JPS59228604A - Light conductive body - Google Patents

Light conductive body

Info

Publication number
JPS59228604A
JPS59228604A JP58242758A JP24275883A JPS59228604A JP S59228604 A JPS59228604 A JP S59228604A JP 58242758 A JP58242758 A JP 58242758A JP 24275883 A JP24275883 A JP 24275883A JP S59228604 A JPS59228604 A JP S59228604A
Authority
JP
Japan
Prior art keywords
polymer
formula
conductive body
light conductive
core
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
Application number
JP58242758A
Other languages
Japanese (ja)
Other versions
JPH0344281B2 (en
Inventor
Akira Omori
晃 大森
Nobuyuki Tomihashi
信行 富橋
Takahiro Kitahara
隆宏 北原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Original Assignee
Daikin Industries Ltd
Daikin Kogyo Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd, Daikin Kogyo Co Ltd filed Critical Daikin Industries Ltd
Priority to JP58242758A priority Critical patent/JPS59228604A/en
Publication of JPS59228604A publication Critical patent/JPS59228604A/en
Publication of JPH0344281B2 publication Critical patent/JPH0344281B2/ja
Granted legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/44Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
    • G02B6/4401Optical cables
    • G02B6/4429Means specially adapted for strengthening or protecting the cables
    • G02B6/443Protective covering

Abstract

PURPOSE:To improve flexibility and heat resistance as well by forming a core and shell of a plastic clad light conductive body of a specified polymer. CONSTITUTION:The core of a plastic clad light conductive body is formed of a polymer having constitutional unit expressed by the formula ( I ) (X is F or CH3) and the shell is formed of a polymer having the constitutional unit expressed by the formula (II) (Rf is fluoroalkyl group). It is preferred that the polymer for the shell component contains >=10mol% constitutional unit (II) for the improvement of the flexibility of a light conductive body. It is also preferred that each component of the polymer contains >=70mol% constitutional unit I or II respectively for the improvement of the softening temp. to >=100 deg.C or of the stability of transparency or for imparting gasoline resistance to the polymer.

Description

【発明の詳細な説明】 本発明は、プラスチック系光伝導体に関する。[Detailed description of the invention] The present invention relates to plastic-based photoconductors.

従来、メチルメタクリレート重合体を芯とし、フルオロ
アルキルメタクリレート重合体を鞘としたプラスチック
糸光伝導体は公知である(特公昭54−24802号公
報)。しかしながら、この光伝導体は可撓性に難点があ
り、また長時間高温下におかれるとその光透過度は著し
く低下してしまい、さらには車輌等に設置したときガソ
リン等の燃料に侵きれやすいという問題も有している。
Conventionally, a plastic thread photoconductor having a core made of a methyl methacrylate polymer and a sheath made of a fluoroalkyl methacrylate polymer is known (Japanese Patent Publication No. 54-24802). However, this photoconductor has problems with its flexibility, and its light transmittance decreases significantly if it is exposed to high temperatures for a long period of time.Furthermore, when it is installed in a vehicle, it is easily eroded by fuel such as gasoline. It also has the problem of being easy to use.

本発明の目的は、従来のフ”ラスチック系光伝導体より
も可撓性が良好で耐熱性にもすぐれ、さらにガソリン等
にも侵されないフ”ラスチック系光伝導体全提供するこ
とにある。
An object of the present invention is to provide a plastic photoconductor that has better flexibility and heat resistance than conventional plastic photoconductors, and is not eroded by gasoline or the like.

かかる本発明の要旨は、プラスチック系タラッド型光伝
導体において、芯が式: X / (式中、XはFまたはCH,を示す。)で表わされる構
造単位を有する重合体、鞘が酸二/ (式中、Rfはフルオロアルキル基を示す。)で表わさ
れる構造単位を有する重合体からなることを特徴とする
光伝導体である。
The gist of the present invention is to provide a plastic Tallard-type photoconductor in which the core is a polymer having a structural unit represented by the formula: / (wherein, Rf represents a fluoroalkyl group) A photoconductor characterized by being made of a polymer having a structural unit represented by the following formula.

本発明に係る光伝導体の鞘成分重合体は、式(b)で表
わされる構造単位t−10モル%以上含有す−ることか
、光伝導体の可撓性を良好にする上で好ましく、また各
成分の重合体がそれぞれ式(a)または式せたり光伝導
体の透明性を保つ上で、またガソリン等に耐性を持たせ
る上で好ましい。
The sheath component polymer of the photoconductor according to the present invention preferably contains t-10 mol% or more of the structural unit represented by formula (b), in order to improve the flexibility of the photoconductor. In addition, each component polymer is preferably of the formula (a) or the formula (a) in order to maintain the transparency of the photoconductor and to make it resistant to gasoline and the like.

式(b)に包含されるRJは、通常炭素数1〜10のフ
ルオロアルキル基である。
RJ included in formula (b) is usually a fluoroalkyl group having 1 to 10 carbon atoms.

上記構造単位(a)を有する芯成分重合体は、通常酸二 X C式中、Xは前記と同じ。) で表わされる単量体のみを重合するか、あるいはこの単
量体とエチルメタクリレート、式(C)で表わされる単
量体以外のメチル−α−フルオロアクリレート、メタク
リル酸等のアクリル酸誘導体とを共重合することによっ
て得ることができる。なお、さらに共単量体として他の
エチレン性不飽和化合物を共重合することも可能である
The core component polymer having the above-mentioned structural unit (a) is usually acidic diX in the formula, where X is the same as above. ), or polymerize this monomer with ethyl methacrylate, methyl-α-fluoroacrylate other than the monomer represented by formula (C), or an acrylic acid derivative such as methacrylic acid. It can be obtained by copolymerization. In addition, it is also possible to further copolymerize other ethylenically unsaturated compounds as comonomers.

上記構造単位(b)を有する鞘成分重合体は、通常酸二
     F / (式中、Rfは前記と同じ。) で表わされる単量体のみを重合するか、あるいはこの単
量体とメチル−α−フルオロアクリレート、メタクリル
酸メチル、メタクリル酸等のアクリル酸誘導体とを共重
合することによって得ることができる。なお、式らに共
単量体として他のエチレン性不飽和化合物を共重合する
ことも可能である。
The sheath component polymer having the above structural unit (b) is usually produced by polymerizing only the monomer represented by the acid diF/ (in the formula, Rf is the same as above), or by polymerizing this monomer and methyl- It can be obtained by copolymerizing α-fluoroacrylate, methyl methacrylate, and acrylic acid derivatives such as methacrylic acid. Note that it is also possible to copolymerize other ethylenically unsaturated compounds as comonomers.

上記芯あるいは鞘成分重合体は、いずれも塊状、溶液、
懸濁、乳化重合等、一般に採用されている重合方法で重
合して製造することができる。重合開始剤としては、塊
状、溶液および懸濁重合においてはアゾ系化合物または
有機過酸化物が用いられ、例えばアゾビスイソブチロニ
トリル、イソブチルバーオキシド。オクタノイルパーオ
キシド、ジ−イソ−10ピルバーオキシージーカーポネ
ート、または式(C1(CF2CFCj)2 CF2c
oo)2、(H(CF2 CF2 )3COO)2 お
よび(CJCF2 CF2 C00)2で表わされる含
フツ素有機過酸化物等が好ましく用いられる。乳化重合
においては、過硫酸塩等の酸化剤、亜硫酸ソーダ等の還
元剤および硫酸鉄(2)等の遷移金属化合物からなるレ
ドックス開始剤が用いられる。
The above-mentioned core or sheath component polymers may be in the form of lumps, solutions,
It can be produced by polymerization using commonly employed polymerization methods such as suspension and emulsion polymerization. As the polymerization initiator, azo compounds or organic peroxides are used in bulk, solution and suspension polymerizations, such as azobisisobutyronitrile and isobutyl peroxide. Octanoyl peroxide, di-iso-10 pyruvaroxy dicarbonate, or formula (C1(CF2CFCj)2 CF2c
Fluorine-containing organic peroxides represented by oo)2, (H(CF2CF2)3COO)2, and (CJCF2CF2C00)2 are preferably used. In emulsion polymerization, a redox initiator consisting of an oxidizing agent such as persulfate, a reducing agent such as sodium sulfite, and a transition metal compound such as iron sulfate (2) is used.

塊状、溶液または懸濁重合において、重合体の熱分解温
度の向上や分子歓分布の調整の目的で、メルカプタン類
等の連鎖移動剤金片いることが好ましい。連鎖移動剤を
用いる場合の連鎖移動剤の添加割合は、単重体100重
量部に対し通常0.O1〜1電量部である。
In bulk, solution or suspension polymerization, it is preferable to use a chain transfer agent such as mercaptans for the purpose of increasing the thermal decomposition temperature of the polymer and adjusting the molecular distribution. When using a chain transfer agent, the addition ratio of the chain transfer agent is usually 0.00 parts by weight per 100 parts by weight of the monomer. O1~1 coulometric part.

溶液重合で重合体を製造する際に用いられる有機溶媒と
しては、Q’CI2 F2 、 CCl2 FCCJF
2 、Cは酢酸グチル、メチルイソブチルケトン、アセ
トニトリル、アセトン、ジメチルホルムアミド等炭化水
素系溶媒が例示できる。
Organic solvents used when producing polymers by solution polymerization include Q'CI2 F2, CCl2 FCCJF
2. Examples of C include hydrocarbon solvents such as gtylacetate, methyl isobutyl ketone, acetonitrile, acetone, and dimethylformamide.

重合温度は通常O〜100°Cの範囲で上記重合開始剤
の分解温度との関係で決められるが、多くの場合lO〜
80℃の範囲が好ましく採用される。
The polymerization temperature is usually in the range of 0 to 100°C and is determined in relation to the decomposition temperature of the polymerization initiator, but in many cases it is in the range of 10 to 100°C.
A temperature range of 80°C is preferably employed.

重合圧力はθ〜50Kg/dゲージの範囲が採用される
The polymerization pressure is in the range of θ to 50 kg/d gauge.

上記重合反応で調製した芯または鞘重合体のゲルパーミ
ェーションクロマトグラフィ、但しカラム:ショーデッ
クスA −808、A −805、A −806の連結
カラム、溶媒ニジメチルホルムアミド、測定温度:室温
、標準サンフ”ル:ポリスチレン、で測定した分子量は
、いずれも通常20万〜500万の分布を有し、示差走
査熱量計を用いlO°C/分の昇温速度で測定した軟化
温度もいずれも通常100〜150℃であるが、屈折率
は、通常芯成分重合体が1.47〜1.51であるのに
対し、鞘成分重合体は1.36〜1.48である。
Gel permeation chromatography of the core or sheath polymer prepared by the above polymerization reaction. Column: connected columns of Showdex A-808, A-805, A-806, solvent dimethylformamide, measurement temperature: room temperature, standard The molecular weight measured with polystyrene generally has a distribution of 200,000 to 5,000,000, and the softening temperature measured using a differential scanning calorimeter at a heating rate of 10°C/min is also normal. The refractive index is usually 1.47 to 1.51 for the core component polymer, while it is 1.36 to 1.48 for the sheath component polymer.

本発明に係る光伝導体は、通常芯あるいは鞘成分重合体
をそれぞれ別に加熱溶融し、ついで複合紡糸することに
よって製造される。
The photoconductor according to the present invention is usually produced by separately heating and melting the core or sheath component polymers, and then subjecting them to composite spinning.

この光伝導体の直径は、通常100〜1oooμmでそ
のうち鞘の厚みは5〜50μmである。
The diameter of this photoconductor is usually 100 to 100 μm, and the thickness of the sheath is 5 to 50 μm.

次に本発明に係る光伝導体(実施例1〜7)および比較
例光伝導体の調製例ならびに試験例を示す。
Next, preparation examples and test examples of photoconductors according to the present invention (Examples 1 to 7) and comparative photoconductors will be shown.

調製例 (実施例1〜7および比較例)なお、この際単
量体100重量部当りアゾビスイソブチロニトリル0.
0Eft部、It−ドデシルメルカフ゛タン0.5重量
部を使用した。
Preparation Examples (Examples 1 to 7 and Comparative Examples) In this case, 0.0.0% of azobisisobutyronitrile was added per 100 parts by weight of monomer.
0 Eft part and 0.5 part by weight of It-dodecylmercaptan were used.

上記得らnた各成分重合体を用い、第1表に示す芯鞘構
造の組合せの光伝導体を、本発明に係る光伝導体は25
0°Cで、比較例の重合体は250°Cでは熱分解し始
めるため220°Cで、8m/分の速度で直径300μ
m(但し鞘厚み15μm)の繊維状に複合紡糸し、その
後これ’!i−180°Cで1゜5倍に延伸して調製し
た。
Using each component polymer obtained above, a photoconductor having a core-sheath structure combination shown in Table 1 was prepared.
At 0°C, the polymer of the comparative example starts to thermally decompose at 250°C, so at 220°C, the polymer has a diameter of 300 μm at a speed of 8 m/min.
m (sheath thickness: 15 μm) composite spun into fibers, and then this'! It was prepared by stretching 1°5 times at i-180°C.

光透過度および可撓性試験 100時間放置後の光透過度の測定を行った。またこの
試料を種々の直径の鋼棒にまきつけ、鞘にひびの入る最
小径を求める可撓性試験を行った。結果を第1表に示す
Light transmittance and flexibility test The light transmittance was measured after being left for 100 hours. In addition, a flexibility test was conducted by wrapping this sample around steel rods of various diameters to determine the minimum diameter at which the sheath would crack. The results are shown in Table 1.

(以下余白、次頁に続く) 第   1   表 なお、表中MMAはメチルメタクリレート、EMAiエ
チルメタクリレート、MFAHメチル−〇−フルオロア
クリレート、MAはメタクリル酸、PEP[ペンタフル
オロプロピル−〇−フルオロアクリレート、HFBは2
.2.8.4.4−ヘキサフルオロブチル−〇−フルオ
ロアクリレート、TFEは2.2.2−トリフルオロエ
チル−〇−フルオロアクリレート、HFBMは2.2.
8.4.4.4−へキサフルオロブチルメタクリレート
を示す。
(The following margins continue on the next page) Table 1 In the table, MMA is methyl methacrylate, EMAi ethyl methacrylate, MFAH methyl-〇-fluoroacrylate, MA is methacrylic acid, PEP [pentafluoropropyl-〇-fluoroacrylate, HFB is 2
.. 2.8.4.4-hexafluorobutyl-〇-fluoroacrylate, TFE is 2.2.2-trifluoroethyl-〇-fluoroacrylate, HFBM is 2.2.
8.4.4.4-hexafluorobutyl methacrylate.

耐ガソリン試験 ガソリンの飽和蒸気をみたした80°Cの恒温槽に、前
記実施例1〜7および比較例で調製した光伝導体を入扛
、500時間放置後光透過度を求めたところ、実施例1
〜7のものはほとんど光透過度の低下ばみられなかった
が、比較例のものは光透過度が5%になった。この比較
例の光伝導体の表面を顕微鏡で観察したところ、表明に
は微小クラックが入り、鞘が部分的に欠落していた。
Gasoline Resistance Test The photoconductors prepared in Examples 1 to 7 and Comparative Examples were placed in a constant temperature bath at 80°C filled with saturated gasoline vapor, and after being left for 500 hours, the light transmittance was determined. Example 1
In the cases of Nos. 7 to 7, there was almost no decrease in light transmittance, but in the case of Comparative Examples, the light transmittance was 5%. When the surface of the photoconductor of this comparative example was observed under a microscope, it was found that the surface had minute cracks and the sheath was partially missing.

以上 特許出願人 ダイキン工業株式会社that's all Patent applicant: Daikin Industries, Ltd.

Claims (1)

【特許請求の範囲】 1、7”ラスチック系クラッド型光伝導体において、芯
が式: %式%() (式中、XはFまたはCH3を示す。)で表わされる構
造単位を有する本合体、鞘が式: %式%() (式中、Rfはフルオロアルキル基を示す。)で表わさ
れる構造単位を有する重合体からなること?特徴とする
光伝導体。 2、鞘が式(b)で表わされる構造単位を10モル%以
上含有する重合体である特許請求の範囲第1項記載の光
伝導体。 3、芯が式(a)で表わされる構造単位を70モル%以
上含有する重合体、鞘が式(b)で表わされる構造単位
を70モル%以上含有する重合体である特許請求の範囲
第1項または第2項記載の光伝導体。
[Claims] A 1,7" plastic clad photoconductor, the core of which has a structural unit represented by the formula: % (wherein, X represents F or CH3). A photoconductor characterized in that the sheath is made of a polymer having a structural unit represented by the formula: % formula % () (wherein Rf represents a fluoroalkyl group).2. ) The photoconductor according to claim 1, which is a polymer containing 10 mol% or more of the structural unit represented by formula (a). 3. The core contains 70 mol% or more of the structural unit represented by formula (a). 3. The photoconductor according to claim 1, wherein the polymer or sheath is a polymer containing 70 mol% or more of the structural unit represented by formula (b).
JP58242758A 1983-12-21 1983-12-21 Light conductive body Granted JPS59228604A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP58242758A JPS59228604A (en) 1983-12-21 1983-12-21 Light conductive body

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58242758A JPS59228604A (en) 1983-12-21 1983-12-21 Light conductive body

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
JP58104500A Division JPS59227908A (en) 1983-06-10 1983-06-10 Fluorine-containing polymer and its use

Publications (2)

Publication Number Publication Date
JPS59228604A true JPS59228604A (en) 1984-12-22
JPH0344281B2 JPH0344281B2 (en) 1991-07-05

Family

ID=17093826

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58242758A Granted JPS59228604A (en) 1983-12-21 1983-12-21 Light conductive body

Country Status (1)

Country Link
JP (1) JPS59228604A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60250310A (en) * 1984-05-28 1985-12-11 Daikin Ind Ltd Clad material for optical fiber
JPS61251807A (en) * 1985-05-01 1986-11-08 Mitsubishi Rayon Co Ltd Plastic optical fiber

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60250310A (en) * 1984-05-28 1985-12-11 Daikin Ind Ltd Clad material for optical fiber
JPH0251483B2 (en) * 1984-05-28 1990-11-07 Daikin Ind Ltd
JPS61251807A (en) * 1985-05-01 1986-11-08 Mitsubishi Rayon Co Ltd Plastic optical fiber

Also Published As

Publication number Publication date
JPH0344281B2 (en) 1991-07-05

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