JPH01242613A - Urethane (meth)acrylate mixture and resin composition and coating agent for optical fiber using this mixture - Google Patents
Urethane (meth)acrylate mixture and resin composition and coating agent for optical fiber using this mixtureInfo
- Publication number
- JPH01242613A JPH01242613A JP63067256A JP6725688A JPH01242613A JP H01242613 A JPH01242613 A JP H01242613A JP 63067256 A JP63067256 A JP 63067256A JP 6725688 A JP6725688 A JP 6725688A JP H01242613 A JPH01242613 A JP H01242613A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- urethane
- mixture
- parts
- 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
Links
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000011248 coating agent Substances 0.000 title claims abstract description 13
- 239000013307 optical fiber Substances 0.000 title claims abstract description 10
- 239000011342 resin composition Substances 0.000 title claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 9
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000003999 initiator Substances 0.000 abstract description 4
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 abstract 2
- 101150034680 Lis-1 gene Proteins 0.000 abstract 1
- 101150084844 PAFAH1B1 gene Proteins 0.000 abstract 1
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 16
- -1 poly(methyl methacrylate) Polymers 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- 238000005253 cladding Methods 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011162 core material Substances 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 4
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007542 hardness measurement Methods 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- BRWYXBQGVNYOBM-UHFFFAOYSA-N 2,2-dichloro-1-(3-phenoxyphenyl)ethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC(OC=2C=CC=CC=2)=C1 BRWYXBQGVNYOBM-UHFFFAOYSA-N 0.000 description 1
- FPKCTSIVDAWGFA-UHFFFAOYSA-N 2-chloroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3C(=O)C2=C1 FPKCTSIVDAWGFA-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910020587 CmF2m+1 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- ZNAAXKXXDQLJIX-UHFFFAOYSA-N bis(2-cyclohexyl-3-hydroxyphenyl)methanone Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C(=O)C1=CC=CC(O)=C1C1CCCCC1 ZNAAXKXXDQLJIX-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 229920002935 deuterated poly(methyl methacrylates) Polymers 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- MHCLJIVVJQQNKQ-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O MHCLJIVVJQQNKQ-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical class CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/104—Coating to obtain optical fibres
- C03C25/106—Single coatings
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、新規なウレタン（メタ）アクリレート混合物
、これを含む樹脂組成物及び元伝送用の光フアイバ用コ
ーティング剤に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel urethane (meth)acrylate mixture, a resin composition containing the same, and a coating agent for optical fibers for original transmission.
（従来の技術）
光ファイバには、無機ガラス系とポリ（メチルメタクリ
レート〕等の合成樹脂系に分けられる。両系とも透明性
に富んだ、屈折率の高い芯（３７９部分と屈折率の小さ
い鞘（クラッド）から成り立っている。クラツド材とし
て、従来より、屈折率が低いシリコン系化合物やポリフ
ルオロアルキルアクリレート等の含フッ累モノマーの重
合体等が提案され又実施されてきた。(Prior art) Optical fibers can be divided into inorganic glass-based fibers and synthetic resin-based fibers such as poly(methyl methacrylate). It consists of a sheath (cladding).As the cladding material, silicon-based compounds with a low refractive index and polymers of fluorine-containing monomers such as polyfluoroalkyl acrylate have been proposed and put into practice.
例えば、コア材としてポリ（メチルメタクリ１／−ト）
を用い、クラツド材として、７ノ素化アルキル基含有（
メタ）アクリレートの重合体、フッ素化アルキル基含有
（メタ）アクリレートと他の七ツマ−との共重合体、又
は、ポリ（テトラフロロエチレン）、ポリ（フン化ビニ
リデン／テトラフロロエチレン）、ポリ（フン化ビニリ
デン／ヘキサフロロプロピレン）等の含フン素重合体を
用いる方法。（特開昭５９−８４２０３゜特開昭５Ｑ−
８４２０４，特開昭５９−９８１１６．特開昭５９−１
４７０１１．特開昭５９−２０４００２）（発明が解決
しようとする課題）
含フン素重合体によりクラッド部分を形成する方法にお
いては、高温の含フツ素重合体の浴融物や溶液を被りす
るため、厚みが不均一になり易い。又、コア部分とクラ
ッド部分との密着性が十分でなく、種々の外的要因、例
えば、屈曲、温度変化等によって層間剥離が生じ易いた
め、耐久性等に間、頂があった。又、含フツ素重合体の
溶融物又は溶液を塗布する製造方法においては、クラッ
ド部分の硬化に長時間要し、また溶液塗布法においては
、特に溶剤を系外に完全に除去する必要性から、生産性
、安全性、経済性等に欠点があった。For example, poly(methyl methacrylate 1/-) is used as the core material.
was used as the cladding material.
Polymers of meth)acrylates, copolymers of fluorinated alkyl group-containing (meth)acrylates and other hexamers, poly(tetrafluoroethylene), poly(vinylidene fluoride/tetrafluoroethylene), poly(vinylidene fluoride/tetrafluoroethylene), A method using a fluorine-containing polymer such as vinylidene fluoride/hexafluoropropylene). (Unexamined Japanese Patent Publication No. 59-84203゜ Unexamined Publication No. 5Q-
84204, JP-A-59-98116. Japanese Patent Publication No. 59-1
47011. JP-A-59-204002) (Problem to be Solved by the Invention) In the method of forming a cladding part using a fluorine-containing polymer, since the cladding portion is covered with a hot fluorine-containing polymer bath melt or solution, the thickness is tends to become uneven. In addition, the adhesion between the core portion and the cladding portion is insufficient, and delamination is likely to occur due to various external factors such as bending and temperature changes, resulting in poor durability. In addition, in production methods that apply a melt or solution of fluorine-containing polymers, it takes a long time to harden the cladding part, and in solution coating methods, it is particularly difficult to completely remove the solvent from the system. However, there were drawbacks in terms of productivity, safety, economy, etc.
（課題を解決するための手段）
上記の問題点を解決するため、本元明者らは、鋭意研究
の結果、新規なウレタン（メタ）アクリレート混合物を
合成し、このウレタン（メタ）アクリレート混合物を用
いて硬化速度が速く、屈折率が低く、コアとの密着性に
優れた元伝送用ファイバのクラッド被復材に適した樹脂
ｔ１１成物を提供することに成功し本発明を完成した。(Means for Solving the Problems) In order to solve the above problems, Akira Hongen et al. synthesized a new urethane (meth)acrylate mixture as a result of intensive research. The present invention has been completed by successfully providing a resin T11 composition suitable for the cladding material of the original transmission fiber, which has a fast curing speed, a low refractive index, and excellent adhesion to the core.
すなわち、本発明は
（Ｉ）一般式ｆｌ）
ＣｎＦ２ｎ＋１−ＣＨ，−ＣＨ−ＣＨ，、−０１１（Ｉ
）品
（式（Ｉ）中、ｎは４〜１０の整数を示す。）又は、一
般式叩
ＣｍＦ２ｍ＋１ （−Ｃ’Ｈ２す１Ｏ−ｃＨ２−ＣＨ−
ｃＨ，−ＯＨｆｉｌ）品
（弐ｆＩｌｌ中、ｔは１又は２であり、ｍは４〜１０の
整数を示す。）
で示される化合物と有機ポリイソシアネートとヒドロキ
シ含有（メタ）アクリレートとの反応物であるウレタン
（メタ）アクリレート混合物。That is, the present invention provides (I) general formula fl) CnF2n+1-CH, -CH-CH,, -011(I
) product (in formula (I), n represents an integer of 4 to 10) or the general formula CmF2m+1 (-C'H2S1O-cH2-CH-
A reaction product of a compound represented by cH, -OHfil) (in which t is 1 or 2, and m is an integer of 4 to 10), an organic polyisocyanate, and a hydroxy-containing (meth)acrylate. A urethane (meth)acrylate mixture.
（２前記ウレタン（メタ）アクリレート混合物を含有す
ることを特徴とする樹脂組成物。(2) A resin composition containing the urethane (meth)acrylate mixture described above.
（３） 前記ウレタン（メタ）アクリレート混合物を
含有することを特徴とする光フアイバ用コーティング剤
に関するものである。(3) The present invention relates to an optical fiber coating agent containing the urethane (meth)acrylate mixture.
本発明のウレタン（メタ）アクリレート混合物は、一般
式（Ｉ）又は一般式（Ｉ１）で示される化合物と有機ポ
リイソシアネートをウレタン化し、次いでヒドロキシ含
有（メタ）アクリレートで（メタ）アクリレート化する
ことによって製造することができる。あるいは、有機ポ
リイソシアネートとヒドロキシ含有（メタ）アクリレー
トを反応させ、次いで一般式（Ｉ）又は（ＩＩ）で示さ
れる化合物と反応させることによって製造できる。The urethane (meth)acrylate mixture of the present invention is produced by urethanizing the compound represented by general formula (I) or general formula (I1) and an organic polyisocyanate, and then (meth)acrylating it with a hydroxy-containing (meth)acrylate. can be manufactured. Alternatively, it can be produced by reacting an organic polyisocyanate with a hydroxy-containing (meth)acrylate, and then reacting it with a compound represented by general formula (I) or (II).
本発明のウレタン（メタ）アクリレート混合物の原料で
ある一般式（Ｉ）及び（Ｉｔ）で示される化合物の具体
例としては、例えば、Ｃ，Ｆ、、ＣＨ，、−ＣＨ（ＩＩ
２−１−Ｉ
−ｏＨ，ｃａｒ、３ｃ）Ｉ、−ｃｌ−ｉ−ｅＨ，−（）
Ｈ，Ｃ？ｓＦ＋７ＣＩＩ２（Ｈ（Ｈ２０Ｈ０Ｈ
−ｏＨ，Ｃ３ＦＩＩＣＦＩ２−０−ＣＩ−Ｉ２へｃＬＴ
−ＣＩ−（２→ＦＩ、ｃ７Ｆ９．Ｃｌ−１２−ＯＨ
ｏ−ｃＨ，−ｃ［Ｉ−ｃｔｘ、−ｏｎ、 Ｃ，Ｆ、、−
ＣＨ２ｅＨ２−（）−ｃｌ１２司ｒＨ−０Ｈ０Ｈ
ＣＨ２−ＯＨ等が挙げられる。有機ポリイソシアネート
の例としては、インホロンジイソシアネート、２．２．
４− ）リメチルヘキサメチレンジイソシアネート、２
，４．４−トリメチルへキサメチレンジインシアネート
、トリレンジイソシアネート、キシリレンジイソシアネ
ート、ジフェニルメタン−４，４′−ジイソシアネート
、ヘキサメチレンジイソシアネート、ダイマー酸ジイン
シアネート等が挙げられる。又、ヒドロキシ含有（メタ
）アクリレートの例としては、ヒドロキジエチル（メタ
）アクリレート、ヒドロキシプロピル（メタ）アクリレ
ート、ε−カプロラクトン−β−ヒドロキシエチル（メ
タ）アクリレート付加物（ダイセル化学工業（掬製、プ
ラクセルＦＡ−１、ＦＭ−１、等）、ヒドロキシブチル
（メタ）アクリレート、ペンタエリスリトールトリ（メ
タ）アクリレート等である。Specific examples of compounds represented by general formulas (I) and (It), which are raw materials for the urethane (meth)acrylate mixture of the present invention, include C, F,, CH,, -CH(II
2-1-I -oH, car, 3c) I, -cl-i-eH, -()
H,C? sF+7CII2(H(H20H0H -oH, cLT to C3FIICFI2-0-CI-I2
-CI-(2→FI, c7F9.Cl-12-OH o-cH, -c[I-ctx, -on, C,F,, -
Examples include CH2eH2-()-cl12rH-0H0H CH2-OH. Examples of organic polyisocyanates include inphorone diisocyanate, 2.2.
4-) Limethylhexamethylene diisocyanate, 2
, 4,4-trimethylhexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, dimer acid diisocyanate, and the like. In addition, examples of hydroxy-containing (meth)acrylates include hydroxydiethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ε-caprolactone-β-hydroxyethyl (meth)acrylate adduct (Daicel Chemical Co., Ltd. (Kimusei, Plaxel) FA-1, FM-1, etc.), hydroxybutyl (meth)acrylate, pentaerythritol tri(meth)acrylate, etc.
一般式（Ｉ）又はｆｉｔ）で示される化合物と有機ポリ
イソシアネートを反応させるウレタン化の場合、反応温
度は３０〜１００°Ｃが好ましく、特に７０〜８０℃が
好ましい。一般式ｆｌＪ又は（ＩＩ）で示される化合物
１モルに対して、有機ポリイソシアネ−） １．２〜２
モル用いるのが好ましく、特に１．５〜２モル用いるの
が好ましい。前記ウレタン化によって得られた生成物と
ヒドロキシ含有（メタ）アクリレートを反応させる場合
、ウレタン化によって得られた生成物のイソシアネート
の１化学当量に対して、ヒドロキシ含有（メタ）アクリ
レートの水酸基の０．９５〜１．５化学当量を用いるの
が好ましく、特に１．０〜１．１化学当量用いるのが好
ましい。又、反応中のラジカル重合によるゲル化を防ぐ
為に、反応前に５０〜２００ ｐｐｍのハイドロキノン
、メチルハイドロキノン、ハイドルキノンモノメチルエ
ーテル、Ｐ−ベンゾキノン、フェノチアジン等の重合禁
止剤を添加してお（ことが好ましい。本発明の樹脂組成
物及び元ファイバ用コーティング剤（以下いずれも組成
物という）において、ウレタン（メタ）アクリレート混
合物は、組成物中１０〜７０重ｉ％の範囲で使用するの
が好ましく、特に３０〜６０重ｔ％の範囲で使用するの
が好ましい。本発明の組成物中、この新規なウレタン（
メタ）アクリレート混合物以外の成分として公知の種々
のエチレン性不飽和化合物が使用できる。エチレン性不
飽和化合物の具体例と（ＣＨｔ ＣＨｓ ）ＣＨ２ＣＨ
２０ＣＣＩ（＝ＣＨ２、Ｃａ Ｆ ＋ｓ ＣＨ２（−Ｉ
２ ＱＣＣＨ＝１１Ｉ
ＣＩ−Ｉ２．（ＣＦ３）２ＣＦＣＨ２０ＣＣＨ＝ＣＨ，
、ＣＨ＝ＣＨ２−０−ＣＨ。In the case of urethanization in which the compound represented by general formula (I) or fit) is reacted with an organic polyisocyanate, the reaction temperature is preferably 30 to 100°C, particularly preferably 70 to 80°C. Organic polyisocyanate) 1.2 to 2 per mol of the compound represented by the general formula flJ or (II)
It is preferable to use mol, especially 1.5 to 2 mol. When the product obtained by the urethanization is reacted with the hydroxyl-containing (meth)acrylate, the amount of hydroxyl groups in the hydroxyl-containing (meth)acrylate is 0.0. It is preferable to use 95 to 1.5 chemical equivalents, particularly preferably 1.0 to 1.1 chemical equivalents. In addition, in order to prevent gelation due to radical polymerization during the reaction, 50 to 200 ppm of a polymerization inhibitor such as hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, P-benzoquinone, or phenothiazine is added before the reaction ( In the resin composition and coating agent for original fibers of the present invention (hereinafter both referred to as compositions), the urethane (meth)acrylate mixture is preferably used in the range of 10 to 70% by weight in the composition. It is preferable to use the novel urethane (
Various known ethylenically unsaturated compounds can be used as components other than the meth)acrylate mixture. Specific examples of ethylenically unsaturated compounds and (CHt CHs )CH2CH
20CCI(=CH2, Ca F +s CH2(-I
2 QCCH=11I CI-I2. (CF3)2CFCH20CCH=CH,
, CH=CH2-0-CH.
ｏＣＦ・
−ＣＦ２＋、Ｃ２Ｈ，（）−Ｃ−ＣＨ＝ＣＨ２等の含７
７素反応性モノマー、アダマンチル（メタコアクリレー
ト、イソボルニル（メタ）アクリレート、フェニルオキ
シエチル（メタ）アクリレート、ノニルフェニルオキシ
ポリプロボキシ（メタ）アクリレート、トリメチロール
プロパントリ（メタ）アクリレート、ペンタエリスリト
ール（メタ）アクリレート、分子中にエーテル基を持つ
ポリエーテルポリオール、カーボネート基を持つカーボ
ネートポリオール、エステル基を持つポリエステルポリ
オール等のポリウレタン（メタ）アクリレート、ポリマ
ーポリオールのポリウレタン（メタ）アクリレート、ポ
リエステル（メタ）アクリレート、例えば、ジオール化
合物（例えハ、エチレングリコール、プロピレングリコ
ール、ジエチレングリコール、ジプロピレングリコール
、１，５−ベンタンジオール、１，６−ヘキサンジオー
ル等）と２塩基酸（例えば、コハク酸、アジピン酸、フ
タル酸、ヘキサヒドロフタル酸、テトラヒドロフタル酸
等）からなるポリエステルジオールの（メタ）アクリレ
ート、ジオール化合物と２塩基酸とε−カプロラクトン
からなるラクトン変性ポリエステルジオールの（メタ）
アクリレート等、ポリカーボネート（メタ）アクリレー
ト、等が挙げられる。特に好ましいエチレン性不飽和化
合物としては、含フツ素反応性モノマー、ポリカーボネ
ートジアクリレート、ポリマーポリオールのポリウレタ
ンアクリレート等が挙げられる。上記エチレン性不飽和
化合物は、必要に応じて１種又は２種以上の化合物を任
意の割合で混合使用することができる。エチレン性不飽
和化合物の使用量は組成物中、３０〜９０重量％の範囲
で使用するのが好ましく、特に４０〜７０重量％の範囲
で使用するめが好ましい。本発明の組成物は、紫外線で
硬化する場合、光重合開始剤を使用する３９元重合開始
剤としては、公知のどのような光重合開始剤であっても
良いが、配合後の貯蔵安定性の良い事が要求される。こ
の様な光重合開始剤としては、例えば、ベンゾインエチ
ルエーテル、ベンゾインイソブチルエーテル、ベンゾイ
ンイソプロピルエーテルなどのベンゾインアルキルエー
テル系、２．２−ジェトキシアセトフェノン、４′−フ
ェノキシ−２，２−ジクロロアセトフェノンなどのアセ
トフェノン系、２−ヒドロキシ−２−メチルプロピオフ
ェノン、４′−イソプロピル−２−ヒドロキシ−２−メ
チルプロピオフェノンなどのプロピオフェノン系、ベン
ジルジメチルケタール、１−ヒドロキシシクロへキシル
フェニルケトン及び２−エチルアントラキノン、２−ク
ロルアントラキノンなどのアントラキノン系、その他、
チオギサントン系元重合開始剤などがあげられる。特に
好ましいものとしては、１−ヒドロキシシクロへキシル
フェニルケトン、ベンジルジメチルケタール等があげら
れる。これら光重合開始剤は、−、−１Φでも、二種以
上任意の割合で混合使用してもかまわない。その使用量
け、通常、組成物のＯ〜１０重計％が好ま１〜く、′持
に１〜５重量係が好ましい。また、本発明の組成物は、
シランカップリング削、酸化防止剤、重合禁止剤等の各
種添加剤を添加することもできる。本発明に係る光フア
イバ用コーティング剤を基材に塗布する方法としては、
当業界公知の種々の方法、例えば、ダイスコーティング
法、浸漬法等が挙げられる。又、本発明に云う光伝送フ
ァイバ芯線としては、石英系並びにポリメチルメタクリ
レート、ポリエチルメタクリレート、重水素化ポリメチ
ルメタクリレート、ポリスチレン、ポリカーボネート等
のプラスチック系が挙げられる。光伝送ファイバのクラ
ッド部を彩成する場合、本発明のコーティング剤による
被膜の厚さは、特に限定されないが通常１０〜３００μ
程度が好ましい。硬化重合する場合、高圧水銀灯、超高
圧水銀灯、メタルノ・ライドラングを光源とする紫外線
を使用することが好ましく、硬化の効率を上げるために
窒素ガス中で照射することが好ましい。本発明の組成物
は、光伝送ファイバのクランド材だけでなく、その低屈
折率を利用し、ガラスまたは、透明プラスチックなどの
コーティング剤、Ｌ Ｅ Ｄ用銅止剤等に使用すること
ができる。oCF・-CF2+, C2H, ()-C-CH=CH2, etc. 7
Seven reactive monomers, adamantyl (methacrylate, isobornyl (meth)acrylate, phenyloxyethyl (meth)acrylate, nonylphenyloxypolyproboxy (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate Acrylates, polyurethane (meth)acrylates such as polyether polyols with ether groups in the molecule, carbonate polyols with carbonate groups, polyester polyols with ester groups, polyurethane (meth)acrylates of polymer polyols, polyester (meth)acrylates, e.g. , diol compounds (e.g., ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,5-bentanediol, 1,6-hexanediol, etc.) and dibasic acids (e.g., succinic acid, adipic acid, phthalic acid, (meth)acrylates of polyester diols consisting of (hexahydrophthalic acid, tetrahydrophthalic acid, etc.), and (meth)acrylates of lactone-modified polyester diols consisting of diol compounds, dibasic acids, and ε-caprolactone.
Examples include acrylate, polycarbonate (meth)acrylate, and the like. Particularly preferred ethylenically unsaturated compounds include fluorine-containing reactive monomers, polycarbonate diacrylates, and polyurethane acrylates of polymer polyols. The above-mentioned ethylenically unsaturated compounds may be used singly or in combination of two or more compounds in any proportion as required. The amount of the ethylenically unsaturated compound used in the composition is preferably from 30 to 90% by weight, particularly preferably from 40 to 70% by weight. When the composition of the present invention is cured by ultraviolet rays, any known photopolymerization initiator may be used as the 39-element polymerization initiator, but the storage stability after blending is Good things are required. Examples of such photopolymerization initiators include benzoin alkyl ethers such as benzoin ethyl ether, benzoin isobutyl ether, and benzoin isopropyl ether, 2,2-jethoxyacetophenone, 4'-phenoxy-2,2-dichloroacetophenone, and the like. acetophenone series, propiophenone series such as 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone and Anthraquinones such as 2-ethylanthraquinone and 2-chloroanthraquinone, others,
Examples include thiogysanthone-based polymerization initiators. Particularly preferred are 1-hydroxycyclohexylphenyl ketone, benzyl dimethyl ketal, and the like. These photopolymerization initiators may be - or -1Φ, or two or more of them may be used as a mixture in any ratio. The amount used is usually 0 to 10% by weight of the composition, preferably 1 to 1% by weight, and preferably 1 to 5% by weight. Moreover, the composition of the present invention has
Various additives such as silane coupling agents, antioxidants, and polymerization inhibitors can also be added. The method for applying the optical fiber coating agent of the present invention to a base material is as follows:
Various methods known in the art include, for example, a die coating method, a dipping method, and the like. Further, the optical transmission fiber core wire referred to in the present invention includes quartz-based materials and plastic-based materials such as polymethyl methacrylate, polyethyl methacrylate, deuterated polymethyl methacrylate, polystyrene, and polycarbonate. When coloring the cladding portion of an optical transmission fiber, the thickness of the coating formed by the coating agent of the present invention is not particularly limited, but is usually 10 to 300 μm.
degree is preferred. In the case of curing polymerization, it is preferable to use ultraviolet rays from a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or a metalnolide lamp as a light source, and in order to increase the curing efficiency, it is preferable to irradiate in nitrogen gas. The composition of the present invention can be used not only as a crund material for optical transmission fibers, but also as a coating agent for glass or transparent plastic, a copper fixing agent for LED, etc. by taking advantage of its low refractive index.
（実施例）
以下、本発明を実施例により具体的に説明する。なお、
実施中の部は、重量部である。(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. In addition,
Working parts are parts by weight.
（ウレタン（メタ）アクリレートａ合物の製造例）
製造例１゜
下記構造式の化合物３９９．０１部、
Ｃ６Ｆ、、−ＣＨ，−ＣＨ−ＣＨ２−０ＨＯＩ−（
トリメチルへキサメチレンジイソシアネート３８２ 、
６ ］、部、を仕込み、温度を７５〜８０℃に保ちなが
ら反応を行なった。９．７９％の遊離インシアネート基
により示される反応の完了まで該反応を継続した。次い
で２−ヒドロキシエチルアクリレート２１７．８７部、
メトギノン０，５部を仕込み、７５〜８０°Ｃの温度で
反応を行なった。約０．３％以下の遊離イソシアネート
基により示される反応の完了まで該反応を継続した。(Production example of urethane (meth)acrylate a compound) Production example 1 399.01 parts of a compound of the following structural formula, C6F,, -CH, -CH-CH2-0HOI- (trimethylhexamethylene diisocyanate 382,
6 parts] were charged, and the reaction was carried out while maintaining the temperature at 75 to 80°C. The reaction was continued until completion as indicated by 9.79% of free incyanate groups. Then 217.87 parts of 2-hydroxyethyl acrylate,
0.5 parts of methoginone was charged, and the reaction was carried out at a temperature of 75 to 80°C. The reaction was continued until completion as indicated by less than about 0.3% free isocyanate groups.
淡黄色の液体を舟た。このものは、粘度（４０°Ｃ）１
５００Ｐ、屈折率（２３°Ｃ）１゜４４８０であった。A pale yellow liquid poured out. This product has a viscosity (40°C) of 1
500P, and the refractive index (23°C) was 1°4480.
製造例２゜
下記構造式の化合物３８８．８０部、
トリメチルへキサメチレンジイソシアネート３７２．８
２部を仕込み、製造例１と同様に遊離インシアネート基
が９．７９％になるまで反応を行ない、次いで、２−ヒ
ドロキシプロピルアクリレート２６８．００部、メトキ
ノン０．４９部を仕込み、製造例１と同様に反応を行な
った。淡黄色の液体を寿だ。このものは、粘度（４０°
Ｃ）２０００Ｐ、屈折率（２３°Ｃ）１．４５１０であ
った。Production Example 2 388.80 parts of a compound with the following structural formula, 372.8 parts of trimethylhexamethylene diisocyanate
2 parts were charged, and the reaction was carried out in the same manner as in Production Example 1 until the free incyanate group became 9.79%. Next, 268.00 parts of 2-hydroxypropyl acrylate and 0.49 parts of methoquinone were charged, and Production Example 1 was charged. The reaction was carried out in the same manner. The light yellow liquid is Kotobuki. This has a viscosity (40°
C) 2000P, refractive index (23°C) 1.4510.
製造例３゜
下記構造式の化合物３４０．３４部、
ィソホロンジイソシアネー） ３１９．２３部を仕込み
、製造例１と同様に遊離インシアネート基が９．１４％
になるまで反応を行ない、次いで２−ヒドロキシエチル
アクリレートに１モルのε−カプロラクトン付加物（ダ
イセル化学工業■製、プラクセルＦＡ−１）３４０．０
３部、メトキノン０．４１部を仕込み、製造例１と同様
に反応を行なった。淡黄色の液体を得た。粘度（４０°
Ｃ）は３０００Ｐ、屈折率（２３°Ｃ）１．４５６０で
あった。Production Example 3 340.34 parts of a compound with the following structural formula and 319.23 parts of isophorone diisocyanate were charged, and the free incyanate group was 9.14% in the same manner as Production Example 1.
The reaction was carried out until 2-hydroxyethyl acrylate was mixed with 1 mol of ε-caprolactone adduct (manufactured by Daicel Chemical Industries, Ltd., Plaxel FA-1) 340.0
3 parts and 0.41 part of methoquinone were charged, and the reaction was carried out in the same manner as in Production Example 1. A pale yellow liquid was obtained. Viscosity (40°
C) was 3000P and had a refractive index (23°C) of 1.4560.
製造例４゜
下記の構造式の化合物５２３．８６部、トリメチルへキ
サメチレンジインシアネート３３４．０４部を仕込み、
製造例１と同様に、遊離イソシアネート基５．１９％に
なるまで反応を行なった。Production Example 4 523.86 parts of a compound having the following structural formula and 334.04 parts of trimethylhexamethylene diincyanate were charged.
In the same manner as in Production Example 1, the reaction was carried out until the free isocyanate groups reached 5.19%.
次いで２−ヒドロキシエチルメタクリレート１４２．１
０部、メトキノン０．５部を仕込み、製造例１と同様に
反応を行なった。淡黄色の液体を得た。粘度（６０℃）
２００Ｐ、屈折率（２３°Ｃ）１．４４８０であった。Then 2-hydroxyethyl methacrylate 142.1
0 parts and 0.5 parts of methoquinone were added, and the reaction was carried out in the same manner as in Production Example 1. A pale yellow liquid was obtained. Viscosity (60℃)
200P, and the refractive index (23°C) was 1.4480.
（樹脂組成物の実施例）
実施例１゜
製造例１で得たウレタンアクリレート混合物４０部、構
造式ＣｇＦ＋ｔＣＨｔＣＨｔＯさＣＨ＝ＣＨ２を有する
アクリレート６０部、及び１−ヒドロキシシクロへキシ
ルフェニルケトン（テバ・ガイギー■斗
製、イルガキーア−１８％）３部を混合し、樹脂組成物
Ａを調製した。硬化物の特性を第１表に示す。(Example of resin composition) Example 1 40 parts of the urethane acrylate mixture obtained in Production Example 1, 60 parts of acrylate having the structural formula CgF+tCHtCHtO, CH=CH2, and 1-hydroxycyclohexyl phenyl ketone (Teva Geigy) Resin composition A was prepared by mixing 3 parts of Irgakia (18%) manufactured by Doto Co., Ltd. Table 1 shows the properties of the cured product.
実施例２゜
製造例２で得たウレタンアクリレート混合物４０部、構
造式Ｈ＋ＣＦ２ ＣＦｚ ＋２ ＣＨｔ ＯＣＣＨ＝Ｃ
Ｉ（２を育するアクリレート５０部、ポリへキサメチレ
ンカーボネートジオールのジアクリレート１０部及び１
−ヒドロキシシクロへキシルフェニルケトン３部を混合
し、樹脂組成物Ｂを調製した。Example 2゜40 parts of the urethane acrylate mixture obtained in Production Example 2, structural formula H+CF2 CFz +2 CHt OCCH=C
I (50 parts of acrylate growing 2, 10 parts of diacrylate of polyhexamethylene carbonate diol and 1
-3 parts of hydroxycyclohexyl phenyl ketone were mixed to prepare resin composition B.
硬化物の特性を第１表に示す。Table 1 shows the properties of the cured product.
実施例３゜
製造例３で得たウレタンアクリレート混合物２０部、製
造例４で得たウレタンメタクリレート混合物２０部、ポ
リウレタンアクリレート〔日本カーバイト園判、二カラ
イトトｌ−４７２（アクリルポリマーポリオール）１モ
ルとイソホロンジインシアネート２モルを反応させ、次
いで２−ヒドロキシエチルアクリレート２．０５モル反
応させた。）〕２２０部構造式
Ｃ？ Ｆ ＋ｓ ＣＨｔ ＯＣＣＨ＝ＣＨ２を有するア
クリレート５゜部及び１−ヒドロキシシクロへキシルフ
ェニルケトン３部を混合し、樹脂組成物Ｃを調製した。Example 3゜20 parts of the urethane acrylate mixture obtained in Production Example 3, 20 parts of the urethane methacrylate mixture obtained in Production Example 4, 1 mol of polyurethane acrylate [Nippon Carbide Enban, Nikalite Tol-472 (acrylic polymer polyol)] 2 moles of isophorone diincyanate were reacted, and then 2.05 moles of 2-hydroxyethyl acrylate were reacted. )] 220 parts Structural formula C? Resin composition C was prepared by mixing 5 parts of acrylate with F +s CHt OCCH=CH2 and 3 parts of 1-hydroxycyclohexylphenyl ketone.
硬化物の特性を第１表に示す。Table 1 shows the properties of the cured product.
第 １ 表
上記第１表において、
（ショア硬度Ｄ）の測定 ：Ａ、Ｂ、Ｃの組成物は、メ
タルハライドランプ（ランプ出力、２部ｗ）を平行に配
した光源下８ｃｒｎの位置で照射して厚さ２５０μｍの
シートを作表し、これを用い測定した。測定法は、ＪＩ
Ｓ−Ｚ２２４６の方法に準じて行った。Table 1 In Table 1 above, (Shore hardness D) measurement: Compositions A, B, and C were irradiated with metal halide lamps (lamp output, 2 parts w) at a position 8 crn below the light source arranged in parallel. A sheet with a thickness of 250 μm was prepared using the same method, and the measurement was performed using this sheet. The measurement method is JI
It was carried out according to the method of S-Z2246.
（ヤング率、Ｋｙ ／ ｍｒｌｌ ）測定 ： 試、験
片は、」−記のショア硬度りの測定に使用したものと同
一の条件で作製した。これを用いて、温度を変化させて
、ヤング率の測定を行った。(Young's Modulus, Ky/mrll) Measurement: Test specimens were prepared under the same conditions as those used for the Shore hardness measurement described in "-". Using this, Young's modulus was measured while varying the temperature.
（屈折率）の測定 ： 試験片は、前記のショア硬度り
の測定に使用したものと同一の条件で作製した。これを
用いて、屈折率の測定を行った。(Refractive index) measurement: A test piece was prepared under the same conditions as those used for the Shore hardness measurement described above. Using this, the refractive index was measured.
（発明の効果）
本発明の新規なウレタン（メタ）アクリレート混合物を
用いる樹、指組成物及び光フアイバ用コーティング剤は
、硬化速度が速く、優られた樹脂被膜は、可撓性があり
屈折率が低く、コアとの密着性に優れ、光伝送用光学フ
ァイバ層に適する。(Effects of the Invention) The coating agents for wood, finger compositions, and optical fibers using the novel urethane (meth)acrylate mixture of the present invention have a fast curing speed, and the excellent resin coating has flexibility and a refractive index. It has low adhesion to the core and is suitable for optical fiber layers for optical transmission.
特許出願人 日本化薬株式会社Patent applicant: Nippon Kayaku Co., Ltd.
Claims (1)
一般式（II） ▲数式、化学式、表等があります▼（II） （式（II）中、ｌは１又は２であり、ｍは４〜１０の整
数を示す。） で示される化合物と有機ポリイソシアネートとヒドロキ
シ含有（メタ）アクリレートとの反応物であるウレタン
（メタ）アクリレート混合物。 ２、第１項記載のウレタン（メタ）アクリレート混合物
を含有することを特徴とする樹脂組成物。 ３、第１項記載のウレタン（メタ）アクリレート混合物
を含有することを特徴とする光ファイバ用コーティング
剤。[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In formula (I), n represents an integer from 4 to 10.) Or,
General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In formula (II), l is 1 or 2, and m is an integer from 4 to 10.) Compounds and organic compounds represented by A urethane (meth)acrylate mixture that is a reaction product of a polyisocyanate and a hydroxy-containing (meth)acrylate. 2. A resin composition containing the urethane (meth)acrylate mixture according to item 1. 3. An optical fiber coating agent containing the urethane (meth)acrylate mixture according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63067256A JP2631501B2 (en) | 1988-03-23 | 1988-03-23 | Resin composition and cladding material for optical fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63067256A JP2631501B2 (en) | 1988-03-23 | 1988-03-23 | Resin composition and cladding material for optical fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01242613A true JPH01242613A (en) | 1989-09-27 |
| JP2631501B2 JP2631501B2 (en) | 1997-07-16 |
Family
ID=13339681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63067256A Expired - Lifetime JP2631501B2 (en) | 1988-03-23 | 1988-03-23 | Resin composition and cladding material for optical fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2631501B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02258822A (en) * | 1989-03-31 | 1990-10-19 | Mitsubishi Metal Corp | Fluorine-containing urethane compound and preparation thereof |
| US5567794A (en) * | 1992-04-07 | 1996-10-22 | Alcatel Cable | Polymer material of the polyurethane acrylate type for coating an optical fiber or for an optical fiber tape |
| FR2791691A1 (en) * | 1999-04-01 | 2000-10-06 | Cit Alcatel | Photo-crosslinkable polyurethane containing acrylate or vinyl-type unsaturation for optical fiber coating, is based on fluorinated diol |
| JP2006117874A (en) * | 2004-10-25 | 2006-05-11 | Nippon Kayaku Co Ltd | Composition of low refractive index resin and cured product of the same |
| JP2015502985A (en) * | 2011-10-17 | 2015-01-29 | オルネクス ベルギウム ソシエテ アノニム | Fluorinated water and oil repellent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5513941A (en) * | 1978-07-17 | 1980-01-31 | Tokyo Erekutoron Kk | Semiconductor wafer with traget for prove |
-
1988
- 1988-03-23 JP JP63067256A patent/JP2631501B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5513941A (en) * | 1978-07-17 | 1980-01-31 | Tokyo Erekutoron Kk | Semiconductor wafer with traget for prove |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02258822A (en) * | 1989-03-31 | 1990-10-19 | Mitsubishi Metal Corp | Fluorine-containing urethane compound and preparation thereof |
| US5567794A (en) * | 1992-04-07 | 1996-10-22 | Alcatel Cable | Polymer material of the polyurethane acrylate type for coating an optical fiber or for an optical fiber tape |
| FR2791691A1 (en) * | 1999-04-01 | 2000-10-06 | Cit Alcatel | Photo-crosslinkable polyurethane containing acrylate or vinyl-type unsaturation for optical fiber coating, is based on fluorinated diol |
| WO2000059976A1 (en) * | 1999-04-01 | 2000-10-12 | Alcatel | Fluorinated diol based polyurethane acrylate or vinyl type material for covering an optical fibre |
| JP2002541282A (en) * | 1999-04-01 | 2002-12-03 | アルカテル | Polyurethane acrylate or vinyl type polymer materials based on fluorinated diols for coating optical fibers |
| JP4763893B2 (en) * | 1999-04-01 | 2011-08-31 | アルカテル−ルーセント | Polyurethane acrylate or vinyl type polymeric materials based on fluorinated diols for coating optical fibers |
| JP2006117874A (en) * | 2004-10-25 | 2006-05-11 | Nippon Kayaku Co Ltd | Composition of low refractive index resin and cured product of the same |
| JP2015502985A (en) * | 2011-10-17 | 2015-01-29 | オルネクス ベルギウム ソシエテ アノニム | Fluorinated water and oil repellent |
| JP2017149985A (en) * | 2011-10-17 | 2017-08-31 | オルネクス ベルギー エス エー | Fluorinated water-oil repellency agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2631501B2 (en) | 1997-07-16 |
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