JP2002327051A - Fluorine-containing copolymer, its production method and optical resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine-containing copolymer having such suitable properties for a clad material of a light-transmitting fiber and the like, having an excellent adhesion to a base material and resin transparency and, further, low refractive index, its production method and an optical resin. SOLUTION: In providing each of the fluorine-containing copolymer, its production method and the optical resin, the fluorine-containing copolymer contains a structural units derived from a bisphenol AF diglycidyl ether and that derived from terephthalic acid(TPA) or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fluorinated copolymer suitable as a material for optical transmission fibers and the like, a method for producing the same, and an optical resin using such a fluorinated copolymer.

[0002]

2. Description of the Related Art Conventionally, optical transmission fiber clad and core materials, photoreceptor materials, optical lens materials, optical waveguide materials, optical film materials, compact disc materials, and anti-reflection film materials have been developed. As an optical resin, polymethyl methacrylate (PMMA) is frequently used because of its excellent transparency, mechanical properties, and workability. However, PMMA is generally highly hygroscopic,
Further, it has a disadvantage such as insufficient heat resistance. Therefore,
In recent years, polycarbonate (P) has recently been used as an optical resin as an alternative to PMMA because of its low hygroscopicity, excellent heat resistance, and excellent transparency and mechanical properties.
Use of C) is under consideration. However, the PC
Poor fluidity, poor processability, and chemical structure
It has a drawback such as high birefringence. Therefore, it has been proposed to copolymerize a PC with a styrene resin having an intrinsic birefringence opposite to that of the PC or to add a styrene resin. However, PC
When styrene-based resin was copolymerized with styrene resin, further problems such as a decrease in transparency or a decrease in adhesion to a substrate were found.

On the other hand, a fluorine-based vinyl compound is preferably used as an optical resin because of its low refractive index and high heat resistance. A composition using such a fluorine-based vinyl compound is disclosed in, for example, JP-A-64-1422.
No. 1 discloses this. This fluorine-based composition,
Compound 10 obtained by reacting a carboxyl group-containing ethylenically unsaturated monomer with a fluorine-containing copolymer comprising 50 to 99.7 parts by weight of a fluorinated vinyl monomer and 0.3 to 50 parts by weight of an acrylate monomer having a glycidyl group
To 90 parts by weight and an acrylic monomer for viscosity adjustment
90 parts by weight and 0.05 to 20 parts by weight of a photopolymerization initiator. However, Japanese Patent Application Laid-Open
While the fluorinated vinyl monomer disclosed in No. 14221 has a problem of low adhesion to a substrate,
There is a problem that the birefringence is large due to the inclusion of a polar monomer. In addition, since it is produced by radical polymerization, the molecular weight distribution is wide, and as a result, there is a problem that the fluidity is low and the optical characteristics vary. In order to improve the above-mentioned fluorine-based vinyl compound, various molding materials of a fluorine-containing polyimide resin and a polysiloxane compound have been proposed. However, there was still a problem that all of the molding materials had poor fluidity and poor molding processability and mechanical properties. Also, these molding materials are
There is also a problem that the birefringence is large, the transparency is poor, and the light loss when guided is large.

[0004]

Therefore, the optical resins conventionally used or studied have a sufficient balance of properties such as transparency, heat resistance, refractive index, birefringence, molecular weight distribution and fluidity. It was hard to say that I was taken. Then, the present inventors, 2,2-bis (4-hydroxyphenyl) hexafluoropropane diglycidyl ether (hereinafter sometimes referred to as BPAFGE) and a specific dicarboxylic acid compound and a specific bisphenol compound, or By performing a polyaddition reaction with either compound, it is excellent in transparency and heat resistance, and has a low refractive index, a small birefringence, a small molecular weight distribution, and a high fluidity. It has been found that a polymer is obtained. That is, an object of the present invention is, for example, a fluorine copolymer suitable for a cladding material of an optical transmission fiber or the like, and having an excellent balance of properties such as heat resistance and refractive index, a method for producing the same, and such a fluorine-containing polymer An object of the present invention is to provide an optical resin using a copolymer.

[0005]

SUMMARY OF THE INVENTION One aspect of the present invention provides
A structural unit derived from 2,2-bis (4-hydroxyphenyl) hexafluoropropane diglycidyl ether (BPAFGE), and a structural unit derived from at least one compound represented by the following formulas (1) to (5): And a fluorine-containing copolymer.

[0006]

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[0007]

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[0008]

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[0009]

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[0010]

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By constituting the fluorine-containing copolymer in this manner, it is excellent in transparency and heat resistance, and has a low refractive index.
Birefringence can be reduced. Further, such a fluorinated copolymer also has a feature that the molecular weight distribution is small and the fluidity is high.

In constituting the fluorine-containing copolymer of the present invention, the number average molecular weight is from 3,000 to 300,000.
It is preferable that the value be in the range of 0. With this configuration, the molecular weight distribution becomes smaller, and the adjustment of fluidity and optical properties becomes easier.

In constituting the fluorine-containing copolymer of the present invention, a fluorine-containing ester-based curing agent is preferably contained. With this configuration, it is possible to obtain a fluorine-containing copolymer having a crosslinked structure, which is excellent in adhesion to a substrate and heat resistance of a resin.

Further, another embodiment of the present invention relates to 2,2-bis (4-hydroxyphenyl) hexafluoropropanediglycidyl ether (BPAFGE) and the above formula (1)
A method for producing a fluorine-containing copolymer, which comprises subjecting at least one compound represented by any one of (1) to (5) to a polyaddition reaction. By producing the fluorinated copolymer in this way, the starting monomers can be quantitatively reacted. In addition, since these raw material monomers are excellent in compatibility, they are excellent in transparency and heat resistance, and have a low refractive index, and efficiently obtain a fluorine-containing copolymer having a low birefringence. be able to.

In practicing the process for producing a fluorine-containing copolymer of the present invention, the method is carried out in the presence of at least one catalyst selected from the group consisting of quaternary onium salts, tertiary amines, and tertiary phosphines. Is preferably subjected to a polyaddition reaction. By using such a catalyst,
The raw material monomer can be subjected to the polyaddition reaction more quickly,
Further, the number average molecular weight and the molecular weight distribution can be easily adjusted.

Still another aspect of the present invention is an optical resin containing the above-mentioned fluorine-containing copolymer. By using a fluorinated copolymer that is excellent in transparency and heat resistance, low in refractive index, and low in birefringence, and has an excellent balance of properties, it can be used as a material for optical transmission fiber (cladding). In addition, optical resins suitable for uses such as optical waveguides, antireflection films, and photoconductors can be effectively provided.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments relating to the fluorinated copolymer in the present invention (first embodiment), embodiments relating to the production method thereof (second embodiment), and embodiments relating to the optical resin (third embodiment) Each of the embodiments will be specifically described.

[First Embodiment] A first embodiment will be described below.
A structural unit derived from 2,2-bis (4-hydroxyphenyl) hexafluoropropanediglycidyl ether (BPAFGE) and a structural unit derived from at least one compound represented by formulas (1) to (5) It is a fluorine-containing copolymer characterized by containing.

Structural Unit Derived from BPAFGE The fluorine-containing copolymer of the first embodiment has a structural unit derived from BPAFGE (which may be referred to as a first structural unit) to provide close adhesion to a substrate. It is possible to obtain a fluorine-containing copolymer which is excellent in transparency and transparency, has a low refractive index and low birefringence. Further, regarding the content of the first structural unit in the fluorinated copolymer,
It is determined in consideration of the use of the fluorine-containing copolymer and the like, but is usually 10 to 10 with respect to the total amount of the fluorine-containing copolymer.
It is preferable to set the value in the range of 80 mol%. The reason is that the content of the first structural unit is 10 mol%.
If the value is less than the above, transparency and heat resistance may decrease, or the values of the refractive index and the birefringence may increase. On the other hand, the content of the first structural unit is 80
If the amount exceeds mol%, the glass transition point may decrease or the mechanical strength may decrease. Therefore, the content of the first structural unit is more preferably set to a value in the range of 20 to 70 mol%, and more preferably to a value in the range of 30 to 60 mol%, based on the total amount of the fluorinated copolymer. More preferably,

(2) Structural units derived from the compounds represented by the formulas (1) to (5) In constituting the fluorine-containing copolymer of the first embodiment, in addition to the first structural units, the above-described formula (1)-(5)
(Hereinafter, may be referred to as a second structural unit) derived from a compound represented by the following formula (hereinafter, referred to as a first copolymer component). This is because the following advantages can be obtained by including the second structural unit derived from the first copolymer component. In the resulting polyester or polyether as a fluorine-containing copolymer, a hydroxyl group can be contained in a side chain. The value of the glass transition point of the fluorinated copolymer can be improved by the intermolecular interaction. Adhesion between the fluorine-containing copolymer and substrates made of various materials can be improved. By including a fluorine element in the second structural unit, the fluorine concentration in the fluorine-containing copolymer can be increased, and as a result, the refractive index can be further reduced. In addition, together with the compounds represented by the formulas (1) to (5) or instead of the compounds represented by the formulas (1) to (5), 2,2-bis (4
-Carboxyphenyl) hexafluoropropane (BC
It is also preferable to use a fluorinated dicarboxylic acid compound such as FP).

The content of the second structural unit is determined in consideration of the use of the fluorinated copolymer and the like.
It is preferable to set the value within the range of 80 mol%. The reason for this is that if the content of the second structural unit is less than 10 mol%, the effect of adding the compounds represented by the formulas (1) to (5) may not be exhibited.
When the amount exceeds mol%, the unreacted amount of the first copolymerization component, which is a compound represented by the formulas (1) to (5), becomes excessively large, and the heat resistance of the obtained fluorine-containing copolymer decreases. Because there is. Therefore, the content of the second structural unit is set at 20 to the total amount of the fluorinated copolymer.
It is more preferably set to a value within the range of 70 to 70 mol%, and further preferably set to a value within the range of 30 to 60 mol%.

(3) Other Copolymer Components In constituting the fluorine-containing copolymer of the first embodiment, another copolymer component different from the first copolymer component (hereinafter referred to as a second copolymer component) is used. It is also preferable to add a polymerization component). That is, a structural unit derived from the second copolymer component (hereinafter, sometimes referred to as a third structural unit) is introduced, and the number average molecular weight, fluorine content, transparency, and heat resistance of the fluorinated copolymer are introduced. This is because birefringence, reactivity at the time of production, and the like can be appropriately adjusted. Examples of such a second copolymer component include other epoxy compounds, polyhydric alcohol compounds, and polycarboxylic acid compounds different from the first copolymer component. Specifically,
Other epoxy compounds include 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether (BFAG
E) 3,3 ', 5,5'-tetramethylbiphenyl-4,
4'-diglycidyl ether (TMBGE), 1,4-butanediol diglycidyl ether (BGGE), biphenyl-
One kind or a combination of two or more kinds such as 4,4'-diglycidyl ether (BGE) is exemplified. Further, as the polyhydric alcohol compound, 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, 2,2,3,3,4,4,
5,5-octafluoro-1,6-hexanediol, 1
H, 1H, 8H, 8H-dodecafluoro-1,8-octanediol, 1H, 1H, 9H, 9H-perfluoro-1,9
-Nonanediol, 1H, 1H, 10H, 10H-perfluoro-1,10-decanediol, 1H, 1H, 12H,
12H-perfluoro-1,12-dodecanediol,
One or a combination of two or more of tetrafluorobenzene-1,3-diol, tetrafluorobenzene-1,4-diol and the like can be mentioned. Further, as the polyvalent carboxylic acid compound, tetrafluorosuccinic acid, dodecafluorosuberic acid, perfluoroazelaic acid, perfluorosebacic acid, perfluoro-1,10-decanedicarboxylic acid, tetrafluoroisophthalic acid, tetrafluorophthalic acid One or a combination of two or more of 2,2-bis (4-carboxyphenyl) hexafluoropropane, 4-trifluoromethylphthalic acid and the like can be mentioned.

The content of the third structural unit is determined in consideration of the use of the fluorine-containing copolymer and the like. For example, the content of the third structural unit is determined by Is preferably in the range of 0.1 to 50 mol% with respect to the total amount of The reason for this is that if the content of the third structural unit is less than 0.1 mol%, the effect of addition may not be exhibited. On the other hand, if the content exceeds 50 mol%, the heat resistance of the fluorinated copolymer is reduced. This is because the properties and birefringence may decrease. Therefore, the content of the third structural unit is more preferably set to a value within the range of 1 to 30 mol%, and more preferably to a value within the range of 10 to 20 mol%, based on the total amount of the fluorinated copolymer. More preferably,

(4) Crosslinking Agent In the fluorinated copolymer of the first embodiment, it is also preferable to add a crosslinking agent during or after the polymerization. That is, by adding a cross-linking agent, the heat resistance and the adhesion to the substrate of the fluorocopolymer, or
This is because the reactivity and the like during the polymerization of the fluorinated copolymer can be appropriately adjusted. As such a crosslinking agent,
It is preferable to use a fluorine-containing ester-based curing agent,
Specifically, 1,3,5-tris (2,4-difluorobenzoyloxy) benzene represented by the following formula (6) or benzene-1,3,5-tricarboxylic acid tris represented by the formula (7) It is preferable to use a fluorine-containing ester-based curing agent such as-(2,4-difluorophenyl) ester. With such a fluorine-containing ester-based curing agent,
It is easy to adjust the fluorine content of the fluorine-containing copolymer, and the loss of the transparency of the fluorine-containing copolymer is reduced.

[0025]

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[0026]

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In order to crosslink using the hydroxyl groups of the fluorine-containing copolymer, it is also possible to use compounds having a reactive group with hydroxyl groups such as isocyanate compounds, bisphenol compounds, dicarboxylic acid compounds and bisepoxy compounds. preferable.

The amount of the crosslinking agent used is determined in consideration of the use of the fluorinated copolymer and the like.
0.1 parts by weight based on 100 parts by weight of the total amount of the fluorinated copolymer.
It is preferred that the value be in the range of 1 to 20 parts by weight. The reason for this is that if the amount of the crosslinking agent used is less than 0.1 part by weight, the effect of addition may not be exhibited,
On the other hand, if it exceeds 20 parts by weight, it may be difficult to control the reaction. Accordingly, the amount of the crosslinking agent used is more preferably set to a value within the range of 0.5 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total amount of the fluorocopolymer. More preferably, the value is within the range.

(5) Number Average Molecular Weight The number average molecular weight (Mn) of the fluorinated copolymer is not particularly limited, but is usually from 3,000 to 30.
Preferably, the value is in the range of 000. The reason is that when the number average molecular weight is less than 3,000,
This is because the resulting fluorinated copolymer may have reduced adhesion to the substrate and reduced heat resistance.
If it exceeds 000, the reaction time may be excessively long or the reaction rate may decrease.
Therefore, since the balance between the adhesion and the like of the fluorocopolymer to the substrate and the reaction rate becomes better, the number average molecular weight of the fluorocopolymer is set to 5,000 to 10
More preferably, the value is within the range of 0000,
More preferably, the value is in the range of 0000 to 50,000. Further, as an index of the molecular weight distribution of the fluorinated copolymer, the value of Mw / Mn is preferably set to a value within a range of 1 to 4, more preferably a value of 1 to 3; More preferably, the value is within the range of 2. In addition, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the fluorinated copolymer can be calculated as polystyrene conversion numbers using gel permeation chromatography (GPC).

(6) Fluorine Content The fluorine content of the fluorinated copolymer is 10 to
It is preferable to set the value in the range of 80 mol%. The reason for this is that if the fluorine content is less than 10 mol%, the birefringence and heat resistance of the resulting fluorine-containing copolymer may be reduced, while the fluorine content is reduced to 80 mol%. If the amount exceeds the above, the mechanical strength and transparency of the fluorinated copolymer may decrease. Therefore, since the balance between the birefringence and the like of the fluorinated copolymer and the mechanical strength and the like becomes better, the fluorinated amount in the fluorinated copolymer is set to a value in the range of 20 to 70 mol%. More preferably, 30 to 60 mol
% Is more preferable. The fluorinated content of the fluorinated copolymer can be measured by the alizarin complexon method. The fluorine content can also be calculated from the amount of fluorine contained in the raw material monomer used and the amount of the raw material monomer used.

(7) Refractive index Further, the refractive index (n _D , 25 ° C.) of the fluorine-containing copolymer
Measurement) is preferably set to a value within the range of 1.40 to 1.65. The reason is that when the refractive index is less than 1.40, the transparency and heat resistance of the obtained fluorinated copolymer are reduced, or the kind of the raw material monomer that can be used is excessively limited. Because there is. On the other hand, if the refractive index exceeds 1.65, birefringence and light loss may become excessively large. Therefore, since the balance between the transparency of the fluorinated copolymer and the birefringence becomes better, the refractive index of the fluorinated copolymer is set to a value within the range of 1.45 to 1.60. More preferably, the value is more preferably in the range of 1.47 to 1.55.

(8) Glass transition point The glass transition point of the fluorine-containing copolymer is set to 30
It is preferable to set the value within the range of 150 ° C. The reason for this is that when the glass transition point is lower than 30 ° C., the heat resistance of the obtained fluorocopolymer may be reduced. On the other hand, when the glass transition point exceeds 150 ° C., the reaction time Is excessively long, or the polymerization efficiency may be reduced. Therefore, since the balance between the heat resistance and the reactivity of the fluorinated copolymer becomes better, the glass transition point of the fluorinated copolymer is preferably set to a value in the range of 50 to 140 ° C. More preferably, the value is in the range of 80 to 130 ° C. The glass transition point of the fluorinated copolymer can be calculated from the point of change in the specific heat of a DSC chart obtained by a differential scanning calorimeter (DSC).

(9) Thermal Decomposition Temperature (Tg ₅ ) The 5% weight thermal decomposition temperature (Tg ₅ ) of the fluorinated copolymer is preferably set to a value within the range of 180 to 450 ° C. The reason is that such Tg ₅ is 180 ° C.
If less than, and may be a case where heat resistance of the fluorine-containing copolymer obtained is decreased, whereas, it takes Tg _5,
If the temperature exceeds 450 ° C., the reaction time becomes excessively long,
Alternatively, usable monomer species may be excessively limited. Therefore, since the balance between the heat resistance and the reactivity of the fluorinated copolymer becomes better, the Tg ₅ in the fluorinated copolymer is set to 200 to
More preferably, the value is in the range of 400 ° C.
More preferably, the value is in the range of 0 to 380 ° C. Incidentally, Tg ₅ in the fluorine-containing copolymer can be measured in a nitrogen-containing gas stream, by thermobalance (TGA).

(10) Others In addition, an antioxidant, an ultraviolet absorber, a plasticizer, and the like may be contained in the fluorinated copolymer without departing from the object of the present invention.
Surfactants, antistatic agents, silane coupling agents, inorganic fillers, pigments, dyes, metal particles, dopants, or reactive diluents, thermosetting agents, photocuring agents, various oligomers,
It is also preferable to add one kind of polymer alone or a combination of two or more kinds.

[Second Embodiment] The second embodiment is a method for producing a fluorine-containing copolymer containing a first structural unit and a second structural unit. Specifically, 2,2-bis (4-
Method for producing fluorine-containing copolymer obtained by polyaddition reaction of (hydroxyphenyl) hexafluoropropanediglycidyl ether (BPAFGE) with compounds represented by formulas (1) to (5) (first copolymerization component) It is. Hereinafter, the reaction conditions and the like will be described, but the obtained fluorinated copolymer is the same as that described in the first embodiment, and the description thereof will be omitted.

(1) Reaction Ratio The reaction ratio between BPAFGE as the raw material monomer and the first copolymerization component is preferably set to a value within a range of 1:10 to 10: 1 by mol ratio. The reason for this is that if the reaction ratio is outside these ranges, a large amount of unreacted components will remain in the BPAFGE and the first copolymer component, or the reactivity and heat resistance of the obtained fluorine-containing copolymer will be high. This is because there is a case where it is lowered. Therefore, the reaction ratio between the BPAFGE and the first copolymerization component is calculated as follows:
The molar ratio is more preferably a value within a range of 3: 7 to 7: 3, and further preferably a value within a range of 4: 6 to 6: 4.

(2) Reaction Temperature The reaction temperature between BPAFGE and the first copolymerization component is not particularly limited, either.
It is preferable that the value be in the range of 50 ° C. The reason for this is that if the reaction temperature is lower than 40 ° C., the reactivity between the fluorine-containing compound and the first copolymerization component may be significantly reduced, while if the reaction temperature exceeds 150 ° C. This is because these reactions may be controlled or the type of solvent used for polymerization may be excessively restricted. Accordingly, the balance between the reactivity of the raw material monomers and the reaction control becomes better, and the reaction temperature is set at 50.
It is more preferable to set the value within the range of 120 ° C to 120 ° C.
More preferably, the value is in the range of 0 to 90 ° C.
FIG. 1 is based on Examples 1 and 9 to 11,
An example of the relationship between the reaction temperature (° C.), the reaction rate (Yield,%) and the number average molecular weight (Mn) is shown. In the case of these examples, it is understood that the reaction rate and the number average molecular weight peak at a reaction temperature in the range of about 60 to 70 ° C. However, as shown in Table 7 and Table 11, when the kind of the raw material monomer, the kind of the solvent, and the like change, the temperature at which the peak of the reaction rate and the number average molecular weight are obtained may also change.

(3) Reaction time The reaction time between BPAFGE and the first copolymerization component is not particularly limited, either.
It is preferable to set the value within a range of 0 hours. The reason for this is that if the reaction time is less than 1 hour, the reactivity between the fluorine-containing compound and the first copolymerization component may be significantly reduced, while if the reaction time exceeds 120 hours. This is because it may be difficult to control these reactions or it may be economically disadvantageous. Therefore, since the balance between the reactivity of the raw material monomers and the reaction control becomes better, the reaction time is more preferably set to a value within the range of 6 to 72 hours,
More preferably, the value is in the range of 12 to 48 hours. FIG. 2 shows an example of the relationship between the reaction time (h), the reaction rate (Yield,%), and the number average molecular weight (Mn) based on Examples 1 and 12 to 15. In these examples, it is understood that the reaction rate and the number average molecular weight peak at a reaction time of about 24 hours.
However, as shown in Table 8, when the raw material monomer type, the solvent type, and the like are changed, the reaction time at which the peak of the reaction rate and the number average molecular weight are obtained may be changed.

(4) Catalyst It is preferable to use a catalyst when performing the polyaddition reaction between BPAFGE and the first copolymerization component. Such catalysts include at least one catalyst selected from the group consisting of quaternary onium salts, tertiary amines, and tertiary phosphines. More specifically, tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride (TBAC), tetrabutylphosphonium bromide (TBPB), tetrabutylphosphonium chloride (TBPC), tetrabutylammonium iodide (TBA
I), tetraphenylphosphonium bromide (TPPB),
Tetraphenylphosphonium chloride (TPPC), tetraphenylphosphonium iodide (TPPI), triphenylphosphine (TPP), 4- (N, N-dimethylamino)
Examples include pyridine (DMAP) and 1,8-diazabicyclo- [5,4,0] -undecene-7 (DBU) alone or in combination of two or more.

[0040] The amount of the catalyst to be added is not particularly limited.
It is preferable to set the value to a value within the range of 0.01 to 30 parts by weight based on 100 parts by weight of the total amount of BPAFGE and the first copolymerization component. The reason for this is that if the amount of the catalyst is less than 0.01 part by weight, the reactivity between BPAFGE and the first copolymerization component may be remarkably reduced. If it exceeds 30 parts by weight, it may be difficult to control the reaction or to perform a purification operation after the reaction is completed. Therefore, the amount of the catalyst to be added is more preferably set to a value within the range of 0.05 to 20 parts by weight with respect to 100 parts by weight of the total amount of the BPAFGE and the first copolymer component. More preferably, the value is in the range of 1 to 10 parts by weight.

(5) Solvent It is preferable that BPAFGE is subjected to a polyaddition reaction with the first copolymer component in a solvent. The reason for this is that by performing the polyaddition reaction in the solvent, the raw material monomers react uniformly, and the molecular weight distribution of the obtained fluorine-containing copolymer is narrowed. Preferred types of solvents include dioxane, toluene, diglyme, o-dichlorobenzene, chlorobenzene, anisole, dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, ethyl acetate, N, N'-dimethylacetamide, methyl ethyl ketone, chloroform, and dichloromethane. , Amyl acetate, acetonitrile, nitrobenzene, cyanobenzene, etc., alone or in combination of two or more. Among these solvents, toluene, diglyme, and o-dichlorobenzene are more preferable because the reactivity of the fluorinated copolymer is also improved. The amount of the solvent used is not particularly limited. For example, the amount of the solvent is set to a value within the range of 10 to 1,000 parts by weight based on 100 parts by weight of the raw material monomer. Is preferred. The reason for this is that when the amount of the solvent used is less than 10 parts by weight, the reactivity between the fluorine-containing compound and the first copolymer component is significantly reduced, and an unnecessary polymer may be formed as a by-product. On the other hand, if the amount of the solvent exceeds 1,000 parts by weight, it may be difficult to control the reaction or to perform a purification operation after the reaction is completed. Accordingly, the amount of the solvent used is more preferably set to a value within the range of 50 to 800 parts by weight, and more preferably set to a value within the range of 100 to 500 parts by weight, based on 100 parts by weight of the raw material monomer. preferable.

Third Embodiment A third embodiment is an optical resin containing the fluorinated copolymer of the first embodiment.

(1) Applications The applications of the optical resin of the third embodiment include cladding materials and core materials of optical transmission fibers, photoreceptor materials, optical lens materials, optical waveguide materials, and optical film materials. ,
Examples include materials for compact disks, materials for anti-reflection films, and sealing materials for electric / electronic parts. For example, FIG.
As shown in (2), when the optical resin is used for the cladding layers 52 and 58 of the optical transmission fiber 50, the refractive index (n _D ) of the optical resin is set to 1.50 in order to reduce the optical loss during transmission. The following values are preferred. Therefore, when forming the optical resin, it is preferable to make the fluorine content relatively large. Although FIG. 22 illustrates the optical transmission fiber 50 connected by providing the frail 64,
Various configuration changes can be made. Further, as shown in FIG. 23, an optical resin is applied to the cladding layer 2 of the optical waveguide 10.
4 and wavelength 1,300 to 1,600n
When light of m (arrows A and B) is used, the refractive index of the optical resin is preferably set to a value within the range of 1.400 to 1.648. In order to reduce the optical loss in the optical waveguide 10 to a value of 0.1 dB / cm or less, the refractive index of the cladding layer 24 is set to a value smaller by 0.002 to 0.5 than the refractive index of the core portion 15. Is more preferred. In FIG. 23, the optical waveguide 1 as an optical switch is shown.
Although 0 is illustrated, various configurations can be changed.

(2) Form Although the form of the optical resin is not particularly limited, it is preferably liquid so that a uniform film can be formed on the substrate or the core of the optical transmission fiber. Therefore, the viscosity of the optical resin is adjusted to, for example, 10 to 10 by adding an organic solvent or a viscosity modifier (including a copolymerizable monomer).
It is preferable to adjust to a value within the range of 000 mPa · s (measuring temperature 25 ° C.). Examples of the organic solvent and viscosity modifier added to the optical resin include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; cyclic ethers such as tetrahydrofuran and dioxane; N, N-dimethylformamide; Amides such as N-dimethylacetamide; aromatic hydrocarbons such as toluene and xylene; and halogenated hydrocarbons such as methylene chloride.

(3) Usage method Coating method In using the optical resin, it is preferable to apply the optical resin so that a uniform film can be formed on the substrate or the core of the optical transmission fiber. Therefore, it is preferable to adopt a dipping method, a roll coating method, a spin coating method, a gravure coating method, or the like as the coating method.

Thermosetting and Photocuring It is preferable to add a thermosetting component or a photocuring component to the optical resin, apply the optical resin, and then heat or irradiate the resin. By performing the heat curing and the light curing in this manner, the adhesion to the substrate and the heat resistance can be significantly improved. Therefore, for example, the heating condition is set to 5
The temperature is preferably in the range of 0 to 120 ° C for 1 to 180 minutes. The light irradiation conditions are 100 to 1000 m.
It is preferable to be in the range of J / cm ² .

[0047]

Hereinafter, embodiments of the present invention will be described in detail.
It goes without saying that the scope of the present invention is not limited to the description of these examples. In the examples, the amounts of the respective components mean parts by weight unless otherwise specified.

Example 1 (1) Synthesis of BPAFGE In a 300 mL three-neck eggplant type flask equipped with a stirrer and a dropping funnel, 20.17 g of bisphenol AF (6
0 mmol) and 46.92 g (144) of cesium carbonate.
mmol) and 180 ml of NMP, and stirred at room temperature for 3 hours to obtain a uniform solution. Then, 19.72 g of epibromohydrin (144 mmol)
l) was dropped from a dropping funnel and reacted with bisphenol AF at 50 ° C. for 48 hours to obtain BPA as a salt.
FGE was generated. After completion of the reaction, BPAFGE was filtered, and ethyl acetate was added to the filtrate, followed by washing with distilled water three times. Then, the organic layer containing BPAFGE was taken out and dried using anhydrous magnesium sulfate as a desiccant. Further, after removing anhydrous magnesium sulfate, ethyl acetate was distilled off under reduced pressure. Then, using a developing solvent consisting of n-hexane and ethyl acetate (mixing ratio 1: 1), the mixture was isolated by silica gel column chromatography,
Further dried under reduced pressure, BPAF which is a powdery white solid
GE (yield 23.08 g, 86%, mp 72 ° C.) was obtained. For reference, FIG. 3 shows the obtained BPAFGE
FIG. 4 shows a ¹ H-NMR chart measured for FIG.
To show the ¹³ C-NMR chart, and FIG. 5, ¹⁹ F
3 shows an NMR chart. Bisphenol AF
And the reaction scheme of epibromohydrin is shown in the following formula (8).

[0049]

Embedded image

(2) Preparation of Fluorine-Containing Copolymer In a dry bag (relative humidity: 10% or less), 0.009 g (2.5 mol) of TBAB was added as a catalyst in an ampoule tube.
1%), and dried under reduced pressure at 60 ° C. for 5 hours. Then, 2,2-bis (4-
(Hydroxyphenyl) hexafluoropropane diglycidyl ether (BPAFGE) 0.224 g (0.5
mmol) and tetrafluoroterephthalic acid (TFTP
A) was charged with 0.119 g (0.5 mmol) of dioxane and 2 mol / L of dioxane, and the raw material monomers were subjected to a polyaddition reaction at 60 ° C. for 24 hours. After completion of the reaction, the reaction solution was diluted with THF, and purified by reprecipitation twice using THF as a good solvent and an ethanol / n-hexane mixture (mixing ratio 1: 5) as a poor solvent.
Thereafter, drying was performed under reduced pressure at 60 ° C. for 5 hours to obtain a white solid polymer as a fluoropolymer. The reaction rate of this fluoropolymer was 93% as calculated from the amount of the raw material monomers used and the amount of the obtained fluorocopolymer. The reaction scheme between BPAFGE and TFTPA is shown in the following formula (9).

[0051]

Embedded image

(3) Evaluation of fluorinated copolymer The obtained fluorinated copolymer was evaluated for ¹
H-NMR measurement, infrared absorption spectrum measurement, refractive index measurement, molecular weight measurement, and the like were performed. Table 1 shows the results.

[0053]¹H-NMR measurement Using an NMR measuring device (MSL400, manufactured by BRUKER)
Using the solvent CDCl _ThreeFluorine-containing copolymer obtained under the following conditions
An NMR measurement of the coalescence was performed. Got¹H-NMR
The chart is shown in FIG. For reference, fluorine-containing
About TFTPA used as raw material monomer of coalescence¹
The H-NMR chart is shown in FIG.

Infrared absorption spectrum measurement Fourier transform infrared spectrometer (manufactured by JASCO Corporation,
Using JIR-5500), the infrared absorption spectrum of the obtained fluorine-containing copolymer was measured at room temperature (25 ° C.) and resolution 4
The measurement was performed under the conditions of cm ⁻¹ , gain of 1, scanning 10 times, and scanning speed TGS. FIG. 8 shows the obtained infrared absorption spectrum. For reference, FIG. 9 shows an infrared absorption spectrum chart of TFTPA used as a raw material monomer of the fluorocopolymer.

Measurement of Refractive Index In accordance with JIS K7105, the refractive index of the fluorocopolymer at 25 ° C. was measured using an Abbe refractometer (L115B manufactured by Gardner).

Measurement of Molecular Weight The number average molecular weight and the weight average molecular weight of the obtained fluorinated copolymer were measured using GPC (HLC8020, manufactured by Tosoh Corporation).

Using a glass transition point DSC (SSC5200DSC120, manufactured by Seiko Denshi Co., Ltd.) under the conditions of a temperature rising rate of 10 ° C./min and a nitrogen stream.
The glass transition point of the obtained fluorinated copolymer was measured.

Transparency The obtained fluorinated copolymer was formed into a film having a thickness of (100) μm by a solvent, and the transparency was measured according to the following criteria.
It was evaluated visually. ：: The entire film is transparent. Δ: Part or all of the film is semi-turbid. X: A part or the whole of the film is clouded.

[Examples 2 to 5] As shown in Table 1, Example 1
Instead of dioxane, the solvent used during the polymerization,
Fluorine-containing copolymer as in Example 1 except that toluene (Example 2), diglyme (Example 3), dimethylformamide (Example 4), and N-methylpyrrolidone (Example 5) were used. Was created and evaluated.

[0060]

[Table 1]

[Examples 6 to 8] As shown in Table 2, Example 1
Instead of TBAB, the catalyst used during the polymerization at
BAC (Example 6), TBPB (Example 7), and T
A fluorinated copolymer was prepared and evaluated in the same manner as in Example 1 except that BPC (Example 8) was used.

[0062]

[Table 2]

[Examples 9 to 11] As shown in Table 3, instead of 60 ° C., which is the reaction polymerization used in Example 1,
50 ° C. (Example 9), 70 ° C. (Example 10), and 8
A fluorinated copolymer was prepared and evaluated in the same manner as in Example 1 except that 0 ° C. (Example 11) was employed.

[0064]

[Table 3]

[Examples 12 to 15] As shown in Table 4, instead of the reaction time of 24 hours used in Example 10 (reaction temperature of 70 ° C.), 12 hours (Example 12),
8 hours (Example 13), 72 hours (Example 14), and 96 hours (Example 15) were employed, respectively.
In the same manner as in Example 10, a fluorinated copolymer was prepared and evaluated.

[0066]

[Table 4]

Example 16 (1) Synthesis of BPAFGE BPAFGE was synthesized in the same manner as in Example 1.

(2) Preparation of Fluorine-Containing Copolymer In a dry bag (relative humidity: 10% or less), 0.009 g (2.5 mol) of TBAB was used as a catalyst in an ampoule tube.
1%) and dried under reduced pressure at 60 ° C. for 5 hours. Next, BPAFGE is placed in this ampoule tube.
0.224 g (0.5 mmol) and terephthalic acid (T
PA) containing 0.083 g (0.5 mmol) and dimethylformamide (DMF) 2 mol / L,
The starting monomers were subjected to a polyaddition reaction at 24 ° C. for 24 hours. After completion of the reaction, the reaction solution was diluted with THF.
THF as a good solvent, ethanol / n as a poor solvent
After performing reprecipitation purification twice using a hexane mixture (mixing ratio 1: 5), the precipitate was dried under reduced pressure at 60 ° C. for 5 hours to obtain a white solid polymer as a fluoropolymer. When the reaction rate of this fluoropolymer was calculated from the amount of the raw material monomers used and the obtained amount of the fluorocopolymer, 45
%Met. The reaction scheme between BPAFGE and TPA is shown in the following formula (10).

[0069]

Embedded image

(3) Evaluation of Fluorinated Copolymer In the same manner as in Example 1, the obtained fluorinated copolymer was evaluated. Table 5 shows the results. The ¹ H-NMR chart and the infrared spectrum chart of the obtained fluorine-containing copolymer are shown in FIGS.

[Examples 17 and 18] As shown in Table 5, dimethylacetone (DMA) was used instead of dimethylformamide (DMF) as a solvent used during the polymerization in Example 16.
c) (Example 17), and N-methylpyrrolidone (N
MP) (Example 18), except that a fluorine-containing copolymer was prepared and evaluated in the same manner as in Example 16.

[0072]

[Table 5]

[Examples 19 to 21] As shown in Table 6, TBAC (Example 19) and TBPB (Example 2) were used in place of TBAB as a catalyst used during the polymerization in Example 16.
0) and TBPC (Example 21)
In the same manner as in Example 16, a fluorinated copolymer was prepared and evaluated.

[0074]

[Table 6]

[Examples 22 to 24] As shown in Table 7, instead of 70 ° C., which is the reaction polymerization employed in Example 16, 60 ° C. (Example 22), 80 ° C. (Example 23), and 90 ° C. ° C (Example 24), respectively.
In the same manner as in Example 16, a fluorinated copolymer was prepared and evaluated.

[0076]

[Table 7]

[Examples 25 to 27] As shown in Table 8, instead of the reaction time of 24 hours used in Example 16, 6 hours (Example 25) and 12 hours (Example 2)
6) and 48 hours (Example 27), respectively, except that a fluorine-containing copolymer was prepared and evaluated in the same manner as in Example 16.

[0078]

[Table 8]

Example 28 (1) Synthesis of BPAFGE BPAFGE was synthesized in the same manner as in Example 1.

(2) Preparation of Fluorine-Containing Copolymer In a dry bag (relative humidity of 10% or less), 0.009 g (2.5 mol) of TBAC was used as a catalyst in an ampoule tube.
1%) and dried under reduced pressure at 60 ° C. for 5 hours. Next, BPAFGE is placed in this ampoule tube.
0.224 g (0.5 mmol) and 0.165 g of 4,4'-octafluorobiphenol (OFBP) (0.
5 mmol) and 2 mol / L of dioxane
And the starting monomers were subjected to a polyaddition reaction at 100 ° C. for 24 hours. After completion of the reaction, the reaction solution was diluted with THF.
And THF as a good solvent and an ethanol / n-hexane mixture as a poor solvent (mixing ratio 1: 5).
After reprecipitating and purifying twice using, it was dried under reduced pressure at 60 ° C for 5 hours to obtain a white solid polymer as a fluoropolymer. The reaction rate of this fluoropolymer was 89% as calculated from the amount of the raw material monomers used and the amount of the obtained fluorocopolymer. In addition, BPAFGE
And the reaction scheme of OFBP is shown in the following formula (11).

[0081]

Embedded image

(3) Evaluation of Fluorinated Copolymer In the same manner as in Example 1, the obtained fluorinated copolymer was evaluated. Table 9 shows the results. The ¹ H-NMR chart and the infrared spectrum chart of the obtained fluorinated copolymer are shown in FIGS. 12 and 13, respectively.

[Examples 29 to 33] As shown in Table 9, dioxane (Diox) which was a solvent used during the polymerization in Example 28 was used.
Tone (Toluene) (Example 2)
9), Diglyme (Example 30), dimethylformamide (DMF) (Example 31), and N-
A fluorinated copolymer was prepared and evaluated in the same manner as in Example 28 except that methylpyrrolidone (NMP) (Example 32) was used. However, in Example 29, since a solvent-insoluble component was partially generated, in Example 33, although toluene was used as the solvent, the reaction temperature was 100 ° C to 90 ° C.
In the same manner as in Example 28, a fluorinated copolymer was prepared and evaluated.

[0084]

[Table 9]

[Examples 34 to 36] As shown in Table 10, TBAB (Example 34) and TBPC (Example 3) were used in place of TBAC as a catalyst used during the polymerization in Example 28.
5) and using TBPB (Example 36)
In the same manner as in Example 28, a fluorinated copolymer was prepared and evaluated.

[0086]

[Table 10]

[Examples 37 to 39] As shown in Table 11, 90 ° C. (Example 37) was used instead of 100 ° C., which is the reaction polymerization employed in Example 36 (using a catalyst TBPB).
110 ° C. (Example 38) and 120 ° C. (Example 3)
9) except that each was adopted, as in Example 36.
A fluorinated copolymer was prepared and evaluated.

[0088]

[Table 11]

Example 40 (1) Synthesis of BPAFGE As in Example 1, BPAFGE was synthesized.

(2) Preparation of Fluorine-Containing Copolymer In a dry bag (relative humidity: 10% or less), 0.014 g (2.5 mol) of TBAC was added as a catalyst in an ampoule tube.
1%), and dried under reduced pressure at 60 ° C. for 5 hours. Then, BPAFGE 0.
224 g (0.5 mmol) and 1,4-bis (hexafluorohydroxyisopropyl) benzene (1,4-
BFHPB) 0.205 g (0.5 mmol) and dioxane (Dioxane) 2 mol / L,
The starting monomers were subjected to a polyaddition reaction at 24 ° C. for 24 hours. After completion of the reaction, the reaction solution was diluted with THF.
THF as a good solvent, ethanol / n as a poor solvent
After performing reprecipitation purification twice using a hexane mixture (mixing ratio 1: 5), the precipitate was dried under reduced pressure at 60 ° C. for 5 hours to obtain a white solid polymer as a fluoropolymer. When the reaction rate of the fluoropolymer was calculated from the amount of the raw material monomer used and the obtained amount of the fluorocopolymer, 24
%Met. In addition, BPAFGE and 1,4-BFHP
The reaction scheme with B is shown in the following formula (12).

[0091]

Embedded image

(3) Evaluation of Fluorinated Copolymer In the same manner as in Example 1, the obtained fluorinated copolymer was evaluated. Table 12 shows the results. In addition, 1,4-BFH used as the obtained fluorine-containing copolymer and its raw material monomer was used.
FIGS. 14 to 16 show the ¹ H-NMR chart and infrared spectrum chart of PB, respectively.

[Examples 41 to 45] As shown in Table 12, dioxane (Diox) as a solvent used during the polymerization in Example 40 was used.
oxane) instead of Toluene (Example 4)
1), Diglyme (Example 42), 0-dichlorobenzene (DCB) (Example 43), dimethylformamide (DMF) (Example 44), and N-methylpyrrolidone (NMP) (Example 45) A fluorine-containing copolymer was prepared and evaluated in the same manner as in Example 40, except that was used.

[0094]

[Table 12]

[Examples 46 to 48] As shown in Table 13, instead of TBAC which is a catalyst used during the polymerization of Example 42 (Diglyme solvent), TBAB (Example 46), TB
A fluorinated copolymer was prepared and evaluated in the same manner as in Example 42 except that PC (Example 47) and TBPB (Example 48) were used.

[0096]

[Table 13]

Example 49 (1) Synthesis of BPAFGE BPAFGE was synthesized in the same manner as in Example 1.

(2) Preparation of Fluorine-Containing Copolymer In a dry bag (relative humidity: 10% or less), 0.007 g (2.5 mol) of TBAC was added as a catalyst in an ampoule tube.
1%), and dried under reduced pressure at 60 ° C. for 5 hours. Next, BPAFGE was added to this ampoule tube in a volume of 0.1 mL.
224 g (0.5 mmol) and 1,3-bis (hexafluorohydroxyisopropyl) benzene (1,3-
BFHPB) and 0.25 g (0.5 mmol) of dioxane (Dioxane) at 2 mol / L.
The starting monomers were subjected to a polyaddition reaction at 24 ° C. for 24 hours. After completion of the reaction, the reaction solution was diluted with THF.
THF as a good solvent, ethanol / n as a poor solvent
After performing reprecipitation purification twice using a hexane mixture (mixing ratio 1: 5), the precipitate was dried under reduced pressure at 60 ° C. for 5 hours to obtain a white solid polymer as a fluoropolymer. When the reaction rate of the fluoropolymer was calculated from the amount of the raw material monomer used and the obtained amount of the fluorocopolymer, 24
%Met. In addition, BPAFGE and 1,3-BFHP
The reaction scheme with B is shown in the following formula (13).

[0099]

Embedded image

(3) Evaluation of Fluorinated Copolymer In the same manner as in Example 1, the obtained fluorinated copolymer was evaluated. Table 14 shows the results. The obtained fluorinated copolymer and 1,3-BFH used as a raw material monomer thereof were used.
FIGS. 17 to 19 show the ¹ H-NMR chart and infrared spectrum chart of PB, respectively.

[Examples 50 to 55] As shown in Table 14, the solvent used during the polymerization in Example 49, dioxane (Dioxane) was used.
oxane), instead of toluene (Example 5)
0), Diglyme (Example 51), 0-dichlorobenzene (DCB) (Example 52), dimethylformamide (DMF) (Example 53), and N-methylpyrrolidone (NMP) (Example 54) Fluorine-containing copolymer was prepared and evaluated in the same manner as in Example 49 except that was used. In Example 55, a fluorine-containing copolymer was prepared and evaluated in the same manner as in Example 49 except that no solvent was used.

[0102]

[Table 14]

[Examples 56 to 58] As shown in Table 15, the catalyst TB used in the polymerization of Example 55 (without solvent) was used.
Instead of AC, TBAB (Example 56), TBPC
A fluorinated copolymer was prepared and evaluated in the same manner as in Example 55 except that (Example 57) and TBPB (Example 58) were used.

[0104]

[Table 15]

Comparative Example 1 (1) Preparation of Copolymer In a dry bag (relative humidity 10% or less), 0.008 g (2.5 mol) of TBAB was used as a catalyst in an ampoule tube.
1%), and dried under reduced pressure at 60 ° C. for 5 hours. Next, 0.17 of BPGE was placed in the ampoule tube.
0 g (0.5 mmol), 0.083 g (0.5 mmol) of terephthalic acid (TPA), and 2 mol / L of dimethylformamide (DMF).
Under the condition of time, the raw material monomers were subjected to a polyaddition reaction. After the completion of the reaction, the reaction solution was diluted with THF, and further purified twice by reprecipitation using THF as a good solvent and an ethanol / n-hexane mixture (mixing ratio 1: 5) as a poor solvent. Drying under reduced pressure at 5 ° C. for 5 hours gave a white solid polymer as a fluoropolymer. The reaction rate of this fluoropolymer was 24% when calculated from the amount of the raw material monomers used and the amount of the obtained fluorocopolymer. The reaction scheme between BPGE and TPA is shown in the following formula (14).

[0106]

Embedded image

(2) Evaluation of copolymer In the same manner as in Example 1, the obtained copolymer was evaluated. Table 15 shows the results. Incidentally, ¹ about the obtained copolymer
The H-NMR chart and the infrared spectrum chart are shown in FIGS.

Example 59 (1) Preparation of Copolymer In a dry bag (relative humidity of 10% or less), 0.008 g (2.5 mol) of TBAB was used as a catalyst in an ampoule tube.
1%), and dried under reduced pressure at 60 ° C. for 5 hours. Next, BPAFGE was added to this ampoule tube in a volume of 0.1 mL.
224 g (0.5 mmol) and 2,2-bis (4-carboxyphenyl) hexafluoropropane (BCF
P) containing 0.196 g (0.5 mmol) of dioxane and 0.25 mL (2 mol / L) of dioxane.
Under the conditions of 4 hours, the starting monomers were subjected to a polyaddition reaction.
After completion of the reaction, the reaction solution was diluted with THF, further purified twice by using THF as a good solvent and an ethanol / n-hexane mixture (mixing ratio 1: 5) as a poor solvent, and purified by reprecipitation twice. Drying under reduced pressure at 5 ° C. for 5 hours gave a white solid polymer (0.172 g) as a fluoropolymer. The reaction rate of this fluoropolymer was 41% as calculated from the amount of the raw material monomers used and the amount of the obtained fluorocopolymer. Note that BPAFGE and BCF
The reaction scheme with P is shown in the following formula (15).

[0109]

Embedded image

(2) Evaluation of copolymer The obtained copolymer was evaluated in the same manner as in Example 1. As a result, the number average molecular weight (Mn) of the obtained copolymer
Is 3,700 and the molecular weight distribution (Mw / Mn) is 1.3.
It was 3. The infrared spectrum chart of the used BCFP and ¹ H-NMR of the obtained copolymer were used.
The chart and the infrared spectrum chart are shown in FIGS.

[0111]

According to the fluorinated copolymer of the present invention, it is possible to exhibit excellent properties such as excellent transparency, heat resistance and low refractive index in a well-balanced manner. Therefore, it is expected that the optical resin is suitably used as a cladding material of an optical transmission fiber or the like. Further, according to the method for producing a fluorine-containing compound copolymer of the present invention, it is possible to efficiently provide a fluorine-containing copolymer having excellent transparency, heat resistance, or properties such as a low refractive index in a well-balanced manner. It has become possible.

[Brief description of the drawings]

FIG. 1 is a diagram showing a relationship between a reaction temperature, a reaction rate and a number average molecular weight.

FIG. 2 is a diagram showing a relationship between a reaction time, a reaction rate, and a number average molecular weight.

FIG. 3 is a ¹ H-NMR chart of BPAFGE.

FIG. 4 is a ¹³ C-NMR chart of BPAFGE.

FIG. 5 is a ¹⁹ F-NMR chart of BPAFGE.

FIG. 6 is a ¹ H-NMR chart of the fluorinated copolymer obtained in Example 1.

FIG. 7 shows ¹ H of TFTPA used in Example 1.
-It is an NMR chart.

FIG. 8 is an infrared spectrum chart of the fluorinated copolymer obtained in Example 1.

FIG. 9 is an infrared spectrum chart of TFTPA used in Example 1.

FIG. 10 is a ¹ H-NMR chart of the fluorinated copolymer obtained in Example 16.

FIG. 11 is an infrared spectrum chart of the fluorinated copolymer obtained in Example 16.

FIG. 12 is a ¹ H-NMR chart of the fluorinated copolymer obtained in Example 28.

FIG. 13 is an infrared spectrum chart of the fluorinated copolymer obtained in Example 28.

FIG. 14 is a ¹ H-NMR chart of the fluorinated copolymer obtained in Example 40.

FIG. 15 is a ¹ H-NMR chart of 1,4-BFHPB used in Example 40.

FIG. 16 is an infrared spectrum chart of the fluorinated copolymer obtained in Example 40.

17 is a ¹ H-NMR chart of the fluorinated copolymer obtained in Example 49. FIG.

FIG. 18 is a ¹ H-NMR chart of 1,3-BFHPB used in Example 49.

FIG. 19 is an infrared spectrum chart of a fluorinated copolymer obtained in Example 49.

FIG. 20 shows ¹ H of the copolymer obtained in Comparative Example 1.
-It is an NMR chart.

FIG. 21 is an infrared spectrum chart of the copolymer obtained in Comparative Example 1.

FIG. 22 is a diagram provided for explaining an optical transmission fiber;

FIG. 23 is a diagram provided to explain an optical waveguide;

FIG. 24 is an infrared spectrum chart of BCFP used in Example 59.

FIG. 25 is an infrared spectrum chart of a fluorine-containing copolymer obtained in Example 59.

FIG. 26 is a ¹ H-NMR chart of a fluorine-containing copolymer obtained in Example 59.

[Description of sign]

 Reference Signs List 10 optical waveguide 12 base material 15 core 24 cladding layer 21, 22 ridge 50 optical fiber 52, 58 core 54, 60 cladding layer 64 Frere

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 6/00366 G02B 6/00 366 391 391 (72) Inventor Atsushi Kameyama Nishi-Kanagawa, Kanagawa-ku, Yokohama-shi, Kanagawa-ken 1-10-3 Clio Higashi-Kanagawa Ichibankan 705 (72) Inventor Akira Nishikawa 2--11-24 Tsukiji, Chuo-ku, Tokyo FSR term in JSR Co., Ltd. (reference) 2H050 AA13 AB48Z 4J002 CF121 CH061 EH066 EH146 FD146 GP00 GP02 4J005 AA12 AA23 AA24 BA00 4J029 AA01 AB01 AB04 AB07 AC01 AE02 AE04 CB06A CG06 JB203 JC091 JC261 JC631 JE152

Claims (6)

[Claims] 1. A structural unit derived from 2,2-bis (4-hydroxyphenyl) hexafluoropropane diglycidyl ether and a structural unit derived from at least one compound represented by the following formulas (1) to (5): And a fluorine-containing copolymer characterized by comprising: Embedded image Embedded image Embedded image Embedded image Embedded image 2. The number average molecular weight is from 3,000 to 300,0.
The fluorinated copolymer according to claim 1, wherein the value is within the range of 00. 3. The fluorine-containing copolymer according to claim 1, further comprising a fluorine-containing ester-based curing agent. 4. A 2,2-bis (4-hydroxyphenyl) hexafluoropropane diglycidyl ether,
A method for producing a fluorine-containing copolymer, comprising subjecting at least one compound represented by the following formulas (1) to (5) to a polyaddition reaction. Embedded image Embedded image Embedded image Embedded image Embedded image 5. The polyaddition reaction according to claim 3, wherein the polyaddition reaction is carried out in the presence of at least one catalyst selected from the group consisting of a quaternary onium salt, a tertiary amine, and a tertiary phosphine. The method for producing a fluorine-containing copolymer of the above. 6. An optical resin comprising the fluorine-containing copolymer according to claim 1. Description: