JP2016085434A - Resin composition for coating optical fiber, optical fiber cable, and optical fiber cable with plug - Google Patents
Resin composition for coating optical fiber, optical fiber cable, and optical fiber cable with plug Download PDFInfo
- Publication number
- JP2016085434A JP2016085434A JP2014220211A JP2014220211A JP2016085434A JP 2016085434 A JP2016085434 A JP 2016085434A JP 2014220211 A JP2014220211 A JP 2014220211A JP 2014220211 A JP2014220211 A JP 2014220211A JP 2016085434 A JP2016085434 A JP 2016085434A
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- JP
- Japan
- Prior art keywords
- optical fiber
- coating
- resin composition
- mass
- resin
- 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.)
- Granted
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- 239000013307 optical fiber Substances 0.000 title claims abstract description 247
- 239000011248 coating agent Substances 0.000 title claims abstract description 79
- 238000000576 coating method Methods 0.000 title claims abstract description 79
- 239000011342 resin composition Substances 0.000 title claims abstract description 74
- 229920005989 resin Polymers 0.000 claims abstract description 92
- 239000011347 resin Substances 0.000 claims abstract description 92
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000011247 coating layer Substances 0.000 claims abstract description 27
- 239000000155 melt Substances 0.000 claims abstract description 23
- 239000004014 plasticizer Substances 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 22
- 239000004925 Acrylic resin Substances 0.000 claims description 18
- 229920000178 Acrylic resin Polymers 0.000 claims description 18
- -1 carbonate compound Chemical class 0.000 claims description 17
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 12
- 238000005452 bending Methods 0.000 claims description 9
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 6
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 6
- 229960001545 hydrotalcite Drugs 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 1
- 230000007774 longterm Effects 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 description 45
- 239000003063 flame retardant Substances 0.000 description 43
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 38
- 239000011162 core material Substances 0.000 description 33
- 239000010410 layer Substances 0.000 description 26
- 239000000463 material Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- 239000012760 heat stabilizer Substances 0.000 description 20
- 239000000370 acceptor Substances 0.000 description 19
- 239000000654 additive Substances 0.000 description 19
- 229920001519 homopolymer Polymers 0.000 description 16
- 125000003709 fluoroalkyl group Chemical group 0.000 description 15
- 230000001771 impaired effect Effects 0.000 description 15
- 239000000049 pigment Substances 0.000 description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 8
- 230000006854 communication Effects 0.000 description 8
- 238000004891 communication Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- 229920000297 Rayon Polymers 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000013308 plastic optical fiber Substances 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000004801 Chlorinated PVC Substances 0.000 description 4
- 239000004709 Chlorinated polyethylene Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- HBZFBSFGXQBQTB-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HBZFBSFGXQBQTB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 3
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000003017 thermal stabilizer Substances 0.000 description 3
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 2
- CDXFIRXEAJABAZ-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CDXFIRXEAJABAZ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007765 extrusion coating Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052731 fluorine Chemical group 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- NZUPFZNVGSWLQC-UHFFFAOYSA-N 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound BrCC(Br)CN1C(=O)N(CC(Br)CBr)C(=O)N(CC(Br)CBr)C1=O NZUPFZNVGSWLQC-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- HJHZALKPKBJRES-UHFFFAOYSA-N aluminum;calcium Chemical compound [Al+3].[Ca+2] HJHZALKPKBJRES-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000007175 bidirectional communication Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007706 flame test Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、光ファイバ被覆用樹脂組成物、光ファイバケーブル及びプラグ付き光ファイバケーブルに関する。 The present invention relates to a resin composition for coating an optical fiber, an optical fiber cable, and an optical fiber cable with a plug.
光ファイバは、通信、センサ、照明、装飾、ディスプレイ等の幅広い用途で用いられている。ガラス系の光ファイバは、広い波長に亘って光伝送性に優れる一方で、加工性や機械特性に劣る等の課題を有する。一方、プラスチック光ファイバは、例えば、ポリメチルメタクリレート等の透明性の高い樹脂からなる芯に、芯よりも低屈折な透明性の高い樹脂で芯の外周を被覆した構造を有するものが挙げられ、ガラス系光ファイバに比べて、加工性や柔軟性に優れる等の特徴を有する。また、プラスチック光ファイバは、近年、製造技術の向上に伴って、伝送可能距離が長くなっていて、その用途が広がっている。 Optical fibers are used in a wide range of applications such as communication, sensors, lighting, decoration, and displays. Glass-based optical fibers have problems such as inferior processability and mechanical properties while being excellent in light transmission over a wide wavelength range. On the other hand, the plastic optical fiber includes, for example, a core made of a highly transparent resin such as polymethyl methacrylate and a structure in which the outer periphery of the core is covered with a highly transparent resin having a lower refractive index than the core. Compared with glass-based optical fiber, it has features such as excellent workability and flexibility. In recent years, plastic optical fibers have a longer transmission distance as the manufacturing technology is improved, and their applications are expanding.
通常、光ファイバを用いる際は、光ファイバ単体で用いられることは少なく、機械特性、難燃性、耐熱性等を付与するために、光ファイバに熱可塑性樹脂等を被覆した光ファイバケーブルとして用いられることが多い。特に、近年、プラスチック製品の難燃化規制が厳しくなってきていて、光ファイバケーブルに対しても優れた難燃性を有することが要望されている。 Normally, when using an optical fiber, it is rarely used as a single optical fiber, and is used as an optical fiber cable in which an optical fiber is coated with a thermoplastic resin in order to impart mechanical properties, flame retardancy, heat resistance, etc. It is often done. In particular, in recent years, regulations for making flame retardant plastic products have become stricter, and optical fiber cables are required to have excellent flame retardancy.
光ファイバに難燃性を付与する方法として、例えば、特許文献１には、可塑剤を含む塩化ビニル樹脂でプラスチック光ファイバを被覆した光ファイバケーブルが提案されている。 As a method for imparting flame retardancy to an optical fiber, for example, Patent Document 1 proposes an optical fiber cable in which a plastic optical fiber is covered with a vinyl chloride resin containing a plasticizer.
しかしながら、特許文献１で提案されている光ファイバケーブルは、難燃性の効果を有するものの、その効果は十分とは言えない。 However, although the optical fiber cable proposed in Patent Document 1 has a flame-retardant effect, the effect is not sufficient.
ところで、塩化ビニル樹脂そのものは、難燃性に優れる樹脂である一方、硬くて脆く、塩化ビニル樹脂のみで用いることは困難である。そのため、塩化ビニル樹脂を用いる際、可塑剤、熱安定剤等の添加剤を併用することが多い。また、工業用途で用いられる光ファイバケーブルの被覆層には、コストダウンを目的として、充填剤等の添加剤を配合することが多い。
しかしながら、これらの添加剤は、多く配合するほど塩化ビニル樹脂本来の特性を悪化させる原因となる。特に、これらの添加剤を含む塩化ビニル樹脂組成物を光ファイバに被覆して光ファイバケーブルとして用いる際、燃焼時のドリップが促進され、難燃性を悪化させる原因となる。したがって、単純に塩化ビニル樹脂にこれらの添加剤を配合するだけでは十分とは言えない。
By the way, while the vinyl chloride resin itself is a resin excellent in flame retardancy, it is hard and brittle, and it is difficult to use only the vinyl chloride resin. Therefore, when using a vinyl chloride resin, additives such as a plasticizer and a heat stabilizer are often used in combination. In addition, an additive such as a filler is often blended in the coating layer of an optical fiber cable used in industrial applications for the purpose of cost reduction.
However, the more these additives are added, the worse the original properties of the vinyl chloride resin. In particular, when a vinyl chloride resin composition containing these additives is coated on an optical fiber and used as an optical fiber cable, drip at the time of combustion is promoted, resulting in deterioration of flame retardancy. Accordingly, it is not sufficient to simply add these additives to the vinyl chloride resin.
そこで、本発明の目的は、光ファイバケーブルの難燃性、長期耐熱性、機械特性に優れる光ファイバ被覆用樹脂組成物を提供することにある。 Then, the objective of this invention is providing the resin composition for optical fiber coating | cover which is excellent in the flame retardance of an optical fiber cable, long-term heat resistance, and a mechanical characteristic.
本発明は、塩化ビニル系樹脂（Ａ）及び溶融張力向上剤（Ｂ）を含む光ファイバ被覆用樹脂組成物に関する。 The present invention relates to a resin composition for coating an optical fiber containing a vinyl chloride resin (A) and a melt tension improver (B).
また、本発明は、光ファイバと、光ファイバの外周に前記光ファイバ被覆用樹脂組成物からなる被覆層とを有する光ファイバケーブルに関する。
更に、本発明は、前記光ファイバケーブルを含むプラグ付き光ファイバケーブルに関する。
Moreover, this invention relates to the optical fiber cable which has an optical fiber and the coating layer which consists of the said resin composition for optical fiber coating | cover on the outer periphery of an optical fiber.
Furthermore, this invention relates to the optical fiber cable with a plug containing the said optical fiber cable.
本発明の光ファイバ被覆用樹脂組成物により、難燃性、長期耐熱性、機械特性に優れる光ファイバケーブルを得ることができる。
また、本発明の光ファイバケーブルは、難燃性、長期耐熱性、機械特性に優れる。
With the resin composition for coating an optical fiber of the present invention, an optical fiber cable excellent in flame retardancy, long-term heat resistance and mechanical properties can be obtained.
The optical fiber cable of the present invention is excellent in flame retardancy, long-term heat resistance, and mechanical properties.
以下、本発明の実施の形態について図面を用いながら説明するが、本発明はこれらの図面に限定されるものではない。 Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to these drawings.
本発明の光ファイバ被覆用樹脂組成物は、塩化ビニル系樹脂（Ａ）及び溶融張力向上剤（Ｂ）を含む。 The optical fiber coating resin composition of the present invention includes a vinyl chloride resin (A) and a melt tension improver (B).
（塩化ビニル系樹脂（Ａ））
塩化ビニル系樹脂（Ａ）は、本発明の光ファイバ被覆用樹脂組成物のマトリックス樹脂であり、安価で、難燃性に優れ、汎用樹脂として広く用いられている。
(Vinyl chloride resin (A))
The vinyl chloride resin (A) is a matrix resin of the resin composition for coating an optical fiber of the present invention, is inexpensive, has excellent flame retardancy, and is widely used as a general-purpose resin.
塩化ビニル系樹脂（Ａ）としては、例えば、塩化ビニル単独重合体、塩化ビニル単位を５０質量％以上含む共重合体等が挙げられる。これらの塩化ビニル系樹脂（Ａ）は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの塩化ビニル系樹脂（Ａ）の中でも、難燃性に優れることから、塩化ビニル単独重合体、塩化ビニル単位を５０質量％以上含む共重合体が好ましく、塩化ビニル単独重合体、塩化ビニル単位を６０質量％以上含む共重合体がより好ましく、塩化ビニル単独重合体、塩化ビニル単位を７０質量％以上含む共重合体が更に好ましく、塩化ビニル単独重合体が特に好ましい。 Examples of the vinyl chloride resin (A) include vinyl chloride homopolymers, copolymers containing 50% by mass or more of vinyl chloride units, and the like. These vinyl chloride resins (A) may be used alone or in combination of two or more. Among these vinyl chloride resins (A), since they are excellent in flame retardancy, vinyl chloride homopolymers and copolymers containing 50% by mass or more of vinyl chloride units are preferred. Vinyl chloride homopolymers, vinyl chloride units Is more preferable, a vinyl chloride homopolymer, a copolymer containing 70% by mass or more of vinyl chloride units is more preferable, and a vinyl chloride homopolymer is particularly preferable.
塩化ビニル単位を５０質量％以上含む共重合体は、塩化ビニルと、塩化ビニルと共重合可能な他の単量体とを、共重合して得られる。
他の単量体としては、例えば、塩化ビニリデン；エチレン、プロピレン等のオレフィン類；メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート等の（メタ）アクリレート類；スチレン、α−メチルスチレン等の芳香族ビニル類；ビニルメチルエーテル、ビニルエチルエーテル等のビニルエーテル類；酢酸ビニル、酪酸ビニル等のカルボン酸ビニル類等が挙げられる。これらの他の単量体は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの他の単量体の中でも、塩化ビニルとの共重合性に優れることから、カルボン酸ビニル類が好ましく、酢酸ビニルがより好ましい。
（メタ）アクリレートとは、アクリレート、メタクリレート又はその両者をいう。
A copolymer containing 50% by mass or more of vinyl chloride units can be obtained by copolymerizing vinyl chloride and other monomers copolymerizable with vinyl chloride.
Other monomers include, for example, vinylidene chloride; olefins such as ethylene and propylene; (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; styrene, α- Examples thereof include aromatic vinyls such as methylstyrene; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; vinyl carboxylates such as vinyl acetate and vinyl butyrate. These other monomers may be used individually by 1 type, and may use 2 or more types together. Among these other monomers, vinyl carboxylates are preferable and vinyl acetate is more preferable because of excellent copolymerizability with vinyl chloride.
(Meth) acrylate refers to acrylate, methacrylate, or both.
塩化ビニル系樹脂（Ａ）は、他の単量体を重合した重合体に塩化ビニルをグラフト重合させたグラフト共重合体でもよい。
グラフト共重合体としては、例えば、エチレン−酢酸ビニル共重合体に塩化ビニルをグラフト重合させたグラフト共重合体等が挙げられる。
The vinyl chloride resin (A) may be a graft copolymer obtained by graft-polymerizing vinyl chloride to a polymer obtained by polymerizing another monomer.
Examples of the graft copolymer include a graft copolymer obtained by graft-polymerizing vinyl chloride to an ethylene-vinyl acetate copolymer.
塩化ビニル系樹脂（Ａ）は、塩化ビニル単独重合体や塩化ビニル単位を５０質量％以上含む共重合体等と相溶する他の樹脂を含んでもよい。
相溶とは、塩化ビニル単独重合体や塩化ビニル単位を５０質量％以上含む共重合体等と相溶する他の樹脂とを溶融混練した際に、両者が均一に分散し、混ざり合うことをいう。
The vinyl chloride resin (A) may contain other resins compatible with a vinyl chloride homopolymer, a copolymer containing 50% by mass or more of vinyl chloride units, and the like.
“Compatible” means that when a vinyl chloride homopolymer or a copolymer containing 50% by mass or more of vinyl chloride units is melt-kneaded with other resins that are compatible, both are uniformly dispersed and mixed. Say.
相溶する他の樹脂としては、例えば、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ樹脂）、エチレン−酢酸ビニル共重合体（ＥＶＡ樹脂）、メチルメタクリレート−ブタジエン−スチレン共重合体（ＭＢＳ樹脂）、塩素化ポリエチレン樹脂（ＣＰＥ樹脂）、塩素化塩化ビニル樹脂（ＣＰＶＣ樹脂）等が挙げられる。これらの相溶する他の樹脂は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの相溶する他の樹脂の中でも、塩化ビニル単独重合体や塩化ビニル単位を５０質量％以上含む共重合体等との相溶性に優れ、塩化ビニル単独重合体や塩化ビニル単位を５０質量％以上含む共重合体等が不足する機能を補うことができることから、ＡＢＳ樹脂、ＥＶＡ樹脂、ＭＢＳ樹脂、ＣＰＥ樹脂、ＣＰＶＣ樹脂が好ましく、ＡＢＳ樹脂、ＣＰＥ樹脂、ＣＰＶＣ樹脂がより好ましい。 Examples of other compatible resins include acrylonitrile-butadiene-styrene copolymer (ABS resin), ethylene-vinyl acetate copolymer (EVA resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), A chlorinated polyethylene resin (CPE resin), a chlorinated vinyl chloride resin (CPVC resin), etc. are mentioned. These other compatible resins may be used alone or in combination of two or more. Among these other compatible resins, it has excellent compatibility with vinyl chloride homopolymers and copolymers containing 50% by mass or more of vinyl chloride units, and contains 50% by mass of vinyl chloride homopolymers and vinyl chloride units. The ABS resin, EVA resin, MBS resin, CPE resin, and CPVC resin are preferable, and the ABS resin, CPE resin, and CPVC resin are more preferable because the functions including the above-described copolymer can be supplemented.
相溶する他の樹脂の含有率は、塩化ビニル系樹脂（Ａ）１００質量％中、５質量％〜５０質量％が好ましく、１０質量％〜４５質量％がより好ましい。相溶する他の樹脂の含有率が５質量％以上であると、相溶する他の樹脂が有する機能が発現する。また、相溶する他の樹脂の含有率が５０質量％以下であると、塩化ビニル系樹脂（Ａ）の本来の性能を損なわない。 The content of the other compatible resin is preferably 5% by mass to 50% by mass and more preferably 10% by mass to 45% by mass in 100% by mass of the vinyl chloride resin (A). When the content of the other compatible resin is 5% by mass or more, the function of the other compatible resin is exhibited. Moreover, the original performance of vinyl chloride-type resin (A) is not impaired as the content rate of the other resin which is compatible is 50 mass% or less.
（溶融張力向上剤（Ｂ））
本発明の光ファイバ被覆用樹脂組成物は、溶融張力向上剤（Ｂ）を含む。
溶融張力向上剤（Ｂ）は、添加することで樹脂や樹脂組成物の溶融張力を向上させるものをいい、本発明の光ファイバ被覆用樹脂組成物に添加する溶融張力向上剤（Ｂ）は、塩化ビニル系樹脂（Ａ）の溶融張力を向上させるものとする。溶融張力は、キャピラリーレオメーターを用いて測定した値とする。
溶融張力向上剤（Ｂ）は、塩化ビニル系樹脂（Ａ）の溶融時の張力を向上させる機能を有するため、光ファイバ被覆用樹脂組成物に溶融張力向上剤（Ｂ）を配合することで、難燃性（特に、燃焼時のドリップの抑制）を更に向上させる効果を有する。
(Melt tension improver (B))
The resin composition for coating an optical fiber of the present invention contains a melt tension improver (B).
The melt tension improver (B) refers to one that improves the melt tension of the resin or the resin composition by adding, and the melt tension improver (B) added to the optical fiber coating resin composition of the present invention is: The melt tension of the vinyl chloride resin (A) is improved. The melt tension is a value measured using a capillary rheometer.
The melt tension improver (B) has a function of improving the tension at the time of melting of the vinyl chloride resin (A). Therefore, by blending the melt tension improver (B) into the optical fiber coating resin composition, It has the effect of further improving flame retardancy (particularly, suppression of drip during combustion).
溶融張力向上剤（Ｂ）としては、例えば、アクリル樹脂系溶融張力向上剤、フッ素樹脂系溶融張力向上剤等が挙げられる。これらの溶融張力向上剤（Ｂ）は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの溶融張力向上剤（Ｂ）の中でも、光ファイバケーブルの燃焼時のドリップを抑制できることから、アクリル樹脂系溶融張力向上剤、フッ素樹脂系溶融張力向上剤が好ましく、フッ素樹脂系溶融張力向上剤がより好ましい。 Examples of the melt tension improver (B) include an acrylic resin melt tension improver and a fluororesin melt tension improver. These melt tension improvers (B) may be used alone or in combination of two or more. Among these melt tension improvers (B), acrylic resin melt tension improvers and fluororesin melt tension improvers are preferred because drip during combustion of the optical fiber cable can be suppressed, and fluororesin melt tension improvers. Is more preferable.
フッ素樹脂系溶融張力向上剤は、塩化ビニル系樹脂（Ａ）と混ざり合い、光ファイバ被覆用樹脂組成物の溶融張力を高めることができるものであれば特に限定されないが、例えば、三菱レイヨン（株）製の「メタブレンＡ」シリーズ等が挙げられる。これらのフッ素樹脂系溶融張力向上剤の中でも、光ファイバ被覆用樹脂組成物中の分散性に優れることから、アクリル樹脂で変性したテトラフルオロエチレン樹脂が好ましい。 The fluororesin melt tension improver is not particularly limited as long as it can mix with the vinyl chloride resin (A) and increase the melt tension of the optical fiber coating resin composition. For example, Mitsubishi Rayon Co., Ltd. ) “Methobrene A” series and the like. Among these fluororesin-based melt tension improvers, a tetrafluoroethylene resin modified with an acrylic resin is preferable because of its excellent dispersibility in the optical fiber coating resin composition.
フッ素樹脂系溶融張力向上剤の数平均分子量は、１００００００〜３０００００００が好ましく、５００００００〜２０００００００がより好ましい。フッ素樹脂系溶融張力向上剤の数平均分子量が１００００００以上であると、塩化ビニル系樹脂（Ａ）の分子主鎖とフッ素樹脂系溶融張力向上剤のフィブリル化したフッ素樹脂とで絡み合いが生じ、光ファイバケーブルの燃焼時のドリップを抑制できる。また、フッ素樹脂系溶融張力向上剤の数平均分子量が３０００００００以下であると、光ファイバ被覆用樹脂組成物の本来の性能を損なわない。
フッ素樹脂系溶融張力向上剤の数平均分子量は、３８０℃で溶融させた際の動的粘弾性を測定し、測定した動的粘弾性から算出した値とする。
The number average molecular weight of the fluororesin melt tension improver is preferably from 1,000,000 to 30,000,000, more preferably from 5,000,000 to 20,000,000. If the number average molecular weight of the fluororesin melt tension improver is 1,000,000 or more, the molecular main chain of the vinyl chloride resin (A) and the fibrillated fluororesin of the fluororesin melt tension improver are entangled. Drip at the time of combustion of the fiber cable can be suppressed. Moreover, the original performance of the resin composition for optical fiber coating is not impaired as the number average molecular weight of the fluororesin melt tension improver is 30000000 or less.
The number average molecular weight of the fluororesin melt tension improver is a value calculated from the measured dynamic viscoelasticity by measuring the dynamic viscoelasticity when melted at 380 ° C.
アクリル樹脂系溶融張力向上剤は、塩化ビニル系樹脂（Ａ）と混ざり合い、光ファイバ被覆用樹脂組成物の溶融張力を高めることができるものであれば特に限定されないが、例えば、三菱レイヨン（株）製の「メタブレンＰ」シリーズ等が挙げられる。 The acrylic resin melt tension improver is not particularly limited as long as it can be mixed with the vinyl chloride resin (A) and can increase the melt tension of the optical fiber coating resin composition. For example, Mitsubishi Rayon Co., Ltd. ) “Metabrene P” series and the like.
アクリル樹脂系溶融張力向上剤の数平均分子量は、１００００００〜８００００００が好ましく、３００００００〜６００００００がより好ましい。アクリル樹脂系溶融張力向上剤の数平均分子量が１００００００以上であると、塩化ビニル系樹脂（Ａ）の分子主鎖とアクリル樹脂系溶融張力向上剤の分子主鎖とで絡み合いが生じ、光ファイバケーブルの燃焼時のドリップを抑制できる。また、アクリル樹脂系溶融張力向上剤の数平均分子量が８００００００以下であると、光ファイバ被覆用樹脂組成物の本来の性能を損なわない。
アクリル樹脂系溶融張力向上剤の数平均分子量は、標準試料として標準ポリスチレンを用い、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した値とする。
The number average molecular weight of the acrylic resin-based melt tension improver is preferably from 1,000,000 to 8,000,000, and more preferably from 300,000 to 6,000,000. If the number average molecular weight of the acrylic resin melt tension improver is 1,000,000 or more, the molecular main chain of the vinyl chloride resin (A) and the molecular main chain of the acrylic resin melt tension improver are entangled, and the optical fiber cable. Drip during combustion can be suppressed. Further, when the number average molecular weight of the acrylic resin melt tension improver is 8000000 or less, the original performance of the resin composition for coating an optical fiber is not impaired.
The number average molecular weight of the acrylic resin melt tension improver is a value measured by gel permeation chromatography (GPC) using standard polystyrene as a standard sample.
溶融張力向上剤（Ｂ）の含有量は、塩化ビニル系樹脂（Ａ）１００質量部に対して、０．０５質量部〜１５質量部が好ましく、０．１質量部〜５質量部がより好ましい。溶融張力向上剤（Ｂ）の含有量が０．０５質量部以上であると、光ファイバケーブルの燃焼時のドリップを抑制できる。また、溶融張力向上剤（Ｂ）の含有量が１５質量部以下であると、光ファイバ被覆用樹脂組成物の本来の性能を損なわない。 The content of the melt tension improver (B) is preferably 0.05 parts by mass to 15 parts by mass and more preferably 0.1 parts by mass to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A). . When the content of the melt tension improver (B) is 0.05 parts by mass or more, drip at the time of burning the optical fiber cable can be suppressed. Moreover, the original performance of the resin composition for optical fiber coating is not impaired as content of a melt tension improving agent (B) is 15 mass parts or less.
（受酸剤（Ｃ））
本発明の光ファイバ被覆用樹脂組成物は、必要に応じて、更に受酸剤（Ｃ）を含んでもよい。
塩化ビニル系樹脂（Ａ）は、燃焼時に熱分解により、塩化水素ガスが発生する。受酸剤（Ｃ）は、塩化ビニル系樹脂（Ａ）の熱分解により生じた塩化水素ガスを捕捉・吸収する機能を有するため、光ファイバ被覆用樹脂組成物に受酸剤（Ｃ）を配合することで、低発煙性を更に向上させる効果を有する。
(Acid acceptor (C))
The optical fiber coating resin composition of the present invention may further contain an acid acceptor (C) as necessary.
The vinyl chloride resin (A) generates hydrogen chloride gas due to thermal decomposition during combustion. Since the acid acceptor (C) has a function of capturing and absorbing hydrogen chloride gas generated by thermal decomposition of the vinyl chloride resin (A), the acid acceptor (C) is added to the optical fiber coating resin composition. By doing, it has the effect of further improving low smoke generation.
受酸剤（Ｃ）としては、例えば、炭酸カルシウム、炭酸マグネシウム等の炭酸塩化合物；マグネシウムとアルミニウムの炭酸塩複合物、マグネシウムと亜鉛とアルミニウムの炭酸塩複合物等のハイドロタルサイト；酸化カルシウム、酸化マグネシウム、酸化鉛、酸化亜鉛等の酸化金属化合物；オキシ水酸化鉄等のオキシ水酸化金属化合物；フェロセン等が挙げられる。これらの受酸剤（Ｃ）は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの受酸剤（Ｃ）の中でも、塩化水素ガスの捕捉・吸収能力に優れることから、炭酸塩化合物、ハイドロタルサイト、酸化金属化合物、オキシ水酸化金属化合物が好ましく、ハイドロタルサイト、オキシ水酸化金属化合物がより好ましい。 Examples of the acid-accepting agent (C) include carbonate compounds such as calcium carbonate and magnesium carbonate; hydrotalcite such as a carbonate composite of magnesium and aluminum, a carbonate composite of magnesium, zinc and aluminum; calcium oxide, Examples thereof include metal oxide compounds such as magnesium oxide, lead oxide and zinc oxide; metal oxyhydroxide compounds such as iron oxyhydroxide; ferrocene and the like. These acid acceptors (C) may be used alone or in combination of two or more. Among these acid acceptors (C), carbonate compounds, hydrotalcite, metal oxide compounds, and metal oxyhydroxide compounds are preferred because of their excellent ability to capture and absorb hydrogen chloride gas. Hydrotalcite, oxywater A metal oxide compound is more preferable.
ハイドロタルサイトの市販品としては、例えば、「ＤＨＴ−４Ａ」（協和化学工業（株）製）、「ＳＴＡＢＩＡＣＥ ＨＴ−７」（堺化学工業（株）製）等が挙げられる。 Examples of commercially available hydrotalcite include “DHT-4A” (manufactured by Kyowa Chemical Industry Co., Ltd.), “STABIACE HT-7” (manufactured by Sakai Chemical Industry Co., Ltd.), and the like.
受酸剤（Ｃ）の数平均粒子径は、１０ｎｍ〜１０００ｎｍが好ましく、２０ｎｍ〜８００ｎｍがより好ましい。受酸剤（Ｃ）の数平均粒子径が１０ｎｍ以上であると、光ファイバ被覆用樹脂組成物中の分散性に優れる。また、受酸剤（Ｃ）の数平均粒子径が１０００ｎｍであると、光ファイバ被覆用樹脂組成物の本来の性能を損なわない。
受酸剤（Ｃ）の数平均粒子径は、顕微鏡で観察した任意の１００個の粒子の粒子径を平均した値とする。
The number average particle diameter of the acid acceptor (C) is preferably 10 nm to 1000 nm, and more preferably 20 nm to 800 nm. When the number average particle diameter of the acid acceptor (C) is 10 nm or more, the dispersibility in the optical fiber coating resin composition is excellent. Moreover, the original performance of the resin composition for optical fiber coating is not impaired as the number average particle diameter of the acid acceptor (C) is 1000 nm.
The number average particle diameter of the acid acceptor (C) is a value obtained by averaging the particle diameters of arbitrary 100 particles observed with a microscope.
受酸剤（Ｃ）の含有量は、塩化ビニル系樹脂（Ａ）１００質量部に対して、１質量部〜６０質量部が好ましく、５質量部〜５０質量部がより好ましい。受酸剤（Ｃ）の含有量が１質量部以上であると、光ファイバケーブルの低発煙性に優れる。また、受酸剤（Ｃ）の含有量が６０質量部以下であると、光ファイバ被覆用樹脂組成物の本来の性能を損なわない。 The content of the acid acceptor (C) is preferably 1 part by mass to 60 parts by mass and more preferably 5 parts by mass to 50 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A). When the content of the acid acceptor (C) is 1 part by mass or more, the low smoke generation property of the optical fiber cable is excellent. Moreover, the original performance of the resin composition for optical fiber coating is not impaired as content of an acid acceptor (C) is 60 mass parts or less.
（可塑剤（Ｄ））
本発明の光ファイバ被覆用樹脂組成物は、必要に応じて、更に可塑剤（Ｄ）を含んでもよい。
可塑剤（Ｄ）は、塩化ビニル系樹脂（Ａ）の柔軟性を改善させる機能を有するため、光ファイバ被覆用樹脂組成物に可塑剤（Ｄ）を配合することで、柔軟性を更に向上させる効果を有する。
(Plasticizer (D))
The optical fiber coating resin composition of the present invention may further contain a plasticizer (D) as necessary.
Since the plasticizer (D) has a function of improving the flexibility of the vinyl chloride resin (A), the flexibility is further improved by adding the plasticizer (D) to the optical fiber coating resin composition. Has an effect.
可塑剤（Ｄ）としては、塩化ビニル系樹脂（Ａ）に適用できる可塑剤であれば特に限定されないが、例えば、トリメリット酸トリ−２−エチルヘキシル、トリメリット酸トリ−ｎ−オクチル、トリメリット酸トリイソデシル等のトリメリット酸エステル化合物；エポキシヘキサヒドロフタル酸ジ−２−エチルヘキシル、エポキシ化脂肪酸−２−エチルヘキシル等のエポキシ系化合物等が挙げられる。これらの可塑剤（Ｄ）は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの可塑剤（Ｄ）の中でも、光ファイバケーブルの柔軟性に優れることから、トリメリット酸エステル化合物が好ましく、トリメリット酸トリ−２−エチルヘキシル、トリメリット酸トリ−ｎ−オクチルがより好ましい。 The plasticizer (D) is not particularly limited as long as it is a plasticizer applicable to the vinyl chloride resin (A). For example, tri-2-ethylhexyl trimellitic acid, tri-n-octyl trimellitic acid, trimellitic Trimellitic acid ester compounds such as triisodecyl acid; and epoxy compounds such as di-2-ethylhexyl epoxyhexahydrophthalate and epoxidized fatty acid-2-ethylhexyl. These plasticizers (D) may be used individually by 1 type, and may use 2 or more types together. Among these plasticizers (D), trimellitic acid ester compounds are preferable because of excellent flexibility of the optical fiber cable, and trimellitic acid tri-2-ethylhexyl and trimellitic acid tri-n-octyl are more preferable.
トリメリット酸エステル化合物の可塑剤（Ｄ）の市販品としては、例えば、花王（株）製の「トリメックス」シリーズ；ＤＩＣ（株）製の「モノサイザー」シリーズ等が挙げられる。
エポキシ系化合物の可塑剤（Ｄ）の市販品としては、例えば、（株）ＡＤＥＫＡ製の「アデカサイザーＯ」シリーズ、「アデカサイザーＤ」シリーズ；新日本理化（株）製の「サンソサイザーＥ」シリーズ等が挙げられる。
As a commercial item of the plasticizer (D) of a trimellitic ester compound, for example, “Trimex” series manufactured by Kao Corporation; “Monocizer” series manufactured by DIC Corporation, and the like can be given.
Examples of commercially available epoxy compound plasticizers (D) include “ADEKA SIZER O” series and “ADEKA SIZER D” series manufactured by ADEKA Corporation; “Sanso Sizer E” manufactured by Shin Nippon Rika Co., Ltd. Series etc. are mentioned.
可塑剤（Ｄ）の分子量は、４００〜２０００が好ましく、５００〜１０００がより好ましい。可塑剤（Ｄ）の分子量が４００以上であると、可塑剤（Ｄ）の光ファイバへの移行が少なく、可塑剤（Ｄ）の光ファイバケーブルからのブリードアウトが少ない。また、可塑剤（Ｄ）の分子量が２０００以下であると、光ファイバケーブルの柔軟性に優れる。 400-2000 are preferable and, as for the molecular weight of a plasticizer (D), 500-1000 are more preferable. When the molecular weight of the plasticizer (D) is 400 or more, migration of the plasticizer (D) to the optical fiber is small, and bleed out of the plasticizer (D) from the optical fiber cable is small. Moreover, when the molecular weight of the plasticizer (D) is 2000 or less, the flexibility of the optical fiber cable is excellent.
可塑剤（Ｄ）の含有量は、塩化ビニル系樹脂（Ａ）１００質量部に対して、１０質量部〜１００質量部が好ましく、４０質量部〜７０質量部がより好ましい。可塑剤（Ｄ）の含有量が１０質量部以上であると、光ファイバケーブルの柔軟性に優れる。また、可塑剤（Ｄ）の含有量が１００質量部以下であると、光ファイバ被覆用樹脂組成物の本来の性能を損なわない。 The content of the plasticizer (D) is preferably 10 parts by mass to 100 parts by mass, and more preferably 40 parts by mass to 70 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A). When the content of the plasticizer (D) is 10 parts by mass or more, the flexibility of the optical fiber cable is excellent. Moreover, the original performance of the resin composition for optical fiber coating is not impaired as content of a plasticizer (D) is 100 mass parts or less.
（難燃剤（Ｅ））
本発明の光ファイバ被覆用樹脂組成物は、必要に応じて、更に難燃剤（Ｅ）を含んでもよい。
難燃剤（Ｅ）は、塩化ビニル系樹脂（Ａ）の難燃性を改善させる機能を有するため、光ファイバ被覆用樹脂組成物に難燃剤（Ｅ）を配合することで、光ファイバケーブルの難燃性を更に向上させる効果を有する。
(Flame retardant (E))
The optical fiber coating resin composition of the present invention may further contain a flame retardant (E) as necessary.
Since the flame retardant (E) has a function of improving the flame retardancy of the vinyl chloride resin (A), the flame retardant (E) is mixed with the resin composition for coating an optical fiber to make it difficult for the optical fiber cable. It has the effect of further improving the flammability.
難燃剤（Ｅ）としては、例えば、臭素化合物、塩素化合物等のハロゲン系難燃剤；リン、リン酸塩化合物、リン酸エステル化合物等のリン系難燃剤；水酸化マグネシウム、水酸化アルミニウム等の水酸化金属系難燃剤；等が挙げられる。これらの難燃剤（Ｅ）は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの難燃剤（Ｅ）の中でも、光ファイバ被覆用樹脂組成物中の分散性に優れ、少量の添加で光ファイバケーブルの難燃性を向上させることから、ハロゲン系難燃剤が好ましく、臭素化合物がより好ましい。 Examples of the flame retardant (E) include halogen flame retardants such as bromine compounds and chlorine compounds; phosphorus flame retardants such as phosphorus, phosphate compounds and phosphate ester compounds; water such as magnesium hydroxide and aluminum hydroxide. Metal oxide flame retardant; and the like. These flame retardants (E) may be used alone or in combination of two or more. Among these flame retardants (E), halogen-based flame retardants are preferred because they are excellent in dispersibility in the resin composition for coating optical fibers and improve the flame retardant properties of optical fiber cables with a small amount of addition. Is more preferable.
臭素化合物としては、例えば、テトラブロモビスフェノールＡ、トリブロモフェノール、デカブロモジフェニルエーテル、ビス（ペンタブロモフェニル）エタン、トリアリルイソシアヌレート臭化物、臭素化エポキシ樹脂、末端封止臭素化エポキシ樹脂、臭素化スチレン樹脂等が挙げられる。これらの臭素化合物は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの臭素化合物の中でも、臭素化合物の光ファイバへの移行が少なく、臭素化合物の光ファイバケーブルからのブリードアウトが少ないことから、臭素化エポキシ樹脂、末端封止臭素化エポキシ樹脂、臭素化スチレン樹脂が好ましく、光ファイバ被覆用樹脂組成物中の分散性に優れることから、末端封止臭素化エポキシ樹脂がより好ましい。
臭素化エポキシ樹脂、末端封止臭素化エポキシ樹脂は、オリゴマーを含む。
Examples of the bromine compound include tetrabromobisphenol A, tribromophenol, decabromodiphenyl ether, bis (pentabromophenyl) ethane, triallyl isocyanurate bromide, brominated epoxy resin, end-capped brominated epoxy resin, brominated styrene. Examples thereof include resins. These bromine compounds may be used individually by 1 type, and may use 2 or more types together. Among these bromine compounds, brominated epoxy resins, end-capped brominated epoxy resins, brominated styrene resins are less migrated to optical fibers and brominated compounds are less bleed out from optical fiber cables. Are preferred, and end-capped brominated epoxy resins are more preferred because of excellent dispersibility in the resin composition for coating optical fibers.
Brominated epoxy resins and end-capped brominated epoxy resins include oligomers.
難燃剤（Ｅ）の含有量は、塩化ビニル系樹脂（Ａ）１００質量部に対して、５質量部〜７０質量部が好ましく、１０質量部〜６０質量部がより好ましい。難燃剤（Ｅ）の含有量が５質量部以上であると、光ファイバケーブルの難燃性に優れる。また、難燃剤（Ｅ）の含有量が７０質量部以下であると、光ファイバ被覆用樹脂組成物の本来の性能を損なわない。 The content of the flame retardant (E) is preferably 5 parts by mass to 70 parts by mass, and more preferably 10 parts by mass to 60 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A). It is excellent in the flame retardance of an optical fiber cable as content of a flame retardant (E) is 5 mass parts or more. Moreover, the original performance of the resin composition for optical fiber coating is not impaired as content of a flame retardant (E) is 70 mass parts or less.
（難燃助剤（Ｆ））
本発明の光ファイバ被覆用樹脂組成物は、必要に応じて、更に難燃助剤（Ｆ）を含んでもよい。
難燃助剤（Ｆ）は、難燃剤（Ｅ）との相互作用により難燃性を改善させる機能を有するため、光ファイバ被覆用樹脂組成物に難燃助剤（Ｆ）を配合することで、光ファイバケーブルの難燃性を更に向上させる効果を有する。
(Flame retardant aid (F))
The resin composition for coating an optical fiber of the present invention may further contain a flame retardant aid (F) as necessary.
Since the flame retardant aid (F) has a function of improving the flame retardance by interaction with the flame retardant (E), the flame retardant aid (F) is blended into the optical fiber coating resin composition. The effect of further improving the flame retardancy of the optical fiber cable.
難燃助剤（Ｆ）としては、例えば、三酸化アンチモン；ホウ酸亜鉛、ホウ酸カルシウム、ホウ酸アルミニウム等のホウ酸塩化合物；ポリジメチルシロキサン、ポリジメチルシロキサンのメチル基の一部が水素、フェニル基、ハロゲン化フェニル基、ハロゲン化アルキル基、フルオロエステル基等の１種以上の官能基で置換された樹脂等のケイ素化合物等が挙げられる。これらの難燃助剤（Ｆ）は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの難燃助剤（Ｆ）の中でも、ハロゲン系難燃剤との相互作用を示し、少量の添加で光ファイバケーブルの難燃性を向上させることから、三酸化アンチモン、ホウ酸塩化合物、ケイ素化合物が好ましく、三酸化アンチモン、ホウ酸塩化合物がより好ましい。 Examples of the flame retardant aid (F) include antimony trioxide; borate compounds such as zinc borate, calcium borate, and aluminum borate; polydimethylsiloxane, a part of methyl group of polydimethylsiloxane is hydrogen, Examples thereof include silicon compounds such as resins substituted with one or more functional groups such as a phenyl group, a halogenated phenyl group, a halogenated alkyl group, and a fluoroester group. These flame retardant aids (F) may be used alone or in combination of two or more. Among these flame retardant aids (F), it exhibits interaction with halogen-based flame retardants and improves the flame retardancy of optical fiber cables with a small amount of addition, so antimony trioxide, borate compounds, silicon Compounds are preferred, and antimony trioxide and borate compounds are more preferred.
難燃助剤（Ｆ）の含有量は、塩化ビニル系樹脂（Ａ）１００質量部に対して、１質量部〜３０質量部が好ましく、３質量部〜２５質量部がより好ましい。難燃助剤（Ｆ）の含有量が１質量部以上であると、光ファイバケーブルの難燃性に優れる。また、難燃助剤（Ｆ）の含有量が３０質量部以下であると、光ファイバ被覆用樹脂組成物の本来の性能を損なわない。 The content of the flame retardant aid (F) is preferably 1 part by mass to 30 parts by mass, and more preferably 3 parts by mass to 25 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A). When the content of the flame retardant aid (F) is 1 part by mass or more, the flame retardancy of the optical fiber cable is excellent. Moreover, the original performance of the resin composition for optical fiber coating is not impaired as content of a flame retardant adjuvant (F) is 30 mass parts or less.
難燃助剤（Ｆ）の含有量は、難燃剤（Ｅ）１００質量部に対して、１質量部〜３００質量部が好ましく、３質量部〜１５０質量部がより好ましい。難燃助剤（Ｆ）の含有量が１質量部以上であると、光ファイバケーブルの難燃性に優れる。また、難燃助剤（Ｆ）の含有量が３００質量部以下であると、光ファイバ被覆用樹脂組成物の本来の性能を損なわない。 1 mass part-300 mass parts are preferable with respect to 100 mass parts of flame retardants (E), and, as for content of a flame retardant adjuvant (F), 3 mass parts-150 mass parts are more preferable. When the content of the flame retardant aid (F) is 1 part by mass or more, the flame retardancy of the optical fiber cable is excellent. Moreover, the original performance of the resin composition for optical fiber coating is not impaired as content of a flame retardant adjuvant (F) is 300 mass parts or less.
（熱安定剤（Ｇ））
本発明の光ファイバ被覆用樹脂組成物は、必要に応じて、更に熱安定剤（Ｇ）を含んでもよい。
塩化ビニル系樹脂（Ａ）は、溶融加工温度と熱分解温度とが近く、加工時に熱分解により塩素原子と水素原子が脱離し、塩化水素ガスを発生しやすい。
熱安定剤（Ｇ）は、塩化ビニル系樹脂（Ａ）の熱分解を抑制する機能を有するため、光ファイバ被覆用樹脂組成物に熱安定剤（Ｇ）を配合することで、低発煙性、耐熱性を更に向上させる効果を有する。
(Thermal stabilizer (G))
The optical fiber coating resin composition of the present invention may further contain a thermal stabilizer (G) as necessary.
The vinyl chloride resin (A) is close in melting processing temperature and thermal decomposition temperature, and chlorine atoms and hydrogen atoms are desorbed by thermal decomposition during processing, and hydrogen chloride gas is easily generated.
Since the heat stabilizer (G) has a function of suppressing the thermal decomposition of the vinyl chloride resin (A), by blending the heat stabilizer (G) into the optical fiber coating resin composition, It has the effect of further improving heat resistance.
熱安定剤（Ｇ）としては、例えば、カルシウム・亜鉛系熱安定剤、バリウム・亜鉛系熱安定剤、マグネシウム・亜鉛系熱安定剤、スズ系熱安定剤、カルシウム・マグネシウム・亜鉛系熱安定剤等の金属系熱安定剤等が挙げられる。これらの熱安定剤（Ｇ）は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの熱安定剤（Ｇ）の中でも、光ファイバ被覆用樹脂組成物の耐熱性に優れることから、金属系熱安定剤が好ましく、カルシウム・マグネシウム・亜鉛系熱安定剤がより好ましい。 Examples of the heat stabilizer (G) include calcium / zinc heat stabilizer, barium / zinc heat stabilizer, magnesium / zinc heat stabilizer, tin heat stabilizer, calcium / magnesium / zinc heat stabilizer. Metal-based heat stabilizers and the like. These heat stabilizers (G) may be used individually by 1 type, and may use 2 or more types together. Among these heat stabilizers (G), a metal-based heat stabilizer is preferable, and a calcium / magnesium / zinc-based heat stabilizer is more preferable because the heat resistance of the optical fiber coating resin composition is excellent.
熱安定剤（Ｇ）の含有量は、塩化ビニル系樹脂（Ａ）１００質量部に対して、０．５質量部〜１５質量部が好ましく、１質量部〜１０質量部がより好ましい。熱安定剤（Ｇ）の含有量が０．５質量部以上であると、光ファイバケーブルの低発煙性、耐熱性に優れる。また、熱安定剤（Ｇ）の含有量が１５質量部以下であると、光ファイバ被覆用樹脂組成物の本来の性能を損なわない。 0.5 mass part-15 mass parts are preferable with respect to 100 mass parts of vinyl chloride-type resin (A), and, as for content of a heat stabilizer (G), 1 mass part-10 mass parts are more preferable. When the content of the heat stabilizer (G) is 0.5 parts by mass or more, the optical fiber cable is excellent in low smoke generation and heat resistance. Moreover, the original performance of the resin composition for optical fiber coating is not impaired as content of a heat stabilizer (G) is 15 mass parts or less.
（顔料（Ｈ））
本発明の光ファイバ被覆用樹脂組成物は、必要に応じて、更に顔料（Ｈ）を含んでもよい。
顔料（Ｈ）は、光ファイバ被覆用樹脂組成物を着色させる機能を有するため、光ファイバ被覆用樹脂組成物に顔料（Ｈ）を配合することで、光ファイバケーブルの識別性、意匠性を更に向上させる効果を有する。
(Pigment (H))
The optical fiber coating resin composition of the present invention may further contain a pigment (H) as necessary.
Since the pigment (H) has a function of coloring the optical fiber coating resin composition, by adding the pigment (H) to the optical fiber coating resin composition, the distinctiveness and design of the optical fiber cable can be further increased. Has the effect of improving.
顔料（Ｈ）としては、例えば、無機系顔料、有機系顔料等が挙げられる。具体的には、黒色顔料としては、例えば、カーボンブラック等；白色顔料としては、例えば、酸化チタン、酸化亜鉛等；黄色顔料としては、例えば、アゾ系有機系顔料、黄鉛、クロム黄、亜鉛黄等；青色顔料としては、例えば、群青（ウルトラマリンブルー）、コバルトブルー等；緑色顔料としては、例えば、酸化クロム等が挙げられる。これらの顔料（Ｈ）は、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the pigment (H) include inorganic pigments and organic pigments. Specifically, as black pigments, for example, carbon black and the like; as white pigments, for example, titanium oxide, zinc oxide and the like; as yellow pigments, for example, azo organic pigments, yellow lead, chromium yellow, zinc Yellow etc .; Examples of blue pigments include ultramarine blue and cobalt blue; Examples of green pigments include chromium oxide. These pigments (H) may be used alone or in combination of two or more.
顔料（Ｈ）の含有量は、塩化ビニル系樹脂（Ａ）１００質量部に対して、０．５質量部〜１０質量部が好ましく、１質量部〜５質量部がより好ましい。顔料（Ｈ）の含有量が０．５質量部以上であると、光ファイバケーブルの識別性、意匠性に優れる。また、顔料（Ｈ）の含有量が１０質量部以下であると、光ファイバ被覆用樹脂組成物の本来の性能を損なわない。 0.5 mass part-10 mass parts are preferable with respect to 100 mass parts of vinyl chloride-type resin (A), and, as for content of a pigment (H), 1 mass part-5 mass parts are more preferable. When the content of the pigment (H) is 0.5 parts by mass or more, the optical fiber cable is excellent in distinguishability and design. Moreover, the original performance of the resin composition for optical fiber coating is not impaired as content of a pigment (H) is 10 mass parts or less.
（他の添加剤（Ｉ））
本発明の光ファイバ被覆用樹脂組成物は、必要に応じて、他の添加剤（Ｉ）を含んでもよい。
(Other additives (I))
The optical fiber coating resin composition of the present invention may contain other additives (I) as necessary.
他の添加剤（Ｉ）としては、例えば、光ファイバケーブルを長期間使用する際、塩化ビニル系樹脂（Ａ）の酸素による塩素原子の脱離を防止する目的で添加する酸化防止剤；光ファイバ被覆用樹脂組成物を溶融成形する際、光ファイバ被覆用樹脂組成物の流動性を向上させる目的で添加する滑剤；光ファイバケーブルを長期間保管する際、光ファイバケーブル同士の密着を防止する目的で添加するアンチブロッキング剤等が挙げられる。これらの他の添加剤（Ｉ）は、１種を単独で用いてもよく、２種以上を併用してもよい。 Other additives (I) include, for example, an antioxidant added for the purpose of preventing the elimination of chlorine atoms by oxygen in the vinyl chloride resin (A) when the optical fiber cable is used for a long period of time; A lubricant added for the purpose of improving the fluidity of the optical fiber coating resin composition when melt-molding the coating resin composition; the purpose of preventing the optical fiber cables from sticking to each other when storing the optical fiber cable for a long period of time And anti-blocking agents to be added. These other additives (I) may be used alone or in combination of two or more.
他の添加剤（Ｉ）の含有量は、塩化ビニル系樹脂（Ａ）１００質量部に対して、１質量部〜１０質量部が好ましく、２質量部〜８質量部がより好ましい。他の添加剤（Ｉ）の含有量が１質量部以上であると、他の添加剤（Ｉ）が有する性能を発現させることができる。また、他の添加剤（Ｉ）の含有量が１０質量部以下であると、光ファイバ被覆用樹脂組成物の本来の性能を損なわない。 1 mass part-10 mass parts are preferable with respect to 100 mass parts of vinyl chloride-type resin (A), and, as for content of another additive (I), 2 mass parts-8 mass parts are more preferable. When the content of the other additive (I) is 1 part by mass or more, the performance of the other additive (I) can be expressed. Further, when the content of the other additive (I) is 10 parts by mass or less, the original performance of the optical fiber coating resin composition is not impaired.
（光ファイバ被覆用樹脂組成物の製造方法）
本発明の光ファイバ被覆用樹脂組成物は、塩化ビニル系樹脂（Ａ）、溶融張力向上剤（Ｂ）、必要に応じて、受酸剤（Ｃ）、可塑剤（Ｄ）、難燃剤（Ｅ）、難燃助剤（Ｆ）、熱安定剤（Ｇ）、顔料（Ｈ）、他の添加剤（Ｉ）を混合することで得られる。
(Manufacturing method of resin composition for optical fiber coating)
The resin composition for coating an optical fiber of the present invention comprises a vinyl chloride resin (A), a melt tension improver (B), and an acid acceptor (C), a plasticizer (D), a flame retardant (E ), Flame retardant aid (F), heat stabilizer (G), pigment (H), and other additives (I).
混合方法としては、例えば、二軸押出機等の装置を用いて溶融混練する方法等が挙げられる。
溶融混練するための装置としては、例えば、添加材料供給フィーダーが主材料ホッパーと押出機との間に取り付けられ、添加材料を直接押出機へ混入するサイドフィード式二軸押出機；押出時の水分や残存モノマー等を脱揮するための装置が付帯されたベント式二軸押出機等が挙げられる。
Examples of the mixing method include a melt kneading method using an apparatus such as a twin screw extruder.
As an apparatus for melt kneading, for example, a side feed type twin screw extruder in which an additive material supply feeder is attached between a main material hopper and an extruder and the additive material is directly mixed into the extruder; moisture during extrusion And a vent type twin screw extruder equipped with an apparatus for devolatilizing residual monomers and the like.
溶融混練の温度は、１５０℃〜１９０℃が好ましく、１６０℃〜１８０℃がより好ましい。混練温度が１５０℃以上であると、光ファイバ被覆用樹脂組成物を十分に混練することができる。また、混練温度が１９０℃以下であると、光ファイバ被覆用樹脂組成物の本来の性能を損なわない。 The temperature for melt kneading is preferably 150 ° C. to 190 ° C., more preferably 160 ° C. to 180 ° C. When the kneading temperature is 150 ° C. or higher, the optical fiber coating resin composition can be sufficiently kneaded. Moreover, the original performance of the resin composition for optical fiber coating is not impaired as kneading | mixing temperature is 190 degrees C or less.
（光ファイバケーブル）
本発明の光ファイバケーブルは、光ファイバと、光ファイバの外周に本発明の光ファイバ被覆用樹脂組成物からなる被覆層とを有する。
本発明の光ファイバケーブルとしては、例えば、図１（ａ）に示すような光ファイバ１０の外周に１層の被覆層２０を有する光ファイバケーブル、図１（ｂ）に示すような光ファイバ１０の外周に２層以上の被覆層２０ａ（最内層）・２０ｂ（最外層）を有する光ファイバケーブル等が挙げられる。
(Optical fiber cable)
The optical fiber cable of the present invention has an optical fiber and a coating layer made of the resin composition for coating an optical fiber of the present invention on the outer periphery of the optical fiber.
As the optical fiber cable of the present invention, for example, an optical fiber cable having one coating layer 20 on the outer periphery of the optical fiber 10 as shown in FIG. 1A, or an optical fiber 10 as shown in FIG. And an optical fiber cable having two or more coating layers 20a (innermost layer) and 20b (outermost layer) on the outer periphery of the cable.
（光ファイバ）
光ファイバは、光ファイバとしての機能を有するものであれば特に限定されず、公知の光ファイバを用いることができる。
光ファイバの種類としては、例えば、ステップ・インデックス型光ファイバ、マルチステップ・インデックス型光ファイバ、グレーテッド・インデックス型光ファイバ、多芯光ファイバ等が挙げられる。これらの光ファイバの種類の中でも、耐熱性に優れることから、ステップ・インデックス型光ファイバ、多芯光ファイバが好ましく、より長距離の通信を可能とすることから、ステップ・インデックス型光ファイバがより好ましい。
(Optical fiber)
The optical fiber is not particularly limited as long as it has a function as an optical fiber, and a known optical fiber can be used.
Examples of the type of optical fiber include a step index type optical fiber, a multistep index type optical fiber, a graded index type optical fiber, and a multi-core optical fiber. Among these types of optical fibers, step index type optical fibers and multi-core optical fibers are preferable because of their excellent heat resistance, and step index type optical fibers are more suitable because they enable longer distance communication. preferable.
ステップ・インデックス型光ファイバは、芯と鞘との界面で光を全反射させ、芯内で光を伝播させる。
ステップ・インデックス型光ファイバとしては、例えば、図２（ａ）に示すような芯１１の外周に１層の鞘１２を有する光ファイバ、図２（ｂ）に示すような芯１１の外周に２層以上の鞘１２ａ（最内層）・１２ｂ（最外層）を有する光ファイバ等が挙げられる。
The step index type optical fiber totally reflects light at the interface between the core and the sheath and propagates the light in the core.
As the step index type optical fiber, for example, an optical fiber having a single layer sheath 12 on the outer periphery of the core 11 as shown in FIG. 2A, and 2 on the outer periphery of the core 11 as shown in FIG. The optical fiber etc. which have the sheath 12a (innermost layer) * 12b (outermost layer) more than the layer are mentioned.
（芯）
芯を構成する材料（芯材）は、透明性の高い材料であれば特に限定されず、使用目的等に応じて適宜選択することができる。
芯材としては、例えば、ガラス；アクリル樹脂、スチレン樹脂、カーボネート樹脂等の樹脂が挙げられる。これらの芯材は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。これらの芯材の中でも、難燃性に劣り、本発明の光ファイバ被覆用樹脂組成物により被覆する必要性が高いことから、樹脂が好ましく、より長距離の通信を可能とすることから、アクリル樹脂が好ましい。
(core)
The material (core material) which comprises a core will not be specifically limited if it is a highly transparent material, According to a use purpose etc., it can select suitably.
Examples of the core material include glass; and resins such as acrylic resin, styrene resin, and carbonate resin. These core materials may be used individually by 1 type, and 2 or more types may be mixed and used for them. Among these core materials, the resin is preferable because it is inferior in flame retardancy and needs to be coated with the resin composition for coating an optical fiber of the present invention. Resins are preferred.
アクリル樹脂としては、例えばメチルメタクリレート単独重合体、メチルメタクリレート単位を５０質量％以上含む共重合体等が挙げられる。これらのアクリル樹脂は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。これらのアクリル樹脂の中でも、光学特性、機械特性、耐熱性、透明性に優れることから、メチルメタクリレート単独重合体、メチルメタクリレート単位を５０質量％以上含む共重合体が好ましく、メチルメタクリレート単独重合体、メチルメタクリレート単位を６０質量％以上含む共重合体がより好ましく、メチルメタクリレート単独重合体、メチルメタクリレート単位を７０質量％以上含む共重合体が更に好ましく、メチルメタクリレート単独重合体が特に好ましい。 Examples of the acrylic resin include a methyl methacrylate homopolymer, a copolymer containing 50% by mass or more of a methyl methacrylate unit, and the like. These acrylic resins may be used individually by 1 type, and 2 or more types may be mixed and used for them. Among these acrylic resins, since they are excellent in optical properties, mechanical properties, heat resistance, and transparency, methyl methacrylate homopolymers and copolymers containing 50% by mass or more of methyl methacrylate units are preferable, methyl methacrylate homopolymers, A copolymer containing 60% by mass or more of methyl methacrylate units is more preferred, a methyl methacrylate homopolymer, a copolymer containing 70% by mass or more of methyl methacrylate units are further preferred, and a methyl methacrylate homopolymer is particularly preferred.
芯材の製造方法としては、例えば、塊状重合法、懸濁重合法、乳化重合法、溶液重合法等が挙げられる。これらの芯材の製造方法の中でも、異物の混入を抑制できることから、塊状重合法、溶液重合法が好ましい。 Examples of the method for producing the core material include a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method. Among these methods for producing the core material, the bulk polymerization method and the solution polymerization method are preferable because contamination of foreign matters can be suppressed.
（鞘）
鞘は、芯の外周に形成される。鞘は、図２（ａ）に示すように１層でもよく、図２（ｂ）に示すように２層以上でもよい。
鞘を構成する材料（鞘材）は、芯材より屈折率の低い材料であれば特に限定されず、芯材の組成や使用目的等に応じて適宜選択することができる。
芯材としてアクリル樹脂を用いる場合、より長距離の通信を可能とすることから、鞘材としてフッ素樹脂を用いることが好ましい。特に、芯材としてメチルメタクリレート単独重合体を用いる場合、より長距離の通信を可能とすることから、鞘材としてフッ素樹脂を用いることが好ましい。
(sheath)
The sheath is formed on the outer periphery of the core. The sheath may have one layer as shown in FIG. 2 (a), or two or more layers as shown in FIG. 2 (b).
The material (sheath material) which comprises a sheath will not be specifically limited if it is a material whose refractive index is lower than a core material, According to the composition of a core material, the intended purpose, etc., it can select suitably.
When an acrylic resin is used as the core material, it is preferable to use a fluororesin as the sheath material because communication over a longer distance is possible. In particular, when a methyl methacrylate homopolymer is used as the core material, it is preferable to use a fluororesin as the sheath material because long-distance communication is possible.
フッ素樹脂としては、例えば、フッ化ビニリデン（ＶＤＦ）単独重合体、ＶＤＦ−トリフルオロエチレン共重合体、ＶＤＦ−テトラフルオロエチレン（ＴＦＥ）共重合体、ＶＤＦ−ヘキサフルオロプロピレン（ＨＦＰ）共重合体、ＶＤＦ−ＴＦＥ−ＨＦＰ共重合体、ＶＤＦ−ＴＦＥ−ＨＦＰ−（パーフルオロ）アルキルビニルエーテル共重合体、ＶＤＦ−ヘキサフルオロアセトン共重合体、ＶＤＦ−ＨＦＰ共重合体、ＶＤＦ−ＴＦＥ−ヘキサフルオロアセトン共重合体、エチレン−ＶＤＦ−ＴＦＥ−ＨＦＰ共重合体、エチレン−ＴＦＥ−ＨＦＰ共重合体、フルオロアルキル（メタ）アクリレート重合体、フルオロアルキル（メタ）アクリレート−アルキル（メタ）アクリレート共重合体等が挙げられる。これらのフッ素樹脂は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。 Examples of the fluororesin include, for example, vinylidene fluoride (VDF) homopolymer, VDF-trifluoroethylene copolymer, VDF-tetrafluoroethylene (TFE) copolymer, VDF-hexafluoropropylene (HFP) copolymer, VDF-TFE-HFP copolymer, VDF-TFE-HFP- (perfluoro) alkyl vinyl ether copolymer, VDF-hexafluoroacetone copolymer, VDF-HFP copolymer, VDF-TFE-hexafluoroacetone copolymer For example, ethylene-VDF-TFE-HFP copolymer, ethylene-TFE-HFP copolymer, fluoroalkyl (meth) acrylate polymer, fluoroalkyl (meth) acrylate-alkyl (meth) acrylate copolymer, and the like. . These fluororesins may be used individually by 1 type, and 2 or more types may be mixed and used for them.
これらのフッ素樹脂の中でも、柔軟性、耐衝撃性、透明性、耐薬品性に優れ、低価格であることから、ＶＤＦ−ＴＦＥ共重合体、ＶＤＦ−ＴＦＥ−ＨＦＰ共重合体、エチレン−ＶＤＦ−ＴＦＥ−ＨＦＰ共重合体、エチレン−ＴＦＥ−ＨＦＰ共重合体、フルオロアルキル（メタ）アクリレート重合体、フルオロアルキル（メタ）アクリレート−アルキル（メタ）アクリレート共重合体が好ましい。
特に、鞘が１層の場合、耐薬品性に優れることから、ＶＤＦ−ＴＦＥ共重合体、ＶＤＦ−ＴＦＥ−ＨＦＰ共重合体、エチレン−ＶＤＦ−ＴＦＥ−ＨＦＰ共重合体、エチレン−ＴＦＥ−ＨＦＰ共重合体、フルオロアルキル（メタ）アクリレート重合体、フルオロアルキル（メタ）アクリレート−アルキル（メタ）アクリレート共重合体が好ましく、機械特性に優れることから、ＶＤＦ−ＴＦＥ共重合体、ＶＤＦ−ＴＦＥ−ＨＦＰ共重合体、エチレン−ＶＤＦ−ＴＦＥ−ＨＦＰ共重合体、エチレン−ＴＦＥ−ＨＦＰ共重合体がより好ましい。
また、鞘が２層の場合、光ファイバを曲げた際に漏光を抑制できることから、最内層（図２（ｂ）でいう１２ａ）はフルオロアルキル（メタ）アクリレート重合体、フルオロアルキル（メタ）アクリレート−アルキル（メタ）アクリレート共重合体が好ましく、最外層（図２（ｂ）でいう１２ｂ）はＶＤＦ−ＴＦＥ共重合体、ＶＤＦ−ＴＦＥ−ＨＦＰ共重合体、エチレン−ＶＤＦ−ＴＦＥ−ＨＦＰ共重合体、エチレン−ＴＦＥ−ＨＦＰ共重合体が好ましい。
Among these fluororesins, they are excellent in flexibility, impact resistance, transparency, chemical resistance, and are inexpensive. Therefore, VDF-TFE copolymer, VDF-TFE-HFP copolymer, ethylene-VDF- TFE-HFP copolymer, ethylene-TFE-HFP copolymer, fluoroalkyl (meth) acrylate polymer, and fluoroalkyl (meth) acrylate-alkyl (meth) acrylate copolymer are preferred.
In particular, when the sheath has a single layer, the chemical resistance is excellent, so that the VDF-TFE copolymer, the VDF-TFE-HFP copolymer, the ethylene-VDF-TFE-HFP copolymer, and the ethylene-TFE-HFP copolymer are used. A polymer, a fluoroalkyl (meth) acrylate polymer, and a fluoroalkyl (meth) acrylate-alkyl (meth) acrylate copolymer are preferable, and because of excellent mechanical properties, VDF-TFE copolymer, VDF-TFE-HFP copolymer More preferred are polymers, ethylene-VDF-TFE-HFP copolymers, and ethylene-TFE-HFP copolymers.
Further, when the sheath has two layers, light leakage can be suppressed when the optical fiber is bent. Therefore, the innermost layer (12a in FIG. 2 (b)) is a fluoroalkyl (meth) acrylate polymer, fluoroalkyl (meth) acrylate. -Alkyl (meth) acrylate copolymer is preferable, and the outermost layer (12b in FIG. 2 (b)) is VDF-TFE copolymer, VDF-TFE-HFP copolymer, ethylene-VDF-TFE-HFP copolymer. Polymers and ethylene-TFE-HFP copolymers are preferred.
フルオロアルキル（メタ）アクリレートとしては、例えば、２−（パーフルオロヘキシル）エチルメタクリレート（１３ＦＭ）、２−（パーフルオロオクチル）エチルメタクリレート（１７ＦＭ）等の下記式（１）に示す長鎖フルオロアルキル（メタ）アクリレート；２，２，２−トリフルオロエチルメタクリレート（３ＦＭ）等の下記式（２）に示す短鎖フルオロアルキル（メタ）アクリレート等が挙げられる。 Examples of the fluoroalkyl (meth) acrylate include long-chain fluoroalkyls represented by the following formula (1) such as 2- (perfluorohexyl) ethyl methacrylate (13FM) and 2- (perfluorooctyl) ethyl methacrylate (17FM) ( (Meth) acrylates; short chain fluoroalkyl (meth) acrylates represented by the following formula (2) such as 2,2,2-trifluoroethyl methacrylate (3FM).
（式中、ｍは１又は２、ｎは５〜１３のいずれかの整数、Ｒは水素原子又はメチル基、Ｘは水素原子又はフッ素原子を示す。）
(In the formula, m represents 1 or 2, n represents an integer of 5 to 13, R represents a hydrogen atom or a methyl group, and X represents a hydrogen atom or a fluorine atom.)
（式中、ｍは１又は２、ｎは１〜４のいずれかの整数、Ｒは水素原子又はメチル基、Ｘは水素原子又はフッ素原子を示す。）
(In the formula, m represents 1 or 2, n represents an integer of 1 to 4, R represents a hydrogen atom or a methyl group, and X represents a hydrogen atom or a fluorine atom.)
フルオロアルキル（メタ）アクリレート重合体やフルオロアルキル（メタ）アクリレート−アルキル（メタ）アクリレート共重合体は、伝送損失を低減させることができることから、上記式（１）に示す長鎖フルオロアルキル（メタ）アクリレートの単位１０〜５０質量％、上記式（２）に示す短鎖フルオロアルキル（メタ）アクリレートの単位２０〜９０質量％及び他の共重合可能な単量体単位０〜５０質量％からなる共重合体が好ましい。具体的には、前記含有率の１７ＦＭ−３ＦＭ−メチルメタクリレート−メタクリル酸共重合体、１３ＦＭ−３ＦＭ−メチルメタクリレート−メタクリル酸共重合体が好ましい。 Since the fluoroalkyl (meth) acrylate polymer and the fluoroalkyl (meth) acrylate-alkyl (meth) acrylate copolymer can reduce transmission loss, the long-chain fluoroalkyl (meth) represented by the above formula (1) A copolymer comprising 10 to 50% by mass of acrylate units, 20 to 90% by mass of short chain fluoroalkyl (meth) acrylate units represented by the above formula (2) and 0 to 50% by mass of other copolymerizable monomer units. Polymers are preferred. Specifically, 17FM-3FM-methyl methacrylate-methacrylic acid copolymer and 13FM-3FM-methyl methacrylate-methacrylic acid copolymer having the above-mentioned contents are preferable.
光ファイバの成形方法としては、例えば、溶融紡糸法等が挙げられる。
溶融紡糸法によるステップ・インデックス型光ファイバや多芯光ファイバの成形方法は、例えば、芯材及び鞘材をそれぞれ溶融し、複合紡糸を行う方法が挙げられる。
光ファイバケーブルを温度差の大きい環境で用いる場合、ピストニングを抑制するため、光ファイバをアニール処理することが好ましい。アニール処理は、光ファイバの材料によって処理条件を適宜設定すればよく、連続でもよく、バッチでもよい。
Examples of the optical fiber forming method include a melt spinning method.
Examples of a method for forming a step index type optical fiber or a multi-core optical fiber by a melt spinning method include a method in which a core material and a sheath material are respectively melted to perform composite spinning.
When using an optical fiber cable in an environment with a large temperature difference, it is preferable to anneal the optical fiber in order to suppress pistoning. The annealing process may be performed by appropriately setting the processing conditions depending on the material of the optical fiber, and may be continuous or batch.
光ファイバの直径は、光ファイバの取り扱い性に優れ、光素子との結合効率や光軸ずれに対する許容度の観点から、０．１ｍｍ〜５ｍｍが好ましく、０．２ｍｍ〜４．５ｍｍがより好ましく、０．３ｍｍ〜４ｍｍが更に好ましい。 The diameter of the optical fiber is excellent in handleability of the optical fiber, and is preferably 0.1 mm to 5 mm, more preferably 0.2 mm to 4.5 mm, from the viewpoint of the coupling efficiency with the optical element and the tolerance for the optical axis deviation. 0.3 mm-4 mm are still more preferable.
ステップ・インデックス型光ファイバにおける芯の直径は、光素子との結合効率や光軸ずれに対する許容度の観点から、ステップ・インデックス型光ファイバの直径に対して８５％以上が好ましく、９０％以上がより好ましく、９５％以上が更に好ましい。 The core diameter of the step index type optical fiber is preferably 85% or more, more preferably 90% or more with respect to the diameter of the step index type optical fiber from the viewpoint of the coupling efficiency with the optical element and the tolerance to the optical axis deviation. More preferred is 95% or more.
ステップ・インデックス型光ファイバにおける鞘の厚さは、光素子との結合効率や光軸ずれに対する許容度の観点から、ステップ・インデックス型光ファイバの直径に対して７．５％以下が好ましく、５％以下がより好ましく、２．５％以下が更に好ましい。 The thickness of the sheath in the step-index type optical fiber is preferably 7.5% or less with respect to the diameter of the step-index type optical fiber, from the viewpoint of the coupling efficiency with the optical element and the tolerance to the optical axis deviation. % Or less is more preferable, and 2.5% or less is still more preferable.
鞘を２層とする場合、最内層（図２（ｂ）でいう１２ａ）と最外層（図２（ｂ）でいう１２ｂ）との厚さの範囲を自由に設定することができる。
鞘を２層とする場合、最内層と最外層の厚さの比は、光ファイバの柔軟性、耐衝撃性、耐薬品性に優れ、光素子との結合効率や光軸ずれに対する許容度の観点から、１：０．１〜１：５が好ましく、１：０．５〜１：４がより好ましく、１：１〜１：３が更に好ましい。
When the sheath has two layers, the thickness range between the innermost layer (12a in FIG. 2B) and the outermost layer (12b in FIG. 2B) can be freely set.
When the sheath has two layers, the ratio of the thickness of the innermost layer to the outermost layer is excellent in the flexibility, impact resistance, and chemical resistance of the optical fiber. From the viewpoint, 1: 0.1 to 1: 5 is preferable, 1: 0.5 to 1: 4 is more preferable, and 1: 1 to 1: 3 is still more preferable.
芯材と鞘材の屈折率は、芯材の屈折率より鞘材の屈折率が低ければ特に限定されないが、光が伝播できる最大角度に対する開口数を大きくできることから、芯材の屈折率が１．４５〜１．５５、鞘材の屈折率が１．３５〜１．５１が好ましく、芯材の屈折率が１．４６〜１．５３、鞘材の屈折率が１．３７〜１．４９がより好ましく、芯材の屈折率が１．４７〜１．５１、鞘材の屈折率が１．３９〜１．４７が更に好ましい。
屈折率は、ＩＳＯ １３４６８に準拠し、２３℃でナトリウムＤ線を用い、アッベ屈折計により測定した値とする。
The refractive index of the core material and the sheath material is not particularly limited as long as the refractive index of the sheath material is lower than that of the core material. However, since the numerical aperture with respect to the maximum angle at which light can propagate can be increased, the refractive index of the core material is 1. .45 to 1.55, the refractive index of the sheath material is preferably 1.35 to 1.51, the refractive index of the core material is 1.46 to 1.53, and the refractive index of the sheath material is 1.37 to 1.49. More preferably, the refractive index of the core material is 1.47 to 1.51, and the refractive index of the sheath material is further preferably 1.39 to 1.47.
The refractive index is a value measured with an Abbe refractometer using a sodium D line at 23 ° C. in accordance with ISO 13468.
（被覆層）
被覆層は、光ファイバの外周を被覆し、本発明の光ファイバ被覆用樹脂組成物からなる。
被覆層は、図１（ａ）に示すように１層でもよく、図１（ｂ）に示すように２層以上でもよい。
被覆層を２層以上とする場合、本発明の光ファイバ被覆用樹脂組成物からなる被覆層は、光ファイバケーブルの難燃性に優れることから、光ファイバケーブルの最外層とすることが好ましい。
(Coating layer)
A coating layer coat | covers the outer periphery of an optical fiber, and consists of a resin composition for optical fiber coating of this invention.
The coating layer may be one layer as shown in FIG. 1 (a), or two or more layers as shown in FIG. 1 (b).
When two or more coating layers are used, the coating layer made of the resin composition for coating an optical fiber of the present invention is preferably the outermost layer of the optical fiber cable because it is excellent in flame retardancy of the optical fiber cable.
被覆層の厚さは、０．１ｍｍ〜２．５ｍｍが好ましく、０．２ｍｍ〜２ｍｍがより好ましい。被覆層の厚さが０．１ｍｍ以上であると、光ファイバケーブルの難燃性に優れる。被覆層の厚さが２．５ｍｍ以下であると、光ファイバケーブルの柔軟性、取り扱い性に優れる。 The thickness of the coating layer is preferably 0.1 mm to 2.5 mm, and more preferably 0.2 mm to 2 mm. When the thickness of the coating layer is 0.1 mm or more, the flame retardancy of the optical fiber cable is excellent. When the thickness of the coating layer is 2.5 mm or less, the flexibility and handling properties of the optical fiber cable are excellent.
光ファイバの外周に被覆層を被覆する方法としては、例えば、クロスヘッドダイを備えた押出被覆装置を用いて被覆する方法が挙げられる。特に、プラスチック光ファイバに被覆層を被覆する場合、均一な直径の光ファイバケーブルを得ることができることから、クロスヘッドダイを備えた押出被覆装置を用いて被覆する方法が好ましい。
被覆層を２層以上とする場合、１層ずつ順に被覆層を被覆してもよく、同時に複数の被覆層を被覆してもよい。
Examples of the method of coating the outer periphery of the optical fiber with a coating layer include a method of coating using an extrusion coating apparatus equipped with a crosshead die. In particular, when a coating layer is coated on a plastic optical fiber, an optical fiber cable having a uniform diameter can be obtained. Therefore, a method of coating using an extrusion coating apparatus equipped with a crosshead die is preferable.
When there are two or more coating layers, the coating layers may be coated one by one in order, or a plurality of coating layers may be coated at the same time.
光ファイバの外周に被覆層を被覆する際の押出の温度は、１５０℃〜１９０℃が好ましく、１６０℃〜１８０℃がより好ましい。光ファイバの外周に被覆層を被覆する際の押出の温度が１５０℃以上であると、光ファイバケーブルの外観に優れる。光ファイバの外周に被覆層を被覆する際の押出の温度が１９０℃以下であると、光ファイバ被覆用樹脂組成物の本来の性能を損なわない。 The extrusion temperature when the coating layer is coated on the outer periphery of the optical fiber is preferably 150 ° C. to 190 ° C., more preferably 160 ° C. to 180 ° C. When the temperature of extrusion at the time of covering the outer periphery of the optical fiber is 150 ° C. or higher, the appearance of the optical fiber cable is excellent. When the extrusion temperature when coating the coating layer on the outer periphery of the optical fiber is 190 ° C. or lower, the original performance of the optical fiber coating resin composition is not impaired.
光ファイバケーブルの直径は、０．３ｍｍ〜１０ｍｍが好ましく、０．５ｍｍ〜８ｍｍがより好ましい。光ファイバケーブルの直径が０．３ｍｍ以上であると、光ファイバケーブルの難燃性に優れる。また、光ファイバケーブルの直径が１０ｍｍ以下であると、光ファイバケーブルの柔軟性、取り扱い性に優れる。 The diameter of the optical fiber cable is preferably 0.3 mm to 10 mm, and more preferably 0.5 mm to 8 mm. When the diameter of the optical fiber cable is 0.3 mm or more, the flame resistance of the optical fiber cable is excellent. Further, when the diameter of the optical fiber cable is 10 mm or less, the optical fiber cable is excellent in flexibility and handleability.
光ファイバケーブルの繰り返し屈曲回数は、光ファイバケーブルの柔軟性に優れることから、１００００回以上が好ましく、２００００回以上がより好ましく、３００００回以上が更に好ましい。
光ファイバケーブルの繰り返し屈曲回数は、ＩＥＣ ６０７９４−１に準拠して測定した値とする。
The number of repeated bendings of the optical fiber cable is preferably 10,000 times or more, more preferably 20000 times or more, and further preferably 30000 times or more, because the flexibility of the optical fiber cable is excellent.
The number of repeated bendings of the optical fiber cable is a value measured in accordance with IEC 60794-1.
光ファイバケーブルの他の実施形態としては、例えば、図３に示すような２本の光ファイバを１つの被覆層により被覆した光ファイバケーブルが挙げられる。
図３に示すような光ファイバケーブルの製造方法は、例えば、２芯用のダイス・ニップルを備えたクロスヘッドに光ファイバを通して被覆層を被覆する方法が挙げられる。
通常、光ファイバケーブルを通信用途で用いる場合、光ファイバケーブルの一端を光源システムに接続し、光ファイバケーブルの他端を受光システムに接続する必要がある。その際、双方向で通信を行う場合、図３に示すような２本の光ファイバを有する光ファイバケーブルを用いるとよい。
As another embodiment of the optical fiber cable, for example, an optical fiber cable in which two optical fibers as shown in FIG.
An example of a method of manufacturing an optical fiber cable as shown in FIG. 3 is a method of coating a coating layer through an optical fiber on a crosshead having a two-core die nipple.
Usually, when an optical fiber cable is used for communication, it is necessary to connect one end of the optical fiber cable to the light source system and connect the other end of the optical fiber cable to the light receiving system. At that time, when bidirectional communication is performed, an optical fiber cable having two optical fibers as shown in FIG. 3 may be used.
本発明の光ファイバケーブルは、難燃性、長期耐熱性、柔軟性に優れるため、センサ、移動媒体内等の通信、機器内外の配線等の用途に好適に用いることができる。 Since the optical fiber cable of the present invention is excellent in flame retardancy, long-term heat resistance, and flexibility, it can be suitably used for applications such as communication in sensors and moving media, wiring inside and outside equipment, and the like.
本発明のプラグ付き光ファイバケーブルは、本発明の光ファイバケーブルを含む。
本発明のプラグ付き光ファイバケーブルの製造方法は、例えば、本発明の光ファイバケーブルの少なくとも一端に、プラグを接続・固定する方法等が挙げられる。
The optical fiber cable with a plug of the present invention includes the optical fiber cable of the present invention.
Examples of the method for manufacturing an optical fiber cable with a plug of the present invention include a method of connecting and fixing a plug to at least one end of the optical fiber cable of the present invention.
プラグの材料は、光ファイバケーブルとの密着性に優れることから、塩化ビニル系樹脂、オレフィン系樹脂が好ましく、塩化ビニル系樹脂がより好ましい。
プラグの形態は、光ファイバケーブルとプラグとの接続・固定が容易であることから、光ファイバケーブルを挿入する挿入口と光ファイバケーブルをプラグに固定するためのストッパとを備えることが好ましい。
The material of the plug is preferably a vinyl chloride resin or an olefin resin, and more preferably a vinyl chloride resin because of excellent adhesion to the optical fiber cable.
The plug is preferably provided with an insertion port for inserting the optical fiber cable and a stopper for fixing the optical fiber cable to the plug because the connection and fixation between the optical fiber cable and the plug are easy.
本発明のプラグ付き光ファイバケーブルは、信号源である光源、検知器に組込まれたユニット、別のプラスチック光ファイバケーブル等との接続が行え、難燃性、長期耐熱性、柔軟性に優れるプラスチック光ファイバケーブルを含むことから、センサ、移動媒体内等の通信、機器内外の配線等の用途に用いることができ、特に工業用センサに好適に用いることができる。 The optical fiber cable with a plug of the present invention can be connected to a light source as a signal source, a unit incorporated in a detector, another plastic optical fiber cable, etc., and has excellent flame resistance, long-term heat resistance, and flexibility. Since it includes an optical fiber cable, it can be used for applications such as sensors, communication within a moving medium, wiring inside and outside the device, and particularly suitable for industrial sensors.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
（難燃性試験）
実施例及び比較例で得られた光ファイバケーブルを、ＵＬ１５８１ ＶＷ−１（一条ケーブル垂直燃焼試験）に準拠して、以下のように燃焼試験を行った。
光ファイバケーブルの接炎試験として、１５秒着火を５回繰り返し、下に敷いた１０ｃｍ角の外科用脱脂綿が燃焼物のドリップによる延焼がなく、また、光ファイバケーブルが着火した場合、６０秒以内に消火すれば合格とした。
上記燃焼試験を１０回行い、合格回数を確認した。
(Flame retardancy test)
The optical fiber cables obtained in the examples and comparative examples were subjected to a combustion test as follows in accordance with UL1581 VW-1 (single cable vertical combustion test).
As a flame test of an optical fiber cable, 15 seconds of ignition was repeated 5 times, and the 10 cm square surgical absorbent cotton spread under the fire did not spread due to the drip of the burned material, and within 60 seconds when the optical fiber cable ignited If we put out the fire, we passed.
The combustion test was conducted 10 times, and the number of passes was confirmed.
（長期耐熱性試験）
実施例及び比較例で得られた光ファイバケーブルについて、以下の条件Ａ〜Ｃの前後での伝送損失（ｄＢ／ｋｍ）を、波長６５０ｎｍ、入射光のＮＡ（開口数）０．１の光を用い、２５ｍ−１ｍのカットバック法により測定した。
条件Ａ：温度８５℃、相対湿度１０％以下で３０００時間曝露
条件Ｂ：温度１０５℃、相対湿度１０％以下で１０００時間曝露
条件Ｃ：温度８５℃、相対湿度９５％で１０００時間曝露
(Long-term heat resistance test)
For the optical fiber cables obtained in the examples and comparative examples, transmission loss (dB / km) before and after the following conditions A to C, light having a wavelength of 650 nm and incident light NA (numerical aperture) 0.1. Used, and measured by a cut-back method of 25m-1m.
Condition A: Exposure for 3000 hours at a temperature of 85 ° C. and a relative humidity of 10% or less Condition B: Exposure for 1000 hours at a temperature of 105 ° C. and a relative humidity of 10% or less Condition C: Exposure for 1000 hours at a temperature of 85 ° C. and a relative humidity of 95%
２５ｍ−１ｍのカットバック法の測定は、ＩＥＣ ６０７９３−１−４０：２００１に準拠して行った。具体的には、２５ｍの光ファイバを測定装置にセットし、出力パワーＰ２を測定した後、光ファイバをカットバック長（入射端から１ｍ）に切断し、出力パワーＰ１を測定し、以下の式を用いて光の伝送損失を算出した。 The measurement of the cut-back method of 25m-1m was performed based on IEC 60793-1-40: 2001. Specifically, to set the optical fiber 25m in the measuring device after measuring the output power P 2, the optical fiber was cut into a cut-back length (1m from the incident end), to measure the output power P 1, the following The optical transmission loss was calculated using the following equation.
（機械特性試験）
［繰り返し屈曲回数］
実施例及び比較例で得られた光ファイバケーブルを、ＩＥＣ ６０７９４−１に準拠して、以下のように屈曲試験を行った。
光ファイバケーブルを繰り返し屈曲装置（機種名「恒温槽付き光ファイバ屈曲試験機」、（株）安田精機製作所製）に取り付け、５００ｇの荷重を加えながら、垂直方向に対して両側に９０°の角度で曲げた。初期値より１ｄＢ損失増加が生じた時点で試験終了とし、終了時点の繰り返し屈曲回数を確認した。
(Mechanical property test)
[Number of repeated bending]
The optical fiber cables obtained in Examples and Comparative Examples were subjected to a bending test as follows in accordance with IEC 60794-1.
Attach an optical fiber cable to a repeated bending device (model name “Optical fiber bending tester with thermostatic bath”, manufactured by Yasuda Seiki Seisakusyo Co., Ltd.), and apply an angle of 90 ° to both sides of the vertical direction while applying a 500 g load Bent in. The test was terminated when an increase in loss of 1 dB from the initial value occurred, and the number of repeated bends at the end was confirmed.
［曲げ弾性力］
実施例及び比較例で得られた光ファイバケーブルを、ＩＳＯ １７８に準拠して、以下のように光ファイバケーブルの３点曲げ（両端自由支持の光ファイバケーブルの中央に力を加える）試験を実施した。
１００ｍｍに切断した光ファイバケーブルの両端を支持台に固定し、支持台で支持した光ファイバケーブルの中央に力を加え、５ｍｍ／分の速度でたわませ、その間のＰＯＦケーブルに負荷される力を測定した。光ファイバケーブルが１ｍｍ変位した際の力を曲げ弾性力（Ｎ）とした。
[Bending elastic force]
The optical fiber cables obtained in the examples and comparative examples were subjected to a three-point bending test (applying force to the center of the optical fiber cable with free support at both ends) according to ISO 178 as follows. did.
The both ends of an optical fiber cable cut to 100 mm are fixed to a support base, and a force is applied to the center of the optical fiber cable supported by the support base to bend at a speed of 5 mm / min. Was measured. The force when the optical fiber cable was displaced by 1 mm was defined as the bending elastic force (N).
（材料）
塩化ビニル系樹脂（Ａ−１）：「カネビニール Ｓ１００３」（商品名、（株）カネカ製）
塩化ビニル系樹脂（Ａ−２）：「セキスイＰＶＣ−ＴＧ ＴＧ−４０」（商品名、積水化学工業（株）製、ＥＶＡ樹脂に塩化ビニルをグラフト重合させたグラフト共重合体）
相溶する他の樹脂（Ａ−３）：「カネカＣＰＶＣ Ｈ５２７」（商品名、（株）カネカ製、塩素化塩化ビニル樹脂）
溶融張力向上剤（Ｂ−１）：「メタブレンＡ３７５０」（商品名、三菱レイヨン（株）製、アクリル樹脂で変性したテトラフルオロエチレン樹脂）
溶融張力向上剤（Ｂ−２）：「メタブレンＡ３８００」（商品名、三菱レイヨン（株）製、アクリル樹脂で変性したテトラフルオロエチレン樹脂）
溶融張力向上剤（Ｂ−３）：「メタブレンＰ１０５０」（商品名、三菱レイヨン（株）製、アクリル樹脂系溶融張力向上剤）
受酸剤（Ｃ−１）：「白艶華ＣＣＲ」（商品名、白石カルシウム（株）製、炭酸カルシウム）
受酸剤（Ｃ−２）：「ＳＴＡＢＩＡＣＥ ＨＴ−７」（商品名、堺化学工業（株）製、ハイドロタルサイト）
受酸剤（Ｃ−３）：オキシ水酸化鉄（和光純薬工業（株）製）
可塑剤（Ｄ−１）：「トリメックス Ｔ−０８」（商品名、花王（株）製、トリメリット酸トリ−２−エチルヘキシル）
難燃剤（Ｅ−１）：「ハイジライト」（商品名、昭和電工（株）製、水酸化アルミニウム）
難燃剤（Ｅ−２）：「ファイアカット Ｐ−６６０ＣＮ」（商品名、（株）鈴裕化学製、イソシアヌル酸トリス（２，３−ジブロモプロピル））
難燃助剤（Ｆ−１）：「ＡＴ−３ＣＮ」（商品名、（株）鈴裕化学製、三酸化アンチモン）
難燃助剤（Ｆ−２）：「アデカスタブ２３３５」（商品名、（株）ＡＤＥＫＡ製、ホウ酸亜鉛）
熱安定剤（Ｇ−１）：「アデカスタブＲＵＰ−１０３」（商品名、（株）ＡＤＥＫＡ製、カルシウム・マグネシウム・亜鉛系熱安定剤）
顔料（Ｈ−１）：「三菱カーボンブラック 汎用カラー ＃４５」（商品名、三菱化学（株）製、カーボンブラック）
他の添加剤（Ｉ−１）：「アデカスタブＡＯ−８０」（商品名、（株）ＡＤＥＫＡ製、フェノール系酸化防止剤）
他の添加剤（Ｉ−２）：ステアリン酸カルシウム（堺化学工業（株）製、滑剤）
(material)
Vinyl chloride resin (A-1): “Kane Vinyl S1003” (trade name, manufactured by Kaneka Corporation)
Vinyl chloride resin (A-2): “Sekisui PVC-TG TG-40” (trade name, manufactured by Sekisui Chemical Co., Ltd., graft copolymer obtained by grafting vinyl chloride to EVA resin)
Other compatible resins (A-3): “Kaneka CPVC H527” (trade name, manufactured by Kaneka Corporation, chlorinated vinyl chloride resin)
Melt tension improver (B-1): “Metabrene A3750” (trade name, manufactured by Mitsubishi Rayon Co., Ltd., tetrafluoroethylene resin modified with acrylic resin)
Melt tension improver (B-2): “Metabrene A3800” (trade name, manufactured by Mitsubishi Rayon Co., Ltd., tetrafluoroethylene resin modified with acrylic resin)
Melt tension improver (B-3): “Metabrene P1050” (trade name, manufactured by Mitsubishi Rayon Co., Ltd., acrylic resin melt tension improver)
Acid acceptor (C-1): "Hakuenka CCR" (trade name, manufactured by Shiraishi Calcium Co., Ltd., calcium carbonate)
Acid acceptor (C-2): “STABIACE HT-7” (trade name, manufactured by Sakai Chemical Industry Co., Ltd., hydrotalcite)
Acid acceptor (C-3): iron oxyhydroxide (manufactured by Wako Pure Chemical Industries, Ltd.)
Plasticizer (D-1): “Trimex T-08” (trade name, manufactured by Kao Corporation, trimellitic acid tri-2-ethylhexyl)
Flame retardant (E-1): “Hijilite” (trade name, manufactured by Showa Denko KK, aluminum hydroxide)
Flame retardant (E-2): “Fire cut P-660CN” (trade name, manufactured by Suzuhiro Chemical Co., Ltd., tris (2,3-dibromopropyl) isocyanurate)
Flame retardant aid (F-1): “AT-3CN” (trade name, manufactured by Suzuhiro Chemical Co., Ltd., antimony trioxide)
Flame retardant aid (F-2): “ADK STAB 2335” (trade name, manufactured by ADEKA, zinc borate)
Heat stabilizer (G-1): “Adeka Stub RUP-103” (trade name, manufactured by ADEKA, calcium / magnesium / zinc heat stabilizer)
Pigment (H-1): “Mitsubishi Carbon Black General-purpose Color # 45” (trade name, manufactured by Mitsubishi Chemical Corporation, carbon black)
Other additives (I-1): “ADK STAB AO-80” (trade name, manufactured by ADEKA, phenolic antioxidant)
Other additives (I-2): calcium stearate (manufactured by Sakai Chemical Industry Co., Ltd., lubricant)
（光ファイバ）
芯材をポリメチルメタクリレート（屈折率１．４９２）、最内層の鞘材を２−（パーフルオロオクチル）エチルメタクリレート−２，２，２−トリフルオロエチルメタクリレート−メチルメタクリレート−メタクリル酸共重合体（２−（パーフルオロオクチル）エチルメタクリレート単位：２，２，２−トリフルオロエチルメタクリレート単位：メチルメタクリレート単位：メタクリル酸単位＝３１：５１：１７：１（質量％）、屈折率１．４０２）、最外層の鞘材をフッ化ビニリデン−テトラフルオロエチレン共重合体（フッ化ビニリデン単位：テトラフルオロエチレン単位＝８０：２０（質量％）、屈折率１．３７４）とし、３層構造の同心円状複合紡糸ノズルを用いて紡糸し、１４０℃の熱風加熱炉中で繊維軸方向に２倍に延伸し、最内層の鞘の厚さが５μｍ、最外層の鞘の厚さが１０μｍの直径１．０ｍｍの光ファイバを得た。
得られた光ファイバを、実施例及び比較例の光ファイバケーブルの光ファイバとして用いた。
(Optical fiber)
The core material is polymethyl methacrylate (refractive index 1.492), and the innermost sheath material is 2- (perfluorooctyl) ethyl methacrylate-2,2,2-trifluoroethyl methacrylate-methyl methacrylate-methacrylic acid copolymer ( 2- (perfluorooctyl) ethyl methacrylate unit: 2,2,2-trifluoroethyl methacrylate unit: methyl methacrylate unit: methacrylic acid unit = 31: 51: 17: 1 (mass%), refractive index 1.402), The outermost sheath material is a vinylidene fluoride-tetrafluoroethylene copolymer (vinylidene fluoride unit: tetrafluoroethylene unit = 80: 20 (mass%), refractive index 1.374), and a three-layer concentric composite Spinning using a spinning nozzle, stretching twice in the fiber axis direction in a 140 ° C hot air heating furnace, The thickness of the sheath layer is 5 [mu] m, the thickness of the outermost layer of the sheath to obtain an optical fiber having a diameter of 1.0mm of 10 [mu] m.
The obtained optical fiber was used as an optical fiber of the optical fiber cable of an Example and a comparative example.
［実施例１］
塩化ビニル系樹脂（Ａ−１）１００質量部、溶融張力向上剤（Ｂ−１）２質量部、受酸剤（Ｃ−１）４５質量部、可塑剤（Ｄ−１）５５質量部、難燃剤（Ｅ−１）２０質量部、難燃助剤（Ｆ−１）６質量部、熱安定剤（Ｇ−１）１質量部、顔料（Ｈ−１）２．５質量部、他の添加剤（Ｉ−１）１質量部、他の添加剤（Ｉ−２）０．５質量部を、二軸押出機（機種名「ＢＴ−４０」、（株）プラスチック工学研究所製）を用いて１７０℃で溶融混練して、光ファイバ被覆用樹脂組成物を得た。
得られた光ファイバ被覆用樹脂組成物を、樹脂被覆用クロスヘッド型４０ｍｍケーブル被覆装置（（株）聖製作所製）に供給し、光ファイバの外周に厚さ０．６ｍｍの被覆層を被覆し、直径２．２ｍｍの光ファイバケーブルを得た。得られた光ファイバケーブルの評価結果を、表２に示す。
[Example 1]
100 parts by mass of vinyl chloride resin (A-1), 2 parts by mass of melt tension improver (B-1), 45 parts by mass of acid acceptor (C-1), 55 parts by mass of plasticizer (D-1), difficult 20 parts by mass of flame retardant (E-1), 6 parts by mass of flame retardant aid (F-1), 1 part by mass of thermal stabilizer (G-1), 2.5 parts by mass of pigment (H-1), other additions 1 part by weight of the agent (I-1) and 0.5 part by weight of the other additive (I-2) using a twin screw extruder (model name “BT-40”, manufactured by Plastic Engineering Laboratory Co., Ltd.) And kneaded at 170 ° C. to obtain an optical fiber coating resin composition.
The obtained resin composition for coating an optical fiber is supplied to a resin-coated crosshead type 40 mm cable coating apparatus (manufactured by Holy Seisakusho Co., Ltd.), and a coating layer having a thickness of 0.6 mm is coated on the outer periphery of the optical fiber. An optical fiber cable having a diameter of 2.2 mm was obtained. Table 2 shows the evaluation results of the obtained optical fiber cable.
［実施例２〜１３、比較例１〜２］
塩化ビニル系樹脂（Ａ）、溶融張力向上剤（Ｂ）、受酸剤（Ｃ）、可塑剤（Ｄ）、難燃剤（Ｅ）、難燃助剤（Ｆ）を表１に示すように変更した以外は、実施例１と同様に操作を行い、光ファイバ被覆用樹脂組成物及び光ファイバケーブルを得た。得られた光ファイバケーブルの評価結果を表２に示す。
[Examples 2 to 13, Comparative Examples 1 and 2]
Table 1 shows changes in vinyl chloride resin (A), melt tension improver (B), acid acceptor (C), plasticizer (D), flame retardant (E), and flame retardant aid (F). Except that, the same operation as in Example 1 was performed to obtain an optical fiber coating resin composition and an optical fiber cable. Table 2 shows the evaluation results of the obtained optical fiber cable.
実施例１〜１３で得られた光ファイバケーブルは、難燃性、長期耐熱性、機械特性に優れた。
一方、溶融張力向上剤（Ｂ）を含まない比較例１〜２で得られた光ファイバケーブルは、機械特性に劣った。
The optical fiber cables obtained in Examples 1 to 13 were excellent in flame retardancy, long-term heat resistance, and mechanical properties.
On the other hand, the optical fiber cables obtained in Comparative Examples 1 and 2 not containing the melt tension improver (B) were inferior in mechanical properties.
本発明の光ファイバケーブルは、難燃性、長期耐熱性、柔軟性に優れるため、センサ、移動媒体内等の通信、機器内外の配線等の用途に好適に用いることができる。 Since the optical fiber cable of the present invention is excellent in flame retardancy, long-term heat resistance, and flexibility, it can be suitably used for applications such as communication in sensors and moving media, wiring inside and outside equipment, and the like.
１０ 光ファイバ
１１ 芯
１２ 鞘
１２ａ 鞘（最内層）
１２ｂ 鞘（最外層）
２０ 被覆層
２０ａ 被覆層（最内層）
２０ｂ 被覆層（最外層）
10 optical fiber 11 core 12 sheath 12a sheath (innermost layer)
12b Sheath (outermost layer)
20 Coating layer 20a Coating layer (innermost layer)
20b Coating layer (outermost layer)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2018100408A (en) * | 2016-12-19 | 2018-06-28 | 積水化学工業株式会社 | Fire-resistant resin composition and fire-resistant resin molding |
| CN113597450A (en) * | 2019-04-03 | 2021-11-02 | 古河电气工业株式会社 | Flame-retardant termite-resistant resin composition, power cable and manufacturing method thereof |
| CN116082767A (en) * | 2023-03-07 | 2023-05-09 | 天长市富达电子科技股份有限公司 | Wrapping wire material with good flexibility and bending resistance for plug and preparation method thereof |
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| CN116082767A (en) * | 2023-03-07 | 2023-05-09 | 天长市富达电子科技股份有限公司 | Wrapping wire material with good flexibility and bending resistance for plug and preparation method thereof |
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