JP3875904B2 - Optical fiber cable and optical fiber cable with plug - Google Patents

Description

【００３７】
【表２】

なお、表中の略号は以下を示す。
ＰＡ１１：ナイロン１１
ＰＡ１２：ナイロン１２
ＰＡ６１２：ナイロン６−１２
ＭＣＮ：メラミンシアヌレート
ＬＤＰＥ：低密度ポリエチレン（商標名：ＮＵＣ８００８、日本ユニカー社製）
ＰＶｄＦ：ポリフッ化ビニリデン（商標名：ＫＹＮＡＲ７１０、アトフィナ・ジャパン社製）
ＶｄＦ/ＨＦＰ：フッ化ビニリデン−ヘキサフルオロプロピレン共重合体
（商標名：Ｆｒｅｅ Ｆｌｏｗ１０、デユポン・ダウ・エラストマージャパン社製）
Ｓｉパウダー(商標名)：シリコーン系難燃剤（東レ・ダウコーニング社製）
【００３８】
二次被覆層に使用する第２のポリアミド系樹脂組成物として、ポリアミド系樹脂１００質量部に対して低密度ポリエチレン（日本ユニカー社製、商標名：ＮＵＣ８００８）を５質量部含有させた実施例１及び２のＰＯＦケーブルは、難燃性が低下することなく高い難燃性を備え、かつ、二次被覆層と一次被覆層との間の引き抜き強度（１７〜１９Ｎ／ｍｍ）、曲げ弾性率Ｅ（９〜１２Ｎ）が適切な範囲に制御されていた。
二次被覆層に使用する第２のポリアミド系樹脂組成物として、ポリアミド系樹脂１００質量部に対してポリフッ化ビニリデン（アトフィナ社製、商標名：ＫＹＮＡＲ７１０）を２〜１０質量部含有させた実施例３〜７のＰＯＦケーブルは、難燃性に優れ、二次被覆層と一次被覆層との間の引き抜き強度（１３〜２５Ｎ/ｍｍ）、曲げ弾性率Ｅ（９〜１４Ｎ）が適切な範囲に制御されていた。
二次被覆層に使用する第２のポリアミド系樹脂組成物として、ポリアミド系樹脂１００質量部に対して、フッ化ビニリデン−ヘキサフルオロプロピレンの共重合体（デュポン・ダウ・エラストマージャパン社製、商標名：Ｆｒｅｅ Ｆｌｏｗ１０）を２〜１０質量部含有させた実施例８〜１０のＰＯＦケーブルでは、難燃性に優れ、二次被覆層と一次被覆層との間の引き抜き強度（１２〜２５Ｎ／ｍｍ）、曲げ弾性率Ｅ（１０〜１１Ｎ）が適切な範囲に制御されていた。
二次被覆層に使用する第２のポリアミド系樹脂組成物として、ポリアミド系樹脂１００質量部に対してシリコーン系樹脂（東レ・ダウコーニング社製、商標名：Ｓｉパウダー）を５質量部含有させた実施例１１のＰＯＦケーブルは、難燃性が良好で、二次被覆層と一次被覆層との間の引き抜き強度、曲げ弾性率Ｅも適切な範囲に制御されていた。
一方、比較例１〜３は、二次被覆層と一次被覆層との間の引き抜き強度（３３Ｎ以上）が過度となった。また、比較例４〜６のように、二次被覆層に使用するポリアミド系樹脂に低密度ポリエチレン、フッ化ビニリデン−ヘキサフルオロプロピレンの共重合体、シリコーン系樹脂のいずれかを過度に添加したＰＯＦケーブルは、曲げ弾性率、二次被覆層と一次被覆層との間の引き抜き強度がいずれも小さすぎ、また、難燃性の低下がみられた。
【００３９】
【発明の効果】
以上説明したように本発明のＰＯＦケーブルは、一次被覆層と二次被覆層との密着性が適度に制御され、二次被覆層が剥離しやすく、プラグの取り付けなどの接続作業が容易である。また、柔軟性に優れているため狭窄部へも敷設し易く、しかも耐薬品性、難燃性も良好である。また、ＰＯＦが、フッ化ビニリデン単位を含む共重合体から形成される最外層を少なくとも有するクラッドを備えていると、一次被覆層との密着性が良好でピストニングが起こりにくい。したがって、このようなＰＯＦケーブルおよびこのＰＯＦケーブルの少なくとも一端に、プラグが接続されたプラグ付き光ファイバケーブルは、光信号伝送の配線、高速光通信のためのコンピュータ接続配線、交換機回りの配線、工場自動機械制御の配線、自動車などの移動体用データ伝送用配線、光センサー用配線などで他の機器などと接続する場合の使用に適し、特に自動車内配線への使用に最適である。
【図面の簡単な説明】
【図１】 本発明における引き抜き強度の測定方法を説明する断面図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an optical fiber cable such as a plastic optical fiber cable and a plug-attached optical fiber cable that are suitably used for wiring in an automobile, for example.
[0002]
[Prior art]
Conventionally, as an optical fiber, a silica-based optical fiber that can perform excellent optical transmission over a wide wavelength region is known and widely used mainly in a trunk line system, but a silica-based optical fiber is expensive. It has the disadvantage of low processability. For this reason, plastic optical fibers (hereinafter referred to as POF) that have advantages such as easy end face processing and handling, low cost, light weight, and large diameter have been developed. It is used in the field of wiring for short / medium distance communications such as OA and LAN.
In recent years, among short- and medium-distance communications applications, especially in the field of in-car communications, the spread of car navigation systems, the response to the increase in the amount of communication information against the background of the introduction of ITC / ETC systems, harness cable There is an increasing demand for construction of an inexpensive communication system, and the development of POF in the in-vehicle communication field is being carried out.
[0003]
On the other hand, when a POF cable is used for wiring in an automobile, the temperature of the interior of the automobile becomes high in summer, and it is used in the vicinity of a high-temperature body such as an engine. The coating material is required to have chemical resistance and flame resistance because stability is required and it is used in an environment where flammable materials such as oil, electrolyte and gasoline exist. .
[0004]
As a means for imparting heat resistance, chemical resistance, heat-resistant dimensional stability, etc. to the POF cable, a technique using a polyamide polymer such as nylon as a coating material is disclosed in JP-A-7-77642, Polyamide resins such as nylon 11 and nylon 12 are also used in automobile POF cables that are proposed in Japanese Patent Laid-Open No. 10-319281, Japanese Patent Laid-Open No. 11-242142, and the like.
Furthermore, in order to further improve the durability and environmental resistance characteristics of the POF cable, a technique of providing a secondary coating layer made of a polyamide-based resin on the outer peripheral portion of the primary coating layer is disclosed in the above-mentioned JP-A-10-319281, It is proposed in Japanese Patent Laid-Open No. 11-242142.
[0005]
The POF cable is used as a POF cable with a plug in which a plug is attached to a cable end for joining with a light source as a signal source, another POF cable, or the like. When a plug is attached to a POF cable having two or more coating layers, a method of fixing the plug from the exposed primary coating layer portion by removing the secondary coating layer is generally used. For this reason, the secondary coating layer of the POF cable is required to be peeled off relatively easily as needed, such as during cable connection work.
As a method for appropriately controlling the adhesion (pull strength) between the primary coating layer and the secondary coating layer, as disclosed in WO01 / 45826, a crosshead type coating apparatus is used to apply the primary to the optical fiber. A method of coating a coating layer and then coating a secondary coating layer is known. In this method, the pulling strength of the primary coating layer and the secondary coating layer can be controlled to a desired value depending on the coating conditions.
[0006]
[Problems to be solved by the invention]
However, in the techniques of the above-mentioned publications, the properties such as heat resistance, heat-resistant dimensional stability, chemical resistance, and durability are excellent, and the adhesion between the primary coating layer and the secondary coating layer is appropriately controlled. It is difficult to obtain an optical fiber cable, and it is difficult to manufacture such an optical fiber cable because it is necessary to precisely control coating conditions and the like.
[0007]
The purpose of the present invention is that the primary coating layer and the secondary coating layer are easy to peel off, so that the connection work such as attachment of the plug is easy, and because it is excellent in flexibility, it is easy to lay in the constricted part, In addition, the present invention provides an optical fiber cable and an optical fiber cable with a plug that have good chemical resistance and flame resistance.
[0008]
[Means for Solving the Problems]
The optical fiber cable of the present invention is an optical fiber cable in which a primary coating layer and a secondary coating layer are sequentially provided on the outer periphery of an optical fiber composed of a core and a cladding formed on the outer periphery of the core, and the primary coating The layer is formed of a first polyamide-based resin composition containing a polyamide-based resin as a main component, and the secondary coating layer is formed of a polyolefin-based polymer and a fluorine-containing polyolefin-based heavy polymer with respect to 100 parts by weight of the polyamide-based resin. It has at least an innermost layer formed from a second polyamide resin composition containing 0.5 to 20 parts by mass of at least one polymer selected from the group consisting of a coalescence and a silicone polymer. .
The optical fiber preferably includes a clad having at least an outermost layer formed of a copolymer including a vinylidene fluoride unit.
It is preferable that the pull-out strength between the primary coating layer and the secondary coating layer is 10 to 30 N, and the flexural modulus E at 1 mm displacement is 8 to 18 (N / mm).
The polyamide resin that is a main component of the first polyamide resin composition is preferably a nylon 11 homopolymer and / or a nylon 12 homopolymer.
The core is preferably formed of polymethyl methacrylate or a copolymer of at least one vinyl monomer and methyl methacrylate.
When the outer diameter of the optical fiber is 700 to 1200 μm, the outer diameter of the optical fiber cable is 1300 to 3000 μm, the sectional area of the secondary coating layer is B, and the sectional area of the optical fiber cable is A B / A is preferably in the range of 0.3 to 0.7.
The polyamide resin contained in the second polyamide resin composition is preferably at least one selected from the group consisting of a polyamide elastomer, a polyamide copolymer, nylon 11 and nylon 12.
The second polyamide resin composition preferably contains 5 to 30 parts by mass of a triazine compound with respect to 100 parts by mass of the polyamide resin.
The triazine compound is preferably melamine cyanurate and / or silica-modified melamine cyanurate.
The optical fiber cable with a plug of the present invention is characterized in that a plug is connected to at least one end of the optical fiber cable.
In the optical fiber cable with a plug, it is preferable that the secondary coating layer is removed at the end of the optical fiber cable to which the plug is connected, and the plug is directly fixed to the primary coating layer.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[Optical fiber]
An optical fiber used for an optical fiber cable has a clad formed on the outer periphery of a core. As the optical fiber, either a silica-based optical fiber or POF can be used, but POF is preferable in order to improve the adhesion between the optical fiber and the primary coating layer. Hereinafter, the present invention will be described using POF as an example, but the present invention is not limited thereto. As a material for forming the core of POF, a known material can be used, either polymethyl methacrylate (PMMA) or a copolymer of one or more kinds of vinyl monomers and methyl methacrylate. It is preferable to use PMMA, and PMMA is more preferable in terms of translucency, material cost, and durability.
[0010]
The clad formed on the outer periphery of the core may be a single layer or a multilayer, and a known material can be used, but at least the outermost layer in contact with the primary coating layer is a co-polymer containing vinylidene fluoride units. It is preferably formed from coalescence. That is, if the clad consists of a single layer, this layer is preferably formed from a copolymer containing vinylidene fluoride units. It is preferable that the clad has an outermost layer formed of such a copolymer because not only the bending resistance, moist heat resistance, and chemical resistance of the POF can be improved, but also the amount of light that can be taken into the POF can be increased. Further, when the cladding has such an outermost layer, and a primary coating layer described later is formed from the first polyamide resin composition mainly composed of a polyamide resin, the outermost layer of the cladding, the primary coating layer, This is preferable because a POF cable having excellent adhesiveness and less pistoning can be obtained. Such adhesion is due to the interaction that occurs between the highly polar C—F bond in the vinylidene fluoride unit constituting the cladding and the highly polar amide bond in the polyamide-based resin contained in the primary coating layer. to cause. In addition, adhesiveness can be evaluated using the below-mentioned pullout strength as a parameter | index.
[0011]
Examples of the copolymer containing a vinylidene fluoride unit used as the outermost layer of the clad include a copolymer of vinylidene fluoride and tetrafluoroethylene, a copolymer of vinylidene fluoride and hexafluoroacetone, and vinylidene fluoride. And trifluoroethylene copolymer, vinylidene fluoride and hexafluoropropylene copolymer, vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene copolymer, vinylidene fluoride, tetrafluoroethylene and hexafluoroacetone And a copolymer of ethylene, tetrafluoroethylene, and hexafluoropropylene.
[0012]
The outer diameter of the POF is not particularly limited, but is preferably in the range of 700 to 1200 μm. If the outer diameter of the POF is less than 700 μm, the POF cannot capture a signal with a sufficient amount of light, which may reduce communication reliability. When it is larger than 1200 μm, it is not preferable because of high cost.
[0013]
[Primary coating layer]
The primary coating layer is formed on the outer periphery of the above-described POF and protects the POF. From the viewpoint of heat resistance, chemical resistance, bending resistance of the POF cable, dimensional stability (heat shrinkability) of the coating layer, and the like. The first polyamide resin composition is mainly composed of a polyamide resin. When the primary coating layer is formed from such a first polyamide-based resin composition, a POF cable that adheres well to the outermost layer of the clad described above and hardly causes pistoning is obtained, and a specific secondary described later Adhesion between the coating layer and the primary coating layer is moderately controlled, and only the secondary coating layer can be easily peeled off during connection work, etc., otherwise the primary coating layer is removed from the secondary coating layer together with the POF. It will not come out.
[0014]
Examples of the polyamide-based resin contained in the first polyamide-based resin composition as a main component, that is, 60% by mass or more, preferably 80% by mass or more include nylon 10, nylon 11, nylon 12, nylon 6, nylon 66, and nylon. Polyamide elastomers that are homopolymers composed of monomer units such as 6-12, copolymers composed of combinations of these monomer units, and copolymers comprising nylon monomer units into which flexible segments are introduced Etc. Since both of these have a low melting temperature, a coating layer can be formed on the outer periphery of the POF at a relatively low temperature, and the use of these is preferable from the point that the transmission performance of the POF is not thermally deteriorated when the coating layer is formed.
In addition, these polyamide resins may be used alone or in combination of two or more, but particularly when nylon 11 homopolymer or nylon 12 homopolymer alone or in combination is used. Good formability in the coating process, not only difficult to cause thermal and mechanical damage to the POF, but particularly adhesion to the copolymer containing vinylidene fluoride units forming the outermost layer of the cladding Is preferable because it is more excellent.
[0015]
In particular, nylon 11 homopolymer is superior to nylon 12 homopolymer in terms of low-temperature impact resistance, bending fatigue resistance, tensile elongation at break, low bending elasticity, and other excellent mechanical properties and wear resistance. It has an excellent feature of low permeability. Therefore, when nylon 11 homopolymer is used as the polyamide resin that is the main component of the first polyamide resin composition, it is more flexible and excellent in fatigue resistance than when nylon 12 homopolymer is used. It is possible to obtain a POF cable with little degradation of the pistoning and transmission characteristics in the environment. Further, the coating layer containing the nylon 12 homopolymer may cause crystallization of the nylon 12 homopolymer after formation, and the POF cable may be gradually hardened. However, the melting point of the coating layer is about 10 than that of the nylon 12 homopolymer. When a nylon 11 homopolymer having a high temperature is used, it is preferable because the POF cable is not cured at all at a temperature of about 80 ° C., which is a normal upper limit of POF using PMMA as a core. In addition, since the nylon 11 homopolymer is excellent in bending resistance and abrasion resistance, even when the POF cable is deformed, the mechanical action such as stress applied to the POF and the shrinkage of the POF in a high temperature environment are further improved. It can also be suppressed.
[0016]
Here, the first polyamide-based resin composition includes a black inorganic component such as other polymer, a flame retardant, a colorant, or carbon black for preventing external light from entering the POF as necessary. Additives and compounds such as can also be included.
In order to make the adhesion between the cladding and the primary coating layer more satisfactory, an organic acid or an organic acid anhydride may be added to the first polyamide resin composition. Thereby, the adhesiveness of POF and a coating layer can be improved further. The addition amount of the organic acid or organic acid anhydride is preferably 0.2 to 10% by mass, more preferably 0.5 to 5% by mass with respect to the resin constituting the coating layer. If the addition amount is less than 0.2% by mass, the desired effect tends not to be sufficiently obtained. If the addition amount exceeds 10% by mass, the fluidity of the resin may be reduced, or the smoothness of the POF cable surface may be reduced. is there. Examples of the organic acid and organic acid anhydride used include acrylic acid, methacrylic acid, maleic acid, fumaric acid, salicylic acid, succinic acid, glutaric acid, phthalic acid, and anhydrides thereof. Among them, maleic anhydride is particularly preferable because a high adhesion effect can be obtained with a small addition amount.
[0017]
The thickness of such a primary coating layer is preferably in the range of 5 to 1000 μm, more preferably in the range of 50 to 600 μm. When the thickness of the primary coating layer is less than 5 μm, the adhesion between the POF and the primary coating layer is lowered, and the pullout strength may be insufficient. Moreover, since the cost of the material used for a primary coating layer will become high when the thickness of a primary coating layer exceeds 1000 micrometers, it is unpreferable.
[0018]
[Secondary coating layer]
The secondary coating layer is formed on the outer periphery of the above-mentioned primary coating layer in order to impart durability, environmental resistance characteristics, etc. with the POF cable, and is appropriately peeled off during connection work of the POF cable. In addition, 0.5 to 20 parts by mass of at least one polymer selected from the group consisting of polyolefin-based polymers, fluorine-containing polyolefin-based polymers, and silicone-based polymers with respect to 100 parts by mass of polyamide-based resin. 2 at least an innermost layer formed from the polyamide-based resin composition.
The secondary coating layer may be a single layer or a multilayer as required, but at least the innermost layer (if it is a single layer) of the secondary coating layer in contact with the primary coating layer When formed from such a second polyamide resin composition, it is possible to appropriately control the adhesion between the first polyamide resin composition and the primary coating layer, and the primary coating layer and the secondary coating layer are It does not adhere too much and easily peels off as necessary, and the primary coating layer does not come off with the POF from the secondary coating layer.
[0019]
In the second polyamide resin composition, at least one polymer selected from the group consisting of a polyolefin polymer, a fluorine-containing polyolefin polymer, and a silicone polymer is 0 with respect to 100 parts by mass of the polyamide resin. It is 5-20 mass parts, Preferably it is 1-15 mass parts. Within such a range, the secondary coating layer adheres appropriately to the primary coating layer formed from the first polyamide-based resin composition without excessively sticking. In addition, when any of the above polymers is blended in such a range, the flexibility of the obtained POF cable also becomes moderate, quick recovery when deformed is excellent in form stability, and it is difficult to cause curling habits, Excellent handleability. If the polymer is less than 0.5 parts by mass, the adhesion between the primary coating layer and the secondary coating layer tends to be too strong, while if it exceeds 20 parts by mass, the primary coating layer and the secondary coating layer The adhesiveness tends to be too weak, and the fluidity of the second polyamide-based resin composition is lowered, or the smoothness of the POF cable surface is lowered. By blending in the range of 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polyamide-based resin, the adhesion between the primary coating layer and the secondary coating layer is appropriately controlled, In addition, the flexibility and form stability of the POF cable are excellent.
[0020]
Examples of the polyamide resin contained in the second polyamide resin composition include monomers such as nylon 11, nylon 12, nylon 6, nylon 66, nylon 612, and nylon 621 that are excellent in chemical resistance and heat resistance. A homopolymer composed of units, a copolymer in which these monomer units are combined, a polyamide-based elastomer, and the like are preferable. These polyamide resins may be used alone or in combination of two or more. However, as will be described later, the POF cable having such a secondary coating layer is bent when displaced by 1 mm. The elastic modulus E is preferably in a specific range, and the flexural modulus is easily affected by the type of polyamide resin used in the second polyamide resin composition. Therefore, as the polyamide-based resin, one or more kinds selected from the group consisting of polyamide-based elastomers, polyamide copolymers such as polyamide 612, nylon 11 and nylon 12 are used alone or in an appropriate mixture, and particularly bent. It is preferable to adjust the elastic modulus E. More preferably, nylon 12, nylon 612, or a mixture thereof is used.
[0021]
Examples of the polyolefin polymer contained in the second polyamide resin composition include low density polyethylene, medium density polyethylene, high density polyethylene, polyvinylidene chloride, polypropylene, ethylene / propylene rubber, and ethylene-methyl methacrylate copolymer. Examples include coalescence (manufactured by Sumitomo Chemical Co., Ltd., trade name: ACLIFT), ionomer (manufactured by Mitsui-Deupon Polychemical Co., Ltd., trade name: High Milan) and the like. The mass ratio of these polyolefin-based polymers is in the range of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polyamide-based resin composition. This is preferable because the adhesiveness can be controlled without significant loss. In addition, when a polyolefin polymer obtained by graft polymerization of an organic acid or an organic acid anhydride is used as a polyolefin polymer, the mixing and dispersibility of the polyolefin polymer and polyamide resin is improved, and the impact resistance is excellent. Therefore, it is preferable.
[0022]
Examples of the fluorine-containing polyolefin polymer to be contained in the second polyamide resin composition include polyvinylidene fluoride, vinylidene fluoride and hexafluoroacetone copolymer, vinylidene fluoride and trifluoroethylene copolymer, and vinylidene fluoride. Examples include hexafluoropropylene copolymers. Among these, polyvinylidene fluoride, or vinylidene fluoride and a hexafluoropropylene copolymer are particularly preferable because they have adhesion control and flame retardancy improving effects, and are commercially available. Specifically, KYNAR series (trade name: manufactured by Atofina) is used as polyvinylidene fluoride or a copolymer of vinylidene fluoride and hexafluoropropylene.
[0023]
Examples of silicone polymers include XC99-series, XR39-series (trade name: manufactured by GE Toshiba Silicone), X40-series, X22-series, FRX01 / 02 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.), Si powder ( Trade name: manufactured by Toray Dow Corning).
[0024]
In addition, the second polyamide-based resin composition includes additives such as other polymers, colorants, and black inorganic components such as carbon black for preventing the incidence of external light on the POF, as necessary. Although a compound can be contained, a flame retardant is preferably contained in order to impart flame retardancy to the obtained POF cable.
Examples of the flame retardant include various known metal hydroxides, phosphorus compounds, triazine compounds, and the like. However, since the effect of improving the flame retardancy of the polyamide resin is large, it is preferable to use a triazine compound. Preferably it is 5-30 mass parts with respect to 100 mass parts of type | system | group resin, More preferably, 8-20 mass parts is contained. If the content of the triazine-based compound is less than 5 parts by mass, the effect of improving the flame retardancy may be insufficient, and if it exceeds 30 parts by mass, the flexural modulus of the material constituting the coating layer is excessively increased, There is a risk that handling of the POF cable may be difficult.
As the triazine compound, melamine cyanurate is particularly preferable. For example, melamine cyanurate such as MC-600 (trade name: manufactured by Nissan Chemical Co., Ltd.), MCN-440, MCN-640 (trade name: manufactured by Nissan Chemical Co., Ltd.), etc. And silica-modified cyanuric acid melamine whose surface is modified with silica.
In addition, when adding a colorant or the like to enhance the distinguishability and designability of the POF cable, a known colorant can be used, but the dye-based colorant moves to POF at a high temperature or the like. Since there is a possibility of increasing transmission loss, it is preferable to use an inorganic pigment.
[0025]
[POF cable]
The POF cable in which the primary coating layer and the secondary coating layer are sequentially formed on the outer periphery of the POF has a flexural modulus E in the range of 8 to 18 N / mm when displaced by 1 mm, preferably 10 N / mm or more, 15 N / mm or less. POF cables with a flexural modulus of less than 8 N / mm are slow to recover when deformed, and are difficult to handle due to poor shape stability. POF cables with a flexural modulus exceeding 18 N / mm are less flexible and have curling habits, etc. It becomes easier to stick and handling becomes worse. When it is 8 to 18 N / mm, the resilience when deformed is moderately high, the form is reasonably stable, and it has excellent flexibility and is easy to handle because it does not easily cause curl.
[0026]
The outer diameter of the POF cable is not particularly limited, but a range of 1300 to 3000 μm is preferable. When the outer diameter of the POF cable is less than 1300 μm, the recovery when the POF cable is deformed is slow, the form stability is deteriorated, and the handling property tends to be lowered. On the other hand, when it exceeds 3000 μm, the flexibility is lowered, the curl is easily attached, and the handleability of the POF cable tends to be deteriorated.
In this POF cable, B / A is preferably in the range of 0.3 to 0.7, where B is the cross-sectional area of the secondary coating layer and A is the cross-sectional area of the POF cable. When B / A is less than 0.3, the heat resistance and chemical resistance of the secondary coating layer tend to be insufficient, and when it exceeds 0.7, the cost of the POF cable increases.
[0027]
In addition, in this POF cable, the secondary coating layer can be peeled off relatively easily as necessary when connecting the POF cable, etc., and the primary coating layer can be removed from the secondary coating layer together with the POF at normal times. The pull-out strength between the primary coating layer and the secondary coating layer is in the range of 10-30N, preferably in the range of 15-25N. If the pulling strength between the primary coating layer and the secondary coating layer is less than 10 N, POF may come off together with the primary coating layer from the secondary coating layer, resulting in poor handling. On the other hand, when it exceeds 30 N, the stripping property is deteriorated, and when the secondary coating layer is peeled off in the connection work of the POF cable, the primary coating layer may be stretched and the handling property may be lowered. As already described above, the pull-out strength between the secondary coating layer and the primary coating layer and the above-described flexural modulus E are determined in the secondary coating layer by including the polyolefin-based polymer, 100 mass parts of the polyamide-based resin. It can be appropriately controlled by using a second polyamide resin composition containing 0.5 to 20 parts by mass of one or more polymers selected from the group consisting of fluoropolyolefin polymers and silicone polymers. it can. In addition, the measuring method of the drawing strength in this invention is demonstrated in the below-mentioned Example.
[0028]
Such a POF cable can be manufactured by a known method. For example, a method of sequentially providing a primary coating layer and a secondary coating layer on the POF by extrusion coating using a crosshead type coating apparatus, or a material for forming the primary coating layer and the secondary coating layer is laminated on the material for forming the POF. And composite spinning. Among these, a method of providing a primary coating layer and a secondary coating layer on POF using a crosshead type coating apparatus is preferable. More specifically, a method in which the primary coating layer and the secondary coating layer are collectively coated on POF is preferable because it is easy to manufacture. In addition, the method of coating the primary coating layer on the POF and then coating the secondary coating layer covers not only the adhesion between the POF and the primary coating layer, but also the adhesion between the primary coating layer and the secondary coating layer. It is preferable because the coating can be controlled more precisely according to the conditions of time.
[0029]
In such a POF cable, the primary coating layer formed on the outer periphery thereof is formed from the first polyamide-based resin composition mainly composed of the polyamide-based resin, and the secondary coating formed on the outer periphery of the primary coating layer. The coating layer is 0.5 to 20 parts by mass of at least one polymer selected from the group consisting of polyolefin polymers, fluorine-containing polyolefin polymers, and silicone polymers with respect to 100 parts by mass of the polyamide resin. It has at least an innermost layer formed from the contained second polyamide-based resin composition. Therefore, the secondary coating layer can be easily peeled from the primary coating layer when necessary. In addition, this POF cable has a reasonably high resilience when deformed, is reasonably stable in shape, is flexible, and has excellent handling properties due to its resistance to curling, etc., and chemical resistance Also, flame retardancy is good.
Furthermore, when the outermost layer of the POF clad is formed of a copolymer containing vinylidene fluoride units, the POF and the primary coating layer are more closely adhered to each other, so that pistoning hardly occurs.
[0030]
[POF cable with plug]
A plug-attached POF cable can be obtained by connecting and fixing a plug to at least one end of the POF cable described above. By connecting and fixing the plug in this way, it is possible to easily connect to a light source as a signal source, a housing of a unit incorporated in a detector, another POF cable, or the like. There is no restriction | limiting in particular in the form of a plug, The thing provided with the stopper for fixing a POF cable to this plug main body with the plug main body in which the insertion hole which inserts a POF cable was formed, etc. can be used. Further, the connection between the POF cable and the plug is preferably performed by a method of fixing the plug to a primary coating layer at an end portion to which the plug is connected. That is, it is preferable that the secondary coating layer at the end is removed to expose the primary coating layer, and the plug is directly fixed to the exposed primary coating layer.
As described above, such a POF cable with a plug is easy to peel off from the primary coating layer and the secondary coating layer, so that connection work such as plug installation is easy, and flexibility is also achieved. Since it is excellent, it is easy to lay in a constricted part, and has good chemical resistance and flame retardancy. Further, the POF clad of this POF cable is formed of a copolymer containing at least the outermost layer of vinylidene fluoride units, so that the adhesion between the POF and the primary coating layer is improved, and the pistoning is performed. Is less likely to occur. Therefore, such plug-attached POF cables include optical signal transmission wiring, computer connection wiring for high-speed optical communication, wiring around switchboards, wiring for factory automatic machine control, data transmission wiring for mobile objects such as automobiles, It is suitable for use when connecting to other devices with optical sensor wiring.
[0031]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. The scope of the present invention is not limited to these examples, and it goes without saying that various modifications can be made without departing from the scope of the present invention.
The evaluation and measurement in the examples were performed by the following methods.
(Transmission loss)
The transmission loss (dB / km) was measured by a 25m-5m cutback method. Light having a measurement wavelength of 650 nm and an incident light NA (numerical aperture) of 0.1 was used.
(Flexural modulus)
The POF cable was fixed at two fixing points, and the POF cable was pressed perpendicularly to the central axis using a cable bending tool. The interval between the fixed points was 15 mm. When pressed, the POF cable had an arc shape with a radius of curvature of 5 mm. The stress (N) applied to the cable bending tool when the cable bending tool was displaced by 1 mm from the start of pressing was measured and taken as the bending elastic modulus (N / mm).
[0032]
(Measurement of pull-out strength)
As shown in FIG. 1, the pull-out strength includes a jig 12 that holds the POF cable 10, a chuck 8 that holds a protrusion 14 formed at one end of the jig 12, and a peeling portion 5 of the POF cable 10. It measured using the measuring apparatus 20 provided with the chuck | zipper 7 to perform. The jig 12 is formed with a holding chamber 13 in which the covering portion 4 of the POF cable 10 is accommodated, and a through hole 15 that is larger than the peeling portion 5 of the POF cable 10 and narrower than the covering portion 4.
In the measurement, a POF cable from which the coating layer on one end side was peeled off was prepared and cut so that the length of the coating part 4 of the POF cable was 30 mm. When measuring the pullout strength between the POF and the primary coating layer, when peeling the primary coating layer and the secondary coating layer and measuring the pullout strength between the primary coating layer and the secondary coating layer Only the secondary coating layer was peeled off.
Next, the covering portion 4 of the POF cable was accommodated in the holding chamber 13 formed in the jig 12, and the peeling portion 5 of the POF cable was extracted from the through hole 15. Next, the protrusion 14 formed at one end of the jig 12 was gripped by the chuck 8, and the peeling portion 5 of the POF cable was gripped by the chuck 7.
Next, along the central axis direction of the POF (POF cable) (in the direction of the arrow in the figure), the chuck 8 is moved at a constant speed of 50 mm / min and the jig 12 is pulled, and the peeling portion 5 of the covering portion 4 of the POF cable is pulled. The thicker part was pulled out. From the curve showing the relationship between the pulling stress at this time and the amount of displacement in the pulling direction of the thicker portion of the coating portion 4 of the POF cable in the pulling portion 5, the peak value of the stress at the time of pulling is read and used as a measured value.
[0033]
(Flame retardance)
The flame retardancy test was performed based on the measurement method according to DIN72551-5. In this measurement method, DIN72551-5, which is a flame retardance measurement method for electric wires, is slightly modified as follows in order to measure the flame retardance of an optical fiber cable. In this measurement method, it is necessary to maintain the electric wire during or after combustion at an angle of 45 °. However, unlike an electric wire, an optical fiber cable is difficult to maintain the optical fiber cable at such an angle of 45 ° when the optical fiber 12 burns. Therefore, in order to maintain the optical fiber cable at an angle of 45 ° during or after combustion, a pair of copper wires are spirally wound around the circumference of the optical fiber cable so that the flame retardant properties are wound around each other. taking measurement. A copper wire having a diameter of 0.7 mmφ is used, and the spiral period is 20 mm in the longitudinal direction of the optical fiber cable.
In addition, the judgment criteria for pass / fail of the flame retardant test is that the flame of the burner is applied to the optical fiber cable for 7 seconds to ignite, then the flame is moved away from the sample and the flame disappears within 30 seconds. Will reject it. Twenty samples were evaluated, and when the number of accepted samples was 18 or more, the sample was evaluated as acceptable.
[0034]
(Example 1)
The POF is a POF having a diameter of 1.0 mm, the core material is PMMA, and the first cladding material is 2,2,2-trifluoroethyl methacrylate (3FM) / 2- (perfluorooctyl) ethyl methacrylate (17FM) / methacrylic. A copolymer of methyl acid / methacrylic acid = 51/31/17/1 (parts by mass), and the second cladding material is vinylidene fluoride / tetrafluoroethylene copolymer = 80/20 (mol%) (refractive index 1. The POF comprising the copolymer of 402) was used. The first clad is the innermost layer of the clad and is in contact with the core. The second clad is formed on the outer periphery of the first clad, and here is the outermost layer of the clad.
For the primary coating layer, a polyamide resin composition in which 1 part by mass of maleic anhydride is mixed with 100 parts by mass of nylon 11 “Rilsan (trade name) BMF-0” (manufactured by Atofina) as the first polyamide resin composition. Things were used.
The POF is coated with the above-mentioned polyamide resin composition using a crosshead cable coating apparatus with a crosshead die set at 220 ° C., and the thickness is 250 μm.
A primary coating layer was formed to obtain a POF cable having an outer diameter of 1.5 mm.
On the outer periphery of this POF cable, 5 parts by mass of low-density polyethylene (NUC8008, manufactured by Nihon Unica) with respect to 100 parts by mass of nylon 612 (Daiamide N1901, manufactured by Daicel Huls), 15 parts of melamine cyanurate as a flame retardant ( MC-600, manufactured by Nissan Chemical Co., Ltd.) was coated with a second polyamide resin composition using a crosshead cable coating device to form a secondary coating layer having a thickness of 350 μm and an outer diameter of 2.2 mm. A POF cable having a two-layer coating structure was obtained.
In this POF cable, B / A was 0.54, where B was the cross-sectional area of the secondary coating layer and A was the cross-sectional area of the POF cable.
Various evaluations of the obtained POF cable were performed, and the results are shown in Table 1.
The pull-out strength between the POF and the primary coating layer was 50 N or more, and the adhesion was excellent.
[0035]
[Examples 2 to 11, Comparative Examples 1 to 6]
A POF cable was produced in the same manner as in Example 1 except that the configuration conditions of the POF cable were as shown in Table 1, and the same POF as in Example 1 was used. Various characteristics of the obtained POF cable were evaluated, and the results are shown in Tables 1 and 2. The pull-out strength between the POF and the primary coating layer was 50 N or more, and the adhesion was excellent.
[0036]
[Table 1]

[0037]
[Table 2]

In addition, the symbol in a table | surface shows the following.
PA11: Nylon 11
PA12: Nylon 12
PA612: Nylon 6-12
MCN: Melamine cyanurate
LDPE: Low density polyethylene (trade name: NUC8008, manufactured by Nihon Unicar)
PVdF: polyvinylidene fluoride (trade name: KYNAR710, manufactured by Atofina Japan)
VdF / HFP: Vinylidene fluoride-hexafluoropropylene copolymer
(Trademark name: Free Flow 10, manufactured by Dupont Dow Elastomer Japan)
Si powder (trade name): Silicone flame retardant (Toray Dow Corning)
[0038]
Example 1 in which 5 parts by mass of low-density polyethylene (trade name: NUC8008, manufactured by Nihon Unicar Co., Ltd.) was added to 100 parts by mass of the polyamide-based resin as the second polyamide-based resin composition used for the secondary coating layer. The POF cable of No. 1 and No. 2 has high flame retardancy without lowering flame retardancy, and has a pulling strength (17 to 19 N / mm) between the secondary coating layer and the primary coating layer, and a flexural modulus E (9 to 12N) was controlled within an appropriate range.
Example in which 2 to 10 parts by mass of polyvinylidene fluoride (trade name: KYNAR710, manufactured by Atofina Co., Ltd.) is contained as a second polyamide resin composition used in the secondary coating layer with respect to 100 parts by mass of the polyamide resin. The 3-7 POF cable has excellent flame retardancy, and the pullout strength (13-25 N / mm) and the flexural modulus E (9-14 N) between the secondary coating layer and the primary coating layer are within appropriate ranges. It was controlled.
As a second polyamide resin composition used for the secondary coating layer, a vinylidene fluoride-hexafluoropropylene copolymer (DuPont Dow Elastomer Japan Co., Ltd., trade name) with respect to 100 parts by mass of the polyamide resin. : The POF cable of Examples 8 to 10 containing 2 to 10 parts by weight of Free Flow 10) is excellent in flame retardancy, and the drawing strength between the secondary coating layer and the primary coating layer (12 to 25 N / mm) The flexural modulus E (10 to 11 N) was controlled within an appropriate range.
As a second polyamide resin composition used for the secondary coating layer, 5 parts by mass of a silicone resin (trade name: Si powder manufactured by Toray Dow Corning Co., Ltd.) is contained with respect to 100 parts by mass of the polyamide resin. The POF cable of Example 11 had good flame retardancy, and the pull-out strength between the secondary coating layer and the primary coating layer and the bending elastic modulus E were also controlled within appropriate ranges.
On the other hand, in Comparative Examples 1 to 3, the pull-out strength (33N or more) between the secondary coating layer and the primary coating layer was excessive. In addition, as in Comparative Examples 4 to 6, POF obtained by excessively adding any one of low-density polyethylene, vinylidene fluoride-hexafluoropropylene copolymer, and silicone resin to the polyamide resin used in the secondary coating layer In the cable, the flexural modulus and the pull-out strength between the secondary coating layer and the primary coating layer were all too small, and the flame retardancy was reduced.
[0039]
【The invention's effect】
As described above, in the POF cable of the present invention, the adhesion between the primary coating layer and the secondary coating layer is moderately controlled, the secondary coating layer is easily peeled off, and connection work such as plug attachment is easy. . Moreover, since it is excellent in flexibility, it can be easily laid in a constricted portion, and also has good chemical resistance and flame retardancy. Moreover, when POF is provided with a clad having at least an outermost layer formed from a copolymer containing a vinylidene fluoride unit, the adhesion with the primary coating layer is good, and pistoning hardly occurs. Therefore, such a POF cable and an optical fiber cable with a plug connected to at least one end of this POF cable are optical signal transmission wiring, computer connection wiring for high-speed optical communication, wiring around an exchange, factory It is suitable for use when connecting to other devices, such as wiring for automatic machine control, wiring for data transmission for moving objects such as automobiles, wiring for optical sensors, etc., and particularly suitable for use in wiring in automobiles.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view illustrating a method for measuring the pulling strength in the present invention.

Claims (4)

An optical fiber cable in which a primary coating layer and a secondary coating layer are sequentially provided on the outer periphery of an optical fiber composed of a core and a cladding formed on the outer periphery of the core,
The primary coating layer is formed from a first polyamide resin composition mainly composed of a polyamide resin,
The secondary coating layer is formed by adding at least one polymer selected from the group consisting of a polyolefin-based polymer, a fluorine-containing polyolefin-based polymer, and a silicone-based polymer to 0.5 to 100 parts by mass of a polyamide-based resin. An optical fiber cable comprising at least an innermost layer formed of a second polyamide-based resin composition containing 20 parts by mass.   The optical fiber cable according to claim 1, wherein the optical fiber includes a clad having at least an outermost layer formed of a copolymer including a vinylidene fluoride unit. Claim 1 or at least one end of the optical fiber cable according to any one of 2, the plug-equipped optical fiber cable, characterized in that the plug is connected. 4. The plugged light according to claim 3 , wherein the secondary coating layer is removed at the end of the optical fiber cable to which the plug is connected, and the plug is directly fixed to the primary coating layer. Fiber cable.

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