JPH11167030A - Distributed refractive index optical resin material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optical resin material which is improved in heat resistance and is low in light transmittance loss by consisting this material of specific fluorine contained polymers and specific fluorine contained polycyclic compds. SOLUTION: One or more fluorine contained polycyclic compds. having a refractive index higher than 0.005 are distributed into the non-crystalline fluorine contained polymer substantially free of C-H bonds by having a concn. gradient at which the concn. decreases from the center toward the peripheral part. The fluorine contained polycyclic compds. are the fluorine contained non-condensed polycyclic compds. in which >=2 pieces of fluorine contained rings i.e., carbon rings or heterocycles having fluorine atoms or perfluoroalkyl groups are bonded by the bond including >=1 kind selected from a group of a triazine ring, oxygen atom, sulfur atom, phosphorus atom and metal atom and the C-H bonds are substantially not contained. The compds. are otherwise the fluorine contained condensed polycyclic compds. which comprise >=3 pieces of the carbon rings or heterocycles and do not substantially have the C-H bonds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gradient-index optical resin material having high transparency and heat resistance, which has been difficult to realize with conventional optical resin materials. 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 for manufacturing an optical fiber.

[0002] The optical transmission material which is the optical resin material of the present invention comprises:
Since it is an amorphous resin, there is no light scattering, and the transparency is extremely high in a wide wavelength band from ultraviolet light to near infrared light, so that 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 wavelengths of 1300 nm and 1550 nm, which are wavelengths used for trunk silica fibers in the optical communication field. Further, the optical transmission material which is the optical resin material of the present invention can withstand severe use conditions such as in an engine room of an automobile, heat resistance, chemical resistance, moisture resistance,
Incombustible.

[0003] The optical transmission material which is the optical resin material of the present invention comprises:
Refractive index distribution type optical fiber, rod lens, optical waveguide,
A wide variety of graded-index optical transmitters such as optical splitters, optical multiplexers, optical demultiplexers, optical attenuators, optical switches, optical isolators, optical transmission modules, optical receiving modules, couplers, deflectors, and optical integrated circuits. Useful as

Here, the refractive index distribution means a region where the refractive index changes continuously along a specific direction of the optical transmission medium,
For example, the refractive index distribution of the graded index optical fiber decreases in the radial direction from the center of the fiber in a curve close to a parabola. When the optical resin material of the present invention is a base material of an optical transmission body, the optical transmission body such as a refractive index distribution type optical fiber can be manufactured by spinning this by heat drawing or the like.

[0005]

2. Description of the Related Art Conventionally, as a resin for a refractive index distribution type plastic optical transmitter, a fluorine-containing polymer having a fluorine-containing aliphatic ring structure in a non-crystalline main chain having no CH bond has been known. (See JP-A-8-5848). A refractive index distribution type plastic optical transmitter obtained by dispersing a diffusing material having a different refractive index from the resin into the resin, which is capable of diffusing into the resin, provides an optical transmission medium such as a methyl methacrylate resin, a carbonate resin, and a norbornene resin. It is known to provide a low-loss optical transmitter at wavelengths of 1300 nm and 1550 nm that could not be reached by the body.

However, there is a problem that when different spreading material refractive index is distributed to form a refractive index distribution is the glass transition temperature T _g of the optical resin decreases is the heat resistance decreases. In particular, in an optical resin material in which a diffusing material having a not so high refractive index is dispersed such as an oligomer (refractive index: 1.41) in which a diffusing material is a pentamer or chlorotrifluoroethylene, the numerical aperture NA [NA = (N ² −m ² ) ^1/2 , n is the maximum value of the refractive index in the gradient index optical resin material, and m is the minimum value of the refractive index in the gradient index optical resin material. ], It is necessary to increase the content of the diffusion material.

On the other hand, the T _g of this oligomer is about -60 ° C.
And low, because at room temperature a liquid compound, T _g decreases as increasing the content of an attempt to increase the NA. As a result, when the optical transmission body is exposed to a high temperature, the refractive index distribution changes and the optical transmission performance changes, so that there is a problem that it is difficult to increase the NA.

Further, the diffusing substances such as dibromotetrafluorobenzene and chloroheptafluoronaphthalene described in JP-A-8-5848 have a high refractive index, so that the amount of addition for obtaining a sufficient numerical aperture NA is small. Even in an optical resin material in which a diffusing substance is dispersed, _Tg is low and heat resistance is not sufficient. Further, since these diffusing substances do not have high solubility in the resin, light scattering is likely to occur, which causes an increase in light transmission loss.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the conventional refractive index distribution type optical resin material and to provide an optical resin material having improved heat resistance and low optical transmission loss. I do.

[0010]

In order to obtain a fluorine-containing optical resin material having heat resistance and low scattering loss, the present inventors have ensured solubility as a diffusing substance for forming a refractive index distribution. It was considered important that the compound has a high refractive index and a high T _{g as} it is, and as such a compound, a specific fluorine-containing polycyclic compound was found to be effective.

That is, according to the present invention, the refractive index of the amorphous fluoropolymer (A) having substantially no C—H bond is 0.005 or more in comparison with the fluoropolymer (A). A concentration gradient in which the concentration of the fluorinated polycyclic compound (B) in the fluorinated polymer (A) decreases from the center to the periphery along the peripheral direction. A refractive index distribution type optical resin material distributed having the following formula (B1), wherein the fluorine-containing polycyclic compound (B) is
A refractive index distribution type optical resin material characterized in that it is at least one kind of fluorine-containing polycyclic compound selected from the group consisting of (B2) and (B3). (B1) one or more selected from the group consisting of a triazine ring, an oxygen atom, a sulfur atom, a phosphorus atom, and a metal atom, wherein two or more of the fluorinated rings that are carbocyclic or heterocyclic and have a fluorine atom or a perfluoroalkyl group A compound containing a fluorine-containing non-condensed polycyclic compound bonded by a bond containing the above, and having substantially no C—H bond. (B2) a fluorine-containing non-condensed polycyclic compound which is a carbocyclic or heterocyclic ring and has three or more fluorine-containing rings having a fluorine atom or a perfluoroalkyl group bonded directly or by a bond containing a carbon atom; And substantially C-
A compound having no H bond. (B3) A fused polycyclic compound composed of three or more carbocycles or heterocycles and having substantially no C—H bond.

The fluorine-containing polycyclic compound (hereinafter referred to as compound (B)) in the present invention has substantially no C—H bond (ie, carbon-hydrogen bond) at which light is absorbed by near-infrared light. The compound has a refractive index of 0.00 as compared with a non-crystalline fluorine-containing polymer (A) having substantially no C—H bond (hereinafter referred to as polymer (A)).
It is a compound that is 5 or more higher.

The compound (B) is a compound of the formula (B1) or (B2)
And at least one fluorine-containing polycyclic compound selected from the group consisting of and (B3). As the compound (B), one kind selected from the above group may be used alone, or two or more kinds selected from the above group may be used in combination.

The compound (B) is preferably a perfluoro compound having a structure in which all hydrogen atoms in the compound are substituted by fluorine atoms or perfluoroalkyl groups. As long as the object of the present invention is not impaired, a part of the fluorine atoms in the perfluoro compound may be substituted with one or two chlorine atoms or bromine atoms. The number average molecular weight of the compound (B) is preferably from ^{3 × 10 2 ~2 × 10 3} , more preferably ^{3 × 10 2 ~1 × 10 3} . The compound (B) preferably has a perfluoroalkyl group from the viewpoint of enhancing the solubility with the polymer (A), and the compound (B) preferably has a perfluoroalkyl group from the viewpoint of increasing the refractive index difference from the polymer (A). Preferably does not have a perfluoroalkyl group.

The fluorinated ring in the present invention is a carbocyclic or heterocyclic ring having a fluorine atom or a perfluoroalkyl group. The carbocycle and heterocycle are preferably selected from those having 4 or more members, and more preferably 4 to 6 members. The atoms constituting the heterocycle are preferably selected from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom and the like. As the perfluoroalkyl group, a perfluoroalkyl group having 1 to 20 carbon atoms is preferable.

The carbon ring includes a cyclic saturated hydrocarbon ring such as a cyclopentane ring and a cyclohexane ring; a benzene ring;
An aromatic hydrocarbon ring such as a ring in which one or two hydrogen atoms of a benzene ring are substituted with a methyl group; a cyclic unsaturated hydrocarbon ring other than an aromatic hydrocarbon ring such as a cyclopentene ring or a cyclohexene ring; No. As the heterocycle, a heteroatom such as a thiophene ring, a furan ring, a pyridine ring, a triazine ring, and a triazole ring is one kind of heterocycle,
Examples include a heterocyclic ring having two kinds of hetero atoms such as an isothiazole ring. Preferred fluorinated rings are fluorinated aromatic hydrocarbon rings, and more preferred fluorinated rings are perfluoroaromatic hydrocarbon rings. As the aromatic hydrocarbon ring, a benzene ring is preferable.

The fluorine-containing non-condensed polycyclic compound in the present invention is a compound in which two or three or more fluorine-containing rings are bonded without sharing two or more atoms. The term "bonding without sharing two or more atoms" means that the fluorine-containing ring bonds and shares one atom, or that the fluorine-containing ring bonds directly or indirectly.
Indirectly bonding a fluorine-containing ring means that the fluorine-containing ring is bonded through one or more atoms.

When two fluorine-containing rings are bonded, the bond is a bond containing at least one selected from the group consisting of a triazine ring, an oxygen atom, a sulfur atom, a phosphorus atom and a metal atom. When three or more fluorine-containing rings are bonded, the bond is a bond containing at least one selected from the group consisting of a triazine ring, an oxygen atom, a sulfur atom, a phosphorus atom, and a metal atom. A bond or a bond containing a carbon atom.

The metal atoms include Zn, Sn, Pb, and G
A divalent to tetravalent metal atom selected from e, Si, Ti, Hg, Tl, As, Se, Te and Cd is preferred. From the viewpoint of providing a fluorine-containing non-fused polycyclic compound having good thermal stability and chemical stability, a more preferred metal atom is Sn.
Is an atom.

As the fluorine-containing non-condensed polycyclic compound in which two or more fluorine-containing rings are bonded by a bond containing a triazine ring, a fluorine-containing aromatic triazine compound represented by any of the following formulas 1 to 3 preferable. In the present specification, Φ
^g (g is an integer of 1 to 6) is g from perfluorobenzene
Represents a residue excluding fluorine atoms. When fluorine atoms remain after removing g fluorine atoms, a structure in which part or all of the fluorine atoms are substituted with a perfluoroalkyl group may be employed.

Examples of the fluorine-containing non-condensed polycyclic compound in which two or more fluorine-containing rings are bonded by a bond containing a phosphorus atom include:
A compound represented by (Φ ¹ ) ₃ -P or a compound bonded by a bond containing a phosphazatriene ring represented by the following formula 4 is preferable.

As the fluorine-containing non-condensed polycyclic compound in which two or more fluorine-containing rings are bonded by a bond containing a sulfur atom, a fluorine-containing aromatic sulfur-containing compound represented by the following formula 5 or 6 is preferable. . However, in Formula 5, h is an integer of 1 to 4, and in Formula 6, k is an integer of 1 to 6.

As the fluorine-containing non-condensed polycyclic compound in which two or more fluorine-containing rings are bonded by a bond containing a metal atom, a fluorine-containing aromatic metal-containing compound represented by the following formula 7 or 8 is preferable. . However, in Equations 7 and 8, M is Z
n, Sn, Pb, Ge, Si, Ti, Hg, Tl, A
It is a metal atom selected from s, Se, Te and Cd, and p and q are valences of the metal M and are integers of 2 to 4.

The fluorine-containing non-condensed polycyclic compound in which three or more fluorine-containing rings are bonded directly or by a bond containing carbon includes a fluorine-containing aromatic compound represented by any of the following formulas 9 to 12. Compounds are preferred. From the viewpoint of not impairing the transparency of the refractive index distribution type optical resin material, the total number of Φ ^{1 to} Φ ^{4 in} the fluorine-containing aromatic compound is preferably 3 to 5.

[0025]

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[0026]

## EQU2 ## F − (− Φ ² −S−) _h −Φ ¹ Equation 5 Φ ^k (−S−Φ ¹ ) _k Equation 6 (Φ ¹ ) _p −M Equation 7 (Φ ¹ −S−) _q − M Equation 8

[0027]

Embedded image F− (Φ ² ) _r −F (r is an integer of 3 to 7) Formula 9

A fused polycyclic compound composed of three or more carbocyclic or heterocyclic rings, wherein a part or all of the hydrogen atoms are substituted by fluorine atoms or fluorine-containing groups. As the carbocycle and heterocycle in the cyclic compound, those having four or more members are preferable,
Six-membered rings are more preferred. Preferred atoms constituting the heterocyclic ring include a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom,
It is selected from phosphorus atoms and the like.

Examples of the fluorinated condensed polycyclic compound include perfluorofluorene, perfluorophenalene, perfluorophenanthrene, perfluoroanthracene, perfluorotriphenylene, perfluoropyrene, perfluorochrysene, and perfluoronaphthacene.
A fluorinated fused polycyclic hydrocarbon composed of four carbon rings or a fluorinated fused polycyclic compound represented by the following formula 13 or 14 is preferred.

[0030]

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From the viewpoint of not hindering the transparency of the refractive index distribution type optical resin material, a fluorinated condensed polycyclic carbon having three carbon rings such as perfluorofluorene, perfluorophenalene, perfluorophenanthrene and perfluoroanthracene. Hydrogen is more preferred.

The compound (B) is preferably selected from those having high thermal stability and high solubility with the polymer (A) and those which do not impair the transparency of the refractive index distribution type optical resin material. As such a compound (B), a fluorine-containing non-condensed polycyclic compound in which two or more fluorine-containing rings are bonded by a bond containing at least a triazine ring is particularly preferable. As the triazine ring, a 1,2,3-triazine ring, 1,2,2
Examples thereof include a 4-triazine ring and a 1,3,5-triazine ring, and a 1,3,5-triazine ring is preferable.

The polymer (A) in the present invention is a polymer that is non-crystalline and has substantially no C—H bond that causes light absorption by near-infrared light. As the polymer (A),
There is no particular limitation as long as it is a non-crystalline fluorine-containing polymer having no CH bond, but a fluorine-containing polymer having a fluorine-containing aliphatic ring structure in the main chain is preferable.

Having a fluorinated aliphatic ring structure in the main chain means that at least one of the carbon atoms constituting the aliphatic ring is a carbon atom in the carbon chain constituting the main chain and the aliphatic ring is constituted. It has a structure in which a fluorine atom or a fluorine-containing group is bonded to at least a part of carbon atoms.
As the fluorinated aliphatic ring structure, a fluorinated aliphatic ether ring structure is more preferred.

The viscosity of the polymer (A) in the molten state is as follows:
A melting point of 200 to 300 ° C. is preferably 10 ³ to 10 ⁵ poise. If the melt viscosity is too high, melt spinning is difficult, and diffusion of the compound (B), which is necessary for forming a refractive index distribution, is difficult to occur, making it difficult to form a refractive index distribution. On the other hand, if the melt viscosity is too low, practical problems arise. That is, when used as an optical transmitter in an electronic device, an automobile, or the like, it is exposed to a high temperature and softened, and the light transmission performance is reduced. The number average molecular weight of the polymer (A) is from 1 × 10 ^{4 to} 5 × 1.
0 ^{6 preferably, 5 × 10 4 ~1 × 10} 6 is more preferable. If the molecular weight is too small, heat resistance may be impaired, and if it is too large, it becomes difficult to form a light transmitting body having a refractive index distribution.

Examples of the polymer having a fluorinated aliphatic ring structure include a polymer obtained by polymerizing a monomer having a fluorinated ring structure, and a fluorinated monomer having two or more polymerizable double bonds. A polymer having a fluorinated aliphatic ring structure in the main chain obtained by cyclopolymerization of is preferred.

A polymer having a fluorinated alicyclic structure in the main chain obtained by polymerizing a monomer having a fluorinated alicyclic structure is known from JP-B-63-18964. That is, perfluoro (2,2-dimethyl-1,
By homopolymerizing a monomer having a fluorinated aliphatic ring structure such as 3-dioxole), it is possible to obtain a radical polymerizable such as tetrafluoroethylene, chlorotrifluoroethylene, or perfluoro (methyl vinyl ether). To obtain a polymer having a fluorinated aliphatic ring structure in the main chain.

A polymer having a fluorinated aliphatic ring structure in the main chain obtained by cyclopolymerization of a fluorinated monomer having two or more polymerizable double bonds is disclosed in 238
111 and JP-A-63-238115. That is, by cyclopolymerizing perfluoro (allyl vinyl ether) or perfluoro (butenyl vinyl ether), or such a monomer and tetrafluoroethylene, chlorotrifluoroethylene,
A polymer having a fluorinated aliphatic ring structure in the main chain can be obtained by copolymerizing a radical polymerizable compound such as perfluoro (methyl vinyl ether).

Further, perfluoro (2,2-dimethyl-
Monomers having a fluorinated aliphatic ring structure such as 1,3-dioxole) and perfluoro (allyl vinyl ether)
A polymer having a fluorinated aliphatic ring structure in the main chain can also be obtained by copolymerizing a fluorinated monomer having two or more polymerizable double bonds such as fluorinated or perfluoro (butenyl vinyl ether).

As the polymer having a fluorinated alicyclic structure, two polymer units having a fluorinated alicyclic structure are used in all polymer units of the polymer having a fluorinated alicyclic structure.
Those containing 0 mol% or more, particularly 40 mol% or more, are preferable in terms of transparency, mechanical properties and the like.

Specific examples of the polymer having a fluorinated aliphatic ring structure include those having a repeating unit represented by any of the following formulas 15 to 18. However, in Formulas 15 to 18, h is an integer of 0 to 5, i is an integer of 0 to 4, j is 0 or 1, h + i + j is 1 to 6,
s is an integer of 0 to 5, t is an integer of 0 to 4, u is 0 or 1, s + t + u is 1 to 6, p, q, and r are each independently an integer of 0 to 5, p + q + r is 1 to 6, R ^{1 to} R ⁶ are each independently a fluorine atom, a chlorine atom, a deuterium atom (D) or a trifluoromethyl group. In addition, the fluorine atom in these polymers having a fluorinated aliphatic ring structure may be partially substituted with a chlorine atom in order to increase the refractive index.

[0042]

Embedded image

As the monomer having a fluorinated aliphatic ring structure, a monomer selected from compounds represented by any of the following formulas 19 to 21 is preferable. However, Expressions 19 to 21
In the formula, R ^{7 to} R ¹⁸ are each independently a fluorine atom, a chlorine atom, a deuterium atom or a trifluoromethyl group, or R ⁹ and R ¹⁰ , R ¹³ and R ^14, and R ¹⁷ and R ¹⁸
Are-(CF ₂ ) _4- and-(CF ₂ ) _{3
-, - (CF 2) 2} -, - CF 2 -O-CF 2 -, -
A divalent group selected from the group consisting of (CF ₂ ) ₂ —O—CF ₂ —, —O— (CF ₂ ) ₂ — and —O— (CF ₂ ) ₃ — may be formed.

[0044]

Embedded image

Specific examples of the compound represented by any of formulas 19 to 21 include compounds represented by any of formulas 22 to 29 below.

[0046]

Embedded image

As the fluorine-containing monomer having two or more polymerizable double bonds, a compound represented by any of the following formulas 30 to 32 is preferable. However, in Formulas 30 to 32, Y ^{1 to} Y ¹⁰ , Z ^{1 to} Z ⁸ and W ^{1 to} W ⁸ are each independently a fluorine atom, a chlorine atom, a deuterium atom or a trifluoromethyl group.

[0048]

Embedded image ^{CY 1 Y 2 = CY 3 OCY} 4 Y 5 CY 6 Y 7 CY 8 = CY 9 Y 10 Formula ^{30 CZ 1 Z 2 = CZ 3} OCZ 4 Z 5 CZ 6 = CZ 7 Z 8 Formula 31 CW ¹ W ² = CW ³ OCW ⁴ W ⁵ OCW ⁶ = CW ⁷ W ⁸ Formula 32

Specific examples of the compounds represented by any of formulas 30 to 32 include the following compounds. _{CF 2 = CFOCF 2 CF 2 CF} = CF 2 CF 2 = CFOCCl 2 CF 2 CF = CF 2 CF 2 = CFOCF 2 CF 2 CCl = 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 ) CCl = CF ₂ CF ₂ = CFOCF ₂ CF = CF ₂ CF ₂ = CFOCF (CF ₃ ) CF = CF _{2 CF 2 = CFOC (CF 3} ) 2 CF = CF 2 CF 2 = CFOCF 2 OCF = CF 2 CF 2 = CClOCF 2 OCCl = CF 2 CF 2 = CFOCCl 2 OCF = CF 2 CF 2 = CFOC (CF 3) 2 OCF = CF ₂

In producing the optical resin material of the present invention, the molding of the resin and the formation of the refractive index distribution may be performed simultaneously or separately. For example, the optical resin material of the present invention can be manufactured by simultaneously forming a resin by spinning or extrusion molding and forming a refractive index distribution. Further, after forming the resin by spinning or extrusion, a refractive index distribution can be formed.
Furthermore, an optical resin material such as an optical fiber can be manufactured by manufacturing a preform (base material) having a refractive index distribution and molding (for example, spinning) the preform. As described above, the optical resin material of the present invention also means a preform having the above-mentioned refractive index distribution.

The optical resin material of the present invention is most preferably a graded index optical fiber. In this optical fiber, since the compound (B) is a substance having a higher refractive index than the polymer (A), the compound (B) has a concentration gradient in which the concentration decreases from the center of the optical fiber to the peripheral direction. Are distributed. This results in a refractive index distribution in which the refractive index decreases from the center of the optical fiber along the peripheral direction. The concentration distribution of the compound (B) can be generally formed by disposing the compound (B) at the center of the polymer (A) in a molten state and diffusing the compound (B) toward the peripheral direction.

Since the refractive index of the compound (B) is higher than that of the polymer (A) by 0.005 or more, the difference between the maximum value n and the minimum value m of the refractive index in the optical resin material can be increased. That is, the numerical aperture NA represented by “(n ² −m ² ) ^1/2 ” can be set to 0.20 or more. Compound (B)
Preferably has a refractive index higher than the polymer (A) by 0.01 or more. Compound (B) has a refractive index of 1.45.
The above is preferable, and 1.47 or more is more preferable.

[0053] T _g of the a generally adding a low molecular weight compound in the polymer the polymer is lowered. When a compound having a not so large refractive index is used as a material for forming a refractive index difference, the content in the polymer must be increased, and as a result, T _g
And heat resistance decreases.

Since the compound (B) in the present invention has a high refractive index, even if it is added in a small amount, for example, even if the concentration of the compound (B) at the center of the optical resin material is 15% by weight or less, the desired refractive index can be obtained. can form the rate difference, is advantageous decrease T _g of less. Further, since the T _g of the compound (B) is high, the T _g of the optical resin material center can be 70 ° C. or higher. The kind of compound (B) a T _g of the optical resin material center may be a 90 ° C. or higher. This allows
The heat resistance of the optical resin material of the present invention is dramatically improved.

The compound (B) has good solubility in the polymer (A), and its saturated solubility is 5 to 20% by weight.
It is. Solubility parameter (SP) which is a measure of solubility
Value) is 6 to 7 (cal / cm ³ ) ^{1/2 for the} polymer (A).
On the other hand, the compound (B) has 8 to 10 (cal /
cm ³ ) It is considered that the solubility is good because it has a value close to ^1/2 . When the content of the compound (B) with respect to the polymer (A) is equal to or less than the above-mentioned saturation solubility, the transparency of the optical resin material of the present invention is good, such as micro phase separation and microcrystals of the compound (B). Light scattering caused by the

The optical transmission material which is the optical resin material of the present invention comprises:
At a wavelength of 700 to 1600 nm, a transmission loss of 100 m is 1
It can be 5 db or less. 700-1600 wavelength
At relatively long wavelengths of nm, such low levels of transmission loss are highly advantageous. That is, since the same wavelength as that of the quartz optical fiber can be used, connection with the quartz optical fiber is easy, and the wavelength of 700 to
There is an advantage that an inexpensive light source can be used as compared with a conventional plastic optical fiber which has to use a wavelength shorter than 1600 nm.

In the transmission characteristics of the optical transmission body, there is a transmission band as an important characteristic together with the transmission loss. In order to transmit a large amount of information at a high speed, a wide transmission band is desired. At present, a silica-based single mode fiber used in long-distance communication has a transmission band of several tens of GHz · km.
Has a wide transmission band.

On the other hand, since the plastic optical fiber has a large fiber diameter and can be easily connected to a light source / light receiving element or between fibers, there is a growing expectation for the construction of an inexpensive short-distance communication system.

An ordinary plastic optical fiber is of a step index type, and has a narrow transmission band of about several MHz · km. In order to solve this, a graded index plastic optical fiber having a wider transmission band as in the present invention has been proposed. In this refractive index distribution type plastic optical fiber, if this refractive index distribution is not thermally stable,
As a result, the transmission band decreases.

Since the heat resistance of the optical resin material of the present invention is dramatically improved, the thermal stability of the refractive index distribution is high.
Even when exposed to a high temperature equal to or higher than room temperature for a long period of time, it is possible to prevent a decrease in the transmission band.

[0061]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the following examples, Examples 1 to 3 are synthesis examples of the polymer (A), Examples 4 to 10 and Examples 16 to 17 are Examples, and Examples 11 to 15 are Comparative Examples.

Example 1 750 g of perfluoro (butenyl vinyl ether) [PBVE], 4 kg of ion-exchanged water, 260 g of methanol and 3.7 g of ((CH
₃ ) ₂ CHOCOO) ₂ was placed in a 5 L glass flask. After purging the system with nitrogen, suspension polymerization was performed at 40 ° C. for 22 hours to obtain 690 g of a polymer having a number average molecular weight of about 5 × 10 ⁴ . The polymer was heated at 250 ° C. in a fluorine / nitrogen mixed gas (fluorine gas concentration: 20% by volume) atmosphere.
By performing the treatment for a time, a polymer having good light transmittance and heat stability (hereinafter, referred to as polymer A1) was obtained.

The intrinsic viscosity [η] of the polymer A1 is perfluoro (2-butyltetrahydrofuran) [PBTHF]
It was 0.3 at 30 ° C. The T _g of the polymer A1 is 108
° C, and at room temperature, it was a tough and transparent glassy polymer. The refractive index is 1.342 and the SP value is 6.6 (ca
1 / cm ³ ) ^1/2 .

Example 2 173 g of PBVE, 27 g of perfluoro (2,2-dimethyl-1,3-dioxole) [PDD], 200 g of PBTHF and 2 g of ((CH ₃ ) ₂ CHOCOOO) ₂ as a polymerization initiator Was placed in a stainless steel autoclave having an internal volume of 1 L. After purging the system with nitrogen, polymerization was carried out at 40 ° C. for 20 hours to obtain 20 g of a transparent polymer having a number average molecular weight of about 1.5 × 10 ⁵ . This polymer is treated at 250 ° C. for 5 hours in an atmosphere of a fluorine / nitrogen mixed gas (fluorine gas concentration: 20% by volume) to obtain a polymer having good light transmittance and thermal stability (hereinafter referred to as polymer A2). Obtained. The T _g of the polymer A2 is 1
50 ° C., refractive index 1.325, SP value 6.5 (cal
/ Cm ³ ) ^1/2 .

[0065] "Example 3" PDD and radical polymerization using a tetrafluoroethylene PBTHF in a weight ratio of 80:20 as the solvent, a number average molecular weight in the T _g is 160 ° C. is about 1.
7 × 10 ⁵ polymers were obtained. This polymer was placed in a fluorine / nitrogen mixed gas (fluorine gas concentration 20% by volume) atmosphere for 25 minutes.
By treating at 0 ° C. for 5 hours, a polymer having good light transmittance and thermal stability (hereinafter, referred to as polymer A3) was obtained.
Polymer A3 is colorless and transparent, has a refractive index of 1.305, and S
The P value was 6.3 (cal / cm ³ ) ^1/2 .

Example 4 A mixture of polymer A1 and perfluoro (tetraphenyltin) [the latter being 7% by weight in the mixture
Was contained in a glass sealed tube and melt-molded at 250 ° C. to obtain a columnar molded body (hereinafter, referred to as molded body a). The molded article a had a refractive index of 1.357 and a T _g of 91 ° C.

Next, a cylindrical tube made of only the polymer A1 was prepared by melt molding, and the molded product a was inserted into the hollow portion of the cylindrical tube, heated to 200 ° C. and united to obtain a preform. By melt-spinning this preform at 230 ° C., an optical fiber whose refractive index gradually decreased from the center toward the periphery was obtained. The optical transmission characteristics of the obtained optical fiber were 200 dB / km at 780 nm and 8 dB.
150 dB / km at 50 nm, 120 d at 1300 nm
B / km, and it was confirmed that the optical fiber could transmit light from visible light to near-infrared light well.

This optical fiber was placed in an oven at 70 ° C. for 1 hour.
After storage for 000 hours, after taking out, the refractive index distribution was measured by an interfaco interference microscope and compared with the refractive index distribution before storage, no change was observed. further,
The transmission characteristics were evaluated by measuring the transmission band by the following pulse method.

That is, a pulsed laser beam is oscillated using a pulse generator, and the pulsed laser beam is incident on an optical fiber.
The emitted light was detected by a sampling oscilloscope. The transmission band was measured by Fourier transforming this detection signal and analyzing the frequency characteristics. Optical fiber at 70 ° C, 10
When the transmission band was measured after storing for 00 hours, it was confirmed that the heat resistance was good because the band was not lowered at 260 MHz · km before and after the storage.

Example 5 A mixture of the polymer A1 and perfluoro (triphenylphosphine) (the latter containing 7% by weight in the mixture) was charged into a glass sealed tube and melt-molded at 250 ° C. to obtain a cylindrical molded product ( Hereinafter, a molded article b) was obtained.
The molded article b had a refractive index of 1.357 and a T _g of 88 ° C.

Next, a cylindrical tube made of only the polymer A1 was prepared by melt molding, and the molded product b was inserted into the hollow portion to form a cylindrical tube.
A preform was obtained by heating to 00 ° C. and coalescing. By melt-spinning this preform at 230 ° C., an optical fiber whose refractive index gradually decreased from the center toward the periphery was obtained. The optical transmission characteristics of the obtained optical fiber were 200 dB / km at 780 nm and 850 n.
150 dB / km at m, 120 dB / k at 1300 nm
m, and it was confirmed that the optical fiber could transmit light from visible light to near-infrared light well.

This optical fiber was placed in an oven at 70 ° C. for 1 hour.
After storage for 000 hours, after taking out, the refractive index distribution was measured with an interfaco interference microscope and compared with the refractive index distribution before storage, no particular change was observed. The transmission band was measured by the same pulse method as in Example 4, and the characteristics before and after storage were compared.
Since the band did not decrease at m, it was confirmed that the heat resistance was good.

Example 6 A mixture of polymer A1 and 1,4-bis (perfluorophenylthio) tetrafluorobenzene (the latter containing 5% by weight in the mixture) was charged into a glass sealed tube and melt-molded at 250 ° C. Cylindrical molded body (hereinafter, referred to as
Molded article c) was obtained. The refractive index of the molded body c is 1.35.
7. T _g was 85 ° C.

Next, a cylindrical tube made of only the polymer A1 was prepared by melt molding, and the molded product c was inserted into the hollow portion to form a cylindrical tube.
A preform was obtained by heating to 00 ° C. and coalescing. By melt-spinning this preform at 230 ° C., an optical fiber whose refractive index gradually decreased from the center toward the periphery was obtained. The optical transmission characteristics of the obtained optical fiber were 200 dB / km at 780 nm and 850 n.
150 dB / km at m, 120 dB / k at 1300 nm
m, and it was confirmed that the optical fiber could transmit light from visible light to near-infrared light well.

This optical fiber was placed in an oven at 70 ° C. for 1 hour.
After storage for 000 hours, after taking out, the refractive index distribution was measured with an interfaco interference microscope and compared with the refractive index distribution before storage, no particular change was observed. The transmission band was measured by the same pulse method as in Example 4, and the characteristics before and after storage were compared.
Since the band did not decrease at m, it was confirmed that the heat resistance was good.

Example 7 Polymer A1 and perfluoro (2,
A mixture with 4,6-triphenyl-1,3,5-triazine [the latter containing 5% by weight in the mixture] was charged into a glass sealed tube, melt-molded at 250 ° C., and formed into a cylindrical molded product (hereinafter, referred to as a “cylindrical molded product”). Molded article d) was obtained. The refractive index of the molded body d is 1.
357, T _g was 95 ° C.

Next, a cylindrical tube made only of the polymer A1 was prepared by melt molding, and the molded product d was inserted into the hollow portion to form a cylindrical tube.
A preform was obtained by heating to 00 ° C. and coalescing. By melt-spinning this preform at 240 ° C., an optical fiber whose refractive index gradually decreased from the center to the periphery was obtained. The optical transmission characteristics of the obtained optical fiber were 120 dB / km at 780 nm and 850 n.
100 dB / km at m and 80 dB / km at 1300 nm
It was confirmed that the optical fiber could transmit light from visible light to near-infrared light well.

This optical fiber was placed in an oven at 70 ° C. for 1 hour.
After storage for 000 hours, after taking out, the refractive index distribution was measured with an interfaco interference microscope and compared with the refractive index distribution before storage, no particular change was observed. The transmission band was measured by the same pulse method as in Example 4, and the characteristics before and after storage were compared.
Since the band did not decrease at m, it was confirmed that the heat resistance was good.

Example 8 A mixture of polymer A1 and perfluoroterphenyl (the latter containing 5% by weight in the mixture) was charged into a glass sealed tube and melt-molded at 250 ° C. to obtain a columnar molded product (hereinafter referred to as a molded product). Body e). The molded article e had a refractive index of 1.357 and a T _g of 95 ° C.

Next, a cylindrical tube made of only the polymer A1 was prepared by melt molding, and the molded product e was inserted into the hollow portion to form a cylindrical tube.
A preform was obtained by heating to 00 ° C. and coalescing. By melt-spinning this preform at 230 ° C., an optical fiber whose refractive index gradually decreased from the center toward the periphery was obtained. The optical transmission characteristics of the obtained optical fiber were 170 dB / km at 780 nm and 850 n.
140 dB / km at m and 110 dB / k at 1300 nm
m, and it was confirmed that the optical fiber could transmit light from visible light to near-infrared light well.

This optical fiber was placed in an oven at 70 ° C. for 1 hour.
After storage for 000 hours, after taking out, the refractive index distribution was measured with an interfaco interference microscope and compared with the refractive index distribution before storage, no particular change was observed. The transmission band was measured by the same pulse method as in Example 4, and the characteristics before and after storage were compared.
Since the band did not decrease at m, it was confirmed that the heat resistance was good.

Example 9 A mixture of polymer A1 and perfluoroquaterphenyl [the latter containing 5% by weight in the mixture]
Was charged in a glass sealed tube and melt-molded at 250 ° C. to obtain a columnar molded body (hereinafter, referred to as molded body f). The refractive index of the molded body f was 1.357, and T _g was 93 ° C.

Next, a cylindrical tube made of only the polymer A1 was prepared by melt molding, and the molded product f was inserted into the hollow portion to form a cylindrical tube.
A preform was obtained by heating to 00 ° C. and coalescing. By melt-spinning this preform at 240 ° C., an optical fiber whose refractive index gradually decreased from the center to the periphery was obtained. The optical transmission characteristics of the obtained optical fiber were 190 dB / km at 780 nm and 850 n.
150 dB / km at m, 120 dB / k at 1300 nm
m, and it was confirmed that the optical fiber could transmit light from visible light to near-infrared light well.

This optical fiber was placed in an oven at 70 ° C. for 1 hour.
After storage for 000 hours, after taking out, the refractive index distribution was measured with an interfaco interference microscope and compared with the refractive index distribution before storage, no particular change was observed. The transmission band was measured by the same pulse method as in Example 4, and the characteristics before and after storage were compared.
Since the band did not decrease at m, it was confirmed that the heat resistance was good.

Example 10 A mixture of polymer A1 and perfluoroanthracene (the latter containing 5% by weight in the mixture) was charged into a glass sealed tube and melt-molded at 250 ° C. to obtain a columnar molded product (hereinafter referred to as a molded product). g). The molded article g had a refractive index of 1.357 and a T _g of 95 ° C.

Next, a cylindrical tube made of only the polymer A1 was prepared by melt molding, and the molded product g was inserted into the hollow portion to form a cylindrical tube.
A preform was obtained by heating to 00 ° C. and coalescing. By melt-spinning this preform at 240 ° C., an optical fiber whose refractive index gradually decreased from the center to the periphery was obtained. The optical transmission characteristics of the obtained optical fiber were 190 dB / km at 780 nm and 850 n.
150 dB / km at m, 120 dB / k at 1300 nm
m, and it was confirmed that the optical fiber could transmit light from visible light to near-infrared light well.

This optical fiber was placed in an oven at 70 ° C. for 1 hour.
After storage for 000 hours, after taking out, the refractive index distribution was measured with an interfaco interference microscope and compared with the refractive index distribution before storage, no particular change was observed. The transmission band was measured by the same pulse method as in Example 4, and the characteristics before and after storage were compared.
Since the band did not decrease at m, it was confirmed that the heat resistance was good.

Example 11 Polymer A1 and chlorotrifluoroethylene oligomer (average molecular weight 850, refractive index 1.
41) was charged in a glass sealed tube and melt-molded at 250 ° C. to obtain a columnar molded body (hereinafter, referred to as molded body h). The molded article h had a refractive index of 1.357 and a T _g of 75 ° C.

Next, a cylindrical tube made of only the polymer A1 was prepared by melt molding, and the molded product h was inserted into the hollow portion to form a cylindrical tube.
A preform was obtained by heating to 00 ° C. and coalescing. By melt-spinning this preform at 230 ° C., a gradient index optical fiber whose refractive index gradually decreased from the center to the periphery was obtained. The optical transmission characteristics of the obtained optical fiber are 110 dB / k at 780 nm.
m, 100 dB / km at 850 nm, 8 at 1300 nm
It was 0 dB / km, and it was confirmed that the optical fiber could transmit light from visible light to near-infrared light well.

The optical fiber was placed in an oven at 70 ° C. for 1 hour.
After storage for 000 hours, the sample was taken out, and the refractive index distribution was measured with an interference microscope. When compared with the refractive index distribution before storage, a decrease in the refractive index was observed near the center of the core. Along with this, the transmission bandwidth is reduced, and before storage,
What was 0MHz · km is 160MHz after storage
・ It was reduced to km.

Example 12 A mixture of polymer A1 and perfluorobiphenyl (refractive index: 1.45) manufactured by Aldrich (the latter containing 7% by weight in the mixture) was charged into a glass sealed tube and melt-molded at 250 ° C. A cylindrical molded body (hereinafter, referred to as molded body i) was obtained. The molded article i has a refractive index of 1.357,
T _g was 73 ° C.

Next, a cylindrical tube made of only the polymer A1 was prepared by melt molding, and the molded product i was inserted into the hollow portion to form a cylindrical tube.
A preform was obtained by heating to 00 ° C. and coalescing. By melt-spinning this preform at 230 ° C., a gradient index optical fiber whose refractive index gradually decreased from the center to the periphery was obtained. The optical transmission characteristics of the obtained optical fiber are 150 dB / k at 780 nm.
m, 120 dB / km at 850 nm, 1 at 1300 nm
It was 00 dB / km, and it was confirmed that the optical fiber could transmit light from visible light to near-infrared light well.

This optical fiber was placed in an oven at 70 ° C. for 1 hour.
After storage for 000 hours, the sample was taken out, and the refractive index distribution was measured with an interference microscope. When compared with the refractive index distribution before storage, a decrease in the refractive index was observed near the center of the core. Along with this, a decrease in the transmission bandwidth is seen, and 200 MHZ before storage.
What was z · km is 110MHz · km after storage
Had fallen.

Example 13 A mixture of polymer A1 and perfluoro (diphenyl sulfide) manufactured by Aldrich (the latter containing 6% by weight in the mixture) was charged into a glass sealed tube.
A columnar molded body melt-molded at 250 ° C.
). The refractive index of the molded body j is 1.357, T _g
Was 77 ° C.

Next, a cylindrical tube made of only the polymer A1 was prepared by melt molding, and the molded body j was inserted into the hollow portion to form a cylindrical tube.
A preform was obtained by heating to 00 ° C. and coalescing. By melt-spinning this preform at 230 ° C., a gradient index optical fiber whose refractive index gradually decreased from the center to the periphery was obtained. The optical transmission characteristics of the obtained optical fiber are 190 dB / k at 780 nm.
m, 150 dB / km at 850 nm, 1 at 1300 nm
It was 20 dB / km, and it was confirmed that the optical fiber could transmit light from visible light to near infrared light well.

This optical fiber was placed in an oven at 70 ° C. for 1 hour.
After storage for 000 hours, the sample was taken out, and the refractive index distribution was measured with an interference microscope. When compared with the refractive index distribution before storage, a decrease in the refractive index was observed near the center of the core. Along with this, a decrease in the transmission band is seen, and 260 MH
What was z · km is 180MHz · km after storage
Had fallen.

Example 14 A mixture of polymer A1 and perfluoronaphthalene (refractive index: 1.48) manufactured by Aldrich (the latter containing 6% by weight in the mixture) was charged into a glass sealed tube and melt-molded at 250 ° C. A cylindrical molded body (hereinafter, referred to as molded body k) was obtained. The refractive index of the molded body k is 1.357,
T _g was 76 ° C.

Next, a cylindrical tube made of only the polymer A1 was prepared by melt molding, and the molded body k was inserted into the hollow portion to form a cylindrical tube.
A preform was obtained by heating to 00 ° C. and coalescing. By melt-spinning this preform at 230 ° C., a gradient index optical fiber whose refractive index gradually decreased from the center to the periphery was obtained. The optical transmission characteristics of the obtained optical fiber are 180 dB / k at 780 nm.
m, 150 dB / km at 850 nm, 1 at 1300 nm
It was 10 dB / km, and it was confirmed that the optical fiber could transmit light from visible light to near-infrared light well.

This optical fiber was placed in an oven at 70 ° C. for 1 hour.
After storage for 000 hours, the sample was taken out, and the refractive index distribution was measured with an interference microscope. When compared with the refractive index distribution before storage, a decrease in the refractive index was observed near the center of the core. Along with this, the transmission bandwidth is reduced, and before storage, 220 MHZ
What was z · km is 110MHz · km after storage
Had fallen.

Example 15 Polymer A1 and PCR 1
A mixture with 3,5-trichloro-2,4,6-trifluorobenzene [the latter containing 6% by weight in the mixture] was charged into a glass sealed tube, melt-molded at 250 ° C., and formed into a columnar molded product (hereinafter, referred to as “a”). Molded article m) was obtained. The refractive index of the molded product m was 1.355, and T _g was 79 ° C.

Next, a cylindrical tube made of only the polymer A1 was prepared by melt molding, and the molded product m was inserted into the hollow portion to form a cylindrical tube.
A preform was obtained by heating to 00 ° C. and coalescing. By melt-spinning this preform at 230 ° C., a gradient index optical fiber whose refractive index gradually decreased from the center to the periphery was obtained. The optical transmission characteristics of the obtained optical fiber are 210 dB / k at 780 nm.
m, 170 dB / km at 850 nm, 1 at 1300 nm
It was 30 dB / km, and it was confirmed that the optical fiber could transmit light from visible light to near-infrared light well.

This optical fiber was placed in an oven at 70 ° C. for 1 hour.
After storage for 000 hours, the sample was taken out, and the refractive index distribution was measured with an interference microscope. When compared with the refractive index distribution before storage, a decrease in the refractive index was observed near the center of the core. Along with this, a decrease in the transmission bandwidth is seen, and 250 MHZ before storage.
What was z · km is 170MHz · km after storage
Had fallen.

Example 16 A mixture of polymer A2 and perfluoro (2,4,6-triphenyl-1,3,5-triazine) (the latter containing 5% by weight in the mixture) was charged into a glass sealed tube. At 250 ° C. to obtain a columnar molded body (hereinafter referred to as molded body n). The molded article n had a refractive index of 1.340 and a T _g of 130 ° C.

Next, a cylindrical tube made of only the polymer A2 was prepared by melt molding, and the molded product n was inserted into the hollow portion to form a cylindrical tube.
A preform was obtained by heating to 30 ° C. and uniting. By melt-spinning this preform at 270 ° C., an optical fiber whose refractive index gradually decreased from the center toward the periphery was obtained. The optical transmission characteristics of the obtained optical fiber were 250 dB / km at 780 nm and 850 n.
200 dB / km at m and 170 dB / k at 1300 nm
m, and it was confirmed that the optical fiber could transmit light from visible light to near-infrared light well.

The optical fiber was placed in an oven at 85 ° C. for 1 hour.
After storage for 000 hours, after taking out, the refractive index distribution was measured with an interfaco interference microscope and compared with the refractive index distribution before storage, no particular change was observed. The transmission band was measured by the same pulse method as in Example 4, and the characteristics before and after storage were compared.
Since the band did not decrease at m, it was confirmed that the heat resistance was good.

Example 17 A mixture of polymer A3 and perfluoro (2,4,6-triphenyl-1,3,5-triazine) (the latter containing 5% by weight in the mixture) was charged into a glass sealed tube. At 250 ° C. to obtain a columnar molded body (hereinafter referred to as molded body p). The molded article p had a refractive index of 1.320 and a T _g of 140 ° C.

Next, a cylindrical tube made of only the polymer A3 was prepared by melt molding, and the molded body p was inserted into the hollow portion to form a cylindrical tube.
A preform was obtained by heating to 30 ° C. and uniting. By melt-spinning this preform at 270 ° C., an optical fiber whose refractive index gradually decreased from the center toward the periphery was obtained. The optical transmission characteristics of the obtained optical fiber were 300 dB / km at 780 nm and 850 n.
250 dB / km at m, 200 dB / k at 1300 nm
m, and it was confirmed that the optical fiber could transmit light from visible light to near-infrared light well.

This optical fiber was placed in an oven at 85 ° C. for 1 hour.
After storage for 000 hours, after taking out, the refractive index distribution was measured with an interfaco interference microscope and compared with the refractive index distribution before storage, no particular change was observed. The transmission band was measured by the same pulse method as in Example 4, and the characteristics before and after storage were compared.
Since the band did not decrease at m, it was confirmed that the heat resistance was good.

[0109]

Since the compounds of the present invention, according to the present invention (B) has a high refractive index, even in small amount, can form a refractive index difference of the objects, advantages decrease less a T _g by addition of the compound (B) There is. By the T _g of the advantages and compound (B) is high, the optical resin material of the present invention is heat resistance is remarkably improved, high thermal stability of the refractive index distribution, long term high temperature above room temperature Even when exposed, it is possible to prevent a decrease in the transmission band. Further, the compound (B) having a high refractive index can increase the numerical aperture NA.

Further, since the compound (B) has good solubility in the polymer (A), the transparency of the optical resin material of the present invention is good, and the phase separation of the compound (B) and the fineness of the compound (B) are small. Light scattering caused by crystals and the like is small.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/5399 C08K 5/5399 C08L 27/12 C08L 27/12 29/10 29/10 45/00 45/00 G02B 1/04 G72B 1/04 6/18 6/18 (72) Inventor Masayuki Tamura 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Inside Asahi Glass Co., Ltd. Inside the company (72) Inventor Jun Irizawa 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa-ken Asahi Glass Co., Ltd.

Claims (7)

[Claims] 1. One or more kinds of non-crystalline fluoropolymers (A) having substantially no C—H bond and having a refractive index higher by 0.005 or more in comparison with the fluoropolymers (A) Having a concentration gradient in which the concentration of the fluorinated polycyclic compound (B) in the fluorinated polymer (A) decreases from the center to the peripheral direction. A distributed refractive index type optical resin material, wherein the fluorinated polycyclic compound (B) comprises the following (B1), (B2) and (B)
3) A refractive index distribution type optical resin material, which is at least one kind of fluorine-containing polycyclic compound selected from the group consisting of: (B1) one or more selected from the group consisting of a triazine ring, an oxygen atom, a sulfur atom, a phosphorus atom, and a metal atom, wherein two or more of the fluorinated rings that are carbocyclic or heterocyclic and have a fluorine atom or a perfluoroalkyl group A compound containing a fluorine-containing non-condensed polycyclic compound bonded by a bond containing the above, and having substantially no C—H bond. (B2) a fluorine-containing non-condensed polycyclic compound which is a carbocyclic or heterocyclic ring and has three or more fluorine-containing rings having a fluorine atom or a perfluoroalkyl group bonded directly or by a bond containing a carbon atom; And substantially C-
A compound having no H bond. (B3) A fused polycyclic compound composed of three or more carbocycles or heterocycles and having substantially no C—H bond. 2. A numerical aperture NA [NA = (n ² −m ² ) ^1/2 , n] in the refractive index distribution type optical resin material according to claim 1.
Is the maximum value of the refractive index in the gradient index optical resin material, and m is the minimum value of the refractive index in the gradient index optical resin material. ] Is 0.20 or more. 3. A refractive index distribution type optical resin material according to claim 1 or 2, wherein the glass transition temperature at the center of the refractive index distribution type optical resin material is 70 ° C. or higher. 4. A fluorine-containing polycyclic compound (B) in the central part of the refractive index distribution type optical resin material according to claim 1, 2 or 3.
Is a refractive index distribution type optical resin material having a concentration of 15% by weight or less. 5. The refractive index distribution type optical resin material according to claim 1, wherein the fluorine-containing polycyclic compound (B) has a refractive index of 1.45 or more. 6. The fluoropolymer (A) is a fluoropolymer having a fluorinated aliphatic ring structure in the main chain.
The refractive index distribution type optical resin material according to any one of the above. 7. The gradient index optical resin material according to claim 1, wherein the optical resin material is a preform for manufacturing a gradient index optical fiber or a gradient index optical fiber.