JPH0990163A - Connected fixed plastic optical fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a connector fixed plastic optical fiber with which the connector fixing force higher than the tensile yield point strength of paired fibers in spite of adhering and fixing a connector to the terminal parts of plastic optical fibers is obtainable and which is usable adequately particularly as a harness information communication medium for automobiles particularly under a high-temp. atmosphere. SOLUTION: The coating material of the resin protective layer part 3 adhered and fixed to the ferrule part 5 of the connector by an adhesive 4 consisting essentially of an epoxy resin of this connector fixed plastic optical fiber is composed of a block copolymer which consists of 30 to 55 pts.wt. component A selected from arom. polyester, polyamide and polyurethane and 70 to 15 pts.wt. component B selected from aliphat. or alicyclic polyether and polyester and has front surface Shore D hardness of 30 to 75.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly reliable connector-bonded plastic optical fiber suitable for use in harsh environments such as automobile harness information and communication media.

[0002]

2. Description of the Related Art Conventionally, optical fibers are made of quartz glass,
Manufactured using multi-component glass or plastic. A silica-based optical fiber has been put to practical use for long-distance communication because of its excellent light transmission performance. On the other hand, plastic optical fibers (hereinafter referred to as POF) are used for short-distance signal transmission and light guides because they are easy to handle and inexpensive.

Polymethylmethacrylate (hereinafter referred to as PMMA) is generally used as the core component of the POF. Since PMMA has excellent transparency and practically has no problem in weather resistance and mechanical properties, it has become the mainstream of the core component material of POF. On the other hand, the sheath component needs to have a lower refractive index than the core component in order to confine light inside the core, and a fluorine-containing polymer is widely used.

This POF is used for protection, especially when it is used for signal transmission, in order to protect it, polyethylene, polypropylene or copolymers or mixtures thereof, olefin polymers containing organic silane groups, ethylene / vinyl acetate copolymers. , A resin such as polyvinyl chloride, chlorinated polyethylene, or polyvinylidene fluoride is used as a cord, and a tension member such as wholly aromatic polyamide fiber "Kevlar" is interposed on the cord. In many cases, it is used as a cable by forming a secondary coating with the same resin as described above.

The connection between the ends of this POF, or
Generally, a unique connector is used to connect the POF end to parts and devices such as a light emitting part and a light receiving part. The connection method between the connector and POF is roughly classified into the following two methods (combination is also possible).

1. A method in which the connector fitted to the POF covering material is caulked and fixed.

[0007] 2. A method in which an adhesive is interposed between the ferrule part of the connector and the POF to fix the adhesive.

In the latter case, the adhesion force (adhesion force) between the POF and the connector ferrule portion (hereinafter simply referred to as a connector) under various environments is the obtained connector adhesion POF.
Greatly affects the reliability of. For example, if the adhesive strength is weak, a phenomenon in which the POF sticks out or retracts from the connector (called "pistoning") occurs, causing problems such as destruction of optical components and a large reduction in the amount of transmitted light. In the extreme case, problems such as peeling off and zero light transmission occur. Therefore, in order to avoid these problems, a two-component mixed epoxy resin adhesive having a glass transition temperature after curing at room temperature or higher is generally used as the adhesive.

[0009] By the way, a general POF containing PMMA as a core component has an insufficient heat resistance, so that the maximum usable temperature is about 8
A POF with a low heat resistance of 5 ° C or less, and therefore excellent in heat resistance, for applications such as automobiles, wiring in electronic devices, and sensors that need to be used in a high temperature atmosphere.
The demand for is increasing in recent years.

As a method for improving the heat resistance of POF, that is, for improving the usable temperature, a method of using a polymer having a high glass transition temperature or a high heat deformation temperature (hereinafter, both are simply referred to as glass transition temperature) as a sheath component, a core A method using a polymer having a high glass transition temperature as a component, a method using a heat-resistant polymer as a coating material, a method using them in combination, and the like have been proposed.

For example, as a sheath component having a high glass transition temperature, an α-fluoroacrylate copolymer (JP-A-59)
-227908), imidized products of fluoroacrylate copolymers (JP-A-61-246703, etc.), and fluorinated polycarbonates (JP-A-1-11220).
No. 7, etc.), cyclic fluoropolymers (JP-A-63-261)
204, 63-302303, JP-A-1-302303
Publications, such as trade name "Teflon AF"), existing ethylene / tetrafluoroethylene copolymer, tetrafluoroethylene / hexapropylene copolymer, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, and When a core component having a high refractive index is used, polymethylmethacrylate, poly-4-methyl-1-pentene, etc. have been proposed.

Further, as the core component having a high glass transition temperature, polycarbonate (JP-A-57-46204, etc.) and modified polycarbonate (JP-A-5-27126) are used.
No. 6-201924, 6-201925, etc.), glutarimide polymer (JP-A-60-18590).
No. 5, etc.), cross-linked acrylic polymer (JP-A-61-3
4503, 61-34504, JP-A-63-2935.
08, etc.), polyorganosiloxane (Japanese Patent Laid-Open Publication No.
1-259202, JP-A-4-188102, JP-A-4-350802, etc.), norbornene (JP-A-4-365003), α-halogenoacrylic acid metal salt copolymer (JP-A-62-109004). Issue),
Methacrylic acid / M having bulky hydrocarbon in the ester part
MA copolymer (JP-A-58-221808, etc.), maleimide / MMA copolymer (JP-A-61-7)
7806, 63-89806, etc.) have been proposed.

Further, as a coating material for the protective layer, polypropylene or a copolymer thereof or a blended product thereof, an olefin polymer containing an organic silane group, and a heat resistant resin such as tetrafluoroethylene / hexafluoropropylene copolymer are used. Used.

The heat-resistant POF is required as an adhesive for fixing the connector, which has excellent heat resistance and has a sufficiently high adhesive force even under the severe environment of use and does not reduce the amount of transmitted light. However, none of the conventional adhesives that have been used for fixing to the connector have sufficient heat resistance, and the connector-fixed POF in which the connector is bonded and fixed using this adhesive is heat-resistant when evaluated in a harsh environment. In addition, the heat cycle resistance is particularly poor, and the reliability is low due to the problems such as the large amount of pistening and the drastic decrease in the amount of transmitted light described above. Therefore, the above requirements cannot be sufficiently satisfied.

Therefore, as an adhesive satisfying the above-mentioned requirements, it was previously proposed that an adhesive containing an epoxy resin as a main component, which has a low glass transition temperature after curing of 0 ° C. or less, is suitable for connector fixing POF. (JP-A-5-20383
6, 224083).

[0016]

However, since the above-mentioned heat-resistant coating materials such as olefin-based polymers and fluoroolefin-based polymers have poor adhesiveness, even if the above-mentioned adhesive containing an epoxy resin as a main component is used. It is difficult to obtain sufficient adhesive strength.

That is, in bonding with this connector, generally, in order to suppress pistening, the POF end portion consisting of the bare fiber portion from which the resin protective layer has been peeled off and the resin protective layer portion where the resin protective layer is present is provided at the connector. When the adhesion between the resin protective layer and the connector is weak, the connector fixing strength is Depends on the adhesive strength between the sheath component surface) and the connector and the tensile yield strength of the bare fiber. Therefore, the connector fixing force is
It was difficult to increase the connector fixing strength to a sufficient level due to the constraints of the adhesive strength between the bare fiber and the connector and the tensile yield strength of the bare fiber.

There are methods such as surface acid treatment, corona discharge treatment, plasma treatment, and primer treatment as methods for improving the adhesive strength with these resin protective layers, but not only the process becomes complicated, but also the POF performance is maintained. It was difficult to improve the adhesive strength as it was. In addition, a method of modifying a polymer by means of containing a carboxyl group such as maleic anhydride (Polymer Chemistry, 25 (274), 432)
(1968)) has also been proposed, but even then, sufficient adhesive strength cannot be obtained, and conversely, the heat aging resistance of the coating material is deteriorated.

As described above, the heat-resistant POF which can be used in a high temperature atmosphere of 100 ° C. or higher is not sufficiently practical because its connector fixing force is still insufficient. Therefore, the main object of the present invention is to When the resin protective layer at the end of the POF and the connector are bonded and fixed,
Even when the terminal resin protective layer part and the bare fiber part are bonded and fixed to the connector, they can be used in a high temperature atmosphere of 100 ° C. or higher, and the tensile yield strength of the bare fiber or higher, especially 10 kgf or higher. Another object of the present invention is to provide a highly reliable connector-fixing POF that can obtain a high connector-fixing force, and particularly to provide a connector-bonding POF that can be used for automobile harnesses and that has good environmental resistance.

[0020]

In order to achieve the above object, the present invention fits and bonds a terminal portion of a POF covered with one or more resin protective layers with a ferrule portion of a connector. In the connector-fixed POF that is fixed, at least the resin protective layer portion and the ferrule portion of the POF end portion are adhesively fixed with an adhesive containing an epoxy resin as a main component, and the adhesively fixed resin protective layer portion is 30 to 85 parts by weight of polyamide, polyurethane, and one or more kinds of A component selected from aromatic polyester obtained from a polymerization raw material containing an aromatic dicarboxylic acid and 1,4-butanediol and a number average molecular weight of 300. ~ 600
A block copolymer having at least one main component of 70 or more parts by weight of B component selected from an aliphatic or alicyclic group of 0, polyether and polyester (provided that component A + component B = 100 parts by weight). And a coating material having a surface Shore D hardness of 30 to 75.

This connector fixed POF is especially 100
Provided is a connector-fixed POF applicable as an automobile harness information communication medium that can be used even under severe conditions such as a high temperature atmosphere of ℃ or more.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The component A of the block copolymer of the coating material constituting the resin protective layer of the present invention is obtained from polyamide, polyurethane, and a polymerization raw material containing an aromatic dicarboxylic acid and 1,4-butanediol. It is one or more polymers selected from aromatic polyesters.

Here, as the aromatic dicarboxylic acid for obtaining one of the aromatic polyesters, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene-
2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, and sodium 3-sulfoneisophthalate may be mentioned. . Among them, terephthalic acid is the most preferable, but even if other aromatic dicarboxylic acid is copolymerized, 1,3
A cycloaliphatic dicarboxylic acid such as cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid, or
A small amount of an aliphatic dicarboxylic acid such as succinic acid, oxalic acid, adipic acid, sebacic acid, glutaric acid, dodecanedioic acid, or dimer acid, or an oxycarboxylic acid such as oxybenzoic acid may be copolymerized. In addition, carboxylic acid derivatives such as dicarboxylic acid lower alkyl ester, dicarboxylic acid lower aryl ester, dicarboxylic acid chloride and carboxylic acid anhydride, which are equivalent to these dicarboxylic acids, are also included.

The diol component for obtaining the aromatic polyester must contain 1,4-butanediol as a main component, and ethylene glycol, 1,
Aliphatic diols such as 3-propanediol, 1,2-propanediol, pentamethylenediol, hexamethylenediol, neopentyl glycol, decamethylene glycol, 1,1-cyclohexanedimethanol,
Alicyclic diols such as 1,4-cyclohexanedimethanol and tricyclodecanedimethanol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p
-Hydroxyphenyl) propane, 2,2-bis (4-
(2-hydroxyethoxy) phenyl) propane, bis (4- (2-hydroxy) phenyl) sulfone, 1,1
Other diols such as aromatic diols such as -bis (4- (2-hydroxyethoxy) phenyl) cyclohexane can also be copolymerized. Further, derivatives such as oxides and carbonates equivalent to these diols are also included.

Other examples of the component A, such as polyamide, include nylon 6, nylon 66, nylon 610, nylon 611, nylon 612, nylon 11, nylon 12, and the like. Among them, nylon 6, nylon 11, nylon 12 is preferred.

Polyurethane, which is another type of the component A, is a diisocyanate component obtained by adding two isocyanate groups to an aromatic compound such as benzene, toluene and diphenylmethane, or another aliphatic or alicyclic diisocyanate component. And a diol component similar to the diol component of the aromatic polyester described above.

The component B of the block copolymer of the coating material constituting the resin protective layer of the present invention has a number average molecular weight of 3
One or more polymers selected from aliphatic or alicyclic polyethers having a number average molecular weight of 300 to 6000, and aliphatic or alicyclic polyethers having a number average molecular weight of 300 to 6000.

The aliphatic or alicyclic polyether in the B component is selected from the same aliphatic or alicyclic diols as described above as the diol component for one aromatic polyester of the A component. The resulting polymer is mentioned, and specifically, poly (ethylene oxide) glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, Examples thereof include ethylene oxide / 1,2-propylene oxide copolymer.

The aliphatic or alicyclic polyester of the component B is an alicyclic dicarboxylic acid such as 1,3-cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid, or succinic acid or oxalic acid. Dicarboxylic acids such as aliphatic dicarboxylic acids such as adipic acid, sebacic acid, glutaric acid, dodecanedioic acid, and dimer acid, and aliphatic or alicyclic diols similar to the diol of the aromatic polyester which is the above-mentioned component A. Any polyester can be used.

The coating material constituting the resin protective layer of the optical fiber of the present invention must be a block copolymer composed of the above-mentioned A component and B component, and the A component is 30
~ 85 parts by weight, B component has a number average molecular weight of 300 to 600
0 and 70 to 15 parts by weight (A component + B component = 1
00 parts by weight).

Furthermore, at least ABA (A component / B component / A component) is more preferable than AB (B component / A component / B component covalent bond) type and BAB (B component / A component / B component covalent bond) type. Covalent bond type) multi-block copolymer, the component A is 45 to 75 parts by weight, and the component B has a number average molecular weight of 500 to 4000 and 5
It is preferably composed of 5 to 25 parts by weight (however, A component + B component = 100 parts by weight). In this preferable range, the compatibility of the two components is good, the two components are in a flexible state within the working temperature range, and they are thermoplastic, so that the processing is easy.

The surface Shore D hardness of the multi-block copolymer of the present invention must be 30-75,
The time is preferably 35 to 65. If it is less than 30, it is too soft and the tensile strength is low. On the other hand, if it exceeds 75, it has poor flexibility and poor handleability as a POF.

This multi-block copolymer has 100
When used in a high temperature such as ℃ or higher, or in a high temperature and high humidity atmosphere, in order to suppress deterioration due to long-term exposure, a heat resistant aging inhibitor and / or a heat resistant water decomposition inhibitor is used. 0.01 to 5 parts by weight is preferable. As the heat deterioration preventing agent, hindered phenol compounds,
Typical examples include arylamine compounds, thioether compounds, and phosphorous acid esters, which may be used in combination or in combination with tin compounds. Furthermore, ultraviolet absorbers, metal deactivators, various reinforcing materials, fillers, pigments,
Dyes, antistatic agents, plasticizers and the like may also be included.

The coating material for the resin protective layer specified in the present invention may be a blend of the above-mentioned block copolymers, and within a small amount range which does not change the gist of the present invention, for example, within 20% by weight. , Other general resins such as polyester resin, polyamide resin, polyurethane resin, polycarbonate resin, polystyrene resin such as ABS resin, polypropylene, polyolefin resin such as polyolefin elastomer, polyvinyl chloride,
A chlorine-containing resin such as polychlorinated polyethylene, a silicone resin, or the like may be copolymerized or blended, or ion-crosslinked or cross-linked with an organic silane for further modification.

As a method for producing the above block copolymer, a known method can be used. For example, a prepolymer obtained by polycondensation or ring-opening polymerization of either the component A or the component B can be used as the other component. Polycondensation with monomers,
It may be polymerized by ring-opening polymerization, or the prepolymer obtained by polycondensation of each of A component and B component and ring-opening polymerization may be linked with a chain extender such as diisocyanate, diol, diamine or hydrazine, You may make it carry out a condensation reaction. In addition, the polymerization catalyst for the polycondensation reaction at that time, and reaction conditions such as temperature, pressure, and time may be those known in the art.

The coating material specified in the present invention needs to be used as a resin protective layer portion which is adhesively fixed to a connector in a POF formed by coating one or a plurality of resin protective layers. The number of resin protective layers to be used may be decided according to the type of connector (inner diameter of the ferrule). For the other resin protective layers, either the coating material of the present invention or a conventional coating material may be used, but it is preferable to use the heat-resistant coating material polymer described above.

Considering the tensile strength particularly when used as a POF for an automobile harness, it is preferable to use a POF having at least two resin protective layers and to bond and fix the secondary protective layer to the connector. It is preferable that the primary protective layer of 1 is composed of a polyolefin-based polymer and / or a halogen-containing polyolefin-based polymer, and the secondary protective layer is composed of the coating material specified in the present invention. When stronger tensile strength is required, it is preferable to interpose a tension member between the primary protective layer and the secondary protective layer. Here, as the polyolefin-based polymer or the halogen-containing polyolefin-based polymer, the heat resistant coating material polymer described above may be used.

The type of POF used in the present invention is not particularly limited, but it is particularly effective in the case of a heat resistant POF that can be used in a high temperature atmosphere of 100 ° C. or higher. A heat-resistant POF that can be used in a high-temperature atmosphere of 100 ° C. or higher is a POF that has a decrease in transmitted light amount of 20% or less (within approximately 1 dB) at a length of 5 m even when left in a high-temperature atmosphere of 100 ° C. for 500 hours. Examples of the POF include a polymer having a high glass transition temperature as the sheath component and / or a polymer having a high glass transition temperature as the core component.

Among them, a heat-resistant POF having a core made of a methylmethacrylate polymer and capable of being used in a high temperature atmosphere of 100 ° C. or higher because of its excellent translucency.
Is preferable, and for example, when severe heat resistance is required, a heat resistant POF having a core of a methyl methacrylate polymer obtained by copolymerizing N-isopropylmaleimide is preferable.

The type of connector used in the present invention is PO
There is no particular limitation as long as it is a system that can be adhesively fixed to the resin protective layer portion of the F terminal portion with an adhesive, and in particular, P
A system in which both the bare fiber portion at the OF terminal and the resin protective layer portion can be bonded and fixed is preferable, and both of metal and resin can be used. For example, a connector having a ferrule with a sectional shape as shown in FIG. 1 can be used.

The bare fiber generally means a POF consisting of a core and a sheath, but the surface of the sheath has a thickness of 20 μm.
It may be a POF having the following thin protective layer formed during the production of an optical fiber (particularly during composite spinning). The thin protective layer is formed of a polymer that can be used as a core component or a sheath component such as a methylmethacrylate-based polymer, polycarbonate, or fluorine-based resin.

The adhesive for adhering the POF end portion and the connector is required to have an epoxy resin as the main component because of its workability, adhesive strength, and the fact that it does not damage the optical fiber. Examples of the epoxy resin include commonly used epoxy resins such as bisphenol A type, bisphenol F type, cycloaliphatic, hydantoin type, novolac type, and glycidyl ester type, and these are used alone or in combination of two or more kinds, or A diluent may be added for use. As a curing agent for the epoxy resin, a polyamine used for a general epoxy resin curing agent such as an aromatic polyamine, an aliphatic polyamine, a dimer acid polyamine, and a trimer acid polyamine, or a general polyamine such as an aromatic polythiol or an aliphatic polythiol. Examples include polythiols, tertiary amines, organic phosphoric acids, acid anhydrides, etc. used for epoxy resin curing agents. These may be used alone or in combination of two or more, or by adding a small amount of a low molecular weight amine / thiol or the like. You can use it.

The adhesive having an epoxy resin as a main component preferably has a glass transition temperature after curing of 0 ° C. or lower, more preferably −20 ° C. or lower, and most preferably the lower limit of use of the plastic optical fiber used. It is below the temperature. The glass transition temperature after curing of the adhesive was 10 using "TMA" (manufactured by Seiko Denshi KK).
It is a value measured under the condition of ° C / min.

The glass transition temperature of this adhesive after curing is set to 0.
The temperature of not higher than 0 ° C can be achieved by mixing and curing the following components with an epoxy resin. Examples include polyoxyalkylenes such as polyoxymethylene, polyoxyethylene, polyoxymethylethylene, and polyoxytrimethylene, rubber polymers such as acrylonitrile / butadiene copolymer rubber, and polydimethylsiloxane. In order to be able to crosslink, it is preferable to have a substituent reactive with the epoxy resin or the curing agent, such as an alkoxysilyl group, an amino group, a thiol group, or a carboxyl group, at these terminals.

The blending amount of the components to be added varies depending on the structure of the epoxy resin, the curing agent such as polyamine / polythiol, etc., but generally it should be at least 15% by weight. Further, in order to keep the temperature at −20 ° C. or lower, it is generally sufficient to contain at least 25% by weight.

These adhesives containing an epoxy resin as a main component, which has a glass transition temperature of 0 ° C. or less after curing, have not only adhesiveness equal to or higher than general epoxy resin adhesives but also the operating temperature of plastic optical fibers. Since it is in the rubber state within the range, the adhesive treatment with the connector can be sufficiently cured without deteriorating the characteristics of the plastic optical fiber, and since the heat cycle resistance is high, it can be used in a high temperature atmosphere of 100 ° C or higher. Even if exposed to such a severe environment, almost no pistening is observed, and there is almost no reduction in the amount of transmitted light, and a highly reliable connector-fixed POF can be obtained.

On the other hand, an epoxy resin type adhesive having a high glass transition temperature is not preferable for the sufficient achievement of the object of the present invention because the performance is drastically deteriorated especially after the heat cycle test.

Further, in addition to the above-mentioned components to be added, a dealcoholization condensation reaction accelerator for alkoxysilane such as an organotin compound, a cross-linking agent such as aminosilane / mercaptosilane / epoxysilane, and a reactive diluent other than the above, A small amount of an organic solvent, an inorganic filler, a pigment, a plasticizer, a stabilizer and the like may be contained.

These are mixed evenly and thoroughly in an appropriate ratio according to the combination so as not to cause spots, and the filling layer between the adherend surfaces is sufficiently filled so that bubbles are not contained as much as possible, and each combination is mixed. The POF end and the connector may be fixed to each other by a method in which the POF end is sufficiently cured at an appropriate temperature and time.

The ferrule part of the connector is fitted to the end of the optical fiber consisting of the bare fiber part where the resin protective layer has been peeled off and the resin protective layer part where the resin protective layer is present, and at least the resin protective layer part and the ferrule part are attached. The method of adhesive fixing may be a usual method. For example, P
The resin coating layer of a fixed length at the end of the OF is stripped off with a dedicated stripper and inserted into the ferrule part. The bare fiber portion from which the resin protective layer has been peeled off is inserted into the small diameter portion at the tip of the ferrule portion, and the tip of the POF projects from the tip of the ferrule portion. The resin protective layer portion where the resin protective layer exists is inserted into the large diameter portion of the ferrule portion. Inject an adhesive between the resin protective layer part and the ferrule part,
Preferably, an adhesive is injected between the bare fiber portion and the ferrule portion and between the resin protective layer portion and the ferrule portion, and heat treatment is performed at a predetermined temperature / time for adhesive fixing.
Then, the ferrule surface and the POF end surface are aligned, and the POF end surface is mirror-finished. When a tension member is interposed between the resin protective layers, the tension member remaining after the resin protective layer is peeled off may be cut off and removed, or in the state of being folded back to the resin protective layer side. Alternatively, it may be inserted into the ferrule part.

In this way, the connector-fixed POF in which the POF end portion and the ferrule portion of the connector are fitted and bonded and fixed has a sectional structure as shown in FIG. 1, for example.

In FIG. 1, 1 is a bare fiber, 2 is a primary protective layer, 3 is a secondary protective layer, 4 is an adhesive, and 5 is a ferrule part.

[0053]

The present invention will be described in more detail with reference to the following examples. The parts used and the evaluation method in the following examples were carried out as follows.

A connector having the following ferrule was used as the connector. A brass ferrule having the cross-sectional shape of FIG. 1 and a structure in which an adhesive can be inserted in two places, a bare fiber portion and a resin coating layer portion, and the size of each portion is a = 3.7 mm. , B = 2.0 mm, C = 1.1 mm, D = 3.2 mm, E = 5.8 mm, F = 12.0 mm (ferrule No. 1), or the size of each part is a = 3 .5m
m, b = 2.0 mm, c = 0.9 mm, d = 2.9 mm, h =
A 5.0 mm and F = 10.0 mm object (ferrule No. 2) was used.

The POF used in each of the examples is 1
It is a heat resistant POF that can be used in a high temperature atmosphere of 00 ° C or more, and has a heat resistance test (100 ° C or 12
Even if it was carried out in an oven at 0 ° C for 500 hours without a connector, there was almost no reduction in the amount of transmitted light.

Heat resistance test of connector-fixed POF: The sample was placed in an oven at a high temperature (100 ° C. or 120 ° C.) for 50 minutes.
After holding it for 0 hours, return it to room temperature and then 660 nm LE
D and an optical power meter (manufactured by Ando Electric Co., Ltd.) were connected, the amount of transmitted light was measured, and the change amount with the amount of transmitted light before the heat resistance test was evaluated (n = 3 average). A negative value represents a decrease in light intensity.

Tensile yield point strength of POF (including cord): Tensilon for drawing elongation-strength curve,
Draw an elongation-strength curve by pulling under the condition of 10 cm / min,
The strength value when the tensile yield point at which the strength reaches its maximum is reached is read, and the tensile strength at the yield point is taken as the average value of n = 10.

Connector fixing strength of connector-fixed POF: A POF having a connector fixed to one end was used as a sample, a tensilon was used, a connector was attached to one end of the POF, and a POF was attached to the other end thereof. Drawing an elongation-strength curve, read the strength value when the tensile yield point at which the strength reaches its maximum is read, and it is shown as the connector adhesion strength, with the average value of n = 10.

POF handleability: Workability when the connector is fixed is relatively evaluated.

Reference Example 1 Dimethyl terephthalate 35
Parts, 39 parts of polytetramethylene oxide having a number average molecular weight of about 2000, and 26 parts of 1,4-butanediol together with 0.02 part of titanium tetrabutoxide catalyst were placed in a reaction vessel equipped with a helical ribbon type stirring blade, and at 210 ° C. The reaction was carried out while heating for 2 hours. At this time, the by-product methanol was discharged out of the system. After 0.2 part of "Irganox 1098" was added to the reaction mixture, the temperature was raised to 245 ° C and the polymerization was further continued for 3 hours while reducing the pressure to 0.2 mmHg.

The resulting block copolymer has a component A /
It was a multi-block copolymer having a component B weight ratio of 50/50 and ABAB or higher, and had a melting point of 197 ° C. and a Shore D hardness of 44.

[Reference Examples 2 to 10] Multiblock copolymers were produced in the same manner as in Reference Example 1 except that the monomer compositions shown in Tables 1 and 2 were changed to the block copolymers shown in Tables 1 and 2.

[0063]

[Table 1]

[0064]

[Table 2]

[Reference Example 11] 100 parts of polyoxymethylene (2% oxyethylene copolymer) in which alkoxysilanes were introduced at both ends with γ-glycidoxypropyltrimethoxysilane, and epoxy made by Asahi Denka Co., Ltd. Resin "E
P4100 "(bisphenol A type diglycidyl ether) 100 parts, Henkel Hakusui Co., Ltd." Versamide "(dimer acid polyamine) 50 parts, Sansha Kisei Co., Ltd. dibutyl tin oxide 3 parts mixed composition Used as an agent, this composition was injected between the POF terminal portion and the ferrule and heat-cured at 80 ° C. for 1 hour to obtain an adhesive having a glass transition temperature of −56 ° C.

[Reference Example 12] 100 parts of epoxy resin "EP4100" (bisphenol A type diglycidyl ether) manufactured by Asahi Denka Co., Ltd., and "Hiker A" manufactured by Ube Industries, Ltd.
A composition (a total of 150 parts) obtained by mixing 100 parts of TBN "(amine-terminated acrylonitrile-butadiene copolymer rubber) and 50 parts of" Versamide "(polyamine dimer acid) manufactured by Henkel Hakusui Co., Ltd. was used as an adhesive. The composition is injected between the end of the POF and the ferrule, 100 ° C
・ Glass transition temperature is -4 by heat curing under the condition of 1 hour.
The adhesive was 0 ° C.

Example 1 As shown in Table 3, the core component was MMA / N-isopropylmaleimide copolymer (copolymerization ratio (% by weight): 70/30), and the sheath component was pentafluoropropyl α-fluoro. Acrylate / methyl α-fluoroacrylate copolymer (copolymerization ratio (% by weight): 8
0/20) The coating material for the primary protective layer is polypropylene (water-crosslinked polypropylene) cross-linked with an organic silane group by heat-moisture treatment, and the core / sheath / primary protective layer obtained by an ordinary method is used. POF (each outer diameter is 0.9
8 / 1.0 / 2.2 mmφ, the tensile yield point strength of bare fiber consisting only of core / sheath is 7.6 kgf), and the polyester block copolymer with Shore D hardness 55 produced in Reference Example 3 is 210 ° C. To form a secondary protective layer while melt-extruding to form an outer diameter of 3.0 mmφ
A POF having two resin coating layers was obtained. This POF
Has a translucency at 650 nm of 230 dB / km and a tensile yield strength of 16.8 kgf at 120 ° C / 50
The change in the amount of transmitted light after 0 hour treatment was -0.1 dB, which was good in heat resistance.

Using the connector of ferrule No. 1 and the adhesive of Reference Example 11, the ferrule parts were fitted and adhered and fixed to both ends of the obtained POF by the method described above.
PO with a shape like
It was set to F. The obtained connector-fixed POF had a high connector-bonding strength of 12.2 kgf, and the change in the amount of transmitted light after treatment at 120 ° C. for 500 hours was −0.4 dB, which was good in heat resistance, and was also excellent in handleability. In addition, even if pulling out beyond the yield point at the time of pulling out, the POF end portion and the connector are still in a fixed state and the resin protective layer is creeping. is there.

[Comparative Examples 1-3, Examples 2-3] Example 1
In the same manner as above, a POF having two resin coating layers having the structure and characteristics shown in Table 3 and a connector-fixed POF were obtained.

Obtained POF and connector-fixed POF
The characteristics of were as shown in Table 3. In Examples 2 and 3, the POF end portion and the connector were in a fixed state even when the drawing was continued beyond the yield point during drawing, and the heat resistance and handleability were good. However, in Comparative Example 1 in which the polypropylene-based elastomer was used for the outer protective layer, the bond failure between the POF terminal part and the ferrule part first occurred at the bonding interface, and the pulling strength of the connector-bonded POF was low. In Comparative Example 2 in which the outer protective layer was a coating material having a BAB type and a large amount of B component and a low Shore hardness, the tensile yield strength of POF was low, and therefore the connector fixing strength (yield strength) was also low. On the contrary, in Comparative Example 3 in which the coating material containing a large amount of A component and high Shore hardness was used for the outer protective layer, the handleability was poor, and the processing temperature had to be increased, so that the POF translucency was deteriorated. .

[0071]

[Table 3]

[Examples 4 to 9] As shown in Table 4, a core component, a sheath component, a primary protective layer and a secondary protective layer were formed, and a tension member (wholly aromatic polyamide fiber "Kevlar") was added. As a structure interposed between the primary protective layer and the secondary protective layer, a POF having two resin coating layers having the characteristics shown in Table 4 was produced in the same manner as in Example 1, and further,
A connector-fixed POF was manufactured in the same manner as in Example 1 using the ferrule No. 2 connector and the adhesives shown in Table 4.

POF consisting of core / sheath / primary protective layer
The outer diameter of each is 0.73 / 0.75 / 1.5 / 2.
The bare fiber having a core / sheath only had a tensile yield strength of 4.2 kgf.

Each of the obtained connector-fixed POFs had good characteristics as in Examples 1 to 3.

[0075]

[Table 4]

[0076]

According to the present invention, even in a connector-fixed POF in which at least the resin protective layer portion at the end of the POF and the connector are adhesively fixed, the resin protective layer and the connector can be strongly adhesively fixed. A strong connector fixing strength (for example, 10 kgf or more) higher than the tensile yield strength of bare fiber can be obtained. Further, it is possible to provide a highly reliable connector-fixed POF that can be sufficiently used even in a high temperature atmosphere of 100 ° C. or higher. As a result, it can be suitably used as a vehicle harness information communication medium, which requires a particularly strong tensile strength at the time of manufacture and use and has a harsh working atmosphere.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an embodiment of a ferrule part fixing portion in a connector fixing POF of the present invention.

[Explanation of symbols]

1: Bare fiber, 2: Primary protective layer, 3: Secondary protective layer, 4: Adhesive, 5: Ferrule part

Claims (14)

[Claims] 1. A connector-bonded plastic optical fiber comprising a plastic optical fiber end coated with one or a plurality of resin protective layers and a ferrule part of a connector fitted and fixed to each other in a connector-attached plastic optical fiber. The resin protective layer portion and the ferrule portion are adhered and fixed by an adhesive containing an epoxy resin as a main component, and the resin protective layer portion adhered and fixed is made of polyamide, polyurethane, and aromatic dicarboxylic acid and 1, 4 3 or more of one or more A components selected from aromatic polyesters obtained from a polymerization raw material containing butanediol.
0 to 85 parts by weight and 70 to 15 parts by weight of an aliphatic or alicyclic B component having a number average molecular weight of 300 to 6000 selected from polyethers and polyesters (provided that A component + B component = 100). (Part by weight) as a main unit, and is a block-copolymer having a surface Shore D hardness of 30 to 75. 2. The connector-fixed plastic according to claim 1, wherein the component A in the block copolymer is an aromatic polyester obtained from a polymerization raw material containing an aromatic dicarboxylic acid and 1,4-butanediol. Optical fiber. 3. The connector-bonded plastic optical fiber according to claim 1, wherein the component A in the block copolymer is polyamide. 4. The connector-bonded plastic optical fiber according to claim 1, wherein the component A in the block copolymer is polyurethane. 5. The resin protective layer portion at the end of the optical fiber and the ferrule portion are adhesively fixed, and the bare fiber portion and the ferrule portion at the end of the optical fiber are also adhesively fixed. Connector fixed plastic optical fiber. 6. The connector-attached plastic optical fiber according to claim 1, wherein the connector-attachment strength between the end portion of the plastic optical fiber and the ferrule portion of the connector is higher than the tensile yield strength of the bare fiber. 7. The plastic optical fiber comprises 100
The connector-bonded plastic optical fiber according to claim 1, which is a heat-resistant plastic optical fiber that can be used in a high temperature atmosphere of ℃ or more. 8. A plastic optical fiber having a core made of a methylmethacrylate-based polymer, and 10
The connector-bonded plastic optical fiber according to claim 7, which is a heat-resistant plastic optical fiber that can be used in a high temperature atmosphere of 0 ° C or higher. 9. The block copolymer comprises at least A
The connector-fixed plastic optical fiber according to claim 1, which is a multi-block copolymer including a BA type block copolymer. 10. A block copolymer comprising 45 to 75 parts by weight of the component A and a number average molecular weight of 500 to 4000.
55 to 25 parts by weight (provided that component A + component B = 100 parts by weight) of at least one B component selected from polyether and polyester, which is aliphatic or alicyclic, and whose surface is The connector-fixed plastic optical fiber according to claim 1, which is a multi-block copolymer having a Shore D hardness of 35 to 65. 11. The resin protective layer comprises a plurality of layers including an inner primary protective layer and an outer secondary protective layer, and the primary protective layer comprises a polyolefin-based polymer and / or a halogen-containing polyolefin-based polymer. And a secondary protective layer adhered and fixed to the ferrule part is selected from polyamide, polyurethane, and aromatic polyester obtained from a polymerization raw material containing aromatic dicarboxylic acid and 1,4-butanediol. 30 to 85 parts by weight of the above component A and 70 to 15 parts by weight of one or more components B selected from aliphatic or alicyclic polyethers and polyesters having a number average molecular weight of 300 to 6000 (where A is Component + B component = 100 parts by weight) as a main unit, and is composed of a coating material having a surface Shore D hardness of 30 to 75. The plastic optical fiber with a fixed connector according to claim 1, wherein 12. The tension member is interposed between the primary protective layer and the secondary protective layer.
1. A plastic optical fiber with a fixed connector. 13. The connector-fixed plastic optical fiber according to claim 1, wherein the adhesive containing an epoxy resin as a main component is an epoxy adhesive having a glass transition temperature after curing of 0 ° C. or lower. 14. The connector-attached plastic optical fiber according to claim 1, which is a connector-attached plastic optical fiber for automobile harness information and communication media.