KR100312040B1 - UV curable compositions for optical fibers - Google Patents
UV curable compositions for optical fibers Download PDFInfo
- Publication number
- KR100312040B1 KR100312040B1 KR1019990007590A KR19990007590A KR100312040B1 KR 100312040 B1 KR100312040 B1 KR 100312040B1 KR 1019990007590 A KR1019990007590 A KR 1019990007590A KR 19990007590 A KR19990007590 A KR 19990007590A KR 100312040 B1 KR100312040 B1 KR 100312040B1
- Authority
- KR
- South Korea
- Prior art keywords
- meth
- acrylate
- urethane
- optical fiber
- secondary coating
- Prior art date
Links
- 239000013307 optical fiber Substances 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 93
- 238000000576 coating method Methods 0.000 claims abstract description 38
- 239000011248 coating agent Substances 0.000 claims abstract description 36
- -1 diisocyanate compound Chemical class 0.000 claims abstract description 28
- 239000011342 resin composition Substances 0.000 claims abstract description 22
- 150000002009 diols Chemical class 0.000 claims abstract description 18
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 150000003077 polyols Chemical class 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 13
- 239000003085 diluting agent Substances 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 5
- OYQYHJRSHHYEIG-UHFFFAOYSA-N ethyl carbamate;urea Chemical compound NC(N)=O.CCOC(N)=O OYQYHJRSHHYEIG-UHFFFAOYSA-N 0.000 claims description 2
- 230000000704 physical effect Effects 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000004202 carbamide Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- LCXDZLXGIHMSPR-UHFFFAOYSA-N ethyl carbamate methane prop-2-enoic acid Chemical compound C(C=C)(=O)O.C.NC(=O)OCC LCXDZLXGIHMSPR-UHFFFAOYSA-N 0.000 abstract 1
- 238000007380 fibre production Methods 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 18
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 12
- 239000004814 polyurethane Substances 0.000 description 12
- 229920002635 polyurethane Polymers 0.000 description 12
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 125000005442 diisocyanate group Chemical group 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 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 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 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 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 5
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 239000003504 photosensitizing agent Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 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
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 229940117969 neopentyl glycol Drugs 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 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
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- GWGWXYUPRTXVSY-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=C(C)C=C1 Chemical compound N=C=O.N=C=O.CC1=CC=C(C)C=C1 GWGWXYUPRTXVSY-UHFFFAOYSA-N 0.000 description 2
- UQBRAHLFLCMLBA-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=CC(C)=C1 Chemical compound N=C=O.N=C=O.CC1=CC=CC(C)=C1 UQBRAHLFLCMLBA-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 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 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 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
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-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
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-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
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-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
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-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
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- ACWBYVIQVCTYBJ-UHFFFAOYSA-N 3-methyloctane-1,8-diol Chemical compound OCCC(C)CCCCCO ACWBYVIQVCTYBJ-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- RFVHVYKVRGKLNK-UHFFFAOYSA-N bis(4-methoxyphenyl)methanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1 RFVHVYKVRGKLNK-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- MHCLJIVVJQQNKQ-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O MHCLJIVVJQQNKQ-UHFFFAOYSA-N 0.000 description 1
- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- KSEBMYQBYZTDHS-HWKANZROSA-N ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQJVBAIESAQUKR-UHFFFAOYSA-N isocyanic acid;prop-2-enoic acid Chemical compound N=C=O.OC(=O)C=C IQJVBAIESAQUKR-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FSPSELPMWGWDRY-UHFFFAOYSA-N m-Methylacetophenone Chemical compound CC(=O)C1=CC=CC(C)=C1 FSPSELPMWGWDRY-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical group C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000000600 sorbitol 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
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 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
- 238000003325 tomography Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- D—TEXTILES; PAPER
- D05—SEWING; EMBROIDERING; TUFTING
- D05D—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES D05B AND D05C, RELATING TO SEWING, EMBROIDERING AND TUFTING
- D05D2303/00—Applied objects or articles
- D05D2303/42—Optical fibers
Abstract
본 발명은 광섬유 제조에 사용되는 자외선 경화형 2차 코팅 수지 조성물에 관한 것이다. 2차 코팅용 수지에 요구되는 중요한 물성으로 높은 인장탄성율 및 높은 신장율을 갖고, 내수성·경화도 등이 우수한 특성을 들 수 있고, 본 발명은 분자내에 다수의 우레탄 결합이나 우레아 결합을 갖는 새로운 올리고머를 합성하여 사용하는 것에 의해 요구 물성을 달성하였다. 본 발명은 우레탄 (메타)아크릴레이트 올리고머; 광경화형의 (메타)아크릴레이트 모노머; 자외선 의해 개시가 가능한 1종 이상의 광개시제를 포함하는 광섬유 2차 코팅용 광경화형 수지조성물에 있어서, 상기 우레탄 (메탄)아크릴레이트 올리고머가 디이소시아네이트 화합물; 분자량이 400미만인 1종 이상의 단분자 디올 및 분자량이 400~3,000인 폴리올의 혼합물; 그리고 수산기를 갖는 (메타)아크릴레이트 화합물로부터 합성한 것임을 특징으로 한다. 본 발명에서 개발한 올리고머를 사용함에 의해 인장탄성율의 향상에 우수한 효과를 보이면서 신장율의 저하가 적아 높은 강인성의 특성을 갖는 2차 코팅 수지의 물성을 용이하게 달성할 수가 있다.The present invention relates to an ultraviolet curable secondary coating resin composition used for optical fiber production. Important properties required for the resin for secondary coating include high tensile modulus and high elongation, excellent water resistance and hardenability, and the present invention provides a new oligomer having a large number of urethane bonds or urea bonds in a molecule. By using synthetically, the required physical properties were achieved. The present invention is a urethane (meth) acrylate oligomer; Photocurable (meth) acrylate monomers; A photocurable resin composition for optical fiber secondary coating comprising at least one photoinitiator capable of being initiated by ultraviolet light, wherein the urethane (methane) acrylate oligomer is a diisocyanate compound; A mixture of at least one monomolecular diol having a molecular weight of less than 400 and a polyol having a molecular weight of 400 to 3,000; And synthesized from a (meth) acrylate compound having a hydroxyl group. By using the oligomer developed in the present invention, it is possible to easily achieve the physical properties of the secondary coating resin having a high toughness characteristic with little decrease in elongation while showing an excellent effect on improving the tensile modulus.
Description
본 발명은 광섬유 코팅용 자외선 경화형 수지 조성물에 관한 것으로서, 더 구체적으로는 경질(rigid)의 우레탄 메타크릴레이트 올리고머 또는 우레탄 아크릴레이트 올리고머{이하 '우레탄 (메타)아크릴레이트 올리고머'로 표기함}; 광경화형의 메타크릴레이트 모노머 또는 아크릴레이트 모노머{이하 '(메타)아크릴레이트 모노머'로 표기함}; 그리고 광개시제가 함유된 광섬유 2차 코팅용 자외선 경화형 수지조성물에 관한 것이다. 광섬유의 단면도 및 단층절개사시도를 도 1 및 도 2에 나타내었다.The present invention relates to an ultraviolet curable resin composition for optical fiber coating, and more specifically, a rigid urethane methacrylate oligomer or a urethane acrylate oligomer (hereinafter referred to as 'urethane (meth) acrylate oligomer'); Photocurable methacrylate monomers or acrylate monomers (hereinafter referred to as '(meth) acrylate monomers'); And it relates to an ultraviolet curable resin composition for optical fiber secondary coating containing a photoinitiator. The cross-sectional view of the optical fiber and the tomographic cutaway perspective view are shown in FIGS. 1 and 2.
광섬유는 일반적으로 굴절율이 높고 빛의 통로 역할을 하는 심(1)과 굴절율이 낮고 빛의 반사면 역할을 하는 클래드(2), 그리고 낮은 유리 전이온도와 낮은 인장탄성율을 갖는 유연한 고분자로 구성되어 유리섬유의 충격 완충 역할을 하는 1차 코팅(4)과 높은 유리전이온도와 높은 인장탄성율을 갖는 단단한 고분자로 구성되어 유리섬유를 외부압력으로부터 보호하는 역할을 하는 2차 코팅(5)으로 이루어져 있다. 광섬유의 광전송원리는 심 부위에 빛이 입사되면 낮은 굴절율을 갖는 클래드와의 경계면에서 굴절율 차이에 의해 전반사 되어 진행전송되는 것을 그 원리로 하고 있다. 그러나 광섬유의 구부러짐 등이 발생하는 경우 심(1) 부위를 진행하던 일부의 빛이 굴절되어 클래드(2) 층으로 빠져나가는 클래드 모드 현상이 발생되고, 이렇게 빠져 나간 빛이 다시 반사되어 심(1) 부위로 되돌아오면 광신호에 노이즈 현상을 발생시키게 된다. 따라서 이것을 방지하기 위하여 1차 코팅(4)의 굴절율을 클래드의 굴절율보다 높은 1.48 이상으로 하고 2차 코팅(5)의 굴절율을 1.50 이상으로 하여 빠져 나간 빛이 모두 심(1) 바깥방향으로 굴절되어 소멸되도록 하는 광학구조를 갖고 있다.Optical fibers are generally composed of a shim (1) that has a high refractive index and serves as a light passage, a clad that has a low refractive index and serves as a reflective surface of light, and a flexible polymer having a low glass transition temperature and a low tensile modulus. It consists of a primary coating (4), which serves as a shock buffer of the fiber, and a secondary coating (5), which serves to protect the glass fiber from external pressure by being composed of a rigid polymer having a high glass transition temperature and a high tensile modulus. The optical transmission principle of the optical fiber is based on the principle that when light is incident on the core part, the light is totally reflected by the difference in refractive index at the interface with the clad having the low refractive index. However, when the optical fiber is bent or the like, a clad mode phenomenon occurs in which part of the light traveling through the seam (1) portion is refracted and exits to the clad (2) layer. Returning to the part causes noise phenomenon in the optical signal. Therefore, in order to prevent this, all of the light exiting with the refractive index of the primary coating 4 set to 1.48 or more higher than the refractive index of the cladding and the refractive index of the secondary coating 5 set to 1.50 or more is refracted toward the seam 1. It has an optical structure that allows it to disappear.
이외에도 1차 및 2차 코팅(4)(5)은 광섬유에 기계적 강도를 부여해 주고, 또한 유리섬유에 내수성 및 내수분침투성 등을 부여하여 외부환경 변화에 따른 장기안정성을 향상 시키며, 특히 광의 전송손실을 발생시키는 가장 큰 원인인 마이크로벤딩 (microbending)을 최소화 시키는데 기여하는 필수적인 구성요소이다. 마이크로벤딩이란 외부의 압력 등에 의해 광섬유에 미세한 구부러짐이 발생하는 현상으로 전송되는 빛의 난반사를 유발시켜 전송손실을 크게 하는 원인이 되는 현상이다. 따라서 마이크로벤딩에 의한 광손실을 줄이기 위하여 1차 코팅은 낮은 유리전이 온도(0℃이하)와 낮은 인장탄성율(5MPa 이하)을 갖는 유연한 수지로 구성되고, 2차 코팅은 외부 충격으로부터 1차 코팅 및 유리섬유를 보호하기 위하여 높은 인장탄성율(25℃, 1000MPa이상)을 갖는 기계적 물성이 우수한 수지로 구성된다.In addition, the primary and secondary coatings (4) and (5) impart mechanical strength to the optical fiber, and also impart water resistance and moisture permeability to the glass fiber to improve long-term stability due to changes in the external environment, and in particular, transmission loss of light. This is an essential component that contributes to minimizing microbending, which is the biggest cause of this problem. Micro bending is a phenomenon in which fine bending occurs in an optical fiber due to external pressure or the like and causes diffuse reflection of light to cause transmission loss. Therefore, in order to reduce light loss due to micro bending, the primary coating is composed of a flexible resin having a low glass transition temperature (below 0 ° C.) and a low tensile modulus (below 5 MPa). In order to protect the glass fiber, it is composed of a resin having excellent mechanical properties with high tensile modulus (25 ° C, 1000 MPa or more).
일반적으로 광섬유 코팅용 자외선 경화형 수지 조성물은 수평균 분자량이 1,000∼15,000의 폴리우레탄 (메타)아크릴레이트와 광경화형의 반응성 모노머 희석제, 그리고 광개시제로 이루어진다. 종래에는 2차 코팅 수지의 기계적 물성을 높이기 위한 방안으로 높은 강도를 갖는 여러 가지 올리고머를 첨가한다든가 다관능성 모노머 희석제를 첨가하는 방안들이 행하여져 왔다. 예를들면, 비스페놀 에이 디아크릴레이트 디글리시딜에테르와 같은 에폭시 아크릴레이트를 폴리우레탄 아크릴레이트 올리고머와 혼합하여 사용하거나(미국특허 제 4,472,019호), 폴리카보네이트 디올과 같은 인장력이 뛰어난 디올을 이소시아네이트와 반응시킨 폴리우레탄 아크릴레이트 올리고머를 첨가(미국특허 제 4,514,037호)하거나, 또는 다관능성 폴리우레탄아크릴레이트 올리고머를 첨가하여 가교도를 높이거나(미국특허 제 4,690,501호, 미국특허 제 4,690,502호), 폴리우레탄 아크릴레이트 올리고머와 이소시아누레이트를 혼합사용하여 물성을 개선(미국특허 제 4,902,440호, 일본특개소 제 62-50315호)한 예도 있다. 또한 폴리우레탄 아크릴레이트 올리고머 내에 아민기를 도입한 것을 적용하기도 하였다(일본특개소 제 62-78131호). 그러나 이상과 같은 방법으로 배합하여 2차 코팅 수지를 제조할 경우, 그 도막이 높은 인장탄성율은 나타내나 신장율이 줄어드는 경향을 보이고, 이로인하여 외부압력, 즉 측압 및 구부림등에 충분히 대응하지 못하며 마이크로벤딩 및 파단등이 발생하여 광의 전송손실을 일으킬 수 있다. 또한 내용제성, 내수성, 수축율의 증가, 혼화성의 저하 등의 문제점도 야기되고 있다.또한, 광섬유 2차 코팅용 광경화형 수지조성물은 통상 경질(rigid) 폴리우레탄 (메타)아크릴레이트를 그 주요 조성 성분으로 하고 있으나, 경질 폴리우레탄 (메타)아크릴레이트는 일반적으로 연질과는 달리 인장탄성율을 증가시키면 신장율이 떨어지는 성질을 가지고 있어 광섬유 2차 코팅용 수지조성물에서 요구되는 높은 인장탄성율을 가지면서 높은 신장율을 함께 부여하기 어려운 문제점이 있다.In general, the ultraviolet curable resin composition for optical fiber coating comprises a polyurethane (meth) acrylate having a number average molecular weight of 1,000 to 15,000, a photocurable reactive monomer diluent, and a photoinitiator. Conventionally, there have been methods for adding various oligomers having high strength or adding polyfunctional monomer diluents to improve the mechanical properties of secondary coating resins. For example, epoxy acrylates such as bisphenol didiacrylate diglycidyl ether may be used in combination with polyurethane acrylate oligomers (US Pat. No. 4,472,019) or high tensile diols such as polycarbonate diols may be used with isocyanates. Addition of reacted polyurethane acrylate oligomer (US Pat. No. 4,514,037) or polyfunctional polyurethane acrylate oligomer to increase crosslinking degree (US Pat. No. 4,690,501, US Pat. No. 4,690,502), polyurethane acrylic There is an example in which physical properties are improved by using a mixture of a late oligomer and isocyanurate (US Pat. No. 4,902,440, Japanese Patent Laid-Open No. 62-50315). Moreover, what introduce | transduced the amine group into the polyurethane acrylate oligomer was also applied (Japanese Patent Laid-Open No. 62-78131). However, when the secondary coating resin is prepared by the above-described method, the coating film shows a high tensile modulus of elasticity but tends to decrease in elongation, and thus does not sufficiently cope with external pressure, that is, side pressure, bending, and the like. And the like can cause light transmission loss. In addition, problems such as solvent resistance, water resistance, an increase in shrinkage rate, and a decrease in miscibility are also caused. Further, a photocurable resin composition for optical fiber secondary coating usually contains rigid polyurethane (meth) acrylate as its main composition. Hard polyurethane (meth) acrylates, unlike soft materials, generally have high tensile modulus and high elongation rate, which are required in resin compositions for optical fiber secondary coatings. There is a problem that is difficult to give together.
본 발명은 상기한 바와 같은 종래의 광섬유 2차 코팅용 자외선 경화형 수지조성물이 갖고 있는 문제점을 해결하고 도막의 신장율 감소등의 특성저하를 최소화하면서 높은 인장탄성율을 갖는 수지조성물을 제공하려는 것이다.일반적으로 디이소시아네이트와 분자량이 적은 단분자 디올만으로 합성한 폴리우레탄의 경우는 수평균분자량이 적은 경질로서 신장율은 크게 떨어지는 반면 인장탄성율은 크고, 디이소시아네티트와 비교적 분자량이 큰 폴리올만으로 합성한 폴리우레탄의 경우는 수평균분자량이 큰 연질로서 신장율은 큰 반면 인장탄성율이 크게 떨어지는 경향이 있다.이에, 본 발명자들은 디이소시아네이트와; 단분자 디올 및 폴리올의 혼합물로 부터 광섬유 2차 코팅제의 물성에 적합한 우레탄 프레폴리머의 개발에 착수하여 장기간의 연구 끝에 본 발명을 완성하였다.분자내에 우레탄 결합을 단순히 다수 도입한 경질의 폴리우레탄 (메타)아크릴레이트는 인장탄성율을 높이면 신장율이 떨어지나, 비교적 분자량이 적은 단분자 디올 또는 단분자 디아민 및 폴리올의 혼합물과; 디이소시아네이트를 적정 몰(mole) 비로 반응시켜 우레탄 결합을 도입하는 경우는 인장탄성율의 증가와 함께 신장율이 증가된다.이에, 본 발명은 1종 이상의 단부자 디올 또는 단분자 디아민과 폴리올의 혼합물과; 디이소시네이트를 반응시켜 고밀도의 우레탄 결합을 갖는 우레탄 또는 우레아 (메타)아크릴레이트 올리고머를 합성한 후, 여기에 광경화형 모노머 희석제 및 광개시제를 혼합함으로써 1000MPa 이상의 인장탄성율을 가지면서 10%이상의 신장율을 갖는 광섬유 2차 코팅용 광경화형 수지조성물을 얻을 수 있었다.The present invention is to solve the problems of the conventional UV-curable resin composition for optical fiber secondary coating as described above, and to provide a resin composition having a high tensile modulus while minimizing the deterioration of characteristics such as decrease in elongation of the coating film. Polyurethanes synthesized only with diisocyanates and monomolecular diols with low molecular weight have a low number-average molecular weight and have a very low elongation, but a high tensile modulus, and a polyurethane synthesized only with diisocyanates and relatively high molecular weight polyols. In this case, the number-average molecular weight is soft and the elongation rate is large while the tensile modulus tends to be greatly decreased. From the mixture of mono-molecular diols and polyols, we have begun to develop urethane prepolymers suitable for the properties of optical fiber secondary coatings, and after a long period of research, we have completed the present invention. ) Acrylate has a low elongation when the tensile modulus is increased, but a mixture of monomolecular diol or monomolecular diamine and polyol having a relatively low molecular weight; In the case where urethane bonds are introduced by reacting the diisocyanate at an appropriate mole ratio, the elongation rate increases with an increase in the tensile modulus. After reacting diisosinate to synthesize a urethane or urea (meth) acrylate oligomer having a high density urethane bond, a photocurable monomer diluent and a photoinitiator are mixed therewith to have a tensile modulus of 1000 MPa or more and an elongation of 10% or more. A photocurable resin composition for optical fiber secondary coating was obtained.
도 1은 광섬유의 단면도1 is a cross-sectional view of an optical fiber
도 2는 광섬유의 단층 절개 사시도Fig. 2 is a perspective view of tomography of an optical fiber
* 도면의 주요 부분에 대한 부호의 설명 ＊* Explanation of symbols on main parts of drawing *
1 ... 심(core) 2 ... 클래드(clad)3 ... 유리섬유 4 ... 1차코팅5 ... 2차코팅1 ... core 2 ... clad 3 ... glass fiber 4 ... 1st coating 5 ... 2nd coating
이하 본 발명을 상세히 설명한다.본 발명의 조성물은 우레탄 (메타)아크릴레이트 올리고머; 광경화형의 (메타)아크릴레이트 모노머 희석제; 및 광개시제를 함유하는 광섬유 2차 코팅용 자외선 경화형 수지조성물에 있어서,상기 우레탄 (메타)아크릴레이트 올리고머가 디이소시아네이트와; 분자량이 400 미만인 1종 이상의 단분자 디올 및 분자량이 400~3,000인 폴리올의 혼합물; 그리고 수산기 함유 (메탈)아크릴레이트 화합물을 반응시켜 분자내에 고밀도의 우레탄 결합(4~12)을 함유하는 수평균 분자량이 800∼5,000인 우레탄 (메타)아크릴레이트 올리고머인 것을 특징으로 하는 광섬유 2차 코팅용 자외선 경화형 수지 조성물에 관한 것이다. 또한, 단분자 디올 대신에 단분자 디아민을 사용하면 우레아 결합을 함유하는 우레탄우레아 (메타)아크릴레이트 올리고머를 제조할 수 있다.또한, 본 발명은 상기 우레탄 (메타)아크릴레이트 올리고머 60~75중량%; 광경화형의 (메타)아크릴레이트 모노머 희석제 20~50중량%; 및 광개시제 1~5중량%를 포함하여 조성된 광섬유 2차 코팅용 자외선 경화용 수지조성물이다.Hereinafter, the present invention will be described in detail. Compositions of the present invention include urethane (meth) acrylate oligomers; Photocurable (meth) acrylate monomer diluents; And an ultraviolet curable resin composition for optical fiber secondary coating containing a photoinitiator, wherein the urethane (meth) acrylate oligomer is a diisocyanate; A mixture of at least one monomolecular diol having a molecular weight of less than 400 and a polyol having a molecular weight of 400 to 3,000; And a urethane (meth) acrylate oligomer having a number average molecular weight of 800 to 5,000 containing a high-density urethane bond (4-12) in the molecule by reacting a hydroxyl-containing (metal) acrylate compound. The ultraviolet curable resin composition for this invention is related. In addition, when monomolecular diamine is used instead of monomolecular diol, the urethane urea (meth) acrylate oligomer containing a urea bond can be manufactured. In addition, this invention is 60-75 weight% of said urethane (meth) acrylate oligomers. ; 20-50% by weight of a photocurable (meth) acrylate monomer diluent; And it is a resin composition for UV curing for optical fiber secondary coating, including 1 to 5% by weight photoinitiator.
상기 분자내의 우레탄 결합(또는 우레아 결합)은 분자량이 400 미만인 1종 이상의 단분자 디올(또는 단분자 디아민)과 분자량이 400~3,000인 폴리올의 혼합물 1~1.67몰(mole)을 디이소시아네이트 2몰(mole)과 반응시켜 수평균분자량이 800 내지 5,000 범위로 중합되도록 반응을 조절함으로써 분자당 수평균 4~12개의 고밀도로 도입할 수 있다.이소시아네이트로 치환된 우레탄 프레폴리머(prepolymer)의 양말단에 이중 결합을 도입하는 방법은 여러가지의 공지의 방법이 있으나, 그 중 바람직한 방법으로는 우레탄 프레폴리머 1몰에 대해 2몰의 수산기 함유 (메타)아크릴레이트를 투입하여 반응시키는 것(프레폴리머법)이고, 이 때 이 수산기 함유 (메타)아크릴레이트는 알킬기에 2~6개의 탄소를 갖으며 바람직하게는 2-하이드록시에틸(메타)아크릴레이트, 2-하이드록시프로필(메타)아크릴레이트, 2-하이드록시부틸(메타)아크릴레이트 등을 사용하는 것이 좋다. 또 다른 방법으로는 1몰의 디이소시아네이트를 수산기 함유 (메타)아크릴레이트 0.34~1몰 반응시킨 후 다시 1종 이상의 단분자 디올과 1종 이상의 폴리올과의 혼합물 0.5~0.83몰과 반응하여 양말단에 이중결합을 갖는 우레탄 디아크릴레이트 올리고머를 제조하는 방법(아크릴레이트 이소시아네이트법)이 있다.상기 디이소시아네이트로는 이소포론디이소시아네이트, 2,4-톨루엔디이소시아네이트 및 그 이성질체, 헥사메틸렌 디이소시아네이트, 라이신 디이소시아네이트, 트리메틸헥사메틸렌 디이소시아네이트, 2,2-비스-4'-프로판이소시아네이트, 6-이소프로필-1,3-페닐디이소시아네이트, 비스(2-이소시아네이트에틸)-퓨마레이트, 1,6-헥산디이소시아네이트, 4,4'-바이페닐렌 디이소시아네이트, 3,3'-디메틸페닐렌디이소시아네이트, 3,3'-디메틸-4,4'-디페닐메탄디이소시아네이트, p-페닐렌 디이소시아네이트, m-페닐렌 디이소시아네이트, 1,5-나프탈렌디이소시아네이트, 1,4-자일렌디이소시아네이트, 1,3-자일렌디이소시아네이트등을 사용할 수 있으며 바람직하게는 2,4-톨루엔디이소시아네이트 및 그 이성질체, 이소포론디이소시아네이트, 1,5-나프탈렌디이소시아네이트, 1,4-자일렌디이소시아네이트, 1,3-자일렌디이소시아네이트 등을 사용하는 편이 좋다. 분자량이 400 미만인 단분자 디올류로는 에틸렌 글리콜, 프로필렌글리콜, 1,3-부탄디올, 1,4-부탄디올, 1,5-펜탄디올, 1,6-헥산디올, 네오펜틸글리콜, 1,4-사이클로헥산 디메타놀, 비스페놀A, 비스페놀F, 환원비스페놀A, 환원비스페놀F, 디사이클로펜타 디올, 트리사이클로데칸디올 등을 사용하고, 분자내에 3개 이상의 수산기를 갖는 화합물, 즉 글리세롤, 트리메틸올에탄, 트리메틸올프로판, 펜타에리트리톨(pentaerythritol), 솔보스(sorbose), 솔비톨(sorbitol)을 혼합하여 사용할 수 있다. 또한, 분자량 400∼3,000의 폴리올로서는 폴리에테르 폴리올, 폴리에스테르 폴리올, 폴리카보네이트 폴리올 또는 폴리카프로락톤 폴리올을 상기 단분자 디올과 함께 혼합하여 사용한다. 사용되는 폴리에테르 폴리올로는 폴리에틸렌글리콜, 1,2-폴리프로필렌글리콜, 1,3-폴리프로필렌글리콜, 폴리테트라메틸렌글리콜, 1,2-폴리부틸렌글리콜 등과 각 폴리올의 공중합 형태가 예시될 수 있고, 폴리에스테르 폴리올로는 에틸렌글리콜, 폴리에틸렌글리콜, 프로필렌글리콜, 폴리프로필렌글리콜, 폴리테트라메틸렌글리콜, 테트라메틸렌글리콜, 1,3-부탄디올, 1,4-부탄디올, 1,6-헥산디올, 네오펜틸글리콜, 1,4-사이클로헥산디메탄올, 3-메틸-1,8-옥탄다이올 등의 다이올과 프탈릭산, 이소프탈릭산, 테레프탈릭산, 말레익산, 퓨말릭산, 아디픽산, 세바식산 등의 산과 반응한 형태의 폴리에스테르 폴리올과 또는 그 공중합형태가 예시될 수 있다. 또한, 폴리카보네이트 폴리올로는 1,6-헥산폴리카보네이트등을 예시할 수 있고 폴리카프로락톤폴리올로는 ε-카프로락톤과 에틸렌글리콜, 폴리에틸렌글리콜, 프로필렌글리콜, 폴리프로필렌글리콜, 1,3-부탄디올, 1,4-부탄디올, 테트라메틸렌 글리콜, 폴리테트라메틸렌 글리콜, 1,2-폴리부틸렌글리콜, 1,6-헥산다이올, 네오펜틸글리콜, 1,4-사이클로헥산디메타놀등의 다이올과 반응한 형태를 예시할 수 있다.The urethane bond (or urea bond) in the molecule is a mixture of 1 to 1.67 mol (mole) of at least one monomolecular diol (or monomolecular diamine) having a molecular weight of less than 400 and a polyol having a molecular weight of 400 to 3,000 to 2 moles of diisocyanate ( Mole) can be introduced at a high density of 4 to 12 densities per molecule by controlling the reaction so that the number average molecular weight is polymerized in the range of 800 to 5,000. There are various known methods for introducing a bond, but preferred methods include reacting with 2 moles of hydroxyl group-containing (meth) acrylate per 1 mole of urethane prepolymer (prepolymer method), At this time, the hydroxyl group-containing (meth) acrylate has 2 to 6 carbons in the alkyl group, preferably 2-hydroxyethyl (meth) acrylate, 2-hydroxyprop (Meth) acrylate, it is preferable to use, 2-hydroxybutyl (meth) acrylate. In another method, 0.34-1 mole of hydroxyl group-containing (meth) acrylate is reacted with 1 mole diisocyanate and then reacted with 0.5-0.83 mole of a mixture of one or more monomolecular diols and one or more polyols. There is a method for producing a urethane diacrylate oligomer having a double bond (acrylate isocyanate method). Examples of the diisocyanate include isophorone diisocyanate, 2,4-toluene diisocyanate and isomers thereof, hexamethylene diisocyanate and lysine di Isocyanate, trimethylhexamethylene diisocyanate, 2,2-bis-4'-propane isocyanate, 6-isopropyl-1,3-phenyldiisocyanate, bis (2-isocyanate ethyl) -fumarate, 1,6-hexanedi Isocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethylphenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane Socyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,4-xylene diisocyanate, 1,3-xylene diisocyanate, etc. can be used, Preferably it is 2, It is preferable to use 4-toluene diisocyanate and its isomers, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 1,4-xylene diisocyanate, 1,3-xylene diisocyanate and the like. Monomolecular diols having a molecular weight of less than 400 include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, 1,4- Cyclohexane dimethanol, bisphenol A, bisphenol F, reduced bisphenol A, reduced bisphenol F, dicyclopenta diol, tricyclodecanediol, and the like, and compounds having three or more hydroxyl groups in the molecule, that is, glycerol, trimethylol ethane, Trimethylolpropane, pentaerythritol, sorbose, and sorbitol may be mixed and used. As the polyol having a molecular weight of 400 to 3,000, a polyether polyol, a polyester polyol, a polycarbonate polyol, or a polycaprolactone polyol is used in combination with the above monomolecular diol. Examples of the polyether polyols used may include copolymerization forms of polyethylene glycol, 1,2-polypropylene glycol, 1,3-polypropylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, and the like. As the polyester polyol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polytetramethylene glycol, tetramethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol , Diols such as 1,4-cyclohexanedimethanol, 3-methyl-1,8-octanediol, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumalic acid, adipic acid, sebacic acid, etc. A polyester polyol in the form reacted with an acid of or a copolymerized form thereof can be exemplified. Examples of polycarbonate polyols include 1,6-hexane polycarbonate, and polycaprolactone polyols include ε-caprolactone and ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, Reaction with diols such as 1,4-butanediol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol One form can be illustrated.
디아민류로는 에틸렌디에민, 프로필렌디아민, 부틸렌디아민, 4,4-디아미노디페닐메탄, 3,3'-디클로로 4,4'-디아미노디페닐메탄, 벤지딘(benzidine), 3,3'-디메틸벤지딘, p-페닐렌디아민 등을 들 수 있다.또한, 광경화형 아크릴레이트 모노머 중 단관능성 모노머로는 디에틸아미노에틸(메타)아크릴레이트, 디메틸아미노에틸(메타)아크릴레이트, t-옥틸(메타)아크릴레이트, N,N-디메틸(메타)아크릴아마이드, N-비닐카프로락탐, N-비닐피롤리돈, 이소부톡시메틸(메타)아크릴아마이드, 디아세톤(메타)아크릴아마이드, 보닐(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 트리사이클로테카닐(메타)아크릴레이트, 디사이클로펜타닐(메타)아크릴레이트, 디사이클로펜타디엔(메타)아크릴레이트, 메톡시폴리프로필렌글리콜(메타)아크릴레이트, 메톡시폴리에틸렌글리콜(메타)아크릴레이트, 에톡시에톡시에틸(메타)아크릴레이트, 메톡시에틸렌글리콜(메타)아크릴레이트, 폴리프로필렌글리콜모노(메타)아크릴레이트, 폴리에틸렌글리콜모노(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트, 사이클로헥실(메타)아크릴레이트, 벤질(메타)아크릴레이트, 에폭시디에틸렌글리콜(메타)아크릴레이트, 부톡시에틸(메타)아크릴레이트, 테트라하이드로퍼퓨릴(메타)아크릴레이트, 스티어릴(메타)아크릴레이트, 옥타데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 도데실(메타)아크릴레이트, 운데실(메타)아크릴레이트, 이소데실(메타)아크릴레이트, 데실(메타)아크릴레이트, 노닐(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 헵틸(메타)아크릴레이트, 헥실(메타)아크릴레이트, 이소아밀(메타)아크릴레이트, 펜틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 이소부틸(메타)아크릴레이트, 아밀(메타)아크릴레이트, 부틸(메탈)아크릴레이트, 이소프로필(메타)아크릴레이트, 프로필(메타)아크릴레이트, 에틸(메타)아크릴레이트, 메틸(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시에틸(메타)아크릴레이트, 7-아미노-3,7-디메틸옥틸(메타)아크릴레이트, N,N-디에틸(메타)아크릴아마이드, N,N'-디메틸-아미노프로필(메타)아크릴레이트 등을 예시할 수 있고, 다관능성 모노머로는 트리메틸올 프로판트리(메타)아크릴레이트, 펜타에리트리톨 트리(메타)아크릴레이트, 에틸렌그리콜 디(메타)아크릴레이트, 1,6-헥산디올디(메타)아크릴레이트, 트리프로필렌 글리콜 디아크릴레이트, 트리메틸올프로판트리옥시에틸(메타)아크릴레이트, 트리사이클로데칸디메타놀디아크릴레이트, 트리스(2-히드록시에틸)이소시아누레이트 디(메타)아크릴레이트, 트리사이클로데칸디메타놀 디(메타)아크릴레이트등을 예시할 수 있다. 또한 도막의 인장성 향상을 위하여 상기 아크릴레이트모노머에 실리콘아크릴레이트를 혼합 사용할 수 있고, 실리콘 아크릴레이트로는 아크릴레이트 변성 폴리실록산 등을 예시할 수 있으며 1종 단독 또는 2종 이상을 혼합하여 사용할 수 있다.Examples of the diamines include ethylenediamine, propylenediamine, butylenediamine, 4,4-diaminodiphenylmethane, 3,3'-dichloro 4,4'-diaminodiphenylmethane, benzidine, 3,3 '-Dimethylbenzidine, p-phenylenediamine and the like can be mentioned. Further, as the monofunctional monomer among the photocurable acrylate monomers, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, t- Octyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N-vinyl caprolactam, N-vinylpyrrolidone, isobutoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, bonyl ( Meta) acrylate, isobonyl (meth) acrylate, tricyclotecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentadiene (meth) acrylate, methoxy polypropylene glycol (meth) Acrylate, methoxy polyethylene glycol ( Meta) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, phenoxyethyl (meth ) Acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, epoxydiethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, styryl (Meth) acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, undecyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) Acrylate, nonyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, octyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) Acrylate, isoamyl (meth) acrylate, pentyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, amyl (meth) acrylate, butyl (metal) acrylate, iso Propyl (meth) acrylate, propyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N'-dimethyl-aminopropyl (meth ) Acrylates and the like, and examples of the polyfunctional monomers include trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, and 1,6-hexane. Dioldi (meth) acrylate, tripropylene glycol dia Relate, trimethylolpropane trioxyethyl (meth) acrylate, tricyclodecanedimethanol diacrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecanedimethol di ( Meth) acrylate etc. can be illustrated. In addition, silicone acrylate may be mixed with the acrylate monomer in order to improve the tensile property of the coating film, and examples of the silicone acrylate may include acrylate-modified polysiloxane and the like, and may be used alone or in combination of two or more thereof. .
본 발명의 조성물은 광개시제를 필요로하며 사용되는 개시제로는 1-히드록시사이클로헥실페닐 케톤, 2,2-디메톡시-2-페닐-아세토페논, 잔톤, 벤즈알데하이드, 안트라퀴논, 3-메틸아세토페논, 4-클로로벤조페논, 4,4'-디메톡시벤조페논, 4,4'-디아미노벤조페논, 벤조인 프로필 에테르, 벤조인에틸 에테르, 1-(4-이소프로필-페놀)-2-히드록시-2-메틸 프로판-1-온, 티오잔톤 등을 예시 할 수 있고 상업용으로 공급되는 제품에는 Irgacure184, 651, 500, 819, 907, 1700, 1800(시바가이기사) 등과 Darocure 1116, 1173(머크사), Lucirine LR8728(바스프사), Ubecyl-936(유씨비사)등이 있으며 이들의 1종 단독 또는 2종 이상을 혼합하여 사용할 수 있다. 디에틸아민과 같은 광증감제도 소량 첨가될 수 있다.The composition of the present invention requires a photoinitiator and used initiators include 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenyl-acetophenone, xanthone, benzaldehyde, anthraquinone, 3-methylaceto Phenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoinethyl ether, 1- (4-isopropyl-phenol) -2 Hydroxy-2-methyl propane-l-one, thioxanthone, etc. can be exemplified, and commercially supplied products include Irgacure184, 651, 500, 819, 907, 1700, 1800 (Shibagai Corporation) and Darocure 1116, 1173. (Merck Co., Ltd.), Lucirine LR8728 (BASF Co., Ltd.), Ubecyl-936 (CBC), etc., and these may be used alone or in combination of two or more thereof. Small photosensitizers such as diethylamine can also be added.
또한, 이상의 조성물에 더하여 산화방지제, 광안정제, 실란커플링제, 열중합금지제, 평활제, 계면활성제 등도 첨가될 수 있다.In addition to the above composition, antioxidants, light stabilizers, silane coupling agents, thermal polymerization inhibitors, leveling agents, surfactants and the like may also be added.
다음에 본 발명을 실시예에 의하여 설명하나 본 발명은 아래의 실시예에 반드시 한정되는 것은 아니다. 또한 %로 표시된 것은 다른 언급이 없는한 모두 중량%이다.Next, the present invention will be described by way of Examples, but the present invention is not necessarily limited to the following Examples. In addition, all expressed in% are weight% unless otherwise stated.
합성예 1.Synthesis Example 1.
교반기가 달린 3리터 둥근바닥 플라스크에 696.0g(4 mole)의 2,4-톨루엔 디이소시아네이트와 0.15g의 디부틸틴디라우레이트(dibutyltindilaurate)를 넣었다. 반응온도를 70℃로 유지한 후 여기에 수평균 분자량 1000의 폴리테트라메틸렌글리콜 1000.0g(1 mole)과 1,4-부탄디올 180.0g(2 mole)혼합액을 2시간동안 반응기에 투입하였다. 투입 종료후 반응물의 NCO농도가 이론 NCO농도에 도달할 때까지 반응시킨 뒤 반응온도를 50℃까지 떨어뜨리고 중합반응 억제제로 1g의 메틸하이드로퀴논을 투입하였다. 이어서 점도의 상승에 의해 반응속도가 느려질 수 있으므로 교반효과를 높혀주기 위해 반응성 희석제 중 부탄다이올디아크릴레이트를 255.5g을 투입하고 232.0g(2 mole)의 2-하이드록시에틸아크릴레이트를 서서히 투입하여 반응을 진행시켰다. 투입이 끝난 후 6시간 동안은 70℃로 반응온도를 유지하면서 적외선 분광기로 2270cm-1의 NCO피크가 사라지는 것을 확인한 후 반응을 종결하였다.Into a 3-liter round bottom flask with a stirrer was added 696.0 g (4 mole) of 2,4-toluene diisocyanate and 0.15 g of dibutyltindilaurate. After the reaction temperature was maintained at 70 ° C., 1000.0 g (1 mole) of polytetramethylene glycol having a number average molecular weight of 1000 and 180.0 g (2 mole) of 1,4-butanediol were added to the reactor for 2 hours. After the completion of the addition, the reaction was allowed to react until the NCO concentration of the reactant reached the theoretical NCO concentration, and the reaction temperature was lowered to 50 ° C. and 1 g of methylhydroquinone was added as a polymerization inhibitor. Subsequently, the reaction rate may be slowed down by the increase of the viscosity. In order to increase the stirring effect, 255.5 g of butanediol diacrylate is added to the reactive diluent and 232.0 g (2 mole) 2-hydroxyethyl acrylate is gradually added. The reaction was advanced. After the addition, the reaction was terminated after confirming that the NCO peak of 2270cm -1 disappeared by infrared spectroscopy while maintaining the reaction temperature at 70 ° C for 6 hours.
실시예 1.Example 1.
교반기가 달린 반응기에 합성예 1에서 합성한 우레탄 아크릴레이트 올리고머를 60중량% 투입하고 4.4중량%의 테트라하이드로퍼퓨릴아크릴레이트, 8.6중량%의 프로필렌글리콜모노아크릴레이트, 20중량%의 부탄다이올디아크릴레이트, 3.0중량%의 아크릴레이트변성폴리실록산(TEGORad 2100(테고사)), 0.5중량%의 산화방지제(Irganox 1035(시바가이기사))와 중합억제제로 0.5중량%의 메틸하이드로퀴논을 투입하였다. 광개시제로는 Irgacure 651(시바가이기사) 2.5중량% 투입하고 광증감제로 디에틸아민을 0.5중량% 투입하여 상온에서 30분 동안 400rpm으로 교반하면서 배합하였다. 50℃에서 1500cps의 점도를 갖는 투명한 액체 조성물을 얻었다.60 wt% of the urethane acrylate oligomer synthesized in Synthesis Example 1 was added to a reactor equipped with a stirrer, 4.4 wt% tetrahydrofurfuryl acrylate, 8.6 wt% propylene glycol monoacrylate, and 20 wt% butanediol diacryl. 0.5% by weight of methylhydroquinone was added as a rate, 3.0% by weight of acrylate-modified polysiloxane (TEGORad 2100 (Tego)), 0.5% by weight of antioxidant (Irganox 1035 (Shibagai Co.)) and polymerization inhibitor. As a photoinitiator, 2.5 wt% of Irgacure 651 (Shibagai Co., Ltd.) was added, and 0.5 wt% of diethylamine was added as a photosensitizer, and the mixture was stirred at 400 rpm for 30 minutes at room temperature. A clear liquid composition having a viscosity of 1500 cps at 50 ° C. was obtained.
얻어진 액체 조성물을 아래와 같은 방법으로 필름을 성형하고 그 물성을 측정하였다.The obtained liquid composition was molded in the following manner and the physical properties thereof were measured.
① 필름성형① Film forming
유리판 위에 바코터(bar coater)를 이용하여 실시예의 수지를 0.1mm의 두께로 코팅한후 자외선 경화기에서 1.0J/cm2으로 조사하여 경화 필름을 제조하였다.Using a bar coater (bar coater) on the glass plate was coated with a thickness of 0.1mm and then irradiated with 1.0J / cm 2 in an ultraviolet curing machine to prepare a cured film.
② 인장특성(인장탄성율, 신장율, 인장강도)② Tensile Properties (Tensile Modulus, Elongation, Tensile Strength)
만능 인장시험기를 이용하여 25℃, 50%상대습도의 조건에서 경화필름 10mm×80mm 크기로 취하고 시편사용 게이지(gauge)의 거리를 50mm로하여 분당 5mm의 속도로 측정한다.Using a universal tensile tester, the cured film was taken in a size of 10 mm x 80 mm at 25 ° C. and 50% relative humidity, and measured at a speed of 5 mm per minute with a distance of 50 mm for a specimen use gauge.
③ 내수성③ water resistance
경화된 필름을 100mm×100mm의 크기로 취하여 무게(A)를 측정하고 그것을 25℃증류수에 72시간 담그어 보관한후 다시 꺼내어 무진휴지로 표면의 물기를 닦아 낸후에 다시 무게(B)를 측정하고 일주일동안 상온상습에서 건조하여 무게(C)를 측정하였다. 최종적으로 다음식을 이용하여 계산하였다.Take the cured film into the size of 100mm × 100mm and measure the weight (A), soak it in 72 ℃ distilled water for 72 hours, take it out again, wipe off the surface with dust-free toilet paper, and measure the weight (B) again. After drying at room temperature and humidity, the weight (C) was measured. Finally, the following equation was used.
무게변화율(%) = (B-A)/A × 100% Change in weight = (B-A) / A × 100
추출율(%) = (A-C)/A × 100% Extraction = (A-C) / A × 100
④ 겔분율(속실렛법)④ Gel fraction (Soxlet method)
경화시킨 필름의 초기무게(Wo)를 측정한후 메틸에틸케톤을 용매로 사용하여 24시간동안 속실렛(soxhlet) 추출 플라스크에서 추출한 후 잔존물을 50℃에서 72시간동안 건조하여 무게(W1)를 측정하고 다음식에 의하여 겔분율을 얻는다.The initial weight (Wo) of the cured film was measured, and then extracted in a soxhlet extraction flask using methyl ethyl ketone as a solvent for 24 hours, and the residue was dried at 50 ° C. for 72 hours to obtain a weight (W 1 ). It measures and obtains a gel fraction by following Formula.
겔분율(%) = W1/Wo × 100Gel fraction (%) = W 1 / Wo × 100
실시예 2.Example 2.
교반기가 달린 반응기에 합성예 1에서 합성한 우레탄 아크릴레이트 올리고머를 70중량% 투입하고 3중량%의 테트라하이드로퍼퓨릴아크릴레이트, 6중량%의 프로필렌글리콜모노아크릴레이트, 14중량%의 부탄다이올디아크릴레이트, 3중랑%의 아크릴레이트 변성폴리실록산(TEGORad 2100(테고사)), 0.5중량%의 산화방지제 (Irgacure 1035, 시바가이기사)와 중합억제제로 0.5중량%의 메틸하이드로퀴논을 투입한다. 광개시제로는 Irgacure 651(시바가이기사) 2.5중량% 투입하고 광증감제로 디에틸아민을 0.5중량% 투입하여 상온에서 30분동안 400rpm으로 교반하면서 배합한다. 50℃에서 2500cps의 점도를 갖는 투명한 액체 조성물이 얻어지고 경화필름의 물성은 실시예 1에서 예시된 방법에 의해 측정하였다.70% by weight of the urethane acrylate oligomer synthesized in Synthesis Example 1 was added to a reactor equipped with a stirrer, 3% by weight of tetrahydrofurfuryl acrylate, 6% by weight of propylene glycol monoacrylate, and 14% by weight of butanediol diacryl. 0.5 wt% of methylhydroquinone is added as a rate, a triangular-% acrylate-modified polysiloxane (TEGORad 2100 (Tego)), 0.5 wt% of an antioxidant (Irgacure 1035, Ciba-Geigy Co.) and a polymerization inhibitor. As a photoinitiator, 2.5 wt% of Irgacure 651 (Shibagai Co., Ltd.) was added, 0.5 wt% of diethylamine was added as a photosensitizer, and the mixture was stirred at 400 rpm for 30 minutes at room temperature. A clear liquid composition having a viscosity of 2500 cps at 50 ° C. was obtained and the physical properties of the cured film were measured by the method illustrated in Example 1.
실시예 3.Example 3.
교반기가 달린 반응기에 합성예 1에서 합성한 우레탄 아크릴레이트를 75중량% 투입하고 2.3중량%의 테트라하이드로퍼퓨릴아크릴레이트, 4.7중량%의 프로필렌글리콜모노아크릴레이트, 11중량%의 부탄다이올디아크릴레이트, 3중량%의 아크릴레이트 변성폴리실록산(TEGORad 2100(테고사)), 0.5중량%의 산화방지제(Irganox 1035(시바가이기사))와 중합억제제로 0.5중량%의 메틸하이드로퀴논을 투입하였다. 광개시제로는 Irgacure 651(시바가이기사)를 2.5중량% 투입하고 광증감제로 디에틸아민을 0.5중량% 투입한후 상온에서 30분동안 400rpm으로 교반하면서 배합하였다. 50℃에서 2800cps의 점도를 갖는 투명한 액체 조성물이 얻어지고 경화필름의 물성은 실시예 1에 예시된 방법에 의해 측정하였다.75% by weight of the urethane acrylate synthesized in Synthesis Example 1 was added to a reactor equipped with a stirrer, 2.3% by weight of tetrahydrofurfuryl acrylate, 4.7% by weight of propylene glycol monoacrylate, and 11% by weight of butanediol diacrylate. , 0.5% by weight of methylhydroquinone was added as 3% by weight of acrylate-modified polysiloxane (TEGORad 2100 (Tego)), 0.5% by weight of antioxidant (Irganox 1035 (Shibagai Co.)) and polymerization inhibitor. As a photoinitiator, 2.5 wt% of Irgacure 651 (Shibagai Co., Ltd.) was added, and 0.5 wt% of diethylamine was added as a photosensitizer, followed by mixing at 400 rpm for 30 minutes at room temperature. A clear liquid composition having a viscosity of 2800 cps at 50 ° C. was obtained and the physical properties of the cured film were measured by the method illustrated in Example 1.
비교예 1.Comparative Example 1.
교반기가 달린 3리터 둥근바닥 플라스크에 500.0g(2.88 mole)의 2,4-톨루엔 디이소시아네이트와 우레탄 반응 촉매로 0.11g의 디부틸틴디라울레이트를 넣었다. 반응온도를 70℃로 유지한 후 여기에 수평균 분자량 1000의 폴리테트라메틸렌글리콜 1436.0g(1.44 mole)을 반응온도가 70℃를 넘지 않게 주의하면서 반응기에 투입한다. 투입 종료 후 반응물의 NCO농도가 이론 NCO농도에 도달할 때까지 반응시킨 뒤 반응온도를 50℃까지 떨어뜨리고 중합반응 억제제로 0.8g의 메틸하이드로퀴논을 투입한다. 그리고 점도의 상승에 의해 반응속도가 느려질 수 있으므로 교반효과를 높혀주기 위해 반응성 희석제중 헥산다이올디아크릴레이트를 153.8g을 투입하고 333.4g(2.88 mole)의 2-히드록시에틸아크릴레이트를 서서히 투입하여 반응을 진행시켰다. 이때 반응온도가 60℃를 넘지 않게 주의해야 하고 투입이 끝난후 5∼6시간 동안은 60℃로 반응온도를 유지하면서 적외선 분광기로 2270cm-1의 NCO 피크가 사라지는 것을 확인한 후 반응을 종결하였다.Into a 3-liter round bottom flask with a stirrer was added 500.0 g (2.88 mole) of 2,4-toluene diisocyanate and 0.11 g of dibutyltin dilaurate as a urethane reaction catalyst. After the reaction temperature was maintained at 70 ° C, 1436.0 g (1.44 mole) of polytetramethylene glycol having a number average molecular weight of 1000 was added thereto while being careful not to exceed the reaction temperature of 70 ° C. After completion of the reaction, the reactant is allowed to react until the NCO concentration of the reactant reaches the theoretical NCO concentration. Then, the reaction temperature is reduced to 50 ° C and 0.8 g of methylhydroquinone is added as a polymerization inhibitor. In addition, 153.8g of hexanediol diacrylate in a reactive diluent is added and 333.4g (2.88 mole) of 2-hydroxyethyl acrylate is gradually added to increase the stirring effect because the reaction rate may be slowed down by the increase of the viscosity. The reaction was advanced. At this time, the reaction temperature should be careful not to exceed 60 ℃ and the reaction was terminated after confirming that the NCO peak of 2270cm -1 disappeared by infrared spectroscopy while maintaining the reaction temperature at 60 ℃ for 5-6 hours after the addition.
이상과 같이 합성한 폴리우레탄 아크릴레이트를 사용하여 실시예 3에서와 같은 방법으로 합성예 1에서 합성한 폴리우레탄 아크릴레이트를 대체시킨 배합을 실시하였다. 50℃에서 1900cps의 점도를 갖는 액체 조성물을 얻었고 경화필름의 물성은 실시예 1에 예시된 방법에 의해 측정하였다.The polyurethane acrylate synthesized in Synthesis Example 1 was substituted in the same manner as in Example 3 using the polyurethane acrylate synthesized as described above. A liquid composition having a viscosity of 1900 cps at 50 ° C. was obtained and the physical properties of the cured film were measured by the method illustrated in Example 1.
비교예 2.Comparative Example 2.
교반기가 달린 반응기에 비교예 1에서 합성한 우레탄 아크릴레이트를 60중량% 투입하고 33중량%의 펜타에리트리톨트리아크릴레이트, 3.0중량%의 아크릴레이트 변성 폴리 실록산(TEGORad 2100(테고사)), 0.5중량%의 산화방지제 (Irganox 1035(시바가이기사))와 중합억제제로 0.5중량%의 메틸하이드로퀴논을 투입한다. 광개시제로는 Irgacure 651(시바가이기사)을 2.5중량% 투입하고 광증감제로 디에틸아민을 0.5중량% 투입하이 상온에서 30분동안 400rpm으로 교반하면서 배합하였다. 50℃에서 2100cps의 점도를 갖는 투명한 액체 조성물이 얻어지고 경화필름의 물성은 실시예 1에서 예시된 방법에 의해 측정하였으며, 이상의 실험결과를 다음 표1에 나타내었다.60% by weight of the urethane acrylate synthesized in Comparative Example 1 was added to a reactor equipped with a stirrer, 33% by weight of pentaerythritol triacrylate, 3.0% by weight of acrylate-modified polysiloxane (TEGORad 2100 (TEGO Co.)), 0.5 0.5% by weight of methylhydroquinone is added as a weight% antioxidant (Irganox 1035 (Shibagai Co.)) and a polymerization inhibitor. As a photoinitiator, 2.5 wt% of Irgacure 651 (Shibagai Co., Ltd.) was added thereto, and 0.5 wt% of diethylamine was added thereto as a photosensitizer. The mixture was stirred at room temperature at 400 rpm for 30 minutes. A transparent liquid composition having a viscosity of 2100 cps at 50 ° C. was obtained, and the physical properties of the cured film were measured by the method exemplified in Example 1, and the experimental results are shown in Table 1 below.
표 1에서 알 수 있듯이 본 발명에서 개발된 올리고머를 사용하여 배합할 경우 경화도막의 물성이 광섬유 2차코팅제에서 요구되는 인장탄성율인 1000MPa이상(미국특허 제 4,904,051호)의 월등한 값을 가짐과 동시에 신장률도 10%이상의 우수한 값을 보인다. 반면에 비교예 1 및 비교예 2에서 나타난 것처럼 저분자량의 단분자디올을 우레탄 세그먼트내에 도입하지 않은 올리고머 즉, 단분자 디올과 폴리글리콜이 함께 우레탄 결합에 도입하지 않은 하드세그멘트의 밀도가 낮은 기존의 올리고머를 사용하여 배합할 경우 필름물성이 전체적으로 저하되고 3관능성 희석제를 사용하여 인장탄성율을 높일 경우에는 신장율의 저하가 현격한 것을 알 수 있다. 이와 같은 결과로 본 발명에서 개발한 광섬유 코팅용 자외선 경화형 수지 조성물이 인장탄성율 및 인장강도의 향상에 탁월한 효과를 보이면서 신장율의 저하가 작고 탁월한 강인성을 갖는다는 것을 알 수 있다. 따라서 본 발명의 액체조성물은 특히 광섬유 2차 코팅용 수지 조성물로 사용하기에 대단히 적합하고 수분 추출물이 0%인 결과에서도 알 수 있듯이 내수성도 우수하여 습기에 매우 강한 것을 알 수 있다. 또한 겔분율이 90%이상으로 경화성도 우수함을 알 수 있다. 전체적으로 측정결과를 종합해보면 기존의 광섬유 2차 코팅용 자외선 경화형 수지조성물에 비하여 뛰어난 특성을 갖고 있음을 알 수 있다.As can be seen from Table 1, when using the oligomers developed in the present invention, the physical properties of the cured coating film have a superior value of 1000 MPa or more (US Patent No. 4,904,051), which is the tensile modulus required for the optical fiber secondary coating agent. Elongation is also excellent value of more than 10%. On the other hand, as shown in Comparative Examples 1 and 2, oligomers in which low molecular weight monomolecular diols are not introduced into the urethane segment, that is, low density of hard segments in which monomolecular diols and polyglycols are not introduced into the urethane bond together It can be seen that the film properties are generally reduced when the mixture is used using an oligomer, and when the tensile modulus is increased by using a trifunctional diluent, a decrease in elongation is remarkable. As a result, it can be seen that the ultraviolet curable resin composition for optical fiber coating developed in the present invention shows an excellent effect on the improvement of tensile modulus and tensile strength, while the decrease in elongation is small and has excellent toughness. Therefore, the liquid composition of the present invention is particularly suitable for use as a resin composition for optical fiber secondary coating, and as can be seen from the result of 0% of water extract, it can be seen that the water resistance is also very strong against moisture. In addition, it can be seen that the gel fraction is more than 90% and excellent in curability. Overall, the results of the measurement show that the optical fiber curable resin composition for the secondary coating has superior characteristics.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990007590A KR100312040B1 (en) | 1999-03-08 | 1999-03-08 | UV curable compositions for optical fibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990007590A KR100312040B1 (en) | 1999-03-08 | 1999-03-08 | UV curable compositions for optical fibers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20000059763A KR20000059763A (en) | 2000-10-05 |
| KR100312040B1 true KR100312040B1 (en) | 2001-11-14 |
Family
ID=19575861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019990007590A KR100312040B1 (en) | 1999-03-08 | 1999-03-08 | UV curable compositions for optical fibers |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100312040B1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101006671B1 (en) * | 2008-10-31 | 2011-01-13 | 에스에스씨피 주식회사 | Uv curable resin composition and process for producing a substrate having a pattern using the same |
| KR20200123562A (en) * | 2019-04-22 | 2020-10-30 | 조광페인트주식회사 | Photo-curable composition for pre-coated metal and method for manufacturing pre-coated metal using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR950018355A (en) * | 1993-12-30 | 1995-07-22 | 김충세 | Photocurable coating composition and method for preparing amine-modified urethane acrylate oligomers used therein |
| KR960011195A (en) * | 1994-09-01 | 1996-04-20 | 쓰지 요시후미 | Dust Pad |
-
1999
- 1999-03-08 KR KR1019990007590A patent/KR100312040B1/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR950018355A (en) * | 1993-12-30 | 1995-07-22 | 김충세 | Photocurable coating composition and method for preparing amine-modified urethane acrylate oligomers used therein |
| KR960011195A (en) * | 1994-09-01 | 1996-04-20 | 쓰지 요시후미 | Dust Pad |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101006671B1 (en) * | 2008-10-31 | 2011-01-13 | 에스에스씨피 주식회사 | Uv curable resin composition and process for producing a substrate having a pattern using the same |
| KR20200123562A (en) * | 2019-04-22 | 2020-10-30 | 조광페인트주식회사 | Photo-curable composition for pre-coated metal and method for manufacturing pre-coated metal using the same |
| KR102209549B1 (en) * | 2019-04-22 | 2021-02-01 | 조광페인트주식회사 | Photo-curable composition for pre-coated metal and method for manufacturing pre-coated metal using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20000059763A (en) | 2000-10-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5496870A (en) | Curable liquid resin composition | |
| KR101001656B1 (en) | Radiation curable resin composition and optical fiber made by using thereof | |
| EP0988335B1 (en) | Radiation curable composition comprising an urethane oligomer having a polyester backbone | |
| JP3715021B2 (en) | Liquid curable resin composition | |
| KR20010006365A (en) | Liquid curable resin composition | |
| KR101021577B1 (en) | Radiation curable Composition | |
| US7764855B2 (en) | Optical fiber with cured polymeric coating | |
| JPS6375072A (en) | Photo-curable paint composition and coated glass optical fiber | |
| WO2000001781A1 (en) | Liquid curable resin composition | |
| JP4341872B2 (en) | Curable liquid resin composition | |
| JP3958201B2 (en) | Liquid curable resin composition | |
| EP1487889B1 (en) | Curable liquid resin composition | |
| KR100312039B1 (en) | UV curable compositions for optical fibers | |
| KR920000014B1 (en) | Ultra violet setting resin composition | |
| KR20010037679A (en) | Resin composition for manufacturing optic fiber ribbon and a method for manufacturing optic fiber ribbon using the same | |
| KR100312040B1 (en) | UV curable compositions for optical fibers | |
| KR920000032B1 (en) | Ultraviolet curing resin composition | |
| JP3345931B2 (en) | UV curable resin composition and optical fiber using the same | |
| JP2002097235A (en) | Liquid curable resin composition and its cured product | |
| WO1997014737A1 (en) | Liquid curable resin composition | |
| KR101006989B1 (en) | Uv curable coating composition having improved water resistance and optical fiber using the same | |
| JP2002338641A (en) | Liquid radiation-curing resin composition, coating composition for optical fibre and optical fiber | |
| JP2002128845A (en) | Liquid radiation curable resin composition of, coating composition for optical fiber and optical fiber | |
| JP3341848B2 (en) | Polymerizable unsaturated polyurethane and ultraviolet-curable resin composition using the same | |
| KR100312041B1 (en) | UV curable matrix compositions for optical fiber ribbons |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20121005 Year of fee payment: 12 |
|
| FPAY | Annual fee payment |
Payment date: 20131105 Year of fee payment: 13 |
|
| FPAY | Annual fee payment |
Payment date: 20141006 Year of fee payment: 14 |
|
| FPAY | Annual fee payment |
Payment date: 20151005 Year of fee payment: 15 |
|
| FPAY | Annual fee payment |
Payment date: 20161205 Year of fee payment: 16 |
|
| FPAY | Annual fee payment |
Payment date: 20171010 Year of fee payment: 17 |
|
| FPAY | Annual fee payment |
Payment date: 20181004 Year of fee payment: 18 |
|
| EXPY | Expiration of term |