルエーテル、トリメチロールプロパントリビニルエーテル、ペンタエリスリトールテトラビニルエーテル、アクリル酸2-(2-ビニロキシエトキシ)エチル、メタクリル酸2-(2-ビニロキシエトキシ)エチル、トリメチロールプロパンジアリルエーテル、ペンタエリスリトールトリアリルエーテル、ジペンタエリスリトールヘキサアクリレート、ペンタエリスリトールテトラアクリレート等が挙げられる。
またポリエステルアクリレート(二価アルコールと二塩基酸との縮合物の両末端をアクリル酸で修飾した化合物:東亞合成社製、商品名アロニックス(M-6100、M-6200、M-6250、M-6500);多価アルコールと多塩基酸との縮合物の水酸基末端をアクリル酸で修飾した化合物:東亞合成社製、商品名アロニックス(M-7100、M-7300K、M-8030、M-8060、M-8100、M-8530、M-8560、M-9050))も利用できる。これらは市販品から入手できる。
Specific examples of the compound (D) having a crosslinkable functional group and no fluorine atom include dipentaerythritol triacrylate triundecylate, dipentaerythritol pentaacrylate monoundecylate, and ethoxylated isocyanuric acid triacrylate. , ε-caprolactone modified tris-(2-acryloxyethyl) isocyanurate, dipentaerythritol polyacrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, polyethylene glycol diacrylate, polyethylene glycol diacrylate Methacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, propoxylated bisphenol A diacrylate, propoxylated bisphenol A dimethacrylate, 1,10-decanediol diacrylate, 1 , 6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, hydroxypivalic acid neopentyl glycol diacrylate, 1,9-nonanediol Diacrylate, 1,9-nonanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate , triallyl cyanurate, triallyl isocyanurate, trimetaallyl isocyanurate, 1,4-butanediol divinyl ether, 1,9-nonanediol divinyl ether, cyclohexanedimethanol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane Trivinyl ether, pentaerythritol tetravinyl ether, 2-(2-vinyloxyethoxy)ethyl acrylate, 2-(2-vinyloxyethoxy)ethyl methacrylate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, dipentaerythritol hexa Examples include acrylate, pentaerythritol tetraacrylate, and the like.
Polyester acrylate (a compound in which both ends of a condensate of dihydric alcohol and dibasic acid are modified with acrylic acid; manufactured by Toagosei Co., Ltd., trade name: Aronix (M-6100, M-6200, M-6250, M-6500) ); Compound in which the hydroxyl end of a condensate of polyhydric alcohol and polybasic acid is modified with acrylic acid: Manufactured by Toagosei Co., Ltd., trade name Aronix (M-7100, M-7300K, M-8030, M-8060, M -8100, M-8530, M-8560, M-9050)) are also available. These are commercially available.
これらの中でも、ポリプロピレングリコールジメタクリレート、1,10-デカンジオールジアクリレートが硬化膜の成形性が良好であるので好ましい。 Among these, polypropylene glycol dimethacrylate and 1,10-decanediol diacrylate are preferred because they provide good moldability of the cured film.
ポリマー光導波路の製造方法は特に限定されず、各種方法を用いることができる。具体的には、複製(スタンパ)法、直接露光法、反応性イオンエッチング(RIE)とフォトリソグラフィプロセスを組み合わせる方法、射出成形をもとにした方法、フォトブリーチング法、直接描画法、自己形成法等を使用できる。 The method for manufacturing the polymer optical waveguide is not particularly limited, and various methods can be used. Specifically, these include replication (stamper) methods, direct exposure methods, methods that combine reactive ion etching (RIE) and photolithography processes, methods based on injection molding, photobleaching methods, direct writing methods, and self-forming methods. law etc. can be used.
本実施形態のポリマー光導波路の製造方法の一例について説明する。
かかる製造方法では下記工程を含む。
基材上に硬化性樹脂組成物(R1)を塗布し、光照射または熱で硬化させ、第一のクラッドを形成する工程、
前記第一のクラッド上に硬化性樹脂組成物(R2)の塗膜を形成し、前記塗膜をフォトリソグラフィ法で加工してコアを形成する工程、及び
前記第一のクラッドおよび前記コア上の一部または全部に硬化性樹脂組成物(R3)を塗布し、光照射または熱で硬化させる工程。
An example of the method for manufacturing the polymer optical waveguide of this embodiment will be described.
This manufacturing method includes the following steps.
a step of applying a curable resin composition (R1) on a substrate and curing it with light irradiation or heat to form a first cladding;
forming a coating film of the curable resin composition (R2) on the first cladding and processing the coating film by photolithography to form a core; A step of applying the curable resin composition (R3) partially or entirely and curing it with light irradiation or heat.
第一のクラッドを形成する工程では、まず、スピンコート法により、基板の上に含フッ素ポリマー(A1)を100質量部、重合開始剤(B1)を0.5~4質量部、及び分子量が140~5000であり、架橋性官能基を有し、フッ素原子を有していない化合物(D1)を5~50質量部含有する硬化性樹脂組成物(R1)を含有する塗布液を塗布する。続いて、光照射又は熱により該硬化性樹脂組成物(R1)を硬化させて第一のクラッドを形成する。
スピンコート法に代えて、スリットコート、ディップコート等の方法を用いてもよい。また硬化には光照射を用いることがより好ましい。
In the step of forming the first cladding, first, 100 parts by mass of the fluorine-containing polymer (A1), 0.5 to 4 parts by mass of the polymerization initiator (B1), and a molecular weight of A coating liquid containing a curable resin composition (R1) containing 5 to 50 parts by mass of a compound (D1) having a crosslinkable functional group and no fluorine atom is applied. Subsequently, the curable resin composition (R1) is cured by light irradiation or heat to form a first cladding.
Instead of the spin coating method, methods such as slit coating and dip coating may be used. Moreover, it is more preferable to use light irradiation for curing.
次にコアを形成する工程では、スピンコート法により、第一のクラッドの上に含フッ素ポリマー(A2)を100質量部、重合開始剤(B2)を0.5~4質量部、及びイソシアヌレート骨格を有する化合物(C2)を3~20質量部を含有する硬化性樹脂組成物(R2)を含有する塗布液を塗布し、塗膜を形成する。続いて、フォトリソグラフィ法により、該硬化性樹脂組成物(R2)の塗膜に対するパターニング等の加工を行い、第一のクラッドの上にコアを形成する。このとき、コアの幅が光の伝搬方向に沿って同一または異なる形状を有していてもよい。異なる形状を形成するには、コアの幅が光の伝搬方向に沿って異なる形状のフォトマスクを用いて露光を行った後、現像することによってコアを形成すればよい。異なる形状とは、コアの幅が光の伝搬方向に沿って先細りになる場合や、テーパー状になる場合を示す。また、スピンコート法に代えて、スリットコート、ディップコート等の方法を用いてもよい。
コアを形成した後、必要に応じてポストベーク(100℃以上で加熱)を行ってもよい。
Next, in the step of forming the core, 100 parts by mass of the fluorine-containing polymer (A2), 0.5 to 4 parts by mass of the polymerization initiator (B2), and isocyanurate are coated on the first cladding by spin coating. A coating liquid containing a curable resin composition (R2) containing 3 to 20 parts by mass of a compound (C2) having a skeleton is applied to form a coating film. Subsequently, the coating film of the curable resin composition (R2) is subjected to processing such as patterning by photolithography to form a core on the first cladding. At this time, the width of the core may have the same or different shapes along the light propagation direction. In order to form different shapes, the cores may be formed by performing exposure using a photomask whose core width differs along the light propagation direction, followed by development. The different shapes refer to cases in which the width of the core is tapered along the light propagation direction or in a tapered shape. Furthermore, instead of the spin coating method, methods such as slit coating and dip coating may be used.
After forming the core, post-baking (heating at 100° C. or higher) may be performed if necessary.
次に第二のクラッドを形成する工程として、スピンコート法により、前記第一のクラッド及び前記コア上の一部または全部に含フッ素ポリマー(A3)を100質量部、重合開始剤(B3)を0.5~4質量部、及び分子量が140~5000であり、架橋性官能基を有し、フッ素原子を有していない化合物(D3)を5~50質量部を含有する硬化性樹脂組成物(R3)を含有する塗布液を塗布する。続いて、光照射又は熱により該硬化性樹脂組成物(R3)を硬化させて第二のクラッドを形成する。第二のクラッドを形成する際、フォトリソグラフィ法より、第二のクラッドが存在せず、コアおよび該コアの周辺の第一のクラッドが露出したコア露出部を形成することもできる。
スピンコート法に代えて、スリットコート、ディップコート等の方法を用いてもよい。また硬化には光照射を用いることがより好ましい。
Next, as a step of forming a second clad, 100 parts by mass of a fluorine-containing polymer (A3) and a polymerization initiator (B3) are applied to a part or all of the first clad and the core by a spin coating method. A curable resin composition containing 0.5 to 4 parts by mass and 5 to 50 parts by mass of a compound (D3) having a molecular weight of 140 to 5000, having a crosslinkable functional group, and having no fluorine atom. A coating liquid containing (R3) is applied. Subsequently, the curable resin composition (R3) is cured by light irradiation or heat to form a second cladding. When forming the second cladding, a core exposed portion in which the second cladding does not exist and the core and the first cladding around the core are exposed can also be formed using a photolithography method.
Instead of the spin coating method, methods such as slit coating and dip coating may be used. Moreover, it is more preferable to use light irradiation for curing.
前記硬化性樹脂組成物(R1)および硬化性樹脂組成物(R3)の組成割合は、光の伝搬損失の観点から同じことが好ましい。また、硬化性樹脂組成物(R2)における含フッ素ポリマー(A2)及び重合開始剤(B2)は、含フッ素ポリマー(A1)又は(A3)、及び重合開始剤(B1)及び(B3)と、光の伝播損失の点から異なることが好ましい。 The composition ratios of the curable resin composition (R1) and the curable resin composition (R3) are preferably the same from the viewpoint of light propagation loss. In addition, the fluorine-containing polymer (A2) and the polymerization initiator (B2) in the curable resin composition (R2) are the fluorine-containing polymer (A1) or (A3), and the polymerization initiators (B1) and (B3), It is preferable that they differ from the viewpoint of light propagation loss.
本実施形態のポリマー光導波路は、シングルモード光導波路が好ましい。 The polymer optical waveguide of this embodiment is preferably a single mode optical waveguide.
以下では実施例により本発明をより具体的に説明するが、本発明は後述する実施例に限定されず、本発明の要旨を変更しない限り、種々の変更が可能である。
なお、例1及び例2は実施例であり、例3及び例4は比較例である。
The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to the Examples described below, and various modifications can be made without changing the gist of the present invention.
Note that Example 1 and Example 2 are examples, and Example 3 and Example 4 are comparative examples.
[合成例]
N,N-ジメチルアセトアミド(以下、DMAcという)溶媒中で、ペルフルオロビフェニル(225g)と、1,3,5-トリヒドロキシベンゼン(40g)とを、炭酸カリウムの存在下に、40℃で6時間反応させた。その後、続けて4-アセトキシスチレン(30g)を48質量%水酸化カリウム水溶液の存在下に反応させて含フッ素ポリマーを合成した。得られた含フッ素ポリマーのDMAc溶液を塩酸水溶液(3.5質量%水溶液)に投入することで再沈精製し、真空乾燥して粉末状の含フッ素ポリマー(A)を得た。
[Synthesis example]
Perfluorobiphenyl (225 g) and 1,3,5-trihydroxybenzene (40 g) were mixed in N,N-dimethylacetamide (hereinafter referred to as DMAc) solvent in the presence of potassium carbonate at 40°C for 6 hours. Made it react. Thereafter, 4-acetoxystyrene (30 g) was reacted in the presence of a 48% by mass aqueous potassium hydroxide solution to synthesize a fluoropolymer. The obtained DMAc solution of the fluoropolymer was poured into an aqueous hydrochloric acid solution (3.5% by mass aqueous solution) for reprecipitation purification, and vacuum-dried to obtain a powdery fluoropolymer (A).
[調製例1]
例1のコアの形成に用いる硬化性樹脂組成物(R-20)を以下の手順で調製した。
上記で得られた含フッ素ポリマー(A)100質量部に対して、2質量部となるように重合開始剤(B)としてIRGACURE OXE01(製品名、チバスペシャリティーケミカルズ社製)、0.03質量部となるように4-tert-ブチルカテコール(東京化成工業社製)を添加した後、ミックスローターを用いて室温で48時間混合した。この溶液の含フッ素ポリマー(A)100質量部に対して、5質量部となるようにイソシアヌレート骨格を有する化合物(C)として化合物(2C-1)(FA-731A、日立化成社製)を添加して、硬化性樹脂組成物(R-20)を得た。
[Preparation example 1]
A curable resin composition (R-20) used for forming the core of Example 1 was prepared according to the following procedure.
IRGACURE OXE01 (product name, manufactured by Ciba Specialty Chemicals) as a polymerization initiator (B), 0.03 parts by mass, to 100 parts by mass of the fluorine-containing polymer (A) obtained above, so that the amount is 2 parts by mass. 4-tert-butylcatechol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added thereto in an amount of 1.0 parts, and then mixed for 48 hours at room temperature using a mixing rotor. Compound (2C-1) (FA-731A, manufactured by Hitachi Chemical Co., Ltd.) was added as a compound (C) having an isocyanurate skeleton in an amount of 5 parts by mass to 100 parts by mass of the fluorine-containing polymer (A) in this solution. A curable resin composition (R-20) was obtained.
[調製例2]
イソシアヌレート骨格を有する化合物(C)として化合物(2C-1)に代えて化合物(2C-5)(NR-1、昭和電工社製)を用いた以外は調製例1と同様にして、例2のコアの形成に用いる硬化性樹脂組成物(R-21)を得た。
[Preparation example 2]
Example 2 was prepared in the same manner as in Preparation Example 1, except that Compound (2C-5) (NR-1, manufactured by Showa Denko) was used as the compound (C) having an isocyanurate skeleton in place of Compound (2C-1). A curable resin composition (R-21) used for forming the core was obtained.
[調製例3]
例3のコアの形成に用いる硬化性樹脂組成物(R-22)を以下の手順で調製した。
上記で得られた含フッ素ポリマー(A)100質量部に対して、2質量部となるように重合開始剤(B)としてIRGACURE OXE01(製品名、チバスペシャリティーケミカルズ社製)、0.03質量部となるように4-tert-ブチルカテコール(東京化成工業社製)を添加した後、ミックスローターを用いて室温で48時間混合した。この溶液の含フッ素ポリマー(A)100質量部に対して、5質量部となるように比較化合物(X-1)として下記式で表されるトリアリルイソシアヌレート(TAIC、三菱ケミカル社製)を添加して、硬化性樹脂組成物(R-22)を得た。
[Preparation example 3]
A curable resin composition (R-22) used for forming the core of Example 3 was prepared according to the following procedure.
IRGACURE OXE01 (product name, manufactured by Ciba Specialty Chemicals) as a polymerization initiator (B), 0.03 parts by mass, to 100 parts by mass of the fluorine-containing polymer (A) obtained above, so that the amount is 2 parts by mass. After adding 4-tert-butylcatechol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) to the mixture, the mixture was mixed for 48 hours at room temperature using a mixing rotor. Triallyl isocyanurate (TAIC, manufactured by Mitsubishi Chemical Corporation) represented by the following formula was added as a comparison compound (X-1) to 100 parts by mass of the fluorine-containing polymer (A) in this solution in an amount of 5 parts by mass. A curable resin composition (R-22) was obtained.
[調製例4]
比較化合物(X-1)に代えて、比較化合物(X-2)として下記式で表されるトリメチロールプロパントリアクリレート(TMPTA、ダイセル・オルネクス社製)を用いた以外は調製例3と同様にして、例4のコアの形成に用いる硬化性樹脂組成物(R-23)を得た。
[Preparation example 4]
Proceed as in Preparation Example 3, except that trimethylolpropane triacrylate (TMPTA, manufactured by Daicel Allnex) represented by the following formula was used as the comparative compound (X-2) instead of the comparative compound (X-1). A curable resin composition (R-23) used for forming the core of Example 4 was obtained.
[調製例5]
クラッドの形成に用いる硬化性樹脂組成物(R-10)および(R-30)を以下の手順で調製した。
上記で得られた含フッ素ポリマー(A)100質量部に対して、2質量部となるように重合開始剤(B)としてIRGACURE OXE01(製品名、チバスペシャリティーケミカルズ社製)、0.03質量部となるように4-tert-ブチルカテコール(東京化成工業社製)を添加した後、ミックスローターを用いて室温で48時間混合した。この溶液の含フッ素ポリマー(A)100質量部に対して、25質量部となるように化合物(D)としてポリプロピレングリコールジメタクリレート(NKエステル 9PG(製品名)、新中村化学工業社製)を添加して、硬化性樹脂組成物(R-10)及び(R-30)を得た。なお、硬化性樹脂組成物(R-10)及び(R-30)は同じ組成物であるが、便宜上、第一のクラッドの形成に用いる組成物を硬化性樹脂組成物(R-10)、第二のクラッドの形成に用いる組成物を硬化性樹脂組成物(R-30)と称する。
[Preparation example 5]
Curable resin compositions (R-10) and (R-30) used for forming cladding were prepared according to the following procedure.
IRGACURE OXE01 (product name, manufactured by Ciba Specialty Chemicals) as a polymerization initiator (B), 0.03 parts by mass, to 100 parts by mass of the fluorine-containing polymer (A) obtained above, so that the amount is 2 parts by mass. 4-tert-butylcatechol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added thereto in an amount of 1.0 parts, and then mixed for 48 hours at room temperature using a mixing rotor. Polypropylene glycol dimethacrylate (NK Ester 9PG (product name), manufactured by Shin Nakamura Chemical Industry Co., Ltd.) was added as a compound (D) to 100 parts by mass of the fluorine-containing polymer (A) in this solution in an amount of 25 parts by mass. Thus, curable resin compositions (R-10) and (R-30) were obtained. Note that the curable resin compositions (R-10) and (R-30) are the same composition, but for convenience, the composition used for forming the first cladding is the curable resin composition (R-10), The composition used to form the second cladding is referred to as a curable resin composition (R-30).
[例1]
スピンコート法により、基板の上に第一のクラッドの構成材料である調製例5で得られた硬化性樹脂組成物(R-10)を含有する塗布液を塗布した。続いて、光照射により該硬化性樹脂組成物(R-10)を硬化させて、膜厚50μmとなるように第一のクラッドを形成した。
次に、スピンコート法により、前記第一のクラッドの上にコアの構成材料である調製例1で得られた硬化性樹脂組成物(R-20)を含有する塗布液を塗布し、塗膜を形成した。続いて、塗膜をフォトリソグラフィ法によりパターニング(加工)し、第一のクラッドの上に、厚さが2.2μmで、幅が2.0μmの部分を有するコアを形成した。
次に、スピンコート法により、第一のクラッド及びコアの上に調製例6で得られた第二のクラッドの構成材料である硬化性樹脂組成物(R-30)を含有する塗布液を塗布した。続いて、光照射により該硬化性樹脂組成物(R-30)を硬化させて、膜厚25μmとなるように第二のクラッドを形成した。
最後に形状を安定させるため窒素雰囲気化でポストベークを行って、ポリマー光導波路を作製した。
[Example 1]
A coating liquid containing the curable resin composition (R-10) obtained in Preparation Example 5, which is a constituent material of the first cladding, was applied onto the substrate by a spin coating method. Subsequently, the curable resin composition (R-10) was cured by light irradiation to form a first cladding with a film thickness of 50 μm.
Next, a coating solution containing the curable resin composition (R-20) obtained in Preparation Example 1, which is a constituent material of the core, is applied onto the first clad by a spin coating method, and a coating film is formed. was formed. Subsequently, the coating film was patterned (processed) by photolithography to form a core having a thickness of 2.2 μm and a width of 2.0 μm on the first cladding.
Next, a coating solution containing the curable resin composition (R-30), which is the constituent material of the second clad obtained in Preparation Example 6, is applied onto the first clad and the core by a spin coating method. did. Subsequently, the curable resin composition (R-30) was cured by light irradiation to form a second cladding with a thickness of 25 μm.
Finally, in order to stabilize the shape, post-baking was performed in a nitrogen atmosphere to fabricate a polymer optical waveguide.
[例2~例4]
コアの構成材料を、調製例2~4で得られた硬化性樹脂組成物(R-21)~(R-23)にそれぞれ変更した以外は例1と同様にして、ポリマー光導波路を作製した。
[Example 2 to Example 4]
Polymer optical waveguides were produced in the same manner as in Example 1, except that the core constituent materials were changed to the curable resin compositions (R-21) to (R-23) obtained in Preparation Examples 2 to 4, respectively. .
[コアの剥離の評価]
各例について、ポリマー光導波路を40サンプルずつ作製し、コアの現像後にコアの剥離を以下の基準で評価した。評価結果はA又はBが好ましく、Aがより好ましい。
A:40枚中全てのサンプルで剥離の発生を目視にて確認できず、顕微鏡による観察でも微小剥離やうねりが発生していなかった。
B:40枚中全てのサンプルで剥離の発生を目視にて確認できず、顕微鏡による観察で僅かにうねりが発生していた。
C:40枚中30枚以上のサンプルで剥離が発生した。
[Evaluation of core peeling]
For each example, 40 samples of polymer optical waveguides were produced, and after the core was developed, the peeling of the core was evaluated based on the following criteria. The evaluation result is preferably A or B, and more preferably A.
A: No peeling could be visually confirmed in any of the 40 samples, and microscopic peeling or waviness was not observed even when observed under a microscope.
B: No peeling could be visually confirmed in any of the 40 samples, and slight waviness was observed when observed under a microscope.
C: Peeling occurred in 30 or more of the 40 samples.
例1~例4における硬化性樹脂組成物(R-20)~(R-23)の組成と、コアの剥離評価の結果を表1に示す。
硬化性樹脂組成物の組成を示す数字はいずれも質量部での値を意味する。
Table 1 shows the compositions of the curable resin compositions (R-20) to (R-23) in Examples 1 to 4 and the results of core peel evaluation.
All numbers indicating the composition of the curable resin composition mean values in parts by mass.
コアとして含フッ素ポリマー(A)、重合開始剤(B)およびイソシアヌレート骨格を有する化合物(C)を含有する硬化性樹脂組成物を用いた例1および例2ではクラッドとの界面でのコアの剥離を抑制する効果が得られた。
これらのうち、イソシアヌレート骨格を有する化合物(C)のうち、アクリレート基を有する化合物(2C-1)を含有する硬化性樹脂組成物を用いた例1では、顕微鏡による観察でも微小剥離やうねりが発生せず、クラッドとの界面でのコアの剥離を抑制する効果が最も高かった。イソシアヌレート骨格を有する化合物(C)のうち、チオール基を官能基として有する化合物(2C-5)を含有する例2では、コアの剥離を抑制する効果は得られたが、顕微鏡による観察により微小なうねりが発生したサンプルが見られた。
例1が最も効果が高かった理由は、化合物(2C-1)の官能基の反応性が高いことが要因であると考えられる。
In Examples 1 and 2, in which a curable resin composition containing a fluorine-containing polymer (A), a polymerization initiator (B), and a compound having an isocyanurate skeleton (C) was used as the core, the core at the interface with the cladding was The effect of suppressing peeling was obtained.
Among these, in Example 1 using a curable resin composition containing a compound (2C-1) having an acrylate group among the compounds (C) having an isocyanurate skeleton, minute peeling and waviness were observed even when observed under a microscope. This did not occur, and the effect of suppressing core separation at the interface with the cladding was the highest. Among the compounds (C) having an isocyanurate skeleton, in Example 2 containing a compound (2C-5) having a thiol group as a functional group, an effect of suppressing the peeling of the core was obtained, but microscopic observation revealed that Some samples were observed to have some waviness.
The reason why Example 1 was the most effective is thought to be due to the high reactivity of the functional group of compound (2C-1).
一方、化合物(X-1)を含有する例3はクラッドとの界面でのコアの剥離を抑制することができなかった。化合物(X-1)は、含フッ素ポリマー(A)との共重合性に乏しく硬化物の分子量が大きくならないためにコアの剥離を抑制しなかったと考えられる。イソシアヌレート骨格を有する化合物(C)を含有しない化合物(X-2)を用いた例4は例1と比べて、クラッドとの界面でのコアの剥離を抑制する効果は見られなかった。 On the other hand, in Example 3 containing Compound (X-1), peeling of the core at the interface with the cladding could not be suppressed. It is considered that compound (X-1) did not suppress core peeling because it had poor copolymerizability with the fluorine-containing polymer (A) and did not increase the molecular weight of the cured product. Compared to Example 1, in Example 4 using the compound (X-2) that does not contain the compound (C) having an isocyanurate skeleton, no effect of suppressing peeling of the core at the interface with the cladding was observed.
Claims (5)
前記含フッ素ポリマー(A)は、下記一般式(1)で表される含フッ素芳香族化合物(X)と、架橋性官能基及びフェノール性水酸基を有する化合物(Y-1)並びに架橋性官能基及びフッ素原子置換芳香環を有する化合物(Y-2)の少なくともいずれか一方と、フェノール性水酸基を3個以上有する化合物(Z)との縮合反応物であり、
前記架橋性官能基及びフェノール性水酸基を有する化合物(Y-1)は、反応性二重結合を有するフェノール類、エチニルフェノール類、ビス(フェニルエチニル)ジヒドロキシビフェニル類、及びジヒドロキシジフェニルアセチレン類からなる群より選ばれる少なくとも1の化合物であり、
前記架橋性官能基及びフッ素原子置換芳香環を有する化合物(Y-2)は、反応性二重結合を有する含フッ素アリール類、三重結合を有する含フッ素アリールアセチレン類、及び含フッ素ジアリールアセチレン類からなる群より選ばれる少なくとも1の化合物であり、
前記イソシアヌレート骨格を有する化合物(C)は、下記一般式(2)で表される化合物であり、
硬化させてポリマー光導波路に用いられる、硬化性樹脂組成物。
(式中、nは0~3の整数を表し、a、bはそれぞれ独立に0~3の整数を表し、Rf1及びRf2はそれぞれ独立に炭素数8以下の含フッ素アルキル基を表し、芳香環内のFはその芳香環の水素原子が全てフッ素原子で置換されていることを表す。)
(式中、R 1 ~R 3 は各々独立して、置換基を有する炭素数1~10のアルキル基、置換基を有する炭素数3~10のシクロアルキル基、アクリロイル基、メタクリロイル基、チオール基を表し、前記置換基はシクロアルキル基、アクリロイル基、メタクリロイル基、チオール基、-OCOCR 4 =CR 5 R 6 、-OCO-CH 2 CH(SH)-CH 3 、及び-OCO-CH 2 CH 2 -SHからなる群より選ばれる少なくとも1種であり、R 4 ~R 6 は各々独立して、水素原子、炭素数1~10のアルキル基、又はチオール基を表す。) Containing 100 parts by mass of the fluorine-containing polymer (A), 0.5 to 4 parts by mass of the polymerization initiator (B), and 3 to 20 parts by mass of the compound (C) having an isocyanurate skeleton,
The fluorine-containing polymer (A) comprises a fluorine-containing aromatic compound (X) represented by the following general formula (1), a compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group, and a crosslinkable functional group. and a condensation reaction product of at least one of the compound (Y-2) having a fluorine atom-substituted aromatic ring and a compound (Z) having three or more phenolic hydroxyl groups,
The compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group is a group consisting of phenols having reactive double bonds, ethynylphenols, bis(phenylethynyl)dihydroxybiphenyls, and dihydroxydiphenylacetylenes. At least one compound selected from
The compound (Y-2) having a crosslinkable functional group and a fluorine-substituted aromatic ring is selected from fluorine-containing aryls having a reactive double bond, fluorine-containing arylacetylenes having a triple bond, and fluorine-containing diarylacetylenes. At least one compound selected from the group consisting of
The compound (C) having an isocyanurate skeleton is a compound represented by the following general formula (2),
A curable resin composition that is cured and used in polymer optical waveguides .
(In the formula, n represents an integer of 0 to 3, a and b each independently represent an integer of 0 to 3, Rf 1 and Rf 2 each independently represent a fluorine-containing alkyl group having 8 or less carbon atoms, F in an aromatic ring indicates that all hydrogen atoms in the aromatic ring are replaced with fluorine atoms.)
(In the formula, R 1 to R 3 each independently represent a substituent-containing alkyl group having 1 to 10 carbon atoms, a substituent-containing cycloalkyl group having 3 to 10 carbon atoms, an acryloyl group, a methacryloyl group, and a thiol group. represents a cycloalkyl group, an acryloyl group, a methacryloyl group, a thiol group, -OCOCR 4 =CR 5 R 6 , -OCO-CH 2 CH(SH)-CH 3 , and -OCO-CH 2 CH 2 -SH, and each of R 4 to R 6 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a thiol group.)
前記第一のクラッド上に硬化性樹脂組成物(R2)の塗膜を形成し、前記塗膜をフォトリソグラフィ法で加工してコアを形成する工程、及び
前記第一のクラッドおよび前記コア上の一部または全部に硬化性樹脂組成物(R3)を塗布し、光照射または熱で硬化させる工程、を含み、
前記硬化性樹脂組成物(R1)は、含フッ素ポリマー(A1)を100質量部、重合開始剤(B1)を0.5~4質量部、及び、分子量が140~5000であり、架橋性官能基を有し、かつフッ素原子を有していない化合物(D1)を5~50質量部含有し、
前記硬化性樹脂組成物(R2)は、含フッ素ポリマー(A2)を100質量部、重合開始剤(B2)を0.5~4質量部、及び、イソシアヌレート骨格を有する化合物(C2)を3~20質量部含有し、
前記硬化性樹脂組成物(R3)は、含フッ素ポリマー(A3)を100質量部、重合開始剤(B3)を0.5~4質量部、及び、分子量が140~5000であり、架橋性官能基を有し、かつフッ素原子を有していない化合物(D3)を5~50質量部含有し、
前記含フッ素ポリマー(A1)、前記含フッ素ポリマー(A2)及び前記含フッ素ポリマー(A3)は、それぞれ独立して、下記一般式(1)で表される含フッ素芳香族化合物(X)と、架橋性官能基及びフェノール性水酸基を有する化合物(Y-1)並びに架橋性官能基及びフッ素原子置換芳香環を有する化合物(Y-2)の少なくともいずれか一方と、フェノール性水酸基を3個以上有する化合物(Z)との縮合反応物であり、
前記架橋性官能基及びフェノール性水酸基を有する化合物(Y-1)は、反応性二重結合を有するフェノール類、エチニルフェノール類、ビス(フェニルエチニル)ジヒドロキシビフェニル類、及びジヒドロキシジフェニルアセチレン類からなる群より選ばれる少なくとも1の化合物であり、
前記架橋性官能基及びフッ素原子置換芳香環を有する化合物(Y-2)は、反応性二重結合を有する含フッ素アリール類、三重結合を有する含フッ素アリールアセチレン類、及び含フッ素ジアリールアセチレン類からなる群より選ばれる少なくとも1の化合物であり、
前記イソシアヌレート骨格を有する化合物(C)は、下記一般式(2)で表される化合物である、ポリマー光導波路の製造方法。
(式中、nは0~3の整数を表し、a、bはそれぞれ独立に0~3の整数を表し、Rf1及びRf2はそれぞれ独立に炭素数8以下の含フッ素アルキル基を表し、芳香環内のFはその芳香環の水素原子が全てフッ素原子で置換されていることを表す。)
(式中、R 1 ~R 3 は各々独立して、置換基を有する炭素数1~10のアルキル基、置換基を有する炭素数3~10のシクロアルキル基、アクリロイル基、メタクリロイル基、チオール基を表し、前記置換基はシクロアルキル基、アクリロイル基、メタクリロイル基、チオール基、-OCOCR 4 =CR 5 R 6 、-OCO-CH 2 CH(SH)-CH 3 、及び-OCO-CH 2 CH 2 -SHからなる群より選ばれる少なくとも1種であり、R 4 ~R 6 は各々独立して、水素原子、炭素数1~10のアルキル基、又はチオール基を表す。) a step of applying a curable resin composition (R1) on a substrate and curing it with light irradiation or heat to form a first cladding;
forming a coating film of the curable resin composition (R2) on the first cladding and processing the coating film by photolithography to form a core; Including a step of applying a curable resin composition (R3) partially or completely and curing with light irradiation or heat,
The curable resin composition (R1) contains 100 parts by mass of a fluorine-containing polymer (A1), 0.5 to 4 parts by mass of a polymerization initiator (B1), and has a molecular weight of 140 to 5,000, and has a crosslinkable functional containing 5 to 50 parts by mass of a compound (D1) having a group and not having a fluorine atom,
The curable resin composition (R2) contains 100 parts by mass of a fluorine-containing polymer (A2), 0.5 to 4 parts by mass of a polymerization initiator (B2), and 3 parts by mass of a compound (C2) having an isocyanurate skeleton. Contains ~20 parts by mass,
The curable resin composition (R3) contains 100 parts by mass of a fluorine-containing polymer (A3), 0.5 to 4 parts by mass of a polymerization initiator (B3), and has a molecular weight of 140 to 5000, and has a crosslinkable functional containing 5 to 50 parts by mass of a compound (D3) having a group and not having a fluorine atom,
The fluorine-containing polymer (A1), the fluorine-containing polymer (A2), and the fluorine-containing polymer (A3) each independently contain a fluorine-containing aromatic compound (X) represented by the following general formula (1), At least one of the compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group and the compound (Y-2) having a crosslinkable functional group and a fluorine atom-substituted aromatic ring, and three or more phenolic hydroxyl groups. A condensation reaction product with compound (Z),
The compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group is a group consisting of phenols having reactive double bonds, ethynylphenols, bis(phenylethynyl)dihydroxybiphenyls, and dihydroxydiphenylacetylenes. At least one compound selected from
The compound (Y-2) having a crosslinkable functional group and a fluorine-substituted aromatic ring is selected from fluorine-containing aryls having a reactive double bond, fluorine-containing arylacetylenes having a triple bond, and fluorine-containing diarylacetylenes. At least one compound selected from the group consisting of
The method for producing a polymer optical waveguide , wherein the compound (C) having an isocyanurate skeleton is a compound represented by the following general formula (2) .
(In the formula, n represents an integer of 0 to 3, a and b each independently represent an integer of 0 to 3, Rf 1 and Rf 2 each independently represent a fluorine-containing alkyl group having 8 or less carbon atoms, F in an aromatic ring indicates that all hydrogen atoms in the aromatic ring are replaced with fluorine atoms.)
(In the formula, R 1 to R 3 each independently represent a substituent-containing alkyl group having 1 to 10 carbon atoms, a substituent-containing cycloalkyl group having 3 to 10 carbon atoms, an acryloyl group, a methacryloyl group, and a thiol group. represents a cycloalkyl group, an acryloyl group, a methacryloyl group, a thiol group, -OCOCR 4 =CR 5 R 6 , -OCO-CH 2 CH(SH)-CH 3 , and -OCO-CH 2 CH 2 -SH, and each of R 4 to R 6 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a thiol group.)
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WO2010107005A1 (en) | 2009-03-18 | 2010-09-23 | 旭硝子株式会社 | Optical waveguide |
JP2013120338A (en) | 2011-12-08 | 2013-06-17 | Asahi Glass Co Ltd | Method for producing optical waveguide |
WO2014034671A1 (en) | 2012-08-31 | 2014-03-06 | 旭硝子株式会社 | Curable composition and method for producing curable film |
WO2018168783A1 (en) | 2017-03-15 | 2018-09-20 | Agc株式会社 | Polymer optical waveguide |
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WO2010107005A1 (en) | 2009-03-18 | 2010-09-23 | 旭硝子株式会社 | Optical waveguide |
JP2013120338A (en) | 2011-12-08 | 2013-06-17 | Asahi Glass Co Ltd | Method for producing optical waveguide |
WO2014034671A1 (en) | 2012-08-31 | 2014-03-06 | 旭硝子株式会社 | Curable composition and method for producing curable film |
WO2018168783A1 (en) | 2017-03-15 | 2018-09-20 | Agc株式会社 | Polymer optical waveguide |
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