JP2003270498A - Optical fiber cable and optical fiber cable with plug - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical fiber cable which makes connecting work such as attaching a plug easy, which has excellent flexibility and preferable chemical resistance and flame resistance, and to provide an optical fiber cable with a plug. <P>SOLUTION: The optical fiber cable comprises an optical fiber and a primary coating layer and a secondary coating layer successively applied around the optical fiber. The primary coating layer is made of a first polyamide resin composition essentially comprising a polyamide resin. The secondary coating layer has at least an innermost layer made of a second polyamide resin composition containing a specified amount of a specified polymer. Preferably, the optical fiber has at least an outermost layer made of a copolymer having a vinylidene fluoride unit, and this prevents pistoning. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical fiber cable such as a plastic optical fiber cable, which is preferably used for wiring in an automobile, and an optical fiber cable with a plug.

[0002]

2. Description of the Related Art Conventionally, as an optical fiber, a silica-based optical fiber capable of excellent optical transmission over a wide wavelength range has been known, and it has been widely put to practical use mainly in a trunk system. Optical fibers have the drawback of being expensive and of low workability. Therefore, the end face processing and handling are easy and inexpensive, and the plastic optical fiber has advantages such as light weight and large diameter (hereinafter,
It is called POF. ) Has been developed and is used in the field of lighting, sensors, etc., and in the field of wiring for short / medium distance communication such as FA, OA, LAN, etc. Furthermore, in recent years,
Among middle-range communication applications, especially in the field of in-vehicle communication, the spread of car navigation systems, ITC / E
Demands for increasing the amount of communication information due to the concept of introducing a TC system, reducing the weight of harness cables, and constructing an inexpensive communication system are increasing.
F is expanding into the in-vehicle communication field.

On the other hand, when a POF cable is used for wiring inside a vehicle, the temperature inside the vehicle becomes high in summer.
Since it is used near high temperature bodies such as engines,
The coating material is required to have heat resistance and heat dimensional stability.
Further, since it is used in an environment in which flammable materials such as oil, electrolytic solution and gasoline are present, the coating material is also required to have chemical resistance and flame retardancy.

As a means for imparting heat resistance, chemical resistance, heat resistant dimensional stability and the like to POF cables, a technique using a polyamide polymer such as nylon as a coating material is disclosed in JP-A-7-77642. JP-A-10-3
Polyamide resins such as nylon 11 and nylon 12 are also used in the POF cables for automobiles, which have been proposed in Japanese Patent Application Laid-Open No. 19281, Japanese Patent Application Laid-Open No. 11-242142, etc. and are currently used. In order to further improve the durability and environmental resistance of POF cables,
Techniques for providing a secondary coating layer made of a polyamide-based resin on the outer peripheral portion of the primary coating layer have been proposed in the above-mentioned JP-A-10-319281 and JP-A-11-242142.

The POF cable is used as a POF cable with a plug having a plug attached to the end of the cable 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, it is common to remove the secondary coating layer and fix the plug on the exposed portion of the primary coating layer. Therefore, the secondary coating layer of the POF cable is required to be able to be peeled off relatively easily as required during cable connection work. As a method for appropriately controlling the adhesiveness (pulling strength) between the primary coating layer and the secondary coating layer, a crosshead type coating device is used as disclosed in WO01 / 45826.
A method is known in which an optical fiber is coated with a primary coating layer, and then a secondary coating layer is coated. In this method, the pull-out strength of the primary coating layer and the secondary coating layer can be controlled to a desired value for coating depending on the coating conditions.

[0006]

However, in the techniques of the above-mentioned respective publications, excellent properties such as heat resistance, heat-resistant dimensional stability, chemical resistance, and durability are provided, and a primary coating layer and a secondary coating layer are provided. It is difficult to obtain an optical fiber cable whose adhesion is properly controlled, and it is difficult to manufacture such an optical fiber cable because it is necessary to precisely control the coating conditions and the like. Met.

An object of the present invention is that the primary coating layer and the secondary coating layer are easily separated from each other, so that connection work such as attachment of a plug is easy, and since it is excellent in flexibility, it is laid even in a narrowed portion. Provided are an optical fiber cable and an optical fiber cable with a plug, which are easy to handle and have good chemical resistance and flame retardancy.

[0008]

The optical fiber cable of the present invention is an optical fiber 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 clad formed on the outer periphery of the core. In the fiber cable, the primary coating layer is formed of a first polyamide resin composition containing a polyamide resin as a main component, and the secondary coating layer is a polyolefin based on 100 parts by mass of the polyamide resin. 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 base polymer, a fluorinated polyolefin polymer and a silicone polymer. It is characterized by having at least an inner layer. The optical fiber preferably comprises a clad having at least an outermost layer formed of a copolymer containing vinylidene fluoride units. The pull-out strength between the primary coating layer and the secondary coating layer is 10 to 10.
30 N, and bending elastic modulus E at 1 mm displacement is 8
It is preferably from 18 (N / mm). The polyamide resin, which is the 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 polymethylmethacrylate or a copolymer of one or more vinyl monomers and methylmethacrylate. The outer diameter of the optical fiber is 70
0 to 1200 μm, the outer diameter of the optical fiber cable is 1300 to 3000 μm, the cross-sectional area of the secondary coating layer is B, and the cross-sectional area of the optical fiber cable is A, B / A is 0. It is preferably in the range of 3 to 0.7. The polyamide resin contained in the second polyamide resin composition is a polyamide elastomer,
It is preferably at least one selected from the group consisting of a polyamide copolymer, nylon 11 and nylon 12. The second polyamide resin composition contains the triazine compound 5 based on 100 parts by mass of the polyamide resin.
It is preferable to contain -30 mass parts. The triazine-based 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, the secondary coating layer is removed at the end of the optical fiber cable to which the plug is connected, and the plug is preferably fixed directly to the primary coating layer.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Optical Fiber] An optical fiber used for an optical fiber cable is one in which a clad is 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 enhance the adhesion between the optical fiber and the primary coating layer. The present invention will be described below by taking POF as an example, but the present invention is not limited thereto. As the material forming the core of the POF, known materials can be used, and either polymethylmethacrylate (PMMA) or a copolymer of one or more vinyl monomers and methylmethacrylate. It is preferable to use PMMA, and PMMA is more preferable in terms of translucency, material cost, and durability.

The clad formed on the outer periphery of the core may be a single layer or a multi-layer, and known materials can be used, but at least the outermost layer in contact with the primary coating layer has a vinylidene fluoride unit. Preferably, it is formed from a copolymer containing That is, when the clad is composed of a single layer, it is preferable that this layer is formed of a copolymer containing a vinylidene fluoride unit. When the clad has the outermost layer formed of such a copolymer, not only can the bending resistance, moist heat resistance, and chemical resistance of POF be improved, but
It is preferable because the amount of light that can be taken into the POF can be increased.
Furthermore, when the clad has such an outermost layer and the primary coating layer described later is formed from the first polyamide-based resin composition containing a polyamide-based resin as a main component, the outermost layer of the clad and the primary coating layer are formed. Is preferable because a POF cable having excellent adhesion and having less pisturing can be obtained. Such adhesion is due to the interaction between the C-F bond having high polarity in the vinylidene fluoride unit constituting the clad and the amide bond having high polarity in the polyamide-based resin contained in the primary coating layer. to cause. The adhesiveness can be evaluated using the pull-out strength described below as an index.

The copolymer containing vinylidene fluoride units used as the outermost layer of the clad is, for example, a copolymer of vinylidene fluoride and tetrafluoroethylene,
Vinylidene fluoride and hexafluoroacetone copolymer, vinylidene fluoride and trifluoroethylene copolymer, vinylidene fluoride and hexafluoropropylene copolymer, vinylidene fluoride and tetrafluoroethylene and hexafluoropropylene Examples thereof include copolymers, vinylidene fluoride-tetrafluoroethylene-hexafluoroacetone copolymers, ethylene-tetrafluoroethylene-hexafluoropropylene copolymers, and the like.

The outer diameter of the POF is not particularly limited, but 70
It is preferably in the range of 0 to 1200 μm. POF
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 the reliability of communication. If it is larger than 1200 μm, the cost becomes high, which is not preferable.

[Primary coating layer] The primary coating layer is the above-mentioned P.
It is formed on the outer circumference of the OF and protects the POF, and is mainly composed of a polyamide resin because of its heat resistance, chemical resistance, bending resistance of the POF cable, and dimensional stability (heat shrinkage) of the coating layer. Is formed from the first polyamide resin composition. When the primary coating layer is formed from such a first polyamide-based resin composition, the PO is well adhered to the outermost layer of the above-mentioned clad, and is resistant to pistoning.
In addition to obtaining the F cable, the adhesion between the specific secondary coating layer and the primary coating layer, which will be described later, is appropriately controlled, and only the secondary coating layer can be easily peeled off during connection work, etc. In addition, the primary coating layer does not come off together with the POF from the secondary coating layer.

The main component of the first polyamide resin composition,
That is, as the polyamide resin contained in an amount of 60% by mass or more, preferably 80% by mass or more, for example, nylon 1
0, Nylon 11, Nylon 12, Nylon 6, Nylon 66, Nylon 66, Nylon 6-12, etc. A homopolymer consisting of each monomer unit, a copolymer consisting of a combination of these monomer units, and a flexible segment were introduced. Examples thereof include polyamide elastomers that are copolymers containing nylon monomer units. Since all 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 in that the transmission performance of the POF is not thermally deteriorated when the coating layer is formed. Further, these polyamide resins may be used alone or in combination of two or more kinds, but especially when nylon 11 homopolymer or nylon 12 homopolymer is used alone or in mixture. , The moldability in the coating process is good, and P
It is preferable because not only thermal and mechanical damage to OF is unlikely to occur, but also the adhesion to the copolymer containing vinylidene fluoride units forming the outermost layer of the clad is more excellent.

Particularly, nylon 11 homopolymer is superior to nylon 12 homopolymer in mechanical properties such as low temperature impact resistance, flex fatigue resistance, tensile elongation at break, and low flexural elasticity, abrasion resistance, and linear expansion. It has excellent characteristics of low coefficient and low gas permeability. Therefore, nylon 1 is used as the polyamide resin that is the main component of the first polyamide resin composition.
When using 1 homopolymer, PO is more flexible and has better fatigue resistance than when using nylon 12 homopolymer, and there is less pistening and deterioration of transmission characteristics in a high temperature environment.
F cable can be obtained. Further, the coating layer containing the nylon 12 homopolymer may have a crystallization of the nylon 12 homopolymer after formation and the POF cable may gradually harden, but has a melting point of about 10% higher than that of the nylon 12 homopolymer. It is preferable to use a nylon 11 homopolymer having a high temperature of 0 ° C., since the POF cable does not cure at a temperature of about 80 ° C. which is the usual upper limit of use of POF using PMMA as a core. Further, since the nylon 11 homopolymer is excellent in bending resistance and abrasion resistance, even when the POF cable is deformed, mechanical action such as stress applied to the POF and shrinkage of the POF in a high temperature environment are more improved. It can be suppressed.

Here, the first polyamide resin composition may contain other polymer, a flame retardant, a coloring agent, if necessary.
Additives and compounds such as black inorganic components such as carbon black for preventing external light from entering the POF may be contained. In addition, an organic acid or an organic acid anhydride may be added to the first polyamide resin composition in order to further improve the adhesion between the clad and the primary coating layer. This can further improve the adhesion between the POF and the coating layer. The amount of organic acid or organic acid anhydride added is 0.2 to 1 with respect to the resin constituting the coating layer.
It is preferably 0% by mass, more preferably 0.5
Is about 5% by mass. If the addition amount is less than 0.2% by mass, the desired effect tends not to be sufficiently obtained, and if it exceeds 10% by mass, the fluidity of the resin may be decreased, or the smoothness of the POF cable surface may be decreased. 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 their anhydrides. Among them, maleic anhydride, since a high adhesion effect can be obtained with a small amount of addition,
Particularly preferred.

The thickness of such a primary coating layer is 5-100.
The range of 0 μm is preferable, and the range of 50 to 600 μm is more preferable. When the thickness of the primary coating layer is less than 5 μm, the adhesiveness between the POF and the primary coating layer decreases,
The pull-out strength may be insufficient. Further, when the thickness of the primary coating layer exceeds 1000 μm, the cost of the material used for the primary coating layer increases, which is not preferable.

[Secondary coating layer] The secondary coating layer is for providing the POF cable with durability, environmental resistance and the like.
It is formed on the outer periphery of the above-mentioned primary coating layer and is appropriately peeled off at the time of connection work of a POF cable. And at least an innermost layer formed of a second polyamide resin composition containing 0.5 to 20 parts by mass of at least one polymer selected from the group consisting of silicone polymers. The secondary coating layer may be a single layer or a multilayer if necessary, but at least the innermost layer of the secondary coating layer (in the case of a single layer, the layer) that is in contact with the primary coating layer. When formed from such a second polyamide resin composition, the adhesion between the first polyamide resin composition and the primary coating layer can be appropriately controlled, and the primary coating layer and the secondary coating layer can be separated. It does not adhere excessively and easily peels off if necessary, and furthermore, the primary coating layer does not come off together with the POF from the secondary coating layer.

In the second polyamide resin composition,
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 is 0.5 to 20 parts by mass with respect to 100 parts by mass of the polyamide-based resin, and preferably Is 1 to 1
5 parts by mass. Within such a range, for the primary coating layer formed from the first polyamide resin composition,
The secondary coating layer does not adhere excessively, but adheres appropriately. Further, when any one of the above polymers is blended in such a range, the flexibility of the obtained POF cable becomes appropriate, the recovery when deformed is fast, the morphological stability is excellent, and the curling habit is less likely to occur. Excellent handleability. When the amount of 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 when it exceeds 20 parts by mass, the primary coating layer and the secondary coating layer are The adhesion tends to be too weak, the fluidity of the second polyamide resin composition is reduced, and the smoothness of the surface of the POF cable is reduced. Adhesion between the primary coating layer and the secondary coating layer is appropriately controlled by blending it 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 resin. Moreover, the flexibility and morphological stability of the POF cable are excellent.

The polyamide-based resin contained in the second polyamide-based resin composition includes nylon 11, nylon 12, nylon 6, nylon 66, nylon 612, nylon 621 and the like, which have excellent chemical resistance and heat resistance. A homopolymer composed of monomer units, a copolymer obtained by combining these monomer units, and a polyamide elastomer are preferable. These polyamide-based resins may be used alone or in combination of two or more kinds. However, as will be described later, a POF cable having such a secondary coating layer bends 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, here, a polyamide-based elastomer and a polyamide 612 are used.
Polyamide copolymers such as Nylon 11 and Nylon 12
It is preferable to use one or more selected from the group consisting of the following alone or in an appropriate mixture to adjust the flexural modulus E. More preferably, nylon 12 and nylon 61
2. Use a mixture of these.

As the polyolefin polymer contained in the second polyamide resin composition, for example, low density polyethylene, medium density polyethylene, high density polyethylene,
Examples include polyvinylidene chloride, polypropylene, ethylene / propylene rubber, ethylene-methyl methacrylate copolymer (Sumitomo Chemical Co., Ltd., trade name: Acryft), ionomer (Mitsui Deupon Polychemical Co., trade name: Himilan). You can The mass ratio of these polyolefin polymers is in the range of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polyamide resin composition, but especially 1
When the amount is 5 parts by mass or less, it is possible to control the adhesion without significantly impairing the high heat resistance of the polyamide resin, which is preferable. Further, as the polyolefin-based polymer, when a polyolefin graft-polymerized with an organic acid or an organic acid anhydride is used, the mixing dispersibility of the polyolefin-based polymer and the polyamide-based resin is improved, and the impact resistance is excellent. Therefore, it is preferable.

The fluorine-containing polyolefin polymer to be contained in the second polyamide resin composition is polyvinylidene fluoride, vinylidene fluoride / hexafluoroacetone copolymer, vinylidene fluoride / trifluoroethylene copolymer, fluorine. Examples thereof include vinylidene chloride and a hexafluoropropylene copolymer. Among these, polyvinylidene fluoride or a vinylidene fluoride / hexafluoropropylene copolymer is particularly preferable because it has effects of controlling adhesion and improving flame retardancy, and that a commercial product can be obtained.
Specifically, polyvinylidene fluoride or a copolymer of vinylidene fluoride and hexafluoropropylene is KY.
NAR series (trade name: manufactured by Atofina) is used.

As the silicone polymer, XC99-
Series, XR39-series (product name: GE Toshiba Silicone Co., Ltd.), X40-series, X22-series, FRX01 / 02 (product name: Shin-Etsu Chemical Co., Ltd.), Si
Powder (trade name: manufactured by Toray Dow Corning) and the like can be mentioned.

In the second polyamide resin composition, other polymers, a colorant, and a black inorganic component such as carbon black for preventing external light from entering the POF may be added as necessary. Although additives and compounds can be contained, it is preferable to contain a flame retardant in order to impart flame retardancy to the obtained POF cable. As a flame retardant,
Known metal hydroxides, phosphorus compounds, triazine-based compounds and the like can be mentioned. However, it is preferable to use the triazine-based compound because it has a large effect of improving the flame retardancy of the polyamide-based resin, and 100 parts by mass of the polyamide-based resin. With respect to 5 to 30 parts by mass, more preferably 8 to
20 parts by mass is contained. If the content of the triazine-based compound is less than 5 parts by mass, the flame retardancy-improving effect may be insufficient, and if it exceeds 30 parts by mass, the bending elastic modulus of the material forming the coating layer may be too high, It may be difficult to handle the POF cable. As the triazine-based compound, melamine cyanurate is particularly preferable. For example, melamine cyanurate such as MC-600 (trade name: manufactured by Nissan Kagaku), MCN-440, MCN-640 (trade name: manufactured by Nissan Kagaku), etc. And silica-modified melamine cyanurate whose surface is modified with silica. Further, in the case of adding a coloring agent or the like to improve the distinguishability and design of the POF cable, a known coloring agent can be used. However, the dye-based coloring agent migrates to the POF at high temperature. It is preferable to use an inorganic pigment because it may increase transmission loss.

[POF Cable] A POF cable in which the above-mentioned primary coating layer and secondary coating layer are sequentially formed on the outer circumference of the POF has a bending elastic modulus E of 8 to 18 N / m when displaced by 1 mm.
m range, preferably 10 N / mm 2 or more, 15
N / mm or less. A POF cable with a flexural modulus of less than 8 N / mm is slow to recover when deformed, and has poor morphological stability, making it difficult to handle.
The OF cable has poor flexibility, is prone to curl, and is poor in handleability. When it is 8 to 18 N / mm, the recovery force when deformed is moderately high, the form is moderately stable, and the flexibility is high and the curling habit is less likely to occur, resulting in excellent handleability.

The outer diameter of the POF cable is not particularly limited, but is preferably in the range of 1300 to 3000 μm.
If the outer diameter of the POF cable is less than 1300 μm, P
When the OF cable is deformed, the recovery is slow, the shape stability is deteriorated, and the handleability tends to be deteriorated. On the other hand, 300
If it exceeds 0 μm, the flexibility tends to decrease, curling tends to occur, and the POF cable tends to have poor handleability. Further, in this POF cable, when the cross-sectional area of the secondary coating layer is B and the cross-sectional area of the POF cable is A, B / A is preferably in the range of 0.3 to 0.7. 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.

Further, in this POF cable, the secondary coating layer can be relatively easily peeled off as required when connecting the POF cable, and the primary coating layer is normally removed from the secondary coating layer together with the POF in normal times. The pull-out strength between the primary coating layer and the secondary coating layer is in the range of 10 to 30 N, preferably 15 to 2
It is in the range of 5N. If the pull-out strength between the primary coating layer and the secondary coating layer is less than 10 N, the POF may come off together with the primary coating layer from the secondary coating layer, resulting in poor handleability. On the other hand, if it exceeds 30 N, the stripping property is deteriorated, and the primary coating layer may be stretched when the secondary coating layer is peeled off during the connection work of the POF cable, and the handleability may be deteriorated. As described above, the pull-out strength between the secondary coating layer and the primary coating layer and the above-mentioned flexural modulus E are such that the secondary coating layer contains 100 parts by mass of the polyamide resin and the polyolefin-based polymer. Appropriate control can be achieved 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. The method for measuring the pull-out strength in the present invention will be described in Examples below.

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 device, or laminating a material forming the primary coating layer and the secondary coating layer on a material forming the POF. And a method of performing composite spinning. Among these, a method of providing a primary coating layer and a secondary coating layer on the POF using a crosshead type coating device is preferable. More specifically, P
The method of collectively coating the OF with the primary coating layer and the secondary coating layer is preferable because it is easy to manufacture. In addition, the method of coating the POF with the primary coating layer and then the secondary coating layer is not limited to the adhesion between the POF and the primary coating layer, and the adhesion between the primary coating layer and the secondary coating layer. It is preferable because the coating can be more precisely controlled and coated depending on the conditions of time.

In such a POF cable, the primary coating layer formed on the outer periphery of the POF cable is formed of the first polyamide resin composition containing a polyamide resin as a main component, and is formed on the outer periphery of the primary coating layer. The secondary coating layer contains 0.5 to 0.5 parts by weight of 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, based on 100 parts by mass of the polyamide-based resin. It has at least the innermost layer formed from the second polyamide resin composition containing 20 parts by mass. Therefore, the secondary coating layer can be easily peeled off from the primary coating layer when necessary. In addition, this POF cable has moderately high recovery power when deformed, its shape is moderately stable, and it has excellent flexibility and is easy to handle because it does not tend to curl easily. The flame retardancy is also good. Further, when the outermost layer of the POF clad is formed of a copolymer containing a vinylidene fluoride unit, the POF and the primary coating layer are more strongly adhered to each other, and the pistoning is less likely to occur.

[POF cable with plug] P mentioned above
A POF cable with a plug can be obtained by connecting and fixing a plug to at least one end of the OF cable. By connecting and fixing the plug in this manner, the plug can be easily connected to a light source that is a signal source, a housing of a unit incorporated in the detector, another POF cable, or the like. There is no particular limitation on the form of the plug, P
A plug body having an insertion hole for inserting the OF cable and a stopper for fixing the POF cable to the plug body can be used. Also, POF
The connection between the cable and the plug is preferably performed by a method of fixing the plug to the primary coating layer of the end portion connecting the plug. That is, it is preferable to remove the secondary coating layer at the end to expose the primary coating layer and fix the plug directly to the exposed primary coating layer. Such a POF cable with a plug is a POF cable, as described above, since the primary coating layer and the secondary coating layer are easily separated from each other, connection work such as attachment of the plug is easy, and flexibility is high. Since it is excellent, it can be easily laid even in narrowed areas, and it has good chemical resistance and flame retardancy. Further, by making the POF clad of this POF cable at least the outermost layer thereof from a copolymer containing a vinylidene fluoride unit, the adhesion between the POF and the primary coating layer becomes better, and the pistening Is less likely to occur. Therefore, such POF with a plug
The cables are optical signal transmission wiring, computer connection wiring for high-speed optical communication, wiring around switches, factory automatic machine control wiring, data transmission wiring for mobiles such as automobiles,
It is suitable for use when connecting to other devices such as optical sensor wiring.

[0031]

The present invention will be described in more detail with reference to the following 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 carried out by the following methods. (Transmission loss) Transmission loss (dB / km) was measured by the 25m-5m cutback method. The measurement wavelength is 650 nm,
Light having an NA (numerical aperture) of incident light 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 center axis using a cable bending tool. The fixed point interval 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 defined as the bending elastic modulus (N / mm).

(Measurement of drawing strength) The drawing strength is
As shown in FIG. 1, 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 chuck 7 that holds a peeled portion 5 of the POF cable 10. It measured using the measuring device 20 provided with. The jig 12 has a holding chamber 13 in which the covering portion 4 of the POF cable 10 is accommodated, and a through hole 15 which is larger than the peeling portion 5 of the POF cable 10 and narrower than the covering portion 4.
Are formed. For the measurement, a POF cable with the coating layer on one end side peeled off was prepared and cut so that the length of the coating portion 4 of the POF cable was 30 mm. When measuring the pull-out strength between the POF and the primary coating layer, when peeling off the primary coating layer and the secondary coating layer and measuring the pull-out strength between the primary coating layer and the secondary coating layer, Then, only the secondary coating layer was peeled off. Next, in the holding chamber 13 formed in the jig 12, the covering portion 4 of the POF cable is
And the peeled portion 5 of the POF cable was pulled out from the through hole 15. Next, the protrusion 14 formed at one end of the jig 12 was held by the chuck 8, and the peeled portion 5 of the POF cable was held by the chuck 7. Next, POF (PO
Along the central axis direction of the F cable) (the direction of the arrow in the figure),
The jig 12 was pulled by moving the chuck 8 at a constant speed of 50 mm / min, and the portion thicker than the peeled portion 5 in the covered portion 4 of the POF cable was pulled out. From the curve showing the relationship between the pull-out stress at this time and the amount of deviation in the pulling direction of the portion thicker than the peeled portion 5 in the covered portion 4 of the POF cable, the peak value of the pulling stress was read and used as the measured value.

(Flame Retardancy) The flame retardancy test is DIN 7255.
1-5 based on the measuring method. This measurement method is DIN 7255 which is a flame retardancy measurement method for electric wires.
1-5 is slightly modified as follows in order to measure the flame retardancy of the optical fiber cable. In this measuring method, it is necessary to maintain the electric wire at an angle of 45 ° during or after combustion. However, unlike an electric wire, an optical fiber cable is difficult to maintain such an oblique 45 ° when the optical fiber 12 burns. Therefore, in order to maintain the optical fiber cable at an angle of 45 ° at the time of burning or after burning, a pair of copper wires are spirally wound around the circumference of the optical fiber cable so as to be flame-retardant. taking measurement. A copper wire having a diameter of 0.7 mmφ is used, and the spiral cycle is 20 mm in the longitudinal direction of the optical fiber cable. In addition, the acceptance criteria for the flame retardancy 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 is extinguished within 30 seconds is regarded as a pass.
Those that have not disappeared are rejected. Twenty samples were evaluated, and when the number of passed samples was 18 or more, it was regarded as acceptable, and when the number was 20 or less, it was regarded as unacceptable.

(Example 1) As POF, diameter 1.0 mm
Of the POF, the core material is PMMA, and the first cladding material is 2,2,2-trifluoroethylmethacrylate (3
FM) / 2- (perfluorooctyl) ethyl methacrylate (17FM) / methyl methacrylate / methacrylic acid = 51/31/17/1 (parts by mass) copolymer, second
A POF was used in which the clad material was a vinylidene fluoride / tetrafluoroethylene copolymer = 80/20 (mol%) (refractive index 1.402) copolymer. 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 this is the outermost layer of the clad here. The primary coating layer contains nylon 1 as the first polyamide resin composition.
A polyamide resin composition was used in which 1 part by mass of maleic anhydride was mixed with 100 parts by mass of 1 "Rilsan (trademark) BMF-0" (manufactured by Atofina). 22 in POF
A crosshead die set to 0 ° C. was used to coat the above polyamide resin composition with a crosshead cable coating device to form a primary coating layer having a thickness of 250 μm. Obtained. Nylon 612 (Dyamide N19
01, made by Daicel Huls) Low density polyethylene (NUC8008, made by Nippon Unica) for 100 parts by mass
A second polyamide resin composition containing 5 parts by mass and 15 parts of melamine cyanurate (MC-600, manufactured by Nissan Kagaku Co., Ltd.) as a flame retardant was coated using a crosshead cable coating device to a thickness of 350 μm. A secondary coating layer was formed to obtain a POF cable having a two-layer coating structure with an outer diameter of 2.2 mm. In this POF cable, when the cross-sectional area of the secondary coating layer is B and the cross-sectional area of the POF cable is A,
B / A was 0.54. Various evaluations were performed on the obtained POF cables, 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.

[Examples 2 to 11, Comparative Examples 1 to 6] POF
Except that the cable configuration conditions are as shown in Table 1,
A POF cable was produced in the same manner as in Example 1, except that the same POF as in Example 1 was used. Various properties 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] The abbreviations in the table indicate the following. PA11: Nylon 11 PA12: Nylon 12 PA612: Nylon 6-12 MCN: Melamine cyanurate LDPE: Low density polyethylene (trade name: NUC800
8, manufactured by Nippon Unicar Co., Ltd. PVdF: polyvinylidene fluoride (trade name: KYNAR)
710, manufactured by Atofina Japan Ltd.) VdF / HFP: vinylidene fluoride-hexafluoropropylene copolymer (trade name: Free Flow10, Deupon Dow.
Elastomer Japan) Si powder (trade name): Silicone flame retardant (Toray Dow Corning)

As the second polyamide resin composition used for the secondary coating layer, low density polyethylene (manufactured by Nippon Unicar, trade name:
Examples 1 and 2 containing 5 parts by mass of NUC8008)
The POF cable of No. 1 has high flame retardancy without lowering the flame retardancy, and has a pull-out strength (17 to 19 N / mm) between the secondary coating layer and the primary coating layer and a bending elastic modulus E (9).
.About.12 N) was controlled in an appropriate range. As the second polyamide-based resin composition used for the secondary coating layer, 2 parts of polyvinylidene fluoride (trade name: KYNAR710, manufactured by Atofina) is added to 100 parts by weight of the polyamide-based resin.
The POF cables of Examples 3 to 7 containing 10 to 10 parts by mass have excellent flame retardancy, pull-out strength (13 to 25 N / mm) between the secondary coating layer and the primary coating layer, and a bending elastic modulus E ( 9
.About.14 N) was controlled in an appropriate range. As the second polyamide-based resin composition used for the secondary coating layer, a copolymer of vinylidene fluoride-hexafluoropropylene (made by DuPont Dow Elastomers Japan, trade name, based on 100 parts by mass of the polyamide-based resin). : Free F
Examples 8 to 1 containing 2 to 10 parts by mass of low 10).
The POF cable of No. 0 has excellent flame retardancy and has a pull-out strength (12 to 25 N / m) between the secondary coating layer and the primary coating layer.
m) and the flexural modulus E (10 to 11 N) were controlled in an appropriate range. As the second polyamide-based resin composition used for the secondary coating layer, a silicone-based resin (manufactured by Toray Dow Corning,
Example 1 containing 5 parts by mass of trade name: Si powder)
The POF cable of No. 1 had good flame retardancy, and the pull-out strength between the secondary coating layer and the primary coating layer and the flexural modulus E were also controlled within appropriate ranges. On the other hand, in Comparative Examples 1 to 3, the pull-out strength (33 N or more) between the secondary coating layer and the primary coating layer was excessive. Further, as in Comparative Examples 4 to 6, POF in which any one of low-density polyethylene, vinylidene fluoride-hexafluoropropylene copolymer, and silicone resin is excessively added to the polyamide resin used for the secondary coating layer. The cable is too small in flexural modulus and pull-out strength between the secondary coating layer and the primary coating layer, and
A decrease in flame retardance was observed.

[0039]

As described above, in the POF cable of the present invention, the adhesion between the primary coating layer and the secondary coating layer is appropriately controlled, the secondary coating layer is easily peeled off, and the connection such as plug attachment is made. Easy to work. Further, since it is excellent in flexibility, it can be easily laid even in a narrowed portion, and further has good chemical resistance and flame retardancy. Further, when the POF is provided with the clad having at least the outermost layer formed of the copolymer containing vinylidene fluoride units, the adhesion with the primary coating layer is good and pisting is unlikely to occur. Therefore, such a POF cable and an optical fiber cable with a plug in which a plug is connected to at least one end of the POF cable is used for optical signal transmission wiring, computer connection wiring for high-speed optical communication, wiring around a switchboard, factory. Wiring for automatic machine control, data transmission wiring for vehicles such as automobiles,
It is suitable for use when connecting to other devices such as optical sensor wiring, and is especially suitable for wiring inside automobiles.

[Brief description of drawings]

FIG. 1 is a cross-sectional view illustrating a method for measuring pull-out strength according to the present invention.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroe Kubo             Mitsubishi Rayon, 3 Kaigan Dori, Toyama City, Toyama Prefecture             Toyama Office Co., Ltd. (72) Inventor Kazumi Nakamura             1-6-41 Konan, Minato-ku, Tokyo Mitsubishi Ray             Within Yong Co., Ltd. F term (reference) 2H001 FF07                 2H050 BA34 BB03Q BB03S BB15S                       BB35Q BB35S BC03

Claims (11)

[Claims] 1. 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 clad formed on the outer periphery of the core, wherein the primary coating layer comprises: The second coating layer is formed from a first polyamide-based resin composition containing a polyamide-based resin as a main component, and the secondary coating layer is based on 100 parts by weight of the polyamide-based resin, a polyolefin-based polymer, a fluorine-containing polyolefin-based polymer, and a silicone. An optical fiber cable having at least an innermost layer formed of a second polyamide resin composition containing 0.5 to 20 parts by mass of at least one polymer selected from the group consisting of polymer series. . 2. The fiber optic cable of claim 1, wherein the optical fiber comprises a cladding having at least an outermost layer formed of a copolymer containing vinylidene fluoride units. 3. The pull-out strength between the primary coating layer and the secondary coating layer is 10 to 30 N, and the bending elastic modulus E when displaced by 1 mm is 8 to 18 (N / mm). The optical fiber cable according to claim 1 or 2. 4. The polyamide-based resin, which is a main component of the first polyamide-based resin composition, is a nylon 11 homopolymer and / or a nylon 12 homopolymer. The optical fiber cable according to any one of 1. 5. The optical fiber according to claim 2, wherein the core is formed of polymethylmethacrylate or a copolymer of one or more vinyl monomers and methylmethacrylate. cable. 6. The outer diameter of the optical fiber is 700 to 120.
0 μm, the outer diameter of the optical fiber cable is 1300 to
When the cross-sectional area of the secondary coating layer is B and the cross-sectional area of the optical fiber cable is A, B / A is 0.3 to 0.7.
The optical fiber cable according to any one of claims 1 to 5, characterized in that 7. The polyamide-based resin contained in the second polyamide-based resin composition is a polyamide-based elastomer, a polyamide copolymer, nylon 11, nylon 1
7. The optical fiber cable according to claim 1, which is at least one selected from the group consisting of 2. 8. The second polyamide resin composition,
The optical fiber cable according to any one of claims 1 to 7, further comprising 5 to 30 parts by mass of a triazine compound with respect to 100 parts by mass of the polyamide resin. 9. The optical fiber cable according to claim 8, wherein the triazine-based compound is melamine cyanurate and / or silica-modified melamine cyanurate. 10. An optical fiber cable with a plug, wherein a plug is connected to at least one end of the optical fiber cable according to any one of claims 1 to 9. 11. The method according to claim 10, 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 fixed directly to the primary coating layer. Optical fiber cable with the described plug.