JPH0457817A - Ultraviolet-curable colorant composition for optical fiber - Google Patents
Ultraviolet-curable colorant composition for optical fiberInfo
- Publication number
- JPH0457817A JPH0457817A JP2170880A JP17088090A JPH0457817A JP H0457817 A JPH0457817 A JP H0457817A JP 2170880 A JP2170880 A JP 2170880A JP 17088090 A JP17088090 A JP 17088090A JP H0457817 A JPH0457817 A JP H0457817A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- ultraviolet
- bisphenol
- urethane
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 239000013307 optical fiber Substances 0.000 title claims abstract description 20
- 239000003086 colorant Substances 0.000 title abstract description 5
- 238000004040 coloring Methods 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 acrylate compound Chemical class 0.000 claims abstract description 11
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims abstract description 11
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- 239000000049 pigment Substances 0.000 abstract description 8
- 239000003999 initiator Substances 0.000 abstract description 6
- 150000003673 urethanes Chemical class 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 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 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- MRIKSZXJKCQQFT-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) prop-2-enoate Chemical group OCC(C)(C)COC(=O)C=C MRIKSZXJKCQQFT-UHFFFAOYSA-N 0.000 description 1
- BWZAUXRKSMJLMH-UHFFFAOYSA-N 1,1-diethoxyethylbenzene Chemical compound CCOC(C)(OCC)C1=CC=CC=C1 BWZAUXRKSMJLMH-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- QCWLJFCGZKSIMZ-UHFFFAOYSA-N 2-(dimethylamino)naphthalene-1-diazonium Chemical compound C1=CC=CC2=C([N+]#N)C(N(C)C)=CC=C21 QCWLJFCGZKSIMZ-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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 241001674048 Phthiraptera Species 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical group C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FSPSELPMWGWDRY-UHFFFAOYSA-N m-Methylacetophenone Chemical compound CC(=O)C1=CC=CC(C)=C1 FSPSELPMWGWDRY-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、光ファイバ用紫外線硬化性着色組成物に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an ultraviolet curable coloring composition for optical fibers.
〔従来の技術及び発明が解決しようとする課顕〕一般に
、光ファイバは石英ファイバの回りに柔らかいプライマ
リ−コーティングが施され、その回りに硬いセカンダリ
−コーティングが施され、さらにその回りに識別を容易
とするため、着色材（インク）がコーティングされてい
る。従来、この着色材としては、熱硬化型又は溶剤乾燥
型のものが使用されているが、これらは硬化又は乾燥に
時間がかかるという問題を有しており、これが光ファイ
バの生産性低下の原因となっていた。[Problems to be solved by the prior art and the invention] Generally, optical fibers have a soft primary coating around the quartz fiber, a hard secondary coating around the quartz fiber, and a hard secondary coating around the quartz fiber for easy identification. To achieve this, it is coated with a coloring material (ink). Conventionally, thermosetting or solvent-drying coloring materials have been used, but these have the problem of taking time to harden or dry, which is the cause of decreased productivity of optical fibers. It became.
このため、最近では硬化速度が比較的高い紫外線硬化性
樹脂が、光ファイバ用着色材として注目されている。こ
のような紫外線硬化性樹脂としては、エポキシアクリレ
ート樹脂、ポリエステルアクリレート樹脂などのアクリ
レートオリゴマーと、単官能及び多官能光重合性モノマ
ーから成るものが使用されている。しかしながら、これ
らの着色材は、硬化後における弾性率が大きくなるため
応力がかかり、光ファイバの伝送ロスが増大してしまい
、光ファイバ用としての伝送特性を十分満足できるもの
ではなかった。For this reason, ultraviolet curable resins, which have a relatively high curing speed, have recently attracted attention as colorants for optical fibers. As such ultraviolet curable resins, those composed of acrylate oligomers such as epoxy acrylate resins and polyester acrylate resins, and monofunctional and polyfunctional photopolymerizable monomers are used. However, these coloring materials have a large elastic modulus after curing and are therefore subject to stress, which increases the transmission loss of the optical fiber and does not fully satisfy the transmission characteristics for use in optical fibers.
従って、本発明の目的は、光ファイバの着色材として適
切な弾性率を有する光ファイバ用紫外線硬化性着色組成
物を提供することにある。Therefore, an object of the present invention is to provide an ultraviolet curable coloring composition for optical fibers that has an appropriate modulus of elasticity as a colorant for optical fibers.
すなわち、本発明は、
（ａ）ビスフェノールＡ又はビスフェノールＦのアルキ
レンオキサイド付加物
（ハ）ジイソシアネート及び
（ｃ）ヒドロキシル基含有（メタ）アクリレート化合物
を反応させてなるウレタン（メタ）アクリレートを含有
することを特徴とする光ファイバ用紫外線硬化性着色組
成物を提供するものである。That is, the present invention contains a urethane (meth)acrylate obtained by reacting (a) an alkylene oxide adduct of bisphenol A or bisphenol F, (c) a diisocyanate, and (c) a hydroxyl group-containing (meth)acrylate compound. The present invention provides a characteristic ultraviolet curable coloring composition for optical fibers.
本発明に用いられる（ａ）成分のビスフェノールＡ（２
，２−ビス（４′−ヒドロキシフェニル）プロパン）又
はビスフェノールＦ（ビス（４−ヒドロキシフェニル）
メタン）のアルキレンオキサイド付加物としては、例え
ばエチレンオキサイド、プロピレンオキサイド、ブチレ
ンオキサイド等の付加物が挙げられる。これらのアルキ
レンオキサイドの付加モル数としては、ビスフェノール
Ａ又はビスフェノールＦ１モル当り１〜１５モルカ好マ
しく、この範囲を超えると硬化後の耐水性が悪くなる傾
向がある。Bisphenol A (2) component (a) used in the present invention
, 2-bis(4'-hydroxyphenyl)propane) or bisphenol F (bis(4-hydroxyphenyl)
Examples of alkylene oxide adducts of methane include adducts of ethylene oxide, propylene oxide, butylene oxide, and the like. The number of moles of these alkylene oxides added is preferably 1 to 15 moles per mole of bisphenol A or bisphenol F, and if this range is exceeded, water resistance after curing tends to deteriorate.
（ｂ）成分のジイソシアネートとしては、例えばトリレ
ンジイソシアネート（ＴＤＩ）、ヘキサメチレンジイソ
シアネート（ＨＤＩ）、ジフェニルメタンジイソシアネ
ー） （ＭＤＩ）、水添ジフェニルメタンジイソシアネ
ート（水添ＭＤＩ＞、イソフォロンジイソシアネート
（ＩＰＤＩ）等が挙げられる。Examples of the diisocyanate of component (b) include tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), isophorone diisocyanate, etc.
(IPDI), etc.
（ｃ）成分のヒドロキシル基含有（メタ）アクリレート
化合物としては、例えば２−ヒドロキシエチル（メタ）
アクリレート、２−ヒドロキシプロピル（メタ）アクリ
レート等が挙げられる。これらのうち、得られる着色組
成物の硬化速度向上の点から、特にメタアクリレート化
合物よりもアクリレート化合物が好ましい。As the hydroxyl group-containing (meth)acrylate compound of component (c), for example, 2-hydroxyethyl (meth)
Examples include acrylate, 2-hydroxypropyl (meth)acrylate, and the like. Among these, acrylate compounds are particularly preferred over methacrylate compounds in terms of improving the curing speed of the resulting colored composition.
これら（ａ）〜（ｃ）を反応させる方法としては、例え
ば触媒の存在下、通常２０〜６０℃で■（ｂ）成分、（
ａ）成分、（ｃ）成分又はら）成分、（ｃ）成分、（ａ
）成分の順序で添加させる方法、■（ａ）、（ｂ）両成
分を反応させた後（ｃ）成分を添加する方法、■（ａ）
、■）、（ｃ）各成分を同時に反応させる方法等が挙げ
られる。触媒とじては、例えばトリエチルアミン等の３
級アミン化合物、ジブチル錫ジラウレート等の有機錫化
合物等が挙げられる。このようにして得られるウレタン
（メタ）アクリレートは、例えば次の一般式％式％
（式中、Ｒ１及びＲ３は、それぞれ水素原子又はメチル
基を示し、Ｒ２は炭素数１〜６のアルキレン基を示し、
Ｒ３はジイソシアネート残基を示し、Ｒ４は水素原子、
メチル基又はエチル基を示し、ｌは１〜１０、ｍ及びｎ
は１〜３０の整数を示す）一般式（１）中、Ｒ２で示さ
れる炭素数１〜６のアルキレン基としては、例えばメチ
レン基、エチレン基、プロピレン基、ブチレン基、ペン
タメチレン基、ヘキサメチレン基などが挙げられる。ま
た、ｌは１〜１０の整数であるが、特に１〜４が好まし
く、ｍ及びｎは１〜３ｏの整数であるが特に１〜１５が
好ましい。As a method for reacting these (a) to (c), for example, in the presence of a catalyst, usually at 20 to 60°C, component (b), (
a) component, (c) component or ra) component, (c) component, (a
) A method in which the components are added in order; ■ A method in which (a) and (b) both components are reacted, and then (c) a method in which the component is added; ■ (a)
, ■), and (c) a method in which each component is reacted simultaneously. Examples of catalysts include triethylamine such as triethylamine, etc.
amine compounds, organic tin compounds such as dibutyltin dilaurate, and the like. The urethane (meth)acrylate obtained in this way is, for example, expressed by the following general formula % (wherein R1 and R3 each represent a hydrogen atom or a methyl group, and R2 represents an alkylene group having 1 to 6 carbon atoms. show,
R3 represents a diisocyanate residue, R4 is a hydrogen atom,
Represents a methyl group or an ethyl group, l is 1 to 10, m and n
represents an integer of 1 to 30) In general formula (1), examples of the alkylene group having 1 to 6 carbon atoms represented by R2 include methylene group, ethylene group, propylene group, butylene group, pentamethylene group, hexamethylene group. Examples include groups. Further, l is an integer of 1 to 10, particularly preferably 1 to 4, and m and n are integers of 1 to 3o, particularly preferably 1 to 15.
一般式（１）で表わされるウレタン（メタ）アクリレー
トは、エチレンオキサイド（又はプロピレンオキサイド
若しくはブチレンオキサイド）変性ビスフェノールＦ（
又はＡ）ウレタン（メタ）アクリレートであり、これら
の市販品としては、例えばＮＫエステルｍｌ−１３０１
Ａ（新中村化学■製） 、ＮＫエステルＵ−７０１＾（
新中村化学■製） 、ＮＫエステルロー４０１Ａ （新
中村化学＠製） 、ＮＫエステルｆ、ｌ−６０１８Ａ（
新中村化学■製） 、ＮＫニステルト１００ＩＢＡ （
新中村化学■製）等が挙げられる。これらウレタン（メ
タ）アクリレートは、着色組成物中に通常５〜８０重量
％（以下、単に「％」で示す）、好ましくは５〜７０％
配合することができる。この範囲を超えると粘度が高く
なり、作業性が悪くなることがある。Urethane (meth)acrylate represented by general formula (1) is ethylene oxide (or propylene oxide or butylene oxide) modified bisphenol F (
or A) urethane (meth)acrylate, commercially available products such as NK ester ml-1301
A (manufactured by Shin Nakamura Chemical), NK Ester U-701^ (
Shin Nakamura Chemical ■), NK Ester Low 401A (Shin Nakamura Chemical @), NK Ester f, l-6018A (
Shin Nakamura Chemical ■), NK Nystelt 100IBA (
(manufactured by Shin Nakamura Chemical ■), etc. These urethane (meth)acrylates are usually 5 to 80% by weight (hereinafter simply expressed as "%"), preferably 5 to 70% by weight in the coloring composition.
Can be blended. If it exceeds this range, the viscosity may increase and workability may deteriorate.
本発明の光ファイバ用紫外線硬化性着色組成物には、前
記ウレタン（メタ）アクリレート以外に、各種の紫外線
硬化性樹脂を併用することができる。In the ultraviolet curable coloring composition for optical fibers of the present invention, various ultraviolet curable resins can be used in combination in addition to the urethane (meth)acrylate.
かかる紫外線硬化性樹脂としては、例えば各種エポキシ
アクリレート樹脂、ポリエステルアクリレート樹脂等の
アクリレートオリゴマーと、ネオペンチルグリコールア
クリレート、Ｎ−ビニルピロリドン、ペンタエリスリト
ールトリアクリレート等のエチレン性不飽和基を有する
単官能及び多官能モノマーから成るもの等が挙げられる
。これらの樹脂は、着色組成物中に通常Ｏ〜９０％、好
ましくは２０〜８０％配合することができる。Examples of such ultraviolet curable resins include acrylate oligomers such as various epoxy acrylate resins and polyester acrylate resins, and monofunctional and polyfunctional resins having ethylenically unsaturated groups such as neopentyl glycol acrylate, N-vinylpyrrolidone, and pentaerythritol triacrylate. Examples include those consisting of functional monomers. These resins can be blended in the coloring composition in an amount of usually 0 to 90%, preferably 20 to 80%.
また、本発明の紫外線硬化性着色組成物には、着色顔料
、光重合開始剤等を配合する。Furthermore, the ultraviolet curable colored composition of the present invention contains a colored pigment, a photopolymerization initiator, and the like.
着色顔料としては、例えばカーボンブラック、酸化チタ
ン、亜鉛華、不溶性アゾ顔料、縮合アゾ顔料、多環式顔
料等が挙げられる。これら着色顔料を、着色組成物中に
通常０．１〜５０％、好ましくは２〜１０％配合するこ
とができる。Examples of colored pigments include carbon black, titanium oxide, zinc white, insoluble azo pigments, condensed azo pigments, and polycyclic pigments. These colored pigments can be blended in the coloring composition in an amount of usually 0.1 to 50%, preferably 2 to 10%.
光重合開始剤としては、例えばベンゾフェノン１、ベン
ゾイン、ベンゾインイソブチルエーテル、ベンジル、ベ
ンゾインエチルエーテル、２．２−ジメトキシ−２−フ
ェニルアセトフェノン、キサントン、フルオレノン、４
−クロロベンゾフェノン、トリフェニルアミン、カルバ
ゾール、３−メチルアセトフェノン、４．４’−ジメト
キシベンゾフェノン、４．４’−ジアミノベンゾフェノ
ン、ミヒラーケトン、ベンゾインプロピルエーテル、ア
セトフェノンジエチルケタール、ベンゾインエチルエー
テル、１−ヒドロキシシクロへキシルフェニルケトン、
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、２−ヒドロキシ−２−メチル−プロ
ピオフェノン、α、α′ジクロロー４−フェノキシアセ
トフェノン、ベンジルジメチルケタール、２．２−ジェ
トキシアセトフェノン、クロロチオキサントン、２−イ
ソプロピルチオキサントン、ジエチルチオキサントン、
３．３−ジメチル−４−メトキシベンゾフェノン、２−
メチル−１−［４−（メチルチオ）フェニルツー２−モ
ルホリノプロパノン、α−ヒドロキシシクロへキシルフ
ェニルケトン、ユベクリルＰ ３６ （ｌｉｃｅ社製高
分子量化ベンゾフェノン）・２・４．６−）リメチルベ
ンゾイルジフェニルホスフィンオキシド等のラジカル系
光重合開始剤、２゜５−ジェトキシ−４−（ｐ−）リル
メルカブト）ベンゼンジアゾ三つムｐＦｇ−１２，４，
６，−）リクロロベンゼンジアゾニウムＰＦ、−１４−
ジメチルアミノナフタレンジアゾニウムＰＦ６−、シク
ロペンタジエニルフエロセニウムＰＦ、−Ｗのイオン系
光重合開始剤等が挙げられる。これら光重合開始剤は、
着色組成物中に通常０．５〜２０％、好ましくは３〜１
０％配合することができる。Examples of the photopolymerization initiator include benzophenone 1, benzoin, benzoin isobutyl ether, benzyl, benzoin ethyl ether, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, 4
-chlorobenzophenone, triphenylamine, carbazole, 3-methylacetophenone, 4.4'-dimethoxybenzophenone, 4.4'-diaminobenzophenone, Michler's ketone, benzoinpropyl ether, acetophenone diethyl ketal, benzoin ethyl ether, 1-hydroxycyclo xylphenyl ketone,
4'-isopropyl-2-hydroxy-2-methyl-
Propiophenone, 2-hydroxy-2-methyl-propiophenone, α, α′ dichloro-4-phenoxyacetophenone, benzyl dimethyl ketal, 2,2-jethoxyacetophenone, chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone,
3.3-dimethyl-4-methoxybenzophenone, 2-
Methyl-1-[4-(methylthio)phenyl-2-morpholinopropanone, α-hydroxycyclohexylphenyl ketone, Jubecryl P 36 (polymerized benzophenone manufactured by LICE), 2.4.6-)limethylbenzoyl Radical photopolymerization initiator such as diphenylphosphine oxide, 2゜5-jetoxy-4-(p-)rilumercabuto)benzenediazotrium pFg-12,4,
6,-)lichlorobenzenediazonium PF, -14-
Examples include ionic photopolymerization initiators such as dimethylaminonaphthalenediazonium PF6-, cyclopentadienylferrocenium PF, and -W. These photoinitiators are
Usually 0.5 to 20%, preferably 3 to 1% in the coloring composition
0% can be blended.
さらに、本発明の光ファイバ用紫外線硬化性着色組成物
には、必要に応じて光増感剤、保存安定剤、レベリング
剤又は紫外線吸収剤であるｎ−ブチルアミン、）Ｕ−ｎ
−ブチルホスフィン、Ｓベンジルイソチウロニウム−Ｒ
−）ルエンスルホネート、トリエチルアミン、ジエチル
アミノエチル（メタ）アクリレート、ハイドロキノンモ
ノメチルエーテル、ｐ−ジメチルアミノ安息香酸エチル
エステル、２．６−ジーｔ−ブチル−ｐ−メチルフェノ
ール等を、本発明の効果を損わない範囲で配合すること
ができる。Furthermore, the ultraviolet curable coloring composition for optical fibers of the present invention may optionally contain n-butylamine, which is a photosensitizer, a storage stabilizer, a leveling agent, or an ultraviolet absorber.
-Butylphosphine, S benzylisothiuronium-R
-) Luenesulfonate, triethylamine, diethylaminoethyl (meth)acrylate, hydroquinone monomethyl ether, p-dimethylaminobenzoic acid ethyl ester, 2,6-di-t-butyl-p-methylphenol, etc., which impair the effects of the present invention. It can be blended within a certain range.
本発明の光ファイバ用紫゛外線硬化性着色組成物は、上
記各成分を常法により混合して製造することができ、こ
れを光ファイバのヤカンダリーコーティングの上層に塗
布後、高圧水銀灯、メタルハライドランプ等により紫外
線を照射して硬化せしめれば光ファイバを着色コ゛−テ
ィングすることができる。The UV-curable coloring composition for optical fibers of the present invention can be produced by mixing the above-mentioned components in a conventional manner. The optical fiber can be colored and coated by curing it by irradiating it with ultraviolet light using a lamp or the like.
次に、実施例を挙げ、本発明をさらに説明するが、本発
明はこれらの実施例に限定されるものではない。Next, the present invention will be further explained with reference to Examples, but the present invention is not limited to these Examples.
実施例１〜３、比較例１〜３
第１表に示す組成の成分をそれぞれ配合し、着色組成物
（インキビヒクル）を調製し、各着色組成物の発色状態
を評価した。各着色組成物を硬化させ、その弾性率につ
いて評価した。結果を第１表に示す。Examples 1 to 3, Comparative Examples 1 to 3 Coloring compositions (ink vehicles) were prepared by blending the components shown in Table 1, and the coloring state of each coloring composition was evaluated. Each colored composition was cured and evaluated for its elastic modulus. The results are shown in Table 1.
く弾性率〉
着色組成物の塗膜に８０Ｗ／ｃｍの高圧水銀灯を用いて
、０．５Ｊ／ｃＩＩ！の紫外線を照射し、厚さ１５μｍ
の硬化シートを作成し、この硬化シートの２０を及び−
４０℃における弾性率を測定した（ＪＩＳ Ｋ ７１１
３「プラスチックの引張り試験方法」に順拠）。尚、弾
性率は低い方が光ファイバの伝送特性に与える影響が小
さく好ましい。Modulus of Elasticity> Using a high-pressure mercury lamp of 80 W/cm on the coating film of the colored composition, the modulus of elasticity was 0.5 J/cII! irradiated with ultraviolet rays to a thickness of 15 μm
20 of this cured sheet and -
The elastic modulus at 40°C was measured (JIS K 711
(Based on 3 “Plastic tensile test method”). Note that a lower modulus of elasticity is preferable because it has less influence on the transmission characteristics of the optical fiber.
く発色状態〉 樹脂の顔料に対するぬれ性を目視で評価した。Colored state> The wettability of the resin to the pigment was visually evaluated.
ぬれ性の良いものを良、悪いものを不良とした。Those with good wettability were evaluated as good, and those with poor wettability were evaluated as poor.
以下余白
本５：三菱油化フアイン■製
京６二日本化薬味製
Ｈａ
宰７：チバガイギー社製光重合開始剤
Ｃ１＋
零８：大日精化製 青色顔料
本９：山陽色素製 赤色顔料
第１表から明らかなように、本発明の光ファイバ用紫外
線硬化性着色組成物は、比較例のものに比べ硬化後シー
トの弾性率が低いものであった。The following margin Book 5: Mitsubishi Yuka Fine Co., Ltd. Kyo 62 Nippon Kayaku Ha Co., Ltd. 7: Photopolymerization initiator C1+ manufactured by Ciba Geigy Co., Ltd. Zero 8: Blue pigment manufactured by Dainichiseika Chemical Book 9: Red pigment manufactured by Sanyo Shiki Co., Ltd. Table 1 As is clear from the above, the ultraviolet curable coloring composition for optical fibers of the present invention had a lower elastic modulus of the sheet after curing than that of the comparative example.
本発明の光ファイバ用紫外線硬化性着色組成物は、紫外
線の照射により硬化し、硬化後は常温及び低温における
弾性率が小さく、光ファイバの伝送損失を小さいものと
することができ、光ファイバ用着色材として極めて有用
なものである。The ultraviolet curable coloring composition for optical fibers of the present invention is cured by irradiation with ultraviolet rays, has a small elastic modulus at room temperature and low temperature after curing, and can reduce the transmission loss of optical fibers. It is extremely useful as a coloring material.
以上 出願人 日本合成ゴム株式会社 出願人 東華色素化学工業株式会社that's all Applicant: Japan Synthetic Rubber Co., Ltd. Applicant: Toka Color Chemical Industry Co., Ltd.
Claims (1)
ルキレンオキサイド付加物 （ｂ）ジイソシアネート及び （ｃ）ヒドロキシル基含有（メタ）アクリレート化合物 を反応させてなるウレタン（メタ）アクリレートを含有
することを特徴とする光ファイバ用紫外線硬化性着色組
成物。[Claims] 1. Contains a urethane (meth)acrylate obtained by reacting (a) an alkylene oxide adduct of bisphenol A or bisphenol F, (b) a diisocyanate, and (c) a hydroxyl group-containing (meth)acrylate compound. An ultraviolet curable coloring composition for optical fibers, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2170880A JP2884003B2 (en) | 1990-06-28 | 1990-06-28 | UV curable coloring composition for optical fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2170880A JP2884003B2 (en) | 1990-06-28 | 1990-06-28 | UV curable coloring composition for optical fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0457817A true JPH0457817A (en) | 1992-02-25 |
| JP2884003B2 JP2884003B2 (en) | 1999-04-19 |
Family
ID=15913027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2170880A Expired - Lifetime JP2884003B2 (en) | 1990-06-28 | 1990-06-28 | UV curable coloring composition for optical fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2884003B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001348412A (en) * | 2000-04-03 | 2001-12-18 | Jsr Corp | Liquid curable resin composition and bilayer film |
| JP2002097235A (en) * | 2000-09-26 | 2002-04-02 | Jsr Corp | Liquid curable resin composition and its cured product |
| WO2002098945A1 (en) * | 1999-07-27 | 2002-12-12 | Alcatel | Colored, radiation-curable compositions |
| US6782176B1 (en) | 1999-07-27 | 2004-08-24 | Robert W. Greer | Colored radiation curable coating compositions for identifying telecommunications elements and telecommunications elements coated thereby |
| CN114736549A (en) * | 2022-03-23 | 2022-07-12 | 武汉长盈鑫科技有限公司 | FRP (fiber reinforced Plastic) coating resin composition suitable for UV-LED (ultraviolet-light emitting diode) curing and preparation method thereof |
-
1990
- 1990-06-28 JP JP2170880A patent/JP2884003B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002098945A1 (en) * | 1999-07-27 | 2002-12-12 | Alcatel | Colored, radiation-curable compositions |
| US6782176B1 (en) | 1999-07-27 | 2004-08-24 | Robert W. Greer | Colored radiation curable coating compositions for identifying telecommunications elements and telecommunications elements coated thereby |
| JP2001348412A (en) * | 2000-04-03 | 2001-12-18 | Jsr Corp | Liquid curable resin composition and bilayer film |
| JP2002097235A (en) * | 2000-09-26 | 2002-04-02 | Jsr Corp | Liquid curable resin composition and its cured product |
| WO2002026854A3 (en) * | 2000-09-26 | 2002-08-08 | Dsm Nv | Liquid curable resin composition and cured products |
| KR100829636B1 (en) * | 2000-09-26 | 2008-05-16 | 코닌클리즈케 디에스엠 엔.브이. | Liquid curable resin composition and cured products |
| CN114736549A (en) * | 2022-03-23 | 2022-07-12 | 武汉长盈鑫科技有限公司 | FRP (fiber reinforced Plastic) coating resin composition suitable for UV-LED (ultraviolet-light emitting diode) curing and preparation method thereof |
| CN114736549B (en) * | 2022-03-23 | 2022-09-30 | 武汉长盈鑫科技有限公司 | FRP (fiber reinforced plastic) coating resin composition suitable for UV-LED (ultraviolet-light emitting diode) curing and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2884003B2 (en) | 1999-04-19 |
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