JPH1031119A - Core/clad type optical resin material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin material with low transmission loss by forming a clad of a fluorine-contg. polymer having lower refractive index by a specified degree than that of the polymer material which constitutes the core. SOLUTION: The core is composed of a fluorine-contg. polymer comprising only a polymer unit having a fluorine-contg. alicyclic structure, while the clad is composed of a fluorine-contg. polymer having lower refractive index by at least 0.001 than the refractive index of the polymer which constitutes the core. Otherwise, the core is composed of a fluorine-contg. polymer which is composed of only a polymer unit having a fluorine-contg. alicyclic structure and contains chlorine atoms or deuterium atoms. The clad is composed of a fluorine-contg. polymer having lower refractive index by at least 0.001 than that of the polymer which constitutes the core. Otherwise, the core is composed of a fluorine-contg. polymer which is composed of only a polymer unit having a fluorine-contg. alicyclic structure produced by cyclization polymn. and contains chlorine atoms or deuterium atoms. The clad is composed of a fluorine-contg. polymer having lower refractive index by at least 0.001 than that of the polymer which constitutes the core.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a core / clad optical resin material having high transparency and heat resistance, which has been difficult to realize with conventional optical resin materials.

[0002] The optical resin material of the present invention may itself be a light transmitting body such as an optical fiber, or may be a base material of a light transmitting body such as a preform of an optical fiber.

[0003] The optical transmission material which is the optical resin material of the present invention comprises:
Because it is amorphous, there is no light scattering, and since it has very high transparency in a wide wavelength band from ultraviolet light to near infrared light,
It can be effectively used for optical systems of various wavelengths. In particular, the present invention provides an optical transmitter having a low loss at 1300 nm and 1550 nm, which are wavelengths used for a main silica fiber in the optical communication field.

[0004] Further, the optical transmission material which is the optical resin material of the present invention has heat resistance and chemical resistance required under severe use conditions such as in an engine room of an automobile, office automation (OA) equipment and home electric appliances. It has resistance, moisture resistance, and nonflammability.

[0005] The optical transmission material which is the optical resin material of the present invention comprises:
Optical fiber, rod lens, optical waveguide, optical splitter, optical multiplexer, optical demultiplexer, optical attenuator, optical switch, optical isolator, optical transmission module, optical reception module, coupler,
It is useful as a wide variety of optical transmitters such as deflectors and optical integrated circuits.

When the optical resin material of the present invention is a base material of an optical transmission body, the optical transmission medium such as an optical fiber can be manufactured by spinning the base material by heat drawing or the like.

[0007]

2. Description of the Related Art Many of conventionally known plastic optical fibers use an optical resin such as a methyl methacrylate resin, a styrene resin, a carbonate resin, a norbornene resin for a core, and a cladding made of a fluoropolymer. However, these have a large absorption loss for light having a wavelength of near-infrared light of 650 nm or more, and in particular, have a drawback that a 1.3 μm or 1.5 μm light source used for communication cannot be used.

In order to solve this problem, a proposal has been made to use a fluorine-containing polymer having a CF bond instead of a CH bond in which vibration absorption occurs in near-infrared light as an optical transmitter (Japanese Patent Laid-Open No. 2-2440).
07, JP-A-4-1704). However, the former has a high glass transition temperature and excellent heat resistance, but because it is a copolymer with an ethylenically unsaturated monomer, loss due to light scattering occurs due to crystallinity and inhomogeneous composition, resulting in transmission loss. Is not small enough. For the latter, a cyclized polymer of perfluoro (butenyl vinyl ether) is used, but heat resistance is not always sufficient.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide an optical resin material having a low transmission loss, which cannot be achieved by a conventional fluoropolymer.

[0010]

The present invention provides the following optical resin materials (1) to (3) based on recognition of the above problems.

(1) The core is made of a fluoropolymer substantially consisting only of polymerized units having a fluorinated aliphatic ring structure, and the cladding has a refractive index smaller than that of the polymer constituting the core by at least 0.001. Core / cladding type optical resin material composed of fluoropolymer.

(2) The core is substantially composed of only a polymerized unit having a fluorinated aliphatic ring structure and is composed of a fluorinated polymer containing a chlorine atom or a deuterium atom, and the clad is composed of the polymer constituting the core. Also have a refractive index of at least 0.1.
001 Core / cladding type optical resin material made of small fluoropolymer.

(3) The core is substantially composed of only a polymerized unit having a fluorinated aliphatic ring structure formed by cyclopolymerization and is composed of a fluorinated polymer containing a chlorine atom or a deuterium atom, and the clad is formed of a core. A core / cladding type optical resin material comprising a fluoropolymer having a refractive index at least 0.001 smaller than the above-mentioned polymer.

Although it is not clear why the copolymer has a large light scattering loss, in general, in the case of a copolymer, monomers having different structures are copolymerized in order to modify the properties of the homopolymer. Often. In this case, the polymer obtained by polymerization has a composition distribution because the reactivity differs among the monomers. Therefore, it is considered that there is optical non-uniformity between copolymer molecules having different compositions, which causes light scattering and causes transmission loss. Therefore, in the present invention, a polymer having no such non-uniform composition is employed as the optical resin material.

[0015] The core part in the present invention has the above (1) to
As shown in (3), it is made of the following specific fluoropolymer. Further, as described later, it is preferable that the fluoropolymer in the clad portion is also selected from the following fluoropolymers except for the difference in the refractive index. However, the fluoropolymer of the clad part in the above (1) does not need to be the same or similar to the fluoropolymer of the core part of the (1), and (2) to (3) And the same or similar fluorinated polymer as the fluorinated polymer in the core portion. The same applies to the fluoropolymer of the clad part in the above (2) and (3).

Fluorine-containing polymer in (1): Fluorine-containing polymer consisting essentially of polymerized units having a fluorinated aliphatic ring structure (hereinafter referred to as polymer A). This polymer A is a homopolymer obtained by polymerizing a monomer having a fluorinated aliphatic ring structure, or a copolymer obtained by polymerizing two or more monomers having a fluorinated aliphatic ring structure. The polymer is a polymer having substantially no polymerized units formed by polymerization of a monomer having no fluorinated aliphatic ring structure. Preferably, it is a homopolymer or a copolymer of two or more monomers having a fluorinated aliphatic ring structure having similar polymerization reactivity. As the monomer having a fluorine-containing aliphatic ring structure having similar polymerization reactivity, a monomer having the same structure except for the presence or absence of a substituent bonded to the ring and the difference in the type of the substituent is preferable.

The fluorine-containing polymer in (2): a fluorine-containing polymer consisting essentially of polymerized units having a fluorine-containing aliphatic ring structure and containing a chlorine atom or a deuterium atom (hereinafter referred to as polymer B). The polymer b may be a homopolymer obtained by polymerizing a monomer having a fluorinated aliphatic ring structure, or a copolymer obtained by polymerizing two or more monomers having a fluorinated aliphatic ring structure. The polymer is a polymer having substantially no polymerized units formed by polymerization of a monomer having no fluorinated aliphatic ring structure. In addition, the polymer B contains a chlorine atom or a deuterium atom (or may contain both), and the polymer B containing a chlorine atom or a deuterium atom is the polymer B containing the chlorine atom or the deuterium atom. It can be obtained by polymerization or by introducing a chlorine atom or a deuterium atom into the polymer after forming the polymer. The polymer B may be a copolymer of the above monomer containing a chlorine atom or a deuterium atom and a monomer not containing them.

Preferably, a monomer 2 having a fluorinated aliphatic ring structure which is a homopolymer or has a similar polymerization reactivity
Or more copolymers. As monomers having a fluorine-containing aliphatic ring structure having similar polymerization reactivity, the presence or absence of a substituent bonded to the ring and the difference in the type of the substituent (especially the presence or absence of a chlorine atom or a deuterium atom and their differences) Are preferably monomers having the same structure.

The fluorine-containing polymer in (3): a fluorine-containing polymer consisting essentially of polymerized units having a fluorine-containing alicyclic structure formed by cyclopolymerization and containing a chlorine atom or a deuterium atom (hereinafter referred to as a fluorine-containing polymer) , Polymer c). Polymer C is a homopolymer obtained by cyclopolymerizing a monomer having no fluorinated aliphatic ring structure and capable of cyclopolymerization, or a polymer obtained by polymerizing two or more monomers capable of cyclopolymerization. Or a copolymer of a monomer capable of cyclopolymerization and a monomer having a fluorinated aliphatic ring structure as described above.
Moreover, the polymer C contains a chlorine atom or a deuterium atom (or may contain both atoms), and the polymer C containing a chlorine atom or a deuterium atom is the above-mentioned monomer containing a chlorine atom or a deuterium atom. It is obtained by polymerization or by introducing a chlorine atom or a deuterium atom into the polymer after forming the polymer. The polymer C may be a copolymer of the above monomer containing a chlorine atom or a deuterium atom and a monomer not containing them.

Preferably, it is a homopolymer or a copolymer of two or more cyclizable monomers having similar polymerization reactivity. Cyclically polymerizable monomers having similar polymerization reactivity include those having the same structure except for the presence or absence of a substituent and the difference in the type of substituent (particularly, the presence or absence of a chlorine atom or a deuterium atom, and the difference). Mers are preferred.

The monomer having a fluorinated aliphatic ring structure is a monomer having a polymerizable double bond in the fluorinated aliphatic ring structure (for example, monomers (1) and (2) described later). Or a monomer in which one carbon atom constituting the aliphatic ring is a carbon atom of a polymerizable double bond (for example, monomer (3) described later). Therefore, the main chain of the polymer obtained from the former monomer has two of the carbon atoms constituting the aliphatic ring.
Consists of repeating carbon atoms. The main chain of the polymer obtained from the latter monomer is composed of one carbon atom constituting the aliphatic ring and one carbon atom not constituting the aliphatic ring. It is preferable that these monomers having a fluorinated aliphatic ring structure have substantially no C—H bond. It has a C—F bond in place of the C—H bond, and optionally also has a C—Cl bond or a C—C bond.
It has a -D bond.

It is preferable that the monomer capable of cyclopolymerization has two or more polymerizable double bonds and has substantially no C—H bond. It has a C—F bond in place of the C—H bond, and optionally also has a C—Cl bond or a C—C bond.
It has a -D bond. The main chain of the polymer obtained by cyclopolymerization of this monomer has two of the carbon atoms constituting the aliphatic ring.
Consists of a repeat of at least one carbon atom.

The polymers b and c are polymers into which chlorine or deuterium has been introduced in order to increase the glass transition temperature. Polymer A is also a polymer into which chlorine or deuterium has been introduced. The upper limit of the content of chlorine atoms or deuterium atoms in these polymers is a range that does not exceed the total number of fluorine atoms in one polymerized unit constituting Polymers I to C, and the lower limit is per polymerized unit. The average is preferably one. Preferably, it is 1 to 2 per polymerization unit. If the content of chlorine atoms or deuterium atoms is too large, the thermal stability of the polymer decreases, which is not preferable. In the case of a copolymer with a monomer containing no chlorine atom or deuterium atom, it may be even lower than the above lower limit, but the above lower limit is preferable in terms of glass transition temperature and refractive index.

The introduction of a chlorine atom may be performed at any of the stage of monomer synthesis, the stage after monomer synthesis, and the stage after polymer formation. In the stage after the synthesis of the monomer, it is preferable that the position be such that the subsequent polymerization is not affected. Examples of the chlorinating agent used for introducing a chlorine atom include hot chlorine gas, light chlorine gas, sulfuryl chloride, metal chloride, carbon tetrachloride in the presence of a metal catalyst, and N-bromosuccinimide.

The deuterium atom is introduced at the stage of monomer synthesis,
Either the stage after the monomer synthesis or the stage after the polymer formation may be used. In particular, a method of introducing at the stage of synthesizing a monomer, that is, a method of introducing at the stage of a raw material compound used for synthesizing a monomer, and then synthesizing a monomer from the raw material compound is preferable. As deuterium sources, D ₂ , D ₂ O, LiD,
NaD, B ₂ D ₆ , LiAlD ₄ , D ₂ SO ₄ , DC
1, DNO _{3 and the} like are used.

The fluoropolymer forming the core has a high glass transition temperature because it has a ring structure in its main chain. Generally, in order to obtain a polymer having an aliphatic ring structure, there are a method of cyclopolymerizing a monomer having two double bonds and a method of polymerizing a cyclic monomer.

In the former method, a ring structure is introduced into the main chain of the polymer, but since there is always one or two CF ₂ bonds between the rings, a rotational motion of the molecule occurs around this bond. Although there is a limit in increasing the glass transition temperature, the glass transition temperature can be increased by replacing some of the fluorine atoms in the molecule with chlorine atoms or deuterium atoms. On the other hand, the latter has a structure in which the rings are directly connected to each other, so that the molecular motion around the main chain is restricted, so that the glass transition temperature increases.

When the optical transmission body is an optical fiber, in practice, it is usually coated with a polyethylene resin or a PVC resin.
In the coating step, the coating resin is melted and covered on the optical fiber. At this time, if the glass transition temperature of the resin constituting the optical fiber is low, the resin extends during the coating and causes an increase in transmission loss. Therefore, it is preferable that the glass transition temperature is high. However, if the glass transition temperature is too high, the melt fluidity deteriorates, and it may be difficult to melt-extrude the fiber strand.

In the present invention, the monomer having a fluorinated aliphatic ring structure which gives the polymer (a) or (b) may have a polymerization site for forming a polymer in the ring structure,
The side chain of the ring structure may have a polymerization site for forming a polymer.

The polymerization site is preferably a polymerizable double bond. This monomer is preferably one that polymerizes to give an amorphous polymer I or II. This monomer is preferably selected from the following (1) to (3).

[0031]

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Wherein X ^{1 to} X ⁴ are F, Cl, D
(Deuterium), CF ₃ , and R ^{1 to} R ⁶ are F, C _n
F _{2n + 1} , C _n F _{2n + 1-q} Cl _{q Or} , C _n F _{2n + 1-q} H _q O
selected from _r , n is 1 to 5, q is 0 to 5, r is 0 to 2, and R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ are linked to form a ring. It may be formed.

Specific compounds of the above (1) include, but are not limited to, the respective compounds shown in Chemical Formula 2. In the chemical formula 2, the upper right table is an example of the combination of R ¹ and R ² in the compound having the upper left structure.

[0034]

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Specific examples of the compound (2) include, but are not limited to, the respective compounds shown in Chemical formula 3. In addition, in the chemical formula 3, the table on the right is an example of the combination of R ³ and R ⁴ in the compound having the structure on the left.

[0036]

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Specific examples of the compound (3) include, but are not limited to, each compound shown in Chemical formula 4. In the chemical formula 4, the table on the right is an example of the combination of R ⁵ and R ⁶ in the compound having the structure on the left.

[0038]

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The monomer which gives the polymer C in the present invention is a fluorinated monomer capable of cyclopolymerization. The monomer preferably has two or more polymerizable double bonds.
This monomer is preferably one that undergoes cyclopolymerization to give an amorphous polymer C. Preferred specific examples are the following (4) to
Selected from (7). Where T in the equations (4) to (7)
^{1 to} T ¹² , Y ^{1 to} Y ¹⁰ , Z ^{1 to} Z ⁸ and W ^{1 to} W ⁸
Is F, Cl, CF ₃ or D.

[0040]

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Specific examples of the compounds (4) to (7) include, but are not limited to, the following.

CF ₂ = CFCH ₂ CF ₂ CF ₂ CF = C
F ₂ , CF ₂ = CFCCl ₂ CF ₂ CF ₂ CF = CF
₂ , CF ₂ = CFCF ₂ CF ₂ CF ₂ CF = CF ₂ , C
F ₂ = CFOCF ₂ CF ₂ CF = CF ₂ , CF ₂ = CF
OCH ₂ CF ₂ CF = CF ₂ , CF ₂ = CFOCD ₂ C
F ₂ CF = CF ₂ , CF ₂ = CFOCCl ₂ CF ₂ CF
_{= CF 2, CF 2 = CFOCF} 2 CF 2 CH = CF 2,
CF ₂ = CFOCF ₂ CF ₂ CCl = CF ₂ , CF ₂ =
CFOCF ₂ CFHCF = CF ₂ , CF ₂ = CFOCF
₂ CFClCF = CF ₂ , CF ₂ = CFOCF ₂ CF ₂
CF = CFCl, CF ₂ = CFOCF ₂ CF (CF ₃ )
CF = CF ₂ , CF ₂ = CFOCF ₂ CF (CF ₃ ) C
H = CF ₂ , CF ₂ = CFOCF ₂ CF (CF ₃ ) CC
1 = CF ₂ , CF ₂ = CFOCF ₂ CF = CF ₂ , CF
₂ = CFOCF (CF ₃ ) CF = CF ₂ , CF ₂ = CF
OCF ₂ OCF = CF ₂ , CF ₂ = CHOCF ₂ OCH
= CF ₂ , CF ₂ = CClOCF ₂ OCCl = CF ₂ ,
CF ₂ = CFOCH ₂ OCF = CF ₂ , CF ₂ = CFO
CCl ₂ OCF = CF ₂ .

In the present invention, the clad is selected from fluoropolymers having a refractive index smaller by at least 0.001 than those of the above-mentioned polymers (a) to (c). This fluorinated polymer may be selected from polymers a to c. In this case, the difference in refractive index between the core and the clad can be obtained by adjusting the content of chlorine atoms or deuterium atoms, or by selecting a polymer structure having a difference in refractive index. Usually, the refractive index increases as the content of chlorine atoms or deuterium atoms increases. The preferred fluoropolymer for the clad portion is selected from the preferred fluoropolymers for the core portion.

In the present invention, the molecular weight of the polymer used for the core and the clad is usually from 10,000 to 5,000,000.
00, preferably from 50,000 to 1,000
It is 0000. If the molecular weight is too small, heat resistance may be impaired, while if it is too large, disadvantages such as inability to melt-mold may occur, which is not preferable.

As the method for producing the optical resin material of the present invention, the following methods (1) and (2) are preferred. (1) A method of using a melt extruder to feed a polymer melt forming a core to the center of the nozzle and a polymer melt forming a clad to the outer periphery of the nozzle to integrate the core / clad. (Extrusion coating method). (2) After using a melt extruder to obtain a core fiber made of a polymer forming a core, a solution in which a polymer forming a clad is dissolved in a fluorine-containing solvent is applied to the core fiber, and the solvent is removed. (Solvent coating method).

The fluorinated solvent includes perfluorodecalin, perfluorocyclohexane, perfluorohexane, perfluorooctane, 1H, 1H, 1H,
2H, 2H-perfluorooctane, 1H, 1H, 1
Fluorinated aliphatic hydrocarbons such as H, 2H, 2H-perfluorodecane, fluorinated alkylamines such as perfluorotripentylamine and perfluorotripropylamine, fluorinated cyclic ethers such as perfluoro (2-butyltetrahydrofuran); Examples thereof include fluorinated aromatic hydrocarbons such as perfluorobenzene. These solvents may be used as a mixture of two or more.

When the optical transmission material which is the optical resin material of the present invention is an optical fiber, a protective coating layer is usually provided on the outermost layer. The type of the polymer constituting the coating layer is not particularly limited, and may be one or more selected from those used for coating a conventional inorganic or plastic optical fiber, or the following fluorine-containing polymers. Can be used.

For example, low-density polyethylene, ethylene-vinyl acetate copolymer,
(Water) Crosslinked polyolefins, polyolefin polymers such as polyolefin elastomers, polyester polymers such as polyethylene terephthalate, vinyl polymers such as soft polyvinyl chloride resin, dimethylpolysiloxane polymer, polyfluoroalkylmethylpolysiloxane polymer Examples include silicone-based polymers such as coalesce, polyamide, (expanded) polystyrene, polycarbonate, polyetherimide, polyphenylene oxide, polysulfone, poly-4-methylpentene-1, and polyamideimide.

Examples of the fluorine-containing polymer include a fluorine-containing rubber,
Trifluoroethylene polymer, chlorotrifluoroethylene polymer, tetrafluoroethylene polymer, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-ethylene- (perfluoroalkyl) ethylene copolymer, tetrafluoroethylene-perfluoro (alkyl (Vinyl ether) copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride polymer, vinylidene fluoride-hexafluoropropylene copolymer, and the like.

In addition to the polymer coating layer, a curable resin such as an ultraviolet curable resin, an electron beam curable resin, or a thermosetting resin is coated on an optical fiber and cured to form a coating layer. You can also. In the case of using an ultraviolet curable resin or an electron beam curable resin, coating can be performed at a relatively low temperature, so that there is an advantage that damage to the optical fiber is small.

Examples of the ultraviolet curable resin and the electron beam curable resin include curable resins such as urethane acrylate, epoxy acrylate, silicon acrylate, polyester acrylate, polybutadiene acrylate and polyfluoroalkyl acrylate resins. Can be When these curable resins are used, a method of applying a liquid resin having an appropriate viscosity to the surface of the optical fiber and then curing the resin is applied. On the other hand, when polyamide or polyimide resin is used, the tensile strength of the fiber cord increases, and the mechanical durability is dramatically improved.

If desired, a plasticizer, a pigment, a cross-linking agent, an adhesive or the like may be added to the polymer or resin as exemplified above which constitutes the coating layer.

The production of the optical fiber having the coating layer is not particularly limited. For example, it can be obtained by forming a coating material on the outside of the optical fiber produced by the above-described method by extrusion coating or solvent coating.

Further, in the present invention, after each optical fiber is coated to form a cord, a plurality of optical fibers can be bundled to form a bundle fiber. The bundle fiber includes a multi-core tape core formed by arranging cords in parallel. The cable can also be made by coating the optical fiber with a plastic or metal reinforced with aromatic polyamide, glass or carbon fiber. Thread the gap inside the cable,
It may be filled with a string, paper, plastic, various cushioning materials, or a grooved spacer.

The optical transmission body of the present invention can be directly connected to a quartz single mode optical fiber, as well as an optical waveguide, an optical splitter, an optical coupler, connected to any optical fiber.
Can be directly connected to optical components such as optical branching devices such as optical multiplexers and demultiplexers, optical switches, optical attenuators, optical isolators, polarizers, optical integrated circuits, optical transmitting modules, optical receiving modules, etc. Therefore, signals can be transmitted without impairing their low loss and high bandwidth.

The optical transmitter according to the present invention comprises a subscriber communication line,
LANs in public facilities such as factory LANs, hospital LANs, school LANs, floor cables, power line monitoring and communication lines, automotive applications, monitor image transmission of train operating conditions, communication in large vessels on ocean routes, Data transmission in aircraft,
High-speed, high-bandwidth video transmission, high-quality video, such as amusement-related games such as arcade game machines,
It can be used in various fields such as transmission of stereoscopic images, wiring in devices such as computers or automatic exchanges, general indoor communication networks, various sensor fields, lighting, illumination fields, energy transmission, and medicine.

The light transmitting body of the present invention is effective as a light guide for infrared light transmission because of good transmission of near-infrared light to infrared light. For example, a water absorption wavelength of 2.8 μm
Alternatively, it is also used as a laser scalpel for surgery using light of 1.4 μm (overtone) or a light guide for dental treatment.
In automotive applications, it is effective for wiring in automobiles that are increasingly electronically controlled, and in the medical field, it is effective for medical light guides that are subjected to heat sterilization.

[0058]

【Example】

"Synthesis Example 1" _{CF 2 = CFOCF 2 CF 2 CF} = CF
₂ : Perfluoro (butenyl vinyl ether) [PBV
E], 35 g of ion-exchanged water, and 90 mg of ((CH ₃ ) ₂ CHOCOO) ₂ as a polymerization initiator
Was placed in a pressure-resistant glass autoclave having an internal volume of 200 mL. After purging the system with nitrogen three times, suspension polymerization was performed at 40 ° C. for 22 hours. As a result, the number average molecular weight was about 1.5.
28 g of a × 10 ⁵ polymer (hereinafter referred to as polymer A) was obtained.

The intrinsic viscosity [η] of the polymer A was 0.50 at 30 ° C. in perfluoro (2-butyltetrahydrofuran) [PBTHF]. The glass transition temperature of the polymer A was 108 ° C., and it was a tough and transparent glassy polymer at room temperature. The 10% thermal decomposition temperature was 465 ° C., and the refractive index was 1.34.

"Synthesis Example 2" CF ₂ = CFOCF ₂ CF
35 g of (CF ₃ ) CF = CF ₂ and 15 g of ion-exchanged water
0 g, and ((CH ₃ ) ₂ CHOC as a polymerization initiator.
OO) ₂ was placed in a pressure-resistant glass autoclave having an internal volume of 200 mL. After purging the system with nitrogen three times, suspension polymerization was performed at 40 ° C. for 20 hours. As a result, a polymer having a number average molecular weight of about 1.0 × 10 ⁵ (hereinafter referred to as polymer B)
25g was obtained.

The intrinsic viscosity [η] of the polymer B is PBTHF
It was 0.35 at 30 ° C. The glass transition temperature of this polymer B was 155 ° C., and it was a tough and transparent glassy polymer at room temperature. The 10% thermal decomposition temperature is 465 ° C
And the refractive index was 1.34.

"Synthesis Example 3" CF ₂ ＣＦCFOCH ₂ CF ₂
35 g of CF = CF ₂ , 150 g of ion-exchanged water, and 90 mg of ((CH ₃ ) ₂ CHOCOO) ₂ as a polymerization initiator were placed in a pressure-resistant glass autoclave having an internal volume of 200 mL. After replacing the inside of the system with nitrogen three times, 40 ° C
For 20 hours. As a result, 30 g of a polymer having a number average molecular weight of about 1.0 × 10 ⁵ was obtained. The intrinsic viscosity [η] of the polymer is 30 ° C. in N, N-dimethylformamide.
Was 0.45.

This polymer was dispersed in chlorotrifluoroethylene low polymer oil (average molecular weight: 500), chlorine gas was introduced while irradiating ultraviolet light with a high-pressure mercury lamp, and reacted at 90 ° C. for 15 hours. The reaction solution became transparent, and it was confirmed that the solubility of the polymer changed with the progress of the reaction. Further, the reaction was completed at 140 to 160 ° C. for 15 hours. As a result, a polymer having a repeating unit represented by Chemical Formula 6 was obtained (hereinafter, referred to as polymer C).

[0064]

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When the IR spectrum of the polymer C was measured,
2940c based on C-H vibration absorption in polymer before reaction
It was confirmed that the peak at m ^-1 disappeared after the reaction and was chlorinated. The glass transition temperature of this polymer C was 155 ° C., and it was a tough and transparent glassy polymer at room temperature.
The 10% thermal decomposition temperature is 415 ° C., and the refractive index is 1.
41.

"Synthesis Example 4" A polymer was synthesized in the same manner as in Synthesis Example 1 except that a monomer having the structure shown in Chemical Formula 7 was used instead of PBVE in Synthesis Example 1. As a result, 15 g of a polymer was obtained (hereinafter, referred to as polymer D). The glass transition temperature of this polymer was 292 ° C., and the refractive index was 1.33. The 10% thermal decomposition temperature was 433 ° C.

[0067]

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"Synthesis Example 5" A polymer was synthesized in the same manner as in Synthesis Example 1 except that a monomer having the structure shown in Chemical Formula 8 was used instead of PBVE in Synthesis Example 1. As a result, 21 g of a polymer was obtained (hereinafter, referred to as polymer E). The glass transition temperature of this polymer was 240 ° C., and the refractive index was 1.32. The 10% thermal decomposition temperature was 440 ° C.

[0069]

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"Synthesis Example 6" 30 g of a 6-membered ring monomer having the structure shown in Chemical formula 9, 150 g of ion-exchanged water, and C ₈ F ₁₇ COON
0.2 g of H ₄ and 150 mg of ammonium persulfate as a polymerization initiator were placed in a pressure-resistant glass autoclave having an internal volume of 200 mL. After purging the system three times with nitrogen, polymerization was carried out at 40 ° C. for 2 days.

As a result, 17 g of a polymer was obtained.
Polymer F). The glass transition temperature of this polymer is 12
The temperature was 0 ° C., and the refractive index was 1.34. 10%
The thermal decomposition temperature was 435 ° C.

[0072]

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"Synthesis Example 7" A polymer was synthesized under the same conditions as in Synthesis Example 6 using a monomer having the structure shown in Chemical Formula 10. As a result, 14 g of a polymer was obtained (hereinafter, referred to as polymer G). The glass transition temperature of this polymer is 142 ° C.,
The refractive index was 1.32. The 10% thermal decomposition temperature was 438 ° C.

[0074]

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"Synthesis Example 8" A polymer was synthesized in the same manner as in Synthesis Example 1 except that a monomer having the structure shown in Chemical Formula 11 was used instead of PBVE in Synthesis Example 1. As a result, 22 g of a polymer was obtained (hereinafter, referred to as polymer H). The glass transition temperature of this polymer was 115 ° C., and the refractive index was 1.33. The 10% thermal decomposition temperature was 398 ° C.

[0076]

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"Synthesis Example 9" A polymer was synthesized in the same manner as in Synthesis Example 1 except that a monomer having the structure shown in Chemical Formula 12 was used instead of PBVE in Synthesis Example 1. As a result, 25 g of a polymer was obtained (hereinafter, referred to as polymer I). The glass transition temperature of this polymer was 168 ° C., and the refractive index was 1.32. The 10% thermal decomposition temperature was 395 ° C.

[0078]

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Example 1 An optical fiber having an outer diameter of 0.6 mm was supplied by using a melt extruder to supply each resin such that the polymer C was supplied to the center of the double nozzle and the polymer A was supplied to the outer periphery thereof. A strand was obtained. When the transmission loss of this optical fiber was measured, it was 200 dB / km at a wavelength of 780 nm, and 1300 nm.
And good transmission characteristics of 160 dB / km. After covering the optical fiber with a polyethylene resin at 120 ° C. to form a cable, the transmission loss was measured again, and almost no change was observed.

Example 2 An optical fiber having an outer diameter of 0.6 mm was supplied by using a melt extruder to supply each resin so that the center of the double nozzle became the polymer C and the outer periphery became the polymer B. A strand was obtained. When the transmission loss of this optical fiber was measured, it was 220 dB / km at 780 nm and 1 dB at 1300 nm.
The transmission characteristics were as good as 80 dB / km. After covering the optical fiber with a polyethylene resin at 120 ° C. to form a cable, the transmission loss was measured again.
Little change was seen.

Example 3 Using a melt extruder, polymer C was used.
Was extruded from the nozzle to obtain a 0.5 mm fiber.
Next, the polymer D was dissolved in PBTHF to obtain a 10% solution. The solution was continuously coated on a polymer C fiber, and the solvent was removed by passing the solution through a heating furnace to obtain an optical fiber. When the transmission loss was measured, 7
180 dB / km at 80 nm, 130 d at 1300 nm
Good transmission characteristics of B / km. After covering the optical fiber with a polyethylene resin at 120 ° C. to form a cable, the transmission loss was measured again, and almost no change was observed.

Example 4 Polymer C was melted using a melt extruder.
Was extruded from the nozzle to obtain a 0.5 mm fiber.
Next, the polymer E was dissolved in PBTHF to obtain a 10% solution. The solution was continuously coated on a polymer C fiber, and the solvent was removed by passing the solution through a heating furnace to obtain an optical fiber. When the transmission loss was measured, 7
180 dB / km at 80 nm, 130 d at 1300 nm
Good transmission characteristics of B / km. After covering the optical fiber with a polyethylene resin at 120 ° C. to form a cable, the transmission loss was measured again, and almost no change was observed.

Example 5 An optical fiber having an outer diameter of 0.6 mm was supplied by using a melt extruder to supply the respective resins so that the polymer C was at the center of the double nozzle and the polymer F was at the outer periphery thereof. A strand was obtained. When the transmission loss of this optical fiber was measured, it was 200 dB / km at 780 nm and 1 dB at 1300 nm.
The transmission characteristics were as good as 50 dB / km. After covering this optical fiber with a polyethylene resin at 120 ° C. to form a cable, when the transmission loss was measured again, almost no change was observed.

Example 6 An optical fiber having an outer diameter of 0.6 mm was supplied by using a melt extruder to supply the respective resins so that the polymer B was at the center of the double nozzle and the polymer G was at the outer periphery thereof. A strand was obtained. When the transmission loss of this optical fiber was measured, it was 230 dB / km at 780 nm and 1 dB at 1300 nm.
Good transmission characteristics of 70 dB / km. After covering the optical fiber with a polyethylene resin at 120 ° C. to form a cable, the transmission loss was measured again.
A slight increase in loss was observed, but it was of no problem.

Example 7 An optical fiber having an outer diameter of 0.6 mm was supplied by using a melt extruder to supply each resin so that the polymer C would be at the center of the double nozzle and the polymer H would be at the outer periphery. A strand was obtained. When the transmission loss of this optical fiber was measured, it was 160 dB / km at 780 nm and 1 dB at 1300 nm.
The transmission characteristics were as good as 20 dB / km. After covering this optical fiber with a polyethylene resin at 120 ° C. to form a cable, when the transmission loss was measured again, almost no change was observed.

Example 8 An optical fiber having an outer diameter of 0.6 mm was supplied by using a melt extruder to supply the respective resins so that the polymer C was at the center of the double nozzle and the polymer I was at the outer periphery thereof. A strand was obtained. When the transmission loss of this optical fiber was measured, it was 210 dB / km at 780 nm and 1 dB at 1300 nm.
Good transmission characteristics of 70 dB / km. After covering this optical fiber with a polyethylene resin at 120 ° C. to form a cable, when the transmission loss was measured again, almost no change was observed.

Example 9 Using a melt extruder, polymer C was supplied to the center of the double nozzle and ethylene-tetrafluoroethylene copolymer resin was supplied to the outer periphery, and an optical fiber element having an outer diameter of 0.6 mm was supplied. Got a line. When the transmission loss of this optical fiber was measured, it was 300 dB / km at 780 nm and 130 dB / km.
At 0 nm, the transmission characteristics were as good as 240 dB / km.
After covering the optical fiber with a PVC resin at 150 ° C. to form a cable, the transmission loss was measured again, and almost no change was observed.

Comparative Example 1 As a core material, perfluoro (2,2-dimethyl-1,3-dioxole) [PD
D] and chlorotrifluoroethylene [CTFE] (CTFE content 35 mol%, refractive index 1.34) and PDD and tetrafluoroethylene [T
FE] (TFE content 35 mol%, refractive index 1.
Using 30), an optical fiber was prepared by melt extrusion molding. When the transmission loss of this optical fiber was measured, 78
420 dB / km at 0 nm, 340 dB at 1300 nm
/ Km.

Comparative Example 2 PBVE homopolymer as the core material and the same PDD / TF as Comparative Example 1 as the cladding material
An optical fiber was prepared by melt extrusion using the E copolymer. When the transmission loss of this optical fiber was measured,
220 dB / km at 780 nm, 190 at 1300 nm
It was dB / km. This fiber is heated to a die temperature of 130.
After coating with a polyethylene resin at a temperature of 4 ° C. and a coating speed of 4 m / min, the transmission loss was measured again.
400 dB / km at 1300 nm at 350 dB / km
Had increased.

[0090]

According to the present invention, the optical transmission material, which is an optical resin material, has heat resistance, chemical resistance, and moisture resistance required under severe use conditions in an engine room of an automobile, OA equipment, home electric appliances, and the like. Has incombustibility and non-combustibility.

Claims (4)

[Claims] 1. A core comprising a fluoropolymer substantially consisting only of polymerized units having a fluorinated aliphatic ring structure, wherein the cladding has a refractive index smaller than that of the polymer constituting the core by at least 0.001. Core made of fluoropolymer /
Cladding type optical resin material. 2. The core is substantially composed of only a polymerized unit having a fluorinated aliphatic ring structure and comprises a fluorinated polymer containing a chlorine atom or a deuterium atom, and the clad is more than the polymer constituting the core. Refractive index at least 0.001
Core / cladding type optical resin material made of small fluoropolymer. 3. The core is substantially composed of only a polymerized unit having a fluorinated aliphatic ring structure formed by cyclopolymerization, and is composed of a fluorinated polymer containing a chlorine atom or a deuterium atom. A core / cladding type optical resin material comprising a fluorine-containing polymer having a refractive index smaller than that of the polymer by at least 0.001. 4. The fluorine-containing polymer substantially consisting only of polymer units having a fluorine-containing aliphatic ring structure is an amorphous polymer having substantially no C—H bond. 3
Core / clad type optical resin material.