JP2002327049A - 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 a bisester compound such as diphenyl terephthalate 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. Therefore, the present inventors have conducted a polyaddition reaction between 2,2-bis (4-hydroxyphenyl) hexafluoropropane diglycidyl ether (hereinafter sometimes referred to as BPAFGE) and a specific bisester compound. ,
It has been found that a fluorocopolymer having excellent transparency and heat resistance, a low refractive index, a small birefringence, a small molecular weight distribution, and a high fluidity can be 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
It contains a structural unit derived from 2,2-bis (4-hydroxyphenyl) hexafluoropropanediglycidyl ether (BPAFGE) and a structural unit derived from a bisester compound represented by the following formula (1). Is a fluorocopolymer.

[0006]

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[0007] 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 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 into which a crosslinked structure is introduced, which is excellent in adhesion to a substrate and heat resistance.

Another aspect of the present invention relates to 2,2-bis (4-hydroxyphenyl) hexafluoropropanediglycidyl ether (BPAFGE), and a compound represented by the following formula (1):
A polyaddition reaction with a bisester compound represented by the following formula:

[0011]

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By producing the fluorinated copolymer in this manner, 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 carrying out the process for producing a fluorine-containing copolymer of the present invention, the method may be 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,
In addition, the adjustment of the average molecular weight and the molecular weight distribution becomes easy.

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.

[0015]

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) hexafluoropropane diglycidyl ether (BPAFGE) and a structural unit derived from a bisester compound represented by the formula (1). Is a fluorine-containing copolymer.

(1) 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). It is possible to obtain a fluorine-containing copolymer having excellent adhesiveness and transparency to a material, a low refractive index, and a small 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 unit derived from bisester compound In constituting the fluorine-containing copolymer of the first embodiment, at least one bisester represented by the formula (1) other than the first structural unit is used. It is characterized by containing a structural unit (hereinafter, may be referred to as a second structural unit) derived from a compound (hereinafter, referred to as a first copolymer component). This is because the following advantages are obtained by including the second structural unit derived from the bisester compound. In the resulting polyester or polyether as a fluorine-containing copolymer, since there is no hydroxyl group in the side chain, the hygroscopicity can be reduced. By esterification, the fluorine concentration in the fluorine-containing copolymer can be greatly increased, and as a result, the refractive index can be further reduced. Since the fluorine concentration in the fluorinated copolymer can be controlled, the refractive index can be easily controlled.

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 bisester compound as the first copolymerization component may not be exhibited, while the content exceeds 80 mol%. This is because the amount of unreacted monomer which is a bisester compound becomes excessively large, and the heat resistance of the obtained fluorine-containing copolymer may decrease. Therefore, the content of the second structural unit is more preferably set to a value within the range of 20 to 70 mol%, and more preferably 30 to 60 mol%, based on the total amount of the fluorinated copolymer.
It is more preferable to set the value within the range.

(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 fluorocopolymer and the like.
It is preferable to set the value in the range of 1 to 50 mol%. The reason is that the content of the third structural unit is 0.1 m
When the amount is less than ol%, the effect of addition may not be exhibited. On the other hand, when the amount exceeds 50 mol%, the fluorine content decreases, and the heat resistance and birefringence of the obtained fluorine-containing copolymer decrease. This is because there are cases. 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 fluorine-containing copolymer of the first embodiment, it is also preferable to add a crosslinking agent during or after 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 (2) or benzene-1,3,5-tricarboxylic acid tris- represented by (3) It is preferable to use a fluorine-containing ester-based curing agent such as (2,4-difluorophenyl) ester. With such a fluorinated ester-based curing agent, the fluorinated content of the fluorinated copolymer can be easily adjusted, and the transparency of the fluorinated copolymer is less likely to be impaired.

[0023]

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[0024]

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In order to crosslink using the hydroxyl groups of the fluorinated 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 fluorine content of the fluorine-containing copolymer can also be measured by the alizarin complexon method. It 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 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 by thermobalance (TGA).

(10) Others In addition, an antioxidant, an ultraviolet absorber, a plasticizer,
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 a polymer or the like.

[Second Embodiment] The second embodiment is a method for producing a fluorinated copolymer containing a first structural unit and a second structural unit. Specifically, 2,2-bis (4-
(Hydroxyphenyl) hexafluoropropane diglycidyl ether (BPAFGE) and a diester compound represented by the formula (1) (hereinafter, a first copolymerization component) are subjected to a polyaddition reaction to produce a fluorine-containing copolymer. is there.
Hereinafter, the reaction conditions and the like will be described. However, since the raw materials and the obtained fluorine-containing copolymer are the same as those described in the first embodiment, description thereof will be omitted.

(1) Reaction Ratio The reaction ratio between BPAFGE and the first copolymer component is represented by m
It is preferable that the ol ratio be a value within the range of 1:10 to 10: 1. The reason for this is that if the reaction ratio is out of these ranges, BPAFGE and the first copolymer component
This is because a large amount of unreacted components may remain, or the reactivity or heat resistance of the obtained fluorine-containing copolymer may be reduced. Therefore, such BPAFGE,
The reaction ratio with the first copolymer component is 3: 7 to
More preferably, the value is in the range of 7: 3.
More preferably, the value is in the range of 6: 4.

(2) Reaction temperature The reaction temperature of BPAFGE with the first copolymerization component is not particularly limited, either.
It is preferable to set the value within the range of 40 ° C. The reason for this is that if the reaction temperature is lower than 80 ° C., the reactivity between the fluorine-containing compound and the first copolymerization component may be significantly reduced, while if the reaction temperature exceeds 140 ° 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 and the reaction control becomes better, so that the reaction temperature is more preferably set to a value in the range of 90 to 130 ° C, and even more preferably to a value in the range of 100 to 120 ° C. . In FIG. 1,
Reaction temperature (° C.) based on Examples 1 and 9-11
And conversion (Yield,%) and number average molecular weight (M
An example of the relationship with n) is shown. In the case of these examples, it is understood that the reaction temperature has a peak of the number average molecular weight in the range of about 100 to 115 ° C.
It is understood that a reaction rate of 90% or more can be obtained at a temperature of not less than ° C. However, the reaction temperature at which the reaction rate and the number average molecular weight peak appear may vary depending on the type of the raw material monomer, the type of the solvent used in the reaction, and the like.

(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 reactivity and reaction control becomes better, the reaction time is more preferably set to a value in the range of 6 to 72 hours, and more preferably to a value in the range of 12 to 48 hours. More preferred. Note that FIG.
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 is shown below. In the case of these examples, it is understood that a reaction rate of 90% or more can be obtained if the reaction time is 12 hours or more. The reaction time is 1
It is understood that if it is 2 hours or more, a number average molecular weight of 10,000 or more can be obtained. However, the reaction time showing the peak of the reaction rate and the number average molecular weight may change depending on the kind of the raw material monomer, the kind of the solvent used in the reaction, and the like.

(4) Catalyst It is preferable to use a catalyst when performing the polyaddition reaction of BPAFGE with 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.

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 Further, it is preferable to cause polyaddition reaction between BPAFGE and the first copolymer component in a solvent. The reason for this is that, by performing a polyaddition reaction in a solvent, the raw material monomers react uniformly, and the molecular weight distribution of the obtained fluorine-containing copolymer becomes extremely narrow. 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, acetonitosol, 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. 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, as shown in FIG. 41, when an optical resin is used for the cladding layers 52 and 58 of the optical transmission fiber 50, the optical resin has a refractive index ( n _D ) is preferably set to a value of 1.50 or less. Therefore, when composing the optical resin,
It is preferable to make the fluorine content relatively large. In addition, FIG. 41 illustrates the optical transmission fiber 50 connected by providing the frail 64, but various configurations can be changed. In addition, as shown in FIG.
Light having a wavelength of 1,300 to 1,600 nm (arrows A and B) used for the cladding layer 24 of the optical waveguide 10
Is used, the refractive index of the optical resin is 1.40.
The value is preferably in the range of 0 to 1.648. Then, the optical loss in the optical waveguide 10 is reduced to 0.1 dB / cm.
In order to obtain the following values, it is more preferable that 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. Although FIG. 42 illustrates the optical waveguide 10 as an optical switch, various configurations can be changed.

(2) Form The form of the optical resin is not particularly limited, but 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 employ a dipping method, a roll coating method, a spin coating method, a gravure coating method, or the like.

Thermal Curing 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. For example, the heating condition is set to 50 to 12
The temperature is preferably set to 0 ° C. for 1 to 180 minutes. Further, it is preferable that the light irradiation conditions be in the range of 100 to 1000 mJ / cm ² .

[0046]

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-necked 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, the ¹ H-NMR chart, ¹³ C-NMR chart, and ¹⁹ F-NMR chart measured for the obtained BPAFGE are shown in FIGS. 3, 4 and 5, respectively. Also, bisphenol AF,
The reaction scheme with epibromohydrin is shown in the following formula (4).

[0048]

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(2) Preparation of fluorinated copolymer 0.016 g (5 mol) of TBAB was added as a catalyst in an ampoule tube in a dry bag (relative humidity: 10% or less).
%), 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 diphenyl terephthalate (DPTP)
Was charged with 0.159 g (0.5 mmol) and 1 mol / L of chlorobenzene (CB), and the raw material monomers were subjected to a polyaddition reaction at 110 ° C. for 24 hours. After completion of the reaction, the reaction solution was diluted with THF, further purified twice by reprecipitation using THF as a good solvent and methanol as a poor solvent, and dried under reduced pressure at 60 ° C. for 5 hours.
A white solid polymer as a fluorinated polymer was obtained. The reaction rate of this fluoropolymer was calculated from the amount of the raw material monomer used and the obtained amount of the fluorocopolymer, and it was 7
7%. The reaction scheme between BPAFGE and DPTP is shown in the following formula (5).

[0050]

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

[0052]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 DPTP used as raw material monomer of coalescence¹H
FIG. 7 shows an NMR chart.

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 DPTP used as a raw material monomer of the fluorine-containing copolymer.

Measurement of Refractive Index According to JIS K7105, the refractive index of the fluorocopolymer at 25 ° C. was measured using an Abbe refractometer (Gardner L115B).

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).

Glass transition point Using a DSC (SSC5200DSC120, manufactured by Seiko Denshi Co., Ltd.), at a heating rate of 10 ° C./min and in 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 determined 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 8] As shown in Table 1, Example 1
Instead of TBAB, the catalyst used during the polymerization at
BAC (Example 2), TBAI (Example 3), TBPB
(Example 4) Fluorine-containing copolymer as in Example 1 except that TBPC (Example 5), TPPB (Example 6), TPPC (Example 7) and TPPI (Example 8) were used. Combinations were made and evaluated.

[0059]

[Table 1]

[Examples 9 to 13] As shown in Table 2, dichlorobenzene (DB) which is a solvent used in the polymerization in Example 1 was used.
Instead, toluene (Toluene) (Example 9), o-dichlorobenzene (ODCB) (Example 10), anisole (AN
S) (Example 11), dimethylformamide (DMF) (Example 12), and N-methylpyrrolidone (NMP) (Example 13), and the same as Example 1 except that TBPC was used as a catalyst. Then, a fluorinated copolymer was prepared and evaluated.

[0061]

[Table 2]

[Examples 14 to 17] As shown in Table 3, instead of the reaction temperature of 110 ° C. used in Example 5 (using a catalyst TBPC), 90 ° C. (Example 14), 10 ° C.
A fluorinated copolymer was prepared and evaluated in the same manner as in Example 5, except that 0 ° C. (Example 15), 120 ° C. (Example 16), and 130 ° C. (Example 17) were employed, respectively. .

[0063]

[Table 3]

[Examples 18 to 21] As shown in Table 4, instead of the reaction time of 24 hours used in Example 5 (using a catalyst TBPC), 6 hours (Example 18) and 12 hours were used.
A fluorine-containing copolymer was prepared and evaluated in the same manner as in Example 5, except that time (Example 19), 48 hours (Example 20), and 72 hours (Example 21) were employed, respectively.

[0065]

[Table 4]

[Examples 22 to 35] As shown in Tables 5 and 6, instead of the diester compound used in Example 5 (using a catalyst TBPC), a fluorine-containing diester compound represented by the following formula (6) ( Example 22), a fluorine-containing diester compound represented by the following formula (7) (Example 2)
3), a fluorinated diester compound represented by the following formula (8) (Example 24), a fluorinated diester compound represented by the following formula (9) (Example 25), represented by the following formula (10) A fluorinated diester compound (Example 26), a fluorinated diester compound represented by the following formula (11) (Example 27), a fluorinated diester compound represented by the following formula (12) (Example 28), and A fluorine-containing copolymer was prepared and evaluated in the same manner as in Example 5 (reaction temperature: 110 ° C.) except that the fluorine-containing diester compound represented by the formula (13) (Example 29) was used, respectively. However, in Example 25, the reaction time was set to 48 hours. Further, in Examples 30 and 31, except that the reaction time was set to 48 hours, Examples 26 and 27 were used.
Fluorine-containing copolymers were prepared and evaluated in the same manner as above. Further, as shown in Table 7, Example 5 (catalyst TBPC
Use) in place of the diester compound used in
A fluorine-containing diester compound represented by the following formula (6) (Example 32), a fluorine-containing diester compound represented by the following formula (7) (Example 33), and a fluorine-containing diester represented by the following formula (8) A compound (Example 34) and a fluorine-containing diester compound represented by the following formula (9) (Example 35) were used, and the reaction temperature was set to 100 ° C. Combinations were made and evaluated. 10 to 38 show a ¹ H-NMR chart and an infrared spectrum chart of the fluorinated copolymer obtained in Examples 22 to 29 and the fluorinated diester compound as a raw material monomer thereof, respectively.

[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

[Table 5]

[0076]

[Table 6]

[0077]

[Table 7]

[Comparative Example 1] (1) Preparation of copolymer 0.015 g (5 mol%) of TBPC as a catalyst in an ampoule tube in dry bag (relative humidity 10% or less)
Was weighed and dried under reduced pressure at 60 ° C. for 5 hours.
Next, 0.170 g of BPGE was placed in the ampoule tube.
(0.5 mmol) and diphenyl terephthalate (D
(PTP) containing 0.159 g (0.5 mmol) and chlorobenzene (Chlorobenzene) 1 mol / L,
Under the conditions of 110 ° C. and 24 hours, the raw material monomers were subjected to a polyaddition reaction. After completion of the reaction, the reaction solution was diluted with THF, further purified twice by reprecipitation using THF as a good solvent and methanol as a poor solvent, and dried under reduced pressure at 60 ° C. for 5 hours. A white solid polymer as a fluorinated polymer was obtained. 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. In addition, BPGE,
The reaction scheme with DPTP is shown in the following formula (14).

[0079]

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(2) Evaluation of Copolymer In the same manner as in Example 1, the obtained copolymer was evaluated. Table 7 shows the results. In addition, ¹ H of the obtained copolymer
FIGS. 39 to 40 show an NMR chart and an infrared spectrum chart, respectively.

[0081]

According to the fluorine-containing copolymer of the present invention,
Excellent transparency by containing a structural unit derived from 2,2-bis (4-hydroxyphenyl) hexafluoropropane diglycidyl ether and a structural unit derived from the bisester compound represented by the formula (1) It is possible to exhibit properties such as heat resistance and low refractive index in a well-balanced manner. Therefore, as an optical resin,
It is expected to be suitably used as a cladding material for optical transmission fibers. Further, according to the method for producing a fluorine-containing compound copolymer of the present invention, a structural unit derived from 2,2-bis (4-hydroxyphenyl) hexafluoropropanediglycidyl ether and a bis unit represented by the formula (1) By reacting with a structural unit derived from an ester compound, it has become possible to efficiently provide a fluorine-containing copolymer having properties such as transparency, heat resistance and low refractive index in a well-balanced manner.

As a modification of the present invention, a fluorine-containing ester-based curing agent represented by the above formula (2) or (3) is used instead of the bisester compound represented by the formula (1). It is also preferable to introduce a crosslinked structure.

[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- for DPTP 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 DPTP used in Example 1.

FIG. 10 is a ¹ H-NMR chart of the fluorinated copolymer obtained in Example 22.

FIG. 11 is a ¹ H-NMR chart of a fluorinated bisester compound used in Example 22.

FIG. 12 is an infrared spectrum chart of the fluorinated copolymer obtained in Example 22.

FIG. 13 is an infrared spectrum chart of a fluorine-containing bisester compound used in Example 22.

FIG. 14 is a ¹ H-NMR chart of the fluorinated copolymer obtained in Example 23.

FIG. 15 is a ¹ H-NMR chart of a fluorinated bisester compound used in Example 23.

FIG. 16 is an infrared spectrum chart of the fluorinated copolymer obtained in Example 23.

FIG. 17 is an infrared spectrum chart of a fluorine-containing bisester compound used in Example 23.

18 is a ¹ H-NMR chart of the fluorinated copolymer obtained in Example 24. FIG.

FIG. 19 is a ¹ H-NMR chart of a fluorinated bisester compound used in Example 24.

FIG. 20 is an infrared spectrum chart of the fluorinated copolymer obtained in Example 24.

FIG. 21 is an infrared spectrum chart of a fluorine-containing bisester compound used in Example 24.

FIG. 22 is a ¹ H-NMR chart of the fluorinated copolymer obtained in Example 25.

FIG. 23 is a ¹ H-NMR chart of a fluorine-containing bisester compound used in Example 25.

FIG. 24 is an infrared spectrum chart of the fluorinated copolymer obtained in Example 25.

FIG. 25 is an infrared spectrum chart of a fluorine-containing bisester compound used in Example 25.

26 is an infrared spectrum chart of a fluorinated bisester compound used in Example 26. FIG.

FIG. 27 is a ¹ H-NMR chart of a fluorinated copolymer obtained in Example 27.

FIG. 28 is a ¹ H-NMR chart of a fluorine-containing bisester compound used in Example 27.

29 is an infrared spectrum chart of a fluorinated copolymer obtained in Example 27. FIG.

FIG. 30 is an infrared spectrum chart of a fluorine-containing bisester compound used in Example 27.

FIG. 31 is a ¹ H-NMR chart of a fluorine-containing copolymer obtained in Example 28.

FIG. 32 is a ¹ H-NMR chart of a fluorine-containing bisester compound used in Example 28.

FIG. 33 is an infrared spectrum chart of a fluorine-containing copolymer obtained in Example 28.

FIG. 34 is an infrared spectrum chart of a fluorine-containing bisester compound used in Example 28.

FIG. 35 is a ¹ H-NMR chart of the fluorinated copolymer obtained in Example 29.

FIG. 36 is a ¹ H-NMR chart of a fluorine-containing bisester compound used in Example 29.

FIG. 37 is an infrared spectrum chart of a fluorine-containing copolymer obtained in Example 29.

38 is an infrared spectrum chart of a fluorinated bisester compound used in Example 29. FIG.

FIG. 39 shows ¹ H of the copolymer obtained in Comparative Example 1.
-It is an NMR chart.

FIG. 40 is an infrared spectrum chart of the copolymer obtained in Comparative Example 1.

FIG. 41 is a diagram provided to explain an optical transmission fiber;

FIG. 42 is a diagram provided for describing an optical waveguide;

[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

Continued on the front page (72) Inventor Atsushi Kameyama 1-10-3 Nishi-Kanagawa Ichibankan 705, Kanagawa-ku, Kanagawa-ku, Yokohama, Kanagawa Prefecture FSR term in JSR Corporation (reference) 2H047 QA05 TA41 2H050 AB47Z AB50Z 4J029 AA01 AB01 AB04 AC01 AD01 AE04 BF19 BF30 CB03A HA05 HB04A JC091 JC541 JC561

Claims (6)

[Claims] 1. A structural unit derived from 2,2-bis (4-hydroxyphenyl) hexafluoropropane diglycidyl ether and a structural unit derived from a bisester compound represented by the following formula (1): A fluorine-containing copolymer characterized by the following. 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 fluorinated copolymer, comprising subjecting a bisester compound represented by the following formula (1) to a polyaddition reaction. 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: