JP5201792B2 - Liquid curable resin composition - Google Patents
Liquid curable resin composition Download PDFInfo
- Publication number
- JP5201792B2 JP5201792B2 JP2005354760A JP2005354760A JP5201792B2 JP 5201792 B2 JP5201792 B2 JP 5201792B2 JP 2005354760 A JP2005354760 A JP 2005354760A JP 2005354760 A JP2005354760 A JP 2005354760A JP 5201792 B2 JP5201792 B2 JP 5201792B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylate
- meth
- resin composition
- curable resin
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000007788 liquid Substances 0.000 title claims description 57
- 239000011342 resin composition Substances 0.000 title claims description 43
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 98
- 239000013307 optical fiber Substances 0.000 claims description 47
- 239000011247 coating layer Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 25
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 239000003504 photosensitizing agent Substances 0.000 claims description 14
- 229920001451 polypropylene glycol Polymers 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 230000005855 radiation Effects 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- YDIYEOMDOWUDTJ-UHFFFAOYSA-N 4-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=C(C(O)=O)C=C1 YDIYEOMDOWUDTJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 claims description 4
- ASUQXIDYMVXFKU-UHFFFAOYSA-N 2,6-dibromo-9,9-dimethylfluorene Chemical compound C1=C(Br)C=C2C(C)(C)C3=CC=C(Br)C=C3C2=C1 ASUQXIDYMVXFKU-UHFFFAOYSA-N 0.000 claims description 2
- OFSAUHSCHWRZKM-UHFFFAOYSA-N Padimate A Chemical compound CC(C)CCOC(=O)C1=CC=C(N(C)C)C=C1 OFSAUHSCHWRZKM-UHFFFAOYSA-N 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004949 mass spectrometry Methods 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 1
- -1 silane compound Chemical class 0.000 description 38
- 239000000463 material Substances 0.000 description 25
- 238000000576 coating method Methods 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 22
- 239000004721 Polyphenylene oxide Substances 0.000 description 21
- 229920000570 polyether Polymers 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 229920005862 polyol Polymers 0.000 description 14
- 150000003077 polyols Chemical class 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000007654 immersion Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 11
- 150000002009 diols Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000005056 polyisocyanate Substances 0.000 description 9
- 229920001228 polyisocyanate Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 150000001869 cobalt compounds Chemical class 0.000 description 6
- 150000001923 cyclic compounds Chemical class 0.000 description 6
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 4
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-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
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 2
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical group 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 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 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 230000002165 photosensitisation Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- UYVWNPAMKCDKRB-UHFFFAOYSA-N 1,2,4,5-tetraoxane Chemical compound C1OOCOO1 UYVWNPAMKCDKRB-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- UKDKWYQGLUUPBF-UHFFFAOYSA-N 1-ethenoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOC=C UKDKWYQGLUUPBF-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- SDXHBDVTZNMBEW-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol Chemical compound CCOC(O)COCCO SDXHBDVTZNMBEW-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- CSCSROFYRUZJJH-UHFFFAOYSA-N 1-methoxyethane-1,2-diol Chemical compound COC(O)CO CSCSROFYRUZJJH-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UFAKDGLOFJXMEN-UHFFFAOYSA-N 2-ethenyloxetane Chemical compound C=CC1CCO1 UFAKDGLOFJXMEN-UHFFFAOYSA-N 0.000 description 1
- XIXWTBLGKIRXOP-UHFFFAOYSA-N 2-ethenyloxolane Chemical compound C=CC1CCCO1 XIXWTBLGKIRXOP-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
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- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、耐温水浸漬特性に優れた光ファイバ素線が得られるとともに、高速硬化が可能な液状硬化性樹脂組成物に関する。 The present invention relates to a liquid curable resin composition capable of obtaining an optical fiber having excellent hot-water immersion characteristics and capable of high-speed curing.
光ファイバは、ガラスを熱溶融紡糸して得たガラスファイバ素線に、保護補強を目的として樹脂を被覆して製造されている。この樹脂被覆としては、光ファイバの表面にまず柔軟な第一次の被覆層（以下、「一次被覆層」ともいう。）を設け、その外側に剛性の高い第二次の被覆層（以下、「二次被覆層」ともいう。）を設けた構造が知られている。これらの第一次、二次被覆層を有する光ファイバを光ファイバ素線という（以下、光ファイバ素線を単に「光ファイバ」ともいう。）。これらの樹脂被覆を施して得られる光ファイバ素線を平面上に複数並べて結束材料で固めた光ファイバテープもよく知られている。光ファイバ素線の第一次の被覆層を形成するための樹脂組成物をプライマリ材、第二次の被覆層を形成するための樹脂組成物をセカンダリ材、テープ状ファイバの結束材として用いられる樹脂組成物をテープ材と称している。これらの樹脂被覆方法としては、液状硬化性樹脂組成物を塗布し、熱または光、特に紫外線により硬化させる方法が広く用いられている。 An optical fiber is manufactured by coating a glass fiber obtained by hot-melt spinning of glass with a resin for the purpose of protection and reinforcement. As this resin coating, a flexible primary coating layer (hereinafter, also referred to as “primary coating layer”) is first provided on the surface of the optical fiber, and a highly rigid secondary coating layer (hereinafter, referred to as “primary coating layer”). A structure provided with a “secondary coating layer” is also known. These optical fibers having the primary and secondary coating layers are referred to as optical fiber strands (hereinafter, the optical fiber strands are also simply referred to as “optical fibers”). An optical fiber tape in which a plurality of optical fiber wires obtained by applying these resin coatings are arranged on a plane and hardened with a binding material is also well known. A resin composition for forming a primary coating layer of an optical fiber is used as a primary material, a resin composition for forming a secondary coating layer is used as a secondary material, and a binding material for tape-like fibers. The resin composition is referred to as a tape material. As these resin coating methods, a method in which a liquid curable resin composition is applied and cured by heat or light, particularly ultraviolet rays, is widely used.
近年、このような液状硬化性樹脂組成物には、未硬化樹脂液の保存安定性に優れ、光ファイバの製造効率の観点から高速硬化性が求められると共に、耐光性の観点から高い耐温水浸漬特性が求められている。
硬化速度は、ラジカル重合性モノマーや光重合開始剤の選択等により、ある程度高くすることが可能であることが知られている。例えば、高速硬化性に有効な代表的なラジカル重合性モノマーであるＮ−ビニルカプロラクタムやＮ−ビニルピロリドン等の環状構造を有するＮ−ビニル化合物を採用すると共に、光増感剤としてジエチルアミン等の塩基性化合物を併用する等の技術が用いられることがある（特許文献１〜３）。
In recent years, such a liquid curable resin composition has excellent storage stability of an uncured resin liquid, high-speed curability is required from the viewpoint of optical fiber production efficiency, and high warm water immersion from the viewpoint of light resistance. Characteristics are required.
It is known that the curing rate can be increased to some extent by selecting a radical polymerizable monomer or a photopolymerization initiator. For example, N-vinyl compounds having a cyclic structure such as N-vinylcaprolactam and N-vinylpyrrolidone, which are representative radical polymerizable monomers effective for high-speed curing, are employed, and bases such as diethylamine as a photosensitizer In some cases, a technique such as using an ionic compound is used (Patent Documents 1 to 3).
しかし、ジエチルアミン等の塩基性化合物は、光ファイバを温水に長時間浸漬したときに透明性の低下を招く場合があり、光ファイバの伝送特性の長期安定性の観点からは必ずしも望ましくない。このように、従来の塩基性化合物の添加により高速硬化性を確保する技術では、高い耐温水浸漬特性と高速硬化性および樹脂液の保存安定性を両立することは困難であった。
本発明の目的は、高い耐温水浸漬特性の光ファイバ素線が得られるとともに、高速硬化性に優れ、保存安定性も良好な液状硬化性樹脂組成物を提供することにある。 An object of the present invention is to provide a liquid curable resin composition that can obtain an optical fiber having high hot water immersion characteristics, is excellent in high-speed curability, and has good storage stability.
本発明者は、この様な状況に鑑みて鋭意研究した結果、液状硬化性樹脂組成物中の亜鉛及びコバルト元素の含有量を一定値に制御することにより、高い耐温水浸漬特性を有する光ファイバ素線が得られ、高速硬化が可能で、保存安定性も良好な液状硬化性樹脂組成物が得られることを見出し、本発明を完成するに至った。 As a result of diligent research in view of such circumstances, the present inventor has determined that the contents of zinc and cobalt elements in the liquid curable resin composition are controlled to a constant value, thereby providing an optical fiber having high hot water immersion characteristics. It has been found that a liquid curable resin composition can be obtained in which a strand can be obtained, high-speed curing is possible, and storage stability is good, and the present invention has been completed.
すなわち、本発明は、組成物全量を１００質量％として、
（Ａ）ポリエーテルポリオール由来の構造を有するウレタン（メタ）アクリレート ３５〜８５質量％、
（Ｂ）（Ａ）以外のエチレン性不飽和基含有化合物 １〜６０質量％、
（Ｃ）アミン系光増感剤 ０．０１〜１質量％、及び
（Ｄ）光重合開始剤 ０．０１〜１０質量％
を含有する液状硬化性樹脂組成物であって、高周波プラズマ発光・質量分析法（ＩＣＰ−ＭＳ）により求めた組成物中の亜鉛及びコバルト元素の合計含有量が０．５〜１０ppmである、液状硬化性樹脂組成物を提供するものである。
また、本発明は、当該液状硬化性樹脂組成物を、放射線により硬化せしめることにより得られる光ファイバ被覆層及び当該被覆層を有する光ファイバを提供するものである。
That is, in the present invention, the total amount of the composition is 100% by mass,
(A) 35 to 85% by mass of urethane (meth) acrylate having a structure derived from polyether polyol,
(B) 1 to 60% by mass of an ethylenically unsaturated group-containing compound other than (A),
(C) Amine-based photosensitizer 0.01 to 1% by mass, and (D) Photopolymerization initiator 0.01 to 10% by mass.
A liquid curable resin composition containing a zinc and cobalt element in the composition determined by high-frequency plasma emission / mass spectrometry (ICP-MS), the total content of which is 0.5 to 10 ppm. A curable resin composition is provided.
The present invention also provides an optical fiber coating layer obtained by curing the liquid curable resin composition with radiation and an optical fiber having the coating layer.
本発明の液状硬化性樹脂組成物は、高い耐温水浸漬特性を有する光ファイバ素線が得られるとともに、高速硬化性に優れるものである。また、保存安定性も良好である。光ファイバ用の被覆材、特にプライマリ材や、種々の光学部材の表面コーティング材、光学接着剤等として有用である。 The liquid curable resin composition of the present invention is excellent in high-speed curability as well as an optical fiber having a high resistance to hot water immersion. Also, the storage stability is good. It is useful as a coating material for optical fibers, particularly a primary material, a surface coating material for various optical members, an optical adhesive, and the like.
本発明の液状硬化性樹脂組成物に用いられる（Ａ）ウレタン（メタ）アクリレートは、ポリエーテルポリオール由来の構造を有していれば特に限定されないが、例えば、少なくとも、（ａ）ポリエーテルポリオール、（ｂ）ポリイソシアネート、および（ｃ）水酸基含有（メタ）アクリレートを反応させて得られる。 The (A) urethane (meth) acrylate used in the liquid curable resin composition of the present invention is not particularly limited as long as it has a structure derived from a polyether polyol. For example, at least (a) a polyether polyol, It is obtained by reacting (b) polyisocyanate and (c) hydroxyl group-containing (meth) acrylate.
この（Ａ）ウレタン（メタ）アクリレートを製造する具体的方法としては、例えば（ａ）ポリエーテルポリオール、（ｂ）ポリイソシアネート、および（ｃ）水酸基含有（メタ）アクリレートを一括して仕込んで反応させる方法；（ａ）ポリエーテルポリオールおよび（ｂ）ポリイソシアネートを反応させ、次いで（ｃ）水酸基含有（メタ）アクリレートを反応させる方法；（ｂ）ポリイソシアネート、および（ｃ）水酸基含有（メタ）アクリレートを反応させ、次いで（ａ）ポリエーテルポリオールを反応させる方法；（ｂ）ポリイソシアネートおよび（ｃ）水酸基含有（メタ）アクリレートを反応させ、次いで（ａ）ポリエーテルポリオールを反応させ、最後に（ｄ）イソシアネート基と反応しうる官能基を有するシラン化合物を反応させる方法等が挙げられる。 As a specific method for producing this (A) urethane (meth) acrylate, for example, (a) polyether polyol, (b) polyisocyanate, and (c) hydroxyl group-containing (meth) acrylate are charged together and reacted. Method: (a) a polyether polyol and (b) a polyisocyanate are reacted, and then (c) a hydroxyl group-containing (meth) acrylate is reacted; (b) a polyisocyanate, and (c) a hydroxyl group-containing (meth) acrylate. (A) a method of reacting a polyether polyol; (b) reacting a polyisocyanate and (c) a hydroxyl group-containing (meth) acrylate, then reacting (a) a polyether polyol, and finally (d) Reacted with a silane compound having a functional group capable of reacting with an isocyanate group That method and the like.
ここで用いる（ａ）ポリエーテルポリオールとしては、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ポリヘキサメチレングリコール、ポリヘプタメチレングリコール、ポリデカメチレングリコールのような一種のイオン重合性環状化合物を開環重合させて得られるポリエーテルジオール、または二種以上のイオン重合性環状化合物を開環共重合させて得られるポリエーテルジオールが挙げられる。イオン重合性環状化合物としては、エチレンオキシド、プロピレンオキシド、ブテン−１−オキシド、イソブテンオキシド、オキセタン、３，３−ジメチルオキセタン、３，３−ビスクロロメチルオキセタン、テトラヒドロフラン、２−メチルテトラヒドロフラン、３−メチルテトラヒドロフラン、ジオキサン、トリオキサン、テトラオキサン、シクロヘキセンオキシド、スチレンオキシド、エピクロルヒドリン、グリシジルメタクリレート、アリルグリシジルエーテル、アリルグリシジルカーボネート、ブタジエンモノオキシド、イソプレンモノオキシド、ビニルオキセタン、ビニルテトラヒドロフラン、ビニルシクロヘキセンオキシド、フェニルグリシジルエーテル、ブチルグリシジルエーテル、安息香酸グリシジルエステル等の環状エーテル類が挙げられる。また、上記イオン重合性環状化合物と、エチレンイミン等の環状イミン類、γ−プロピオラクトン、グリコール酸ラクチド等の環状ラクトン酸、あるいはジメチルシクロポリシロキサン類とを開環共重合させたポリエーテルジオールを使用することもできる。上記二種以上のイオン重合性環状化合物の具体的な組み合わせとしては、テトラヒドロフランとプロピレンオキシド、テトラヒドロフランと２−メチルテトラヒドロフラン、テトラヒドロフランと３−メチルテトラヒドロフラン、テトラヒドロフランとエチレンオキシド、プロピレンオキシドとエチレンオキシド、ブテン−１−オキシドとエチレンオキシド、テトラヒドロフラン、ブテン−１−オキシド、エチレンオキシドの３元重合体等を挙げることができる。これらのイオン重合性環状化合物の開環共重合体はランダムに結合していてもよいし、ブロック状の結合をしていてもよい。得られる硬化物に耐ジェリー性および耐水性を付与する点から、これらのポリエーテルジオールのうち、ポリプロピレングリコールがより好ましく、ゲルパーミエーションクロマトグラフ法（ＧＰＣ法）によるポリスチレン換算の数平均分子量で１０００〜７０００のポリプロピレングリコールが特に好ましい。 As the (a) polyether polyol used here, a kind of ion-polymerizable cyclic compound such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol is opened. Examples thereof include polyether diols obtained by polymerization, or polyether diols obtained by ring-opening copolymerization of two or more ion-polymerizable cyclic compounds. Examples of the ion polymerizable cyclic compound include ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, oxetane, 3,3-dimethyloxetane, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, and 3-methyl. Tetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monooxide, isoprene monooxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl Cyclic ethers such as glycidyl ether and benzoic acid glycidyl ester Ethers, and the like. Polyether diol obtained by ring-opening copolymerization of the above ion polymerizable cyclic compound with cyclic imines such as ethyleneimine, cyclic lactone acids such as γ-propiolactone and glycolic acid lactide, or dimethylcyclopolysiloxanes. Can also be used. Specific combinations of the two or more ion-polymerizable cyclic compounds include tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, butene-1- Examples thereof include terpolymers of oxide and ethylene oxide, tetrahydrofuran, butene-1-oxide, and ethylene oxide. The ring-opening copolymer of these ion-polymerizable cyclic compounds may be bonded at random or may be bonded in a block form. Of these polyether diols, polypropylene glycol is more preferable from the viewpoint of imparting jelly resistance and water resistance to the resulting cured product, and the number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC method) is 1000. ˜7000 polypropylene glycol is particularly preferred.
これらのポリエーテルジオールは、例えばＰＴＭＧ６５０、ＰＴＭＧ１０００、ＰＴＭＧ２０００（以上、三菱化学社製）、エクセノール １０２０、２０２０、３０２０、プレミノール ＰＭＬ−４００２、ＰＭＬ−Ｓ−４１０２、ＰＭＬ−５００５（以上、旭硝子ウレタン社製）、ユニセーフ ＤＣ１１００、ＤＣ１８００、ＤＣＢ１０００（以上、日本油脂社製）、ＰＰＴＧ１０００、ＰＰＴＧ２０００、ＰＰＴＧ４０００、ＰＴＧ４００、ＰＴＧ６５０、ＰＴＧ１０００、ＰＧＴ２０００、ＰＴＧ−Ｌ１０００、ＰＴＧ−Ｌ２０００（以上、保土谷化学工業社製）、Ｚ−３００１−４、Ｚ−３００１−５、ＰＢＧ２０００（以上、第一工業製薬社製）、Ａｃｃｌａｉｍ ２２００、２２２０、３２０１、３２０５、４２００、４２２０、８２００、１２０００（以上、住化バイエルウレタン社製）等の市販品として入手することができる。 These polyether diols are, for example, PTMG650, PTMG1000, PTMG2000 (manufactured by Mitsubishi Chemical Corporation), Exenol 1020, 2020, 3020, Preminol PML-4002, PML-S-4102, PML-5005 (manufactured by Asahi Glass Urethane Co., Ltd.) ), Unisafe DC1100, DC1800, DCB1000 (above, manufactured by NOF Corporation), PPTG1000, PPTG2000, PPTG4000, PTG400, PTG650, PTG1000, PGT2000, PTG-L1000, PTG-L2000 (above, manufactured by Hodogaya Chemical Co., Ltd.), Z -3001-4, Z-3001-5, PBG2000 (Daiichi Kogyo Seiyaku Co., Ltd.), Acclaim 2200, 2220, 3201, 3205, 4200, 4220 8200,12000 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) can be commercially available, such as.
（ａ）ポリエーテルポリオールとしては、上記ポリエーテルジオールが好ましいが、この他にポリエステルジオール、ポリカーボネートジオール、ポリカプロラクトンジオール等も併用することができる。これらの構造単位の重合様式は特に制限されず、ランダム重合、ブロック重合、グラフト重合のいずれであってもよい。 (A) As the polyether polyol, the above polyether diol is preferable, but in addition, polyester diol, polycarbonate diol, polycaprolactone diol and the like can be used in combination. The polymerization mode of these structural units is not particularly limited, and may be any of random polymerization, block polymerization, and graft polymerization.
（Ａ）ウレタン（メタ）アクリレートの合成に用いられる（ｂ）ポリイソシアネートとしては、芳香族ジイソシアネート、脂環族ジイソシアネート、脂肪族ジイソシアネート等が挙げられる。具体的化合物として、好ましい例としては、芳香族ジイソシアネートおよび脂環式ジイソシアネート、より好ましくは、２，４−トリレンジイソシアネートおよびイソホロンジイソシアネートが挙げられる。これらのジイソシアネートは単独で用いても、２種以上併用しても良い。 (A) As polyisocyanate (b) used for the synthesis | combination of urethane (meth) acrylate, aromatic diisocyanate, alicyclic diisocyanate, aliphatic diisocyanate, etc. are mentioned. Specific examples of the specific compound include aromatic diisocyanates and alicyclic diisocyanates, and more preferably 2,4-tolylene diisocyanate and isophorone diisocyanate. These diisocyanates may be used alone or in combination of two or more.
（Ａ）ウレタン（メタ）アクリレートの合成に用いられる（ｃ）水酸基含有（メタ）アクリレートとしては、ポリイソシアネートのイソシアネート基との反応性の点から、水酸基が第一級炭素原子に結合した水酸基含有（メタ）アクリレート（第一水酸基含有（メタ）アクリレートという）および水酸基が第二級炭素原子に結合した水酸基含有（メタ）アクリレート（第二水酸基含有（メタ）アクリレートという）が好ましい。 (A) As a hydroxyl group-containing (meth) acrylate used for the synthesis of urethane (meth) acrylate, from the viewpoint of reactivity with the isocyanate group of polyisocyanate, a hydroxyl group containing a hydroxyl group bonded to a primary carbon atom Preferred are (meth) acrylates (referred to as primary hydroxyl group-containing (meth) acrylates) and hydroxyl group-containing (meth) acrylates (referred to as secondary hydroxyl group-containing (meth) acrylates) in which the hydroxyl group is bonded to a secondary carbon atom.
第一水酸基含有（メタ）アクリレートとしては、例えば、２−ヒドロキシエチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、１，６−ヘキサンジオールモノ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ネオペンチルグリコールモノ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールエタンジ（メタ）アクリレート等が挙げられる。 Examples of the primary hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, and pentaerythritol tri (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, and the like.
第二水酸基含有（メタ）アクリレートとしては、例えば、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシ−３−フェニルオキシプロピル（メタ）アクリレート、４−ヒドロキシシクロヘキシル（メタ）アクリレート等が挙げられ、さらに、アルキルグリシジルエーテル、アリルグリシジルエーテル、グリシジル（メタ）アクリレート等のグリシジル基含有化合物と、（メタ）アクリル酸との付加反応により得られる化合物が挙げられる。
これらの水酸基含有（メタ）アクリレート化合物は１種単独で、あるいは２種以上組み合わせて使用できる。
Examples of the second hydroxyl group-containing (meth) acrylate include 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4-hydroxycyclohexyl ( (Meth) acrylate etc. are mentioned, Furthermore, the compound obtained by addition reaction with glycidyl group containing compounds, such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid is mentioned.
These hydroxyl group-containing (meth) acrylate compounds can be used alone or in combination of two or more.
（Ａ）ウレタン（メタ）アクリレートの合成に用いる（ａ）ポリエーテルポリオール、（ｂ）ポリイソシアネート、および（ｃ）水酸基含有（メタ）アクリレートの使用割合は、ポリエーテルポリオールに含まれる水酸基１当量に対してポリイソシアネートに含まれるイソシアネート基が１．１〜２当量、水酸基含有（メタ）アクリレートの水酸基が０．１〜１当量となるようにするのが好ましい。 The ratio of (A) polyether polyol, (b) polyisocyanate, and (c) hydroxyl group-containing (meth) acrylate used for the synthesis of (A) urethane (meth) acrylate is 1 equivalent of hydroxyl group contained in the polyether polyol. On the other hand, it is preferable that the isocyanate group contained in the polyisocyanate be 1.1 to 2 equivalents and the hydroxyl group of the hydroxyl group-containing (meth) acrylate to be 0.1 to 1 equivalents.
また、（Ａ）ウレタン（メタ）アクリレートの合成において、ポリエーテルポリオールとともにジアミンを併用することも可能であり、このようなジアミンとしては、エチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、パラフェニレンジアミン、４，４′−ジアミノジフェニルメタン等のジアミンや、ヘテロ原子を含むジアミン、ポリエーテルジアミン等が挙げられる。 In the synthesis of (A) urethane (meth) acrylate, it is also possible to use a diamine together with a polyether polyol. Examples of such a diamine include ethylene diamine, tetramethylene diamine, hexamethylene diamine, paraphenylene diamine, 4 Diamines such as 4,4'-diaminodiphenylmethane, diamines containing heteroatoms, polyether diamines, and the like.
水酸基含有（メタ）アクリレートの一部をアルコール類に置き換えて用いることもできる。アルコール類としては、例えば、メタノール、エタノール、イソプロピルアルコール、ｎ−ブチルアルコール、ｔ−ブチルアルコール等が挙げられる。これらの化合物を使用することにより、樹脂のヤング率を調節することができる。 A part of the hydroxyl group-containing (meth) acrylate may be replaced with alcohols. Examples of alcohols include methanol, ethanol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol and the like. By using these compounds, the Young's modulus of the resin can be adjusted.
（Ａ）ウレタン（メタ）アクリレートの合成においては、ナフテン酸銅、ナフテン酸コバルト、ナフテン酸亜鉛、ジブチル錫ジラウレート、ジオクチル錫ジラウレート、テトラブトキシチタン、ジルコニウムテトラアセチルアセテート、オクテン酸ビスマス、ネオデカン酸ビスマス、トリエチルアミン、１，４−ジアザビシクロ〔２．２．２〕オクタン、２，６，７−トリメチル−１，４−ジアザビシクロ〔２．２．２〕オクタン等のウレタン化触媒を、反応物の総量に対して０．０１〜１質量％用いるのが好ましい。また、反応温度は、通常５〜９０℃、特に１０〜８０℃が好ましい。 (A) In the synthesis of urethane (meth) acrylate, copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, dioctyltin dilaurate, tetrabutoxytitanium, zirconium tetraacetylacetate, bismuth octenoate, bismuth neodecanoate, The urethanization catalyst such as triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1,4-diazabicyclo [2.2.2] octane is used with respect to the total amount of the reactants. 0.01 to 1% by mass is preferably used. Moreover, reaction temperature is 5-90 degreeC normally, Especially 10-80 degreeC is preferable.
（Ａ）ウレタン（メタ）アクリレートの好ましい分子量は、硬化物の良好な破断伸びおよび液状硬化性樹脂組成物の適度な粘度を得る観点から、ＧＰＣ法によるポリスチレン換算の数平均分子量で、通常５００〜４０，０００であり、特に７００〜３０，０００が好ましい。
また、（Ａ）ウレタン（メタ）アクリレートとしては、ポリプロピレングリコールに由来する構造を有するウレタン（メタ）アクリレートが好ましい。
The preferred molecular weight of (A) urethane (meth) acrylate is the number average molecular weight in terms of polystyrene by the GPC method from the viewpoint of obtaining good elongation at break of the cured product and appropriate viscosity of the liquid curable resin composition, and is usually 500 to It is 40,000, and 700 to 30,000 is particularly preferable.
Further, (A) urethane (meth) acrylate is preferably urethane (meth) acrylate having a structure derived from polypropylene glycol.
（Ａ）ウレタン（メタ）アクリレートは、硬化物のヤング率、破断伸び等の良好な力学特性および液状硬化性樹脂組成物の適度な粘度を得る観点から、本発明の液状硬化性樹脂組成物中に、３５〜８５質量％、さらに５５〜８５質量％、特に７０〜８５質量％配合するのが好ましい。８５質量％を超えると硬化物のヤング率が２．０MPaを超えてしまうため、光ファイバ被覆用樹脂としては好ましくなく、また液状硬化性樹脂組成物の粘度が６．０Pa・sを超えてしまうため作業性も低下し、また硬化物の耐水性も悪化する。３５質量％未満では破断強度が悪化してしまう。 (A) Urethane (meth) acrylate is contained in the liquid curable resin composition of the present invention from the viewpoint of obtaining good mechanical properties such as Young's modulus and elongation at break and a suitable viscosity of the liquid curable resin composition. 35 to 85% by mass, more preferably 55 to 85% by mass, and particularly preferably 70 to 85% by mass. If it exceeds 85% by mass, the Young's modulus of the cured product will exceed 2.0 MPa, so it is not preferred as a resin for optical fiber coating, and the viscosity of the liquid curable resin composition will exceed 6.0 Pa · s. Therefore, workability also decreases, and the water resistance of the cured product also deteriorates. If it is less than 35% by mass, the breaking strength is deteriorated.
本発明の液状硬化性樹脂組成物に使用される（Ｂ）成分は、（Ａ）成分以外のエチレン性不飽和基含有化合物であり、典型的には、反応性希釈剤である。（Ｂ）成分としては、例えば（Ｂ１）エチレン性不飽和基を１個有する化合物（以下、「重合性単官能性化合物」という。）、（Ｂ２）エチレン性不飽和基を２個以上有する化合物（以下、「重合性多官能性化合物」という。）が挙げられる。 The component (B) used in the liquid curable resin composition of the present invention is an ethylenically unsaturated group-containing compound other than the component (A), and is typically a reactive diluent. Examples of the component (B) include (B1) a compound having one ethylenically unsaturated group (hereinafter referred to as “polymerizable monofunctional compound”), and (B2) a compound having two or more ethylenically unsaturated groups. (Hereinafter referred to as “polymerizable polyfunctional compound”).
（Ｂ１）重合性単官能性化合物としては、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム等のＮ−ビニル化合物、イソボルニル（メタ）アクリレート、ボルニル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等の脂環式構造含有（メタ）アクリレート、ベンジル（メタ）アクリレート、４−ブチルシクロヘキシル（メタ）アクリレート、アクリロイルモルホリン、ビニルイミダゾール、ビニルピリジン等が挙げられる。さらに、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、アミル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、メトキシエチレングリコール（メタ）アクリレート、エトキシエチル（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、ジアセトン（メタ）アクリルアミド、イソブトキシメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、ｔ−オクチル（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、７−アミノ−３，７−ジメチルオクチル（メタ）アクリレート、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、ヒドロキシブチルビニルエーテル、ラウリルビニルエーテル、セチルビニルエーテル、２−エチルヘキシルビニルエーテル、２−ヒドロキシ−３−フェノキシプロピルアクリレート、ノニルフェノールエチレンオキサイド変性（メタ）アクリレート、下記一般式で表される化合物等が挙げられる。 (B1) As the polymerizable monofunctional compound, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, di- Examples include alicyclic structure-containing (meth) acrylates such as cyclopentanyl (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, and vinylpyridine. Furthermore, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) ) Acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) ) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodec (Meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate , Ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) Acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate , Diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7- Amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, Examples include 2-hydroxy-3-phenoxypropyl acrylate, nonylphenol ethylene oxide-modified (meth) acrylate, and compounds represented by the following general formula.
［式中、Ｒ1は、水素原子又はメチル基である。Ｒ2及びＲ3は、それぞれ独立に、水素原子、炭素数１〜１０のアルキル基又はフェニル基である。ｎは、０〜１０である。］ [Wherein, R 1 represents a hydrogen atom or a methyl group. R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. n is 0-10. ]
これら（Ｂ１）重合性単官能性化合物のうち、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム等のＮ−ビニル化合物、および炭素数１０以上の脂肪族炭化水素基を有する単官能性（メタ）アクリレートが好ましい。ここで炭素数１０以上の脂肪族炭化水素基としては、直鎖、分岐鎖および脂環式のいずれも含まれ、炭素数は１０〜２４のものが好ましい。これらのうち、イソボルニル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレートが好ましく、イソボルニル（メタ）アクリレートおよび／またはイソデシル（メタ）アクリレートが特に好ましい。これら（Ｂ１）重合性単官能性化合物の市販品としては、ＩＢＸＡ（大阪有機化学工業社製）、アロニックスＭ−１１０、Ｍ−１１１、Ｍ−１１３、Ｍ１１４、Ｍ−１１７、ＴＯ−１２１０（以上、東亞合成社製）、エポキシエステルＭ−６００Ａ（共栄社化学社製）等を使用することができる。 Among these (B1) polymerizable monofunctional compounds, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and monofunctional (meth) acrylates having an aliphatic hydrocarbon group having 10 or more carbon atoms are included. preferable. Here, as the aliphatic hydrocarbon group having 10 or more carbon atoms, any of straight chain, branched chain and alicyclic is included, and those having 10 to 24 carbon atoms are preferable. Of these, isobornyl (meth) acrylate, isodecyl (meth) acrylate, and lauryl (meth) acrylate are preferable, and isobornyl (meth) acrylate and / or isodecyl (meth) acrylate are particularly preferable. Commercially available products of these (B1) polymerizable monofunctional compounds include IBXA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Aronix M-110, M-111, M-113, M114, M-117, TO-1210 (or more Epoxy ester M-600A (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be used.
（Ｂ２）重合性多官能性化合物としては、光ファイバ用樹脂組成物として使用できるものであれば特に制限はないが、好ましい例としては、ポリエチレングリコールジアクリレート、トリシクロデカンジイルジメチレンジ（メタ）アクリレート、エチレンオキサイドを付加させたビスフェノールＡのジ（メタ）アクリレート、トリス（２−ヒドロキシエチル）イアオシアヌレートトリ（メタ）アクリレート、ヘキサンジオールジアクリレート（ＨＤＤＡ）等が挙げられる。これら（Ｂ２）重合性多官能性化合物の市販品としては、例えば、ライトアクリレート９ＥＧ−Ａ、４ＥＧ−Ａ（以上、共栄社化学社製）、ユピマーＵＶ、ＳＡ１００２（以上、三菱化学社製）、アロニックスＭ−２１５、Ｍ−３１５、Ｍ−３２５（以上、東亞合成社製）等が挙げられる。 (B2) The polymerizable polyfunctional compound is not particularly limited as long as it can be used as a resin composition for optical fibers. Preferred examples include polyethylene glycol diacrylate, tricyclodecanediyl dimethylene di (meth). Examples include acrylate, di (meth) acrylate of bisphenol A to which ethylene oxide is added, tris (2-hydroxyethyl) iaocyanurate tri (meth) acrylate, hexanediol diacrylate (HDDA), and the like. Commercially available products of these (B2) polymerizable polyfunctional compounds include, for example, light acrylate 9EG-A, 4EG-A (above, manufactured by Kyoeisha Chemical Co., Ltd.), Iupimer UV, SA1002 (above, manufactured by Mitsubishi Chemical Corporation), Aronix M-215, M-315, M-325 (above, manufactured by Toagosei Co., Ltd.) and the like.
これらの（Ｂ１）重合性単官能性化合物と（Ｂ２）重合性多官能性化合物を併用して用いることもできる。 These (B1) polymerizable monofunctional compound and (B2) polymerizable polyfunctional compound may be used in combination.
これらの（Ｂ）成分は、本発明の液状硬化性樹脂組成物中に１〜６０質量％、特に２〜４５質量％配合することが好ましい。１質量％未満であると硬化性を損ねる可能性があり、６０質量％を超えると低粘度による塗布形状の変化が起き、塗布が安定しない。 These components (B) are preferably blended in the liquid curable resin composition of the present invention in an amount of 1 to 60% by mass, particularly 2 to 45% by mass. If it is less than 1% by mass, the curability may be impaired. If it exceeds 60% by mass, the coating shape changes due to low viscosity, and the coating is not stable.
本発明の（Ｃ）成分であるアミン系光増感剤は、光増感剤であるアミン系化合物であれば、特に限定されず、公知のアミン系光増感剤を使用することができる。ここで、光増感剤とは、後述の（Ｄ）光重合開始剤の硬化を補助して光硬化性を向上させる添加剤である。本発明で用いる（Ｃ）成分は、光増感機能の他にも光安定剤としての機能等をも有するので、特に光増感機能を目的として配合された場合に限定されるものではなく、例えば、光安定剤として配合されたアミン系化合物であっても、その化合物が光増感剤としての機能を潜在的に有するものであれば、（Ｃ）成分に該当する。
（Ｃ）成分の好ましい具体例としては、トリエチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、Ｎ−メチルジエタノールアミン、エタノールアミン、４−ジメチルアミノ安息香酸、４−ジメチルアミノ安息香酸メチル、４−ジメチルアミノ安息香酸エチル、４−ジメチルアミノ安息香酸イソアミル等を挙げることができる。これらは、１種単独で用いることもできるし、２種以上を併用することもできる。市販品としては、ユベクリルＰ１０２、１０３、１０４、１０５（以上、ＵＣＢ社製）等が挙げられる。
The amine photosensitizer that is the component (C) of the present invention is not particularly limited as long as it is an amine compound that is a photosensitizer, and a known amine photosensitizer can be used. Here, the photosensitizer is an additive that assists the curing of the photopolymerization initiator (D) described later and improves photocurability. The component (C) used in the present invention has not only a photosensitizing function but also a function as a light stabilizer, etc., and is not particularly limited when it is formulated for the purpose of a photosensitizing function. For example, even if it is an amine type compound mix | blended as a light stabilizer, if the compound has the function as a photosensitizer potentially, it corresponds to (C) component.
Preferred specific examples of the component (C) include triethylamine, diethylamine, dipropylamine, dibutylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. And ethyl acetate, isoamyl 4-dimethylaminobenzoate, and the like. These can be used alone or in combination of two or more. As a commercial item, Ubekrill P102, 103, 104, 105 (above, UCB company make) etc. are mentioned.
（Ｃ）成分のアミン系光増感剤は、本発明の液状硬化性樹脂組成物中に０．０１〜１０質量％、特に０．０５〜５質量％配合することが好ましい。０．０１質量％未満であると、硬化速度が低下する場合があり、１質量％を超えると、光ファイバ被覆層の耐温水浸漬特性が低下する場合がある。 The amine photosensitizer (C) is preferably blended in the liquid curable resin composition of the present invention in an amount of 0.01 to 10% by mass, particularly 0.05 to 5% by mass. If it is less than 0.01% by mass, the curing rate may be reduced, and if it exceeds 1% by mass, the hot water immersion property of the optical fiber coating layer may be reduced.
本発明の（Ｄ）成分は、光重合開始剤である。（Ｄ）光重合開始剤としては、例えば１−ヒドロキシシクロヘキシルフェニルケトン、２，２−ジメトキシ−２−フェニルアセトフェノン、キサントン、フルオレノン、ベンズアルデヒド、フルオレン、アントラキノン、トリフェニルアミン、カルバゾール、３−メチルアセトフェノン、４−クロロベンゾフェノン、４，４′−ジメトキシベンゾフェノン、４，４′−ジアミノベンゾフェノン、ミヒラーケトン、ベンゾインプロピルエーテル、ベンゾインエチルエーテル、ベンジルジメチルケタール、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、チオキサントン、ジエチルチオキサントン、２−イソプロピルチオキサントン、２−クロロチオキサントン、２−メチル−１−〔４−（メチルチオ）フェニル〕−２−モルホリノ−プロパン−１−オン、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス−（２，６−ジメトキシベンゾイル）−２，４，４−トリメチルペンチルホスフィンオキシド等が挙げられる。これらの市販品としては、イルガキュア１８４、３６９、６５１、５００、９０７、８１９、Ｉｒｇａｃｕｒｅ１７００、Ｉｒｇａｃｕｒｅ１８５０、ＣＧＩ１８７０、ＣＧ２４６１、ダロキュア１１１６、１１７３（以上、チバ・スペシャルティ・ケミカルズ社製）、ＬＵＣＩＲＩＮ ＴＰＯ（ＢＡＳＦ社製）、ユベクリルＰ３６（ＵＣＢ社製）等が挙げられる。 The component (D) of the present invention is a photopolymerization initiator. (D) As the photopolymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2- Lorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like. These commercially available products include Irgacure 184, 369, 651, 500, 907, 819, Irgacure 1700, Irgacure 1850, CGI 1870, CG2461, Darocur 1116, 1173 (above, manufactured by Ciba Specialty Chemicals), LUCIRIN TPO (manufactured by BASF) ), Ubekrill P36 (manufactured by UCB) and the like.
（Ｄ）重合開始剤は、本発明の液状硬化性樹脂組成物中に０．０１〜１０質量％、特に０．０５〜５質量％配合することが好ましい。 (D) It is preferable to mix | blend a polymerization initiator 0.01-10 mass% in the liquid curable resin composition of this invention, especially 0.05-5 mass%.
また、本発明の液状硬化性樹脂組成物には、上記成分以外に各種添加剤、例えば着色剤、（Ｃ）成分以外の光増感剤、シランカップリング剤、酸化防止剤、熱重合禁止剤、レベリング剤、界面活性剤、保存安定剤、可塑剤、滑剤、溶媒、フィラー、老化防止剤、濡れ性改良剤、塗面改良剤等を必要に応じて配合することができる。ここで光増感剤としては、例えばチヌビン ２９２、１４４、６２２ＬＤ（以上、チバ・スペシャルティ・ケミカルズ社製）、サノールＬＳ７７０（三共社製）、ＴＭ−０６１（住友化学工業社製）、ＳＥＥＳＯＲＢ１０１、ＳＥＥＳＯＲＢ１０３、ＳＥＥＳＯＲＢ７０９（以上、シプロ化成社製）、Ｓｕｍｉｓｏｒｂ１３０（住友化学社製）等が挙げられる。シランカップリング剤としては、例えばγ−アミノプロピルトリエトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メタアクリロキシプロピルトリメトキシシラン、市販品として、ＳＨ６０６２、ＳＺ６０３０（以上、東レ・ダウ・コーニングシリコーン社製）、ＫＢＥ９０３、６０３、４０３（以上、信越化学工業社製）等が挙げられる。酸化防止剤としては、例えばＳｕｍｉｌｉｚｅｒ ＧＡ−８０（住友化学社製）、Ｉｒｇａｎｏｘ１０１０、Ｉｒｇａｎｏｘ１０３５（以上、チバ・スペシャリティ・ケミカルズ社製）等が挙げられる。 In addition to the above components, the liquid curable resin composition of the present invention includes various additives such as colorants, photosensitizers other than the component (C), silane coupling agents, antioxidants, thermal polymerization inhibitors. , A leveling agent, a surfactant, a storage stabilizer, a plasticizer, a lubricant, a solvent, a filler, an anti-aging agent, a wettability improver, a coating surface improver, and the like can be blended as necessary. Here, examples of the photosensitizer include Tinuvin 292, 144, 622LD (manufactured by Ciba Specialty Chemicals), Sanol LS770 (manufactured by Sankyo Co., Ltd.), TM-061 (manufactured by Sumitomo Chemical Co., Ltd.), SEESORB101, SESORB103. SEESORB 709 (manufactured by Cypro Kasei Co., Ltd.), Sumisorb 130 (Sumitomo Chemical Co., Ltd.), and the like. Examples of silane coupling agents include γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and commercially available products such as SH6062, SZ6030 (above, Toray Dow Corning Silicone). Co., Ltd.), KBE903, 603, 403 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Examples of the antioxidant include Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Irganox 1010, Irganox 1035 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and the like.
本発明の液状硬化性樹脂組成物は、亜鉛及びコバルト元素の合計含有量が０．５〜１０ppm、好ましくは１〜８ppm、さらに好ましくは２〜５ppmであることが必要である。これらの元素の含有量は、高周波プラズマ発光・質量分析法（Inductively coupled plasma mass spectroscopy；ＩＣＰ−ＭＳ）により求められる。これらの金属元素は、主に、（Ａ）成分の原料であるポリエーテルポリオール標品中に含まれる錯体触媒に由来する。これらの元素の合計含有量が、０．５ppm未満であると、（Ｃ）成分の化合物とこれらの金属元素の錯体との錯形成が不十分となるため、親水性の高い（Ｃ）成分を核として吸水が進行し、耐温水浸漬特性が低下する場合がある。また、これらの元素の含有量が、１０ppmを超えると、ポリエーテルポリオール標品中に含まれる錯体触媒として存在するこれらの元素の化合物が、通常、イオン性物質であるため、本発明の液状硬化性樹脂組成物の製造時に帯電フィルターを使用して濾過をより厳密に行う必要を生じ、生産性を低下させることがある。 The liquid curable resin composition of the present invention needs to have a total content of zinc and cobalt elements of 0.5 to 10 ppm, preferably 1 to 8 ppm, more preferably 2 to 5 ppm. The content of these elements is determined by inductively coupled plasma mass spectroscopy (ICP-MS). These metal elements are mainly derived from the complex catalyst contained in the polyether polyol preparation which is the raw material of the component (A). When the total content of these elements is less than 0.5 ppm, complex formation between the compound of component (C) and the complex of these metal elements becomes insufficient. Water absorption proceeds as a nucleus, and the resistance to warm water immersion may deteriorate. Further, when the content of these elements exceeds 10 ppm, the compound of these elements present as a complex catalyst contained in the polyether polyol preparation is usually an ionic substance. When manufacturing the conductive resin composition, it is necessary to perform filtration more strictly using a charged filter, which may reduce productivity.
本発明の液状硬化性樹脂組成物の２５℃における粘度は、１．０〜６．０Pa・sが好ましい。また、光ファイバプライマリ層として用いる場合、硬化物のヤング率は０．１〜２．０MPaが好ましい。 The viscosity at 25 ° C. of the liquid curable resin composition of the present invention is preferably 1.0 to 6.0 Pa · s. Moreover, when using as an optical fiber primary layer, the Young's modulus of hardened | cured material has preferable 0.1-2.0 MPa.
本発明の液状硬化性樹脂組成物は、放射線によって硬化される。ここで放射線とは、赤外線、可視光線、紫外線、Ｘ線、α線、β線、γ線、電子線等であるが、特に紫外線が好ましい。 The liquid curable resin composition of the present invention is cured by radiation. Here, the radiation includes infrared rays, visible rays, ultraviolet rays, X-rays, α rays, β rays, γ rays, electron rays, and the like, and ultraviolet rays are particularly preferable.
本発明の別の態様は、以上述べた液状硬化性樹脂組成物を、ガラスファイバ素線または他の光ファイバ被覆層の上に塗布して、放射線により硬化せしめることに得られる光ファイバ被覆層である。放射線として紫外線を用いる場合における、好ましい照射条件は、５０〜３００Ｊ／cm2である。本発明の光ファイバ被覆層は、光ファイバの被覆層の任意の一部の層又は全部の層を成すものであるが、好ましくは、光ファイバの一次被覆層を成す。 Another aspect of the present invention is an optical fiber coating layer obtained by applying the liquid curable resin composition described above on a glass fiber strand or other optical fiber coating layer and curing it by radiation. is there. Preferable irradiation conditions when using ultraviolet rays as radiation are 50 to 300 J / cm 2 . The optical fiber coating layer of the present invention forms any part or all of the coating layer of the optical fiber, but preferably forms the primary coating layer of the optical fiber.
本発明のさらに別の態様は、上記の光ファイバ被覆層を有する光ファイバである。本発明の光ファイバは、上記光ファイバ被覆層を有していれば、その被覆層がいずれの層であるかによって限定されるものではないが、好ましくは、上記光ファイバ被覆層が一次被覆層であって、さらに二次被覆層を有する光ファイバ、又は、複数本の光ファイバをテープ材で結束した光ファイバテープを挙げることができる。本発明の光ファイバは、石英母材を溶融して得られるガラスファイバ素線に、例えば、一次被覆材を塗布し放射線を照射して硬化させた後に、さらに、二次被覆材を塗布し放射線を照射して硬化させることによって得られる。本発明の光ファイバは、高い耐温水浸漬特性を有している。 Yet another embodiment of the present invention is an optical fiber having the above optical fiber coating layer. As long as the optical fiber of the present invention has the above-mentioned optical fiber coating layer, it is not limited by which layer the coating layer is, but preferably the optical fiber coating layer is a primary coating layer. In addition, an optical fiber having a secondary coating layer or an optical fiber tape in which a plurality of optical fibers are bundled with a tape material can be exemplified. The optical fiber of the present invention is prepared by, for example, applying a primary coating material to a glass fiber obtained by melting a quartz base material and irradiating and curing the radiation, and then applying a secondary coating material to the radiation. Is obtained by irradiating and curing. The optical fiber of the present invention has a high resistance to hot water immersion.
以下に本発明を実施例により具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
合成例１（ウレタン（メタ）アクリレートの合成）
撹拌機を備えた反応容器に、亜鉛及びコバルト化合物を６〜８ppm含んだ数平均分子量が２０００のポリプロピレングリコール５０．９６８部、イソホロンジイソシアネート７．９２０部、２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．０１５部、フェノチアジン０．００５部を仕込み、これらを撹拌しながら液温度が１５℃となるまで冷却した。ジブチル錫ジラウレート０．４９部を添加した後、攪拌しながら液温度を１時間かけて３５℃まで徐々に上げた。その後、液温度を５０℃に上げて反応させた。残留イソシアネート基濃度が１．４５質量％（仕込量に対する割合）以下となった後、２−ヒドロキシエチルアクリレート２．３６５部を添加し、液温度約６０℃にて撹拌し、反応させた。残留イソシアネート基濃度が０．１質量％以下になった時を反応終了とした。得られたウレタンアクリレートオリゴマーをオリゴマーＡとする。
Synthesis Example 1 (Synthesis of urethane (meth) acrylate)
In a reaction vessel equipped with a stirrer, 50.968 parts of polypropylene glycol having a number average molecular weight of 2000 containing 6-8 ppm of zinc and cobalt compounds, 7.920 parts of isophorone diisocyanate, 2,6-di-t-butyl-p -0.015 part of cresol and 0.005 part of phenothiazine were charged, and these were cooled until the liquid temperature became 15 ° C while stirring. After adding 0.49 part of dibutyltin dilaurate, the liquid temperature was gradually raised to 35 ° C. over 1 hour with stirring. Thereafter, the liquid temperature was raised to 50 ° C. for reaction. After the residual isocyanate group concentration became 1.45% by mass (ratio to the charged amount) or less, 2.365 parts of 2-hydroxyethyl acrylate was added and stirred at a liquid temperature of about 60 ° C. for reaction. The reaction was terminated when the residual isocyanate group concentration was 0.1% by mass or less. Let the obtained urethane acrylate oligomer be the oligomer A.
合成例２（ウレタン（メタ）アクリレートの合成）
撹拌機を備えた反応容器に、亜鉛及びコバルト化合物を６〜８ppm含んだ数平均分子量が２０００のポリプロピレングリコール６６．７８部、２，４−トリレンジイソシアネート８．１４１部、２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．０１９部、フェノチアジン０．００５部を仕込み、これらを撹拌しながら液温度が１５℃となるまで冷却した。ジブチル錫ジラウレート０．６２部を添加した後、攪拌しながら液温度を１時間かけて３５℃まで徐々に上げた。その後、液温度を５０℃に上げて反応させた。残留イソシアネート基濃度が１．５２質量％（仕込量に対する割合）以下となった後、２−ヒドロキシエチルアクリレート３．１０２部を添加し、液温度約６０℃にて撹拌し、反応させた。残留イソシアネート基濃度が０．１質量％以下になった時を反応終了とした。得られたウレタンアクリレートオリゴマーをオリゴマーＤとする。
Synthesis Example 2 (Synthesis of urethane (meth) acrylate)
In a reaction vessel equipped with a stirrer, 66.78 parts of polypropylene glycol containing 6-8 ppm of zinc and cobalt compounds and having a number average molecular weight of 2000, 8,141 parts of 2,4-tolylene diisocyanate, 2,6-di- 0.019 part of t-butyl-p-cresol and 0.005 part of phenothiazine were charged and cooled until the liquid temperature reached 15 ° C. while stirring. After adding 0.62 part of dibutyltin dilaurate, the liquid temperature was gradually raised to 35 ° C. over 1 hour with stirring. Thereafter, the liquid temperature was raised to 50 ° C. for reaction. After the residual isocyanate group concentration became 1.52% by mass (ratio to the charged amount) or less, 3.102 parts of 2-hydroxyethyl acrylate was added, and the mixture was stirred and reacted at a liquid temperature of about 60 ° C. The reaction was terminated when the residual isocyanate group concentration was 0.1% by mass or less. Let the obtained urethane acrylate oligomer be the oligomer D.
比較合成例１（ウレタン（メタ）アクリレートの合成）
亜鉛及びコバルト化合物を６〜８ppm含んだ数平均分子量が２０００のポリプロピレングリコールに替えて、亜鉛及びコバルト化合物を１〜２ppm含んだ数平均分子量が２０００のポリプロピレングリコールを用いた以外は、合成例１と同様にして、ウレタンアクリレートオリゴマーを合成した。得られたウレタンアクリレートオリゴマーをオリゴマーＢとする。
Comparative Synthesis Example 1 (Synthesis of urethane (meth) acrylate)
Synthetic Example 1 except that polypropylene glycol having a number average molecular weight of 2,000 containing 1 to 2 ppm of zinc and cobalt compound was used instead of polypropylene glycol having a number average molecular weight of 2,000 containing 6 to 8 ppm of zinc and cobalt compounds. Similarly, a urethane acrylate oligomer was synthesized. Let the obtained urethane acrylate oligomer be the oligomer B.
比較合成例２（ウレタン（メタ）アクリレートの合成）
亜鉛及びコバルト化合物を６〜８ppm含んだ数平均分子量が２０００のポリプロピレングリコールに替えて、亜鉛及びコバルト化合物を１５〜２５ppm含んだ数平均分子量が２０００のポリプロピレングリコールを用いた以外は、合成例１と同様にして、ウレタンアクリレートオリゴマーを合成した。得られたウレタンアクリレートオリゴマーをオリゴマーＣとする。
Comparative Synthesis Example 2 (Synthesis of urethane (meth) acrylate)
Synthetic Example 1 except that polypropylene glycol having a number average molecular weight of 2000 containing 15 to 25 ppm of zinc and cobalt compound was used instead of polypropylene glycol having a number average molecular weight of 2000 containing 6 to 8 ppm of zinc and cobalt compound. Similarly, a urethane acrylate oligomer was synthesized. Let the obtained urethane acrylate oligomer be the oligomer C.
合成例３（二次被覆材の調製）
撹拌機を備えた反応容器に、イソホロンジイソシアネート１５．４部、２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．０１３部、ジブチル錫ジラウレート０．０４７部を仕込み、これらを撹拌しながら液温度が１０℃以下になるまで氷冷した。ヒドロキシエチルアクリレートを液温度が２０℃以下になるように制御しながら１１．３２ｇ滴下した後、さらに、１時間撹拌し、反応させた。次に数平均分子量１，０００のポリテトラメチレングリコール２５．４ｇおよび数平均分子量４００のビスフェノールＡのアルキレンオキサイド付加ジオール９．３６ｇを加え、液温度７０〜７５℃にて３時間撹拌を継続させ、残留イソシアネートが０．１質量％以下になった時を反応終了とした。液温度５０〜６０℃に冷却し、イソボニルアクリレート９．７ｇ、ＳＡ−１００２（三菱化学社製）１４．５５ｇ、Ｎ−ビニルカプロラクタム９．７ｇ、Ｉｒｇａｃｕｒｅ１８４（チバスペシャリティーケミカルズ社製）２．９１ｇおよびスミライザー ＧＡ−８０（住友化学社製）０．３ｇを加え、均一になるまで撹拌して、液状硬化性樹脂組成物を得た。
Synthesis Example 3 (Preparation of secondary coating material)
A reaction vessel equipped with a stirrer is charged with 15.4 parts of isophorone diisocyanate, 0.013 part of 2,6-di-t-butyl-p-cresol, and 0.047 part of dibutyltin dilaurate, and the liquid is stirred while stirring. The mixture was cooled on ice until the temperature reached 10 ° C or lower. 11.32 g of hydroxyethyl acrylate was dropped while controlling the liquid temperature to be 20 ° C. or lower, and the mixture was further stirred for 1 hour to be reacted. Next, 25.4 g of polytetramethylene glycol having a number average molecular weight of 1,000 and 9.36 g of alkylene oxide addition diol of bisphenol A having a number average molecular weight of 400 are added, and stirring is continued at a liquid temperature of 70 to 75 ° C. for 3 hours. The reaction was terminated when the residual isocyanate was 0.1% by mass or less. Cooled to a liquid temperature of 50 to 60 ° C., 9.7 g of isobornyl acrylate, 14.55 g of SA-1002 (manufactured by Mitsubishi Chemical), 9.7 g of N-vinylcaprolactam, 2.91 g of Irgacure 184 (manufactured by Ciba Specialty Chemicals) Then, 0.3 g of Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.) was added and stirred until uniform to obtain a liquid curable resin composition.
合成例４（二次被覆材の調製）
攪拌機を備えた反応容器に、数平均分子量１０００のポリプロピレングリコール１８０．８８ｇ、数平均分子量１００００のポリプロピレングリコール９．０２ｇ、２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．１８２ｇ、トリレンジイソシアネート２５７．２２ｇ、２−エチルヘキシルアクリレート９５．８０ｇを仕込み、これらを攪拌しながら、液温度が１５℃となるまで冷却した。ジブチル錫ジラウレート０．６０５ｇを添加した後、温度が４０℃以上にならないように注意しながら、１時間ほど攪拌した。室温になるまで攪拌した後、２−ヒドロキシプロピルアクリレート８８．８９ｇを、液温度が３０℃を越えないように調節しながら滴下した。滴下終了後、液温度４０℃で１時間撹拌した。次に、２−ヒドロキシエチルアクリレート２２０．７７ｇを、液温度が６０℃を越えないように調節しながら滴下した。滴下終了後、液温度６０℃で撹拌した。残留イソシアネート基濃度が０．１重量％以下になった時を反応終了とし、ウレタン（メタ）アクリレートオリゴマーを得た（これを重合性オリゴマーとする）。液温度を５０〜６０℃に冷却し、２−エチルへキシルアクリレート１１４．９５ｇ、Ｉｒｇａｎｏｘ２４５（チバスペシャリティーケミカルズ社製）２．９０ｇ、Ｉｒｇａｃｕｒｅ１８４（チバスペシャリティーケミカルズ社製）２９．０３ｇを加え、均一な樹脂液になるまで撹拌して、液状硬化性樹脂組成物を得た。
Synthesis Example 4 (Preparation of secondary coating material)
In a reaction vessel equipped with a stirrer, 180.88 g of polypropylene glycol having a number average molecular weight of 1000, 9.02 g of polypropylene glycol having a number average molecular weight of 10,000, 0.182 g of 2,6-di-t-butyl-p-cresol, tolylene diisocyanate 257.22 g and 2-ethylhexyl acrylate 95.80 g were charged, and the mixture was cooled to a liquid temperature of 15 ° C. while stirring. After adding 0.605 g of dibutyltin dilaurate, the mixture was stirred for about 1 hour, taking care not to increase the temperature to 40 ° C. or higher. After stirring to room temperature, 88.89 g of 2-hydroxypropyl acrylate was added dropwise while adjusting the liquid temperature so as not to exceed 30 ° C. After completion of dropping, the mixture was stirred at a liquid temperature of 40 ° C. for 1 hour. Next, 220.77 g of 2-hydroxyethyl acrylate was added dropwise while adjusting the liquid temperature so as not to exceed 60 ° C. After completion of dropping, the mixture was stirred at a liquid temperature of 60 ° C. The reaction was terminated when the residual isocyanate group concentration was 0.1% by weight or less, and a urethane (meth) acrylate oligomer was obtained (this is referred to as a polymerizable oligomer). The liquid temperature was cooled to 50 to 60 ° C., and 114.95 g of 2-ethylhexyl acrylate, 2.90 g of Irganox 245 (manufactured by Ciba Specialty Chemicals), 29.03 g of Irgacure 184 (manufactured by Ciba Specialty Chemicals) were added, and uniform A liquid curable resin composition was obtained by stirring until a new resin solution was obtained.
実施例１〜２、比較例１〜３（一次被覆材の調製）
撹拌機を備えた反応容器に表１に示す配合比（質量部）で化合物を仕込み、均一な溶液になるまで液温度５０℃で攪拌し、実施例及び比較例の液状硬化性樹脂組成物を得た。
Examples 1-2, Comparative Examples 1-3 (Preparation of primary coating material)
A reaction vessel equipped with a stirrer was charged with the compound at a blending ratio (parts by mass) shown in Table 1, and stirred at a liquid temperature of 50 ° C. until a uniform solution was obtained. Obtained.
製造例１（光ファイバ素線の製造）
光ファイバ線引き装置（吉田工業製）を使用して、石英ガラスファイバ上に一次被覆材として、実施例又は比較例の組成物を塗布硬化させた後、二次被覆材を塗布し硬化させた。光ファイバの製造条件は以下のように行った。
光ファイバの線径は、ガラスファイバは直径１２５μｍであったが、これに実施例又は比較例で得られた一次被覆材を塗布硬化させ、直径が２００μｍになるように調整した。さらに形成された一次被覆層の上に、合成例３で得られた二次被覆材を塗布し、硬化した時点で２４５μｍになるように調節して塗布した。紫外線照射装置はＯＲＣ社製ＵＶランプ（ＳＭＸ３．５ｋｗ）を使用した。光ファイバの線引き速度は２００ｍ／minとした。
Production Example 1 (Manufacture of optical fiber)
Using an optical fiber drawing device (manufactured by Yoshida Kogyo Co., Ltd.), the composition of the example or comparative example was applied and cured as a primary coating material on the quartz glass fiber, and then the secondary coating material was applied and cured. The manufacturing conditions of the optical fiber were as follows.
The fiber diameter of the optical fiber was 125 μm for the glass fiber, but the primary coating material obtained in the example or the comparative example was applied and cured to this to adjust the diameter to 200 μm. Furthermore, on the formed primary coating layer, the secondary coating material obtained in Synthesis Example 3 was applied, and adjusted to 245 μm when applied and applied. As an ultraviolet irradiation device, a UV lamp (SMX 3.5 kW) manufactured by ORC was used. The drawing speed of the optical fiber was 200 m / min.
製造例２（光ファイバ素線の製造）
合成例２で得られた液状硬化性樹脂組成物を一次被覆材とし、合成例４で得られた液状硬化性樹脂組成物を二次被覆材として、それぞれ用いた他は製造例１と同様にして、光ファイバ素線を製造した。
Production Example 2 (Manufacture of optical fiber)
The liquid curable resin composition obtained in Synthesis Example 2 was used as the primary coating material, and the liquid curable resin composition obtained in Synthesis Example 4 was used as the secondary coating material. An optical fiber was manufactured.
試験例
（１）硬化性：
実施例および比較例で得られた液状硬化性樹脂組成物の硬化性を測定した。２００μｍ厚のアプリケーターバーを用いてガラス板上に液状硬化性樹脂組成物を塗布し、これを空気中で２０mＪ／cm2および５００mＪ／cm2のエネルギーの紫外線を照射して硬化させ、試験用フィルム二種類を得た。この硬化フィルム二種類からそれぞれ延伸部が幅６mm、長さ２５mmとなるよう、短冊状サンプルを作成した。温度２３℃、湿度５０％下で引張り試験機ＡＧＳ−１ＫＮＤ（島津製作所社製）を用い、ＪＩＳ Ｋ７１２７に準拠して引張試験を行った。引張速度は１mm／minで２．５％歪みでの抗張力からヤング率を求めた。２０mＪ／cm2で硬化させた試験用フィルムのヤング率と５００mＪ／cm2で硬化させた試験用フィルムのヤング率の比を式（１）より算出して、組成物の硬化速度を評価した。
硬化性 ＝（２０mJ／cm2時のヤング率）／（５００mJ／cm2時のヤング率）（１）
Test Example (1) Curability:
The curability of the liquid curable resin composition obtained in Examples and Comparative Examples was measured. With 200μm thickness applicator bar curable liquid resin composition was applied to a glass plate, which was cured by irradiation with energy ultraviolet of 20 mJ / cm 2 and 500 mJ / cm 2 in air, test film Got two kinds. A strip-shaped sample was prepared from each of the two types of cured films so that the stretched portion had a width of 6 mm and a length of 25 mm. A tensile test was performed in accordance with JIS K7127 using a tensile tester AGS-1KND (manufactured by Shimadzu Corporation) at a temperature of 23 ° C. and a humidity of 50%. The Young's modulus was obtained from the tensile strength at a tensile rate of 1 mm / min and a strain of 2.5%. The ratio of Young's modulus of the test film cured at 20 mJ / cm 2 and Young's modulus of the test film cured at 500 mJ / cm 2 was calculated from the formula (1), and the curing rate of the composition was evaluated.
Curability = (Young's modulus at 20 mJ / cm 2 ) / (Young's modulus at 500 mJ / cm 2 ) (1)
（２）耐温水浸漬特性：
実施例および比較例で得られた液状硬化性樹脂組成物の温水浸漬試験を行った。７０μｍ厚のアプリケーターバーを用いてガラス板上に合成例３で調製した二次被覆材を塗布し、これを空気中で１００mＪ／cm2の紫外線を照射し硬化させた。次に、作製した硬化フィルム上に１３０μｍ厚のアプリケーターバーを用いて実施例及び比較例で調製した一次被覆材を塗布し、これを窒素中で５００mＪ／cm2の紫外線を照射して硬化させた。さらに、２００μｍ厚のアプリケーターバーを用いてガラス板上に合成例３で調製した二次被覆材を塗布し、これを窒素中で５００mＪ／cm2の紫外線を照射して硬化させ、試験用フィルムを得た。この硬化フィルムからそれぞれ幅１０mm、長さ３０mmとなるよう、短冊状サンプルを作成した。短冊サンプルを温度６０℃の温水に浸漬させ、光学顕微鏡で観察した。７２０時間温水に浸漬した後に、１０μｍ以上の発泡が認められない場合を「○」、１０μｍ以上の発泡が認められる場合を「×」と評価した。
(2) Warm water immersion characteristics:
A hot water immersion test was performed on the liquid curable resin compositions obtained in Examples and Comparative Examples. The secondary coating material prepared in Synthesis Example 3 was applied onto a glass plate using an applicator bar having a thickness of 70 μm, and this was cured by irradiating with 100 mJ / cm 2 ultraviolet rays in the air. Next, the primary coating material prepared in Examples and Comparative Examples was applied onto the produced cured film using an applicator bar having a thickness of 130 μm, and this was cured by irradiation with ultraviolet rays of 500 mJ / cm 2 in nitrogen. . Further, the secondary coating material prepared in Synthesis Example 3 was applied onto a glass plate using an applicator bar having a thickness of 200 μm, and this was cured by irradiating with 500 mJ / cm 2 of ultraviolet light in nitrogen. Obtained. A strip-shaped sample was prepared from the cured film so as to have a width of 10 mm and a length of 30 mm. The strip sample was immersed in warm water at a temperature of 60 ° C. and observed with an optical microscope. A case where foaming of 10 μm or more was not observed after immersion in warm water for 720 hours was evaluated as “◯”, and a case where foaming of 10 μm or more was observed was evaluated as “X”.
（３）濾過性：
実施例および比較例で得られた液状硬化性樹脂組成物の濾過性試験を行った。組成物１００ｇをメチルエチルケトン１００ｇに溶解させ、ＰＴＦＥメンブレンフィルター（１．０μｍ、４７mm：ＡＤＶＡＮＴＥＣ社製）を使用し濾過した。３０分の濾過で得られた濾液量を測定した。
(3) Filterability:
The filterability test of the liquid curable resin compositions obtained in the examples and comparative examples was performed. 100 g of the composition was dissolved in 100 g of methyl ethyl ketone, and filtered using a PTFE membrane filter (1.0 μm, 47 mm: manufactured by ADVANTEC). The amount of filtrate obtained by filtration for 30 minutes was measured.
（４）判定：
硬化性が０．８０以上で、耐温水浸漬試験が「○」評価であり、濾過性試験で１００ｇ以上の場合を合格と判定した。
(4) Judgment:
The curability was 0.80 or more, the hot water immersion test was “◯” evaluation, and the filterability test was determined to be 100 g or more.
以上の結果を表１に併せて示す。表中の各成分の配合量を示す数値は、質量部である。 The above results are also shown in Table 1. The numerical value which shows the compounding quantity of each component in a table | surface is a mass part.
表１中、
アロニックスＭ−１１３：ノニルフェノールエチレンオキサイド変性アクリレート、東亞合成社製
Ｉｒｇａｎｏｘ１０３５：チオジエチレンビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］（チバ・スペシャルティ・ケミカルズ社製）ＳＥＥＳＯＲＢ１０１：２−ヒドロキシ−４−メトキシベンゾフェノン（シプロ化成社製）
ＳＨ６０６２：γ−メルカプトキシプロピルトリメトキシシラン（東レ・ダウコーニング・シリコーン社製）
In Table 1,
Aronix M-113: Nonylphenol ethylene oxide-modified acrylate, Irganox 1035 manufactured by Toagosei Co., Ltd .: Thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals) SEESORB101: 2-hydroxy-4-methoxybenzophenone (manufactured by Cypro Kasei Co., Ltd.)
SH6062: γ-mercaptooxypropyltrimethoxysilane (Toray Dow Corning Silicone)
Claims (4)
（Ａ）ポリプロピレングリコール由来の構造を有するウレタン（メタ）アクリレート ３５〜８５質量％、
（Ｂ）（Ａ）以外のエチレン性不飽和基含有化合物 １〜６０質量％、
（Ｃ）アミン系光増感剤 ０．０１〜１質量％、及び
（Ｄ）光重合開始剤 ０．０１〜１０質量％
を含有する液状硬化性樹脂組成物であって、高周波プラズマ発光・質量分析法（ＩＣＰ−ＭＳ）により求めた組成物中の亜鉛及びコバルト元素の合計含有量が０．５〜１０ppmである、液状硬化性樹脂組成物。 The total amount of the composition is 100% by mass,
(A) 35 to 85% by mass of urethane (meth) acrylate having a structure derived from polypropylene glycol ,
(B) 1 to 60% by mass of an ethylenically unsaturated group-containing compound other than (A),
(C) Amine-based photosensitizer 0.01 to 1% by mass, and (D) Photopolymerization initiator 0.01 to 10% by mass.
A liquid curable resin composition containing a zinc and cobalt element in the composition determined by high-frequency plasma emission / mass spectrometry (ICP-MS), the total content of which is 0.5 to 10 ppm. Curable resin composition.
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