JP2003321530A - Alicyclic copolymer, method for producing the same and optical resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alicyclic copolymer excellent in heat resistance and/or optical characteristics and to produce a method for producing the copolymer and to provide an optical resin using the alicyclic copolymer. <P>SOLUTION: The alicyclic copolymer comprises a structural unit derived from an alicyclic bisepoxy compound represented by general formula (1) and/or (2) and a structural unit derived from an alicyclic bisepoxy compound represented by general formula (3) and/or (4) [wherein Cy is an adamantylene group; R<SP>1</SP>is a phenylene group; R<SP>2</SP>is a hydrogen atom or a pentafluorophenyl group]. The alicyclic copolymer is excellent in heat resistance and/or optical characteristics and can be used for optical applications such as clad layers 12 and 14 of a fiber 10 for optical transmission. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an alicyclic copolymer suitable as a material for a fiber for optical transmission, a method for producing the same,
And an optical resin using such an alicyclic copolymer.

[0002]

2. Description of the Related Art Conventionally, polymethylmethacrylate (PMMA), which has excellent mechanical properties such as transparency, weather resistance and moldability and has well-balanced mechanical properties, has been used for optical resins such as clad materials and core materials of optical transmission fibers. ) Is often used. However, PMMA generally has a drawback of high hygroscopicity and poor heat resistance, and a drawback of deteriorating the light transmission function when guiding light over a certain distance.

Therefore, as an optical resin replacing PMMA, use of polycarbonate (PC), which has high heat resistance and is excellent in transparency, impact resistance, flame retardancy, etc., is being studied.
However, PC has the major drawbacks of poor fluidity and high birefringence.

As a means for solving such a drawback,
It has been proposed to copolymerize a styrene-based resin having an intrinsic birefringence opposite to that of PC or to add a styrene-based resin to PC. However, when PC and styrenic resin are copolymerized, further problems such as a decrease in transparency and a decrease in adhesion to a substrate were observed.

Therefore, in recent years, an amorphous / alicyclic hydrocarbon-based polymer having no excess polar group and no aromatic ring having large polarization anisotropy has been attracting attention. For example, a ring-opening metathesis polymer hydrogenated polymer (HROP) of a norbornene-based monomer has characteristics equal to or higher than those of PMMA and PC.

[0006]

However, there is a further demand for an optical resin having a well-balanced characteristic such as transparency, heat resistance, refractive index, birefringence, molecular weight distribution and fluidity. It is an object of the present invention to provide an alicyclic copolymer having excellent heat resistance and / or optical properties, a method for producing the same, and an optical resin using such an alicyclic copolymer. The present inventors have found that an alicyclic copolymer obtained by polyaddition reaction of a specific alicyclic bisepoxy compound and a specific alicyclic compound can solve the above problems, and the present invention Completed

[0007]

According to a first aspect of the present invention, a structural unit derived from an alicyclic bisepoxy compound represented by the following general formula (1) and / or (2), and An alicyclic copolymer containing a structural unit derived from an alicyclic compound represented by the general formula (3) and / or (4) is provided.

[Chemical 3] [In the formula, Cy is a divalent alicyclic hydrocarbon having 3 to 10 carbon atoms.
R is a base¹Are mutually independent, fluorine-substituted or non-substituted
A substituted arylene group having 6 to 12 carbon atoms, R ^TwoIs
Mutually independent hydrogen atoms, fluorine-substituted or unsubstituted carbon
Alkyl groups of 1 to 5 or fluorine-substituted or unsubstituted fluorine groups
It is a phenyl group]

According to the second aspect of the present invention, the alicyclic bisepoxy compound represented by the general formula (1) and / or (2) and the general formula (3) and / or ( There is provided a method for producing an alicyclic copolymer, which comprises subjecting an alicyclic compound represented by 4) to a polyaddition reaction.

According to a third aspect of the present invention, there is provided an optical resin containing the above alicyclic copolymer.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Alicyclic Ring Copolymer] The alicyclic ring copolymer of the present invention is
A structural unit derived from the alicyclic bisepoxy compound represented by the following general formula (1) and / or (2) (hereinafter referred to as a first structural unit), and the following general formula (3) and / or (4) )
Structural unit derived from an alicyclic compound represented by (hereinafter,
A second structural unit). By including such a structural unit, an alicyclic copolymer having excellent optical properties and heat resistance can be formed. In particular, in the copolymer of the present invention, since the main chain is introduced with an alicyclic structure having small polarization anisotropy instead of an aromatic ring having large polarization anisotropy, the refractive index of the copolymer is It can be further lowered.

[0011]

[Chemical 4]

[In the formula, Cy is a divalent C 3-10
R is an alicyclic hydrocarbon group,¹Are mutually independent,
It is an unsubstituted or substituted arylene group having 6 to 12 carbon atoms.
R ^TwoAre hydrogen atoms, fluorine-substituted or
Unsubstituted alkyl group having 1 to 5 carbon atoms, or fluorine-substituted or
Is an unsubstituted phenyl group]

In the above general formulas (1) to (4), Cy
Examples of the divalent alicyclic hydrocarbon group of, for example, cyclopropylene group, cyclobutylene group, cyclopentylene group,
Examples thereof include a cyclohexylene group and an adamantylene group.
Of these, an adamantylene group is preferred, and a 1,3-adamantylene group and a 2,2′-adamantylene group are more preferred.

In the above general formulas (2) and (4), R
The ^first fluorine-substituted or unsubstituted arylene group having 6 to 12 carbon atoms, e.g., fluorine-substituted or unsubstituted phenylene group, a naphthylene group and a biphenylene group.

In the above general formula (3), the fluorine-substituted or unsubstituted C 1-5 alkyl group for R ² is
For example, a fluorine-substituted or unsubstituted methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
Examples thereof include an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group and a neopentyl group. Examples of the fluorine-substituted or unsubstituted phenyl group represented by R ² include a phenyl group, a fluorophenyl group and a difluorophenyl group. , Trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group. R ² is preferably hydrogen, a trifluoromethyl group or a fluorine-substituted phenyl group, and more preferably hydrogen, a trifluoromethyl group or a pentafluorophenyl group.

Specific examples of the general formula (1) include alicyclic bisepoxy esters of the following formula (5).

[0017]

[Chemical 5]

Specific examples of the general formula (2) include alicyclic bisepoxy ethers of the following formulas (6) and (7).

[0019]

[Chemical 6]

Specific examples of the compound of the above general formula (3) include an alicyclic diester of the following formula (8) and the following formula (9).
And the alicyclic dicarboxylic acid.

[0021]

[Chemical 7]

Specific examples of the compound represented by the general formula (4) include alicyclic diols represented by the following formulas (10) and (11).

[0023]

[Chemical 8]

The content of the first structural unit is not particularly limited, but is usually 10 to 10 with respect to the total amount of the alicyclic copolymer.
It is preferably set to 80 mol%. This content is 10m
If it is less than ol%, the transparency and heat resistance of the copolymer may be lowered, or the refractive index and birefringence of the copolymer may be increased. On the other hand, if it exceeds 80 mol%, the glass transition temperature and mechanical strength of the copolymer may decrease.
The content of the first structural unit is more preferably 20 to 70.
mol%, more preferably 30 to 60 mol%
Is.

The content of the second structural unit is not particularly limited, but is 10 to 80 m based on the total amount of the alicyclic copolymer.
It is preferably ol%. This content is 10 mol%
If it is less than the above range, the effect of adding the alicyclic compound may not be exhibited. On the other hand, if it exceeds 80 mol%, the unreacted amount of the alicyclic compound may be excessively increased, and the heat resistance of the copolymer may be lowered. The content of the second structural unit is more preferably 20 to 70 mol%, further preferably 30 to 60 mol%.

The alicyclic ring copolymer of the present invention may contain a structural unit derived from a compound other than the alicyclic bisepoxy compound and the alicyclic compound (hereinafter referred to as a third structural unit). . As other compounds, for example, 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether (BFAGE), 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diglycidyl ether ( TM
Epoxy compounds such as BGE), 1,4-butanediol diglycidyl ether (BGGE) and biphenyl-4,4′-diglycidyl ether (BGE); 2,2,3,3,
4,4-hexafluoro-1,5-pentanediol,
2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 1H, 1H, 8H, 8H-dodecafluoro-1,8-octanediol, 1H, 1H, 9H, 9H-
Perfluoro-1,9-nonanediol, 1H, 1H, 1
0H, 10H-perfluoro-1,10-decanediol, 1H, 1H, 12H, 12H-perfluoro-1,12
-Dodecanediol, tetrafluorobenzene-1,3
-Polyhydric alcohols such as diol and tetrafluorobenzene-1,4-diol; tetrafluorosuccinic acid, dodecafluorosuberic acid, perfluoroazelaic acid,
Such as perfluorosebacic acid, perfluoro-1,10-decanedicarboxylic acid, tetrafluoroisophthalic acid, tetrafluorophthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 4-trifluoromethylphthalic acid Examples thereof include one kind or a combination of two or more kinds of polyvalent carboxylic acids.

The content of the third structural unit is not particularly limited, but may be, for example, 0.1% to the total amount of the alicyclic copolymer.
It is preferably 1 to 50 mol%. If this content is less than 0.1 mol%, the effect of addition may not be exhibited. On the other hand, if it exceeds 50 mol%, the heat resistance and the birefringence of the copolymer may decrease. The content of the third structural unit is more preferably 1 to 30 mol%, further preferably 10 to 20 mol%.

Further, in the alicyclic copolymer of the present invention, a crosslinking agent may be added during or after the polymerization. By adding a cross-linking agent, the heat resistance of the copolymer, the adhesion to the substrate, the reactivity during polymerization of the copolymer, etc. can be adjusted appropriately. As such a crosslinking agent, it is preferable to use a fluorine-containing ester type curing agent, and specifically, 1,3,5-tris (2,4-difluorobenzoyloxy) represented by the following formula (12). It is preferable to use a fluorine-containing ester-based curing agent such as benzene or benzene-1,3,5-tricarboxylic acid tris- (2,4-difluorophenyl) ester represented by the formula (13). With such a curing agent, fluorine can be introduced into the copolymer, and the content thereof can be easily adjusted. In addition, the transparency of the copolymer is less damaged.

[0029]

[Chemical 9]

When the alicyclic copolymer has a hydroxyl group, an isocyanate compound, a bisphenol compound,
It is also preferable to use a compound that reacts with a hydroxyl group, such as a dicarboxylic acid compound or a bisepoxy compound, as a crosslinking agent.

The amount of the crosslinking agent used is not particularly limited, but is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the alicyclic copolymer. If the amount 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. The amount of the crosslinking agent used is more preferably 0.5 to
15 parts by weight, more preferably 1 to 10 parts by weight.

Number average molecular weight (Mn) of alicyclic copolymer
Is preferably 2,000 to 300,000. When the number average molecular weight is less than 2,000, the adhesion and heat resistance of the copolymer with respect to the substrate may decrease. on the other hand,
If it exceeds 300,000, the reaction time may become excessively long or the reaction rate may decrease. The number average molecular weight is more preferably 3,000 to 100,000, further preferably 5,000 to 50,000. In addition, the molecular weight distribution (Mw / Mn) of the alicyclic copolymer
1-4 are preferable, 1-3 are more preferable, and 1-2
Is more preferable.

The alicyclic copolymer preferably contains fluorine. If it contains fluorine, the refractive index becomes low. The fluorine content is, for example, 0 to 80 mol%. If the content of fluorine is high, the mechanical strength and transparency of the copolymer may decrease. The fluorine content is preferably 10 to 30 mol%.

The refractive index (n _D , measured at 25 ° C.) of the alicyclic copolymer is preferably 1.40 to 1.65. If the refractive index is less than 1.40, the transparency and heat resistance of the copolymer may be reduced, or the types of raw material monomers that can be used may be excessively limited. On the other hand, if it exceeds 1.65, birefringence and optical loss may become excessively large. The refractive index is more preferably 1.45 to 1.60, and further preferably 1.47 to 1.55.

The glass transition temperature of the alicyclic copolymer is preferably 30 to 170 ° C. If this temperature is lower than 30 ° C., the heat resistance of the copolymer may decrease. On the other hand, if it exceeds 170 ° C, the reaction time may be excessively long or the polymerization efficiency may be lowered. The glass transition temperature is more preferably 50 to 140 ° C, further preferably 60 to 130 ° C.

5% weight thermal decomposition temperature of the alicyclic copolymer (T
g ₅₎ is preferably one hundred and eighty to four hundred fifty ° C.. If this temperature is lower than 180 ° C., the heat resistance of the copolymer may decrease. On the other hand, if the temperature exceeds 450 ° C, the reaction time may be excessively long or the usable monomer species may be excessively limited. The 5% weight pyrolysis temperature is more preferably 250 to 430 ° C., further preferably 30.
It is 0 to 430 ° C.

The alicyclic copolymer of the present invention contains an antioxidant, an ultraviolet absorber, a plasticizer, a surfactant, an antistatic agent, a silane coupling agent within the range not departing from the object of the present invention. Inorganic fillers, pigments, dyes, metal particles, dopants, reactive diluents, thermosetting agents, photocuring agents, various oligomers, polymers, etc. may be added alone or in combination of two or more.

[Production Method of Aliphatic Ring Copolymer] In the present invention, the alicyclic bisepoxy compound represented by the general formula (1) and / or (2) and the general formula (3) and / or Alternatively, the alicyclic compound represented by (4) is subjected to a polyaddition reaction to produce an alicyclic copolymer. Hereinafter, the reaction conditions and the like will be described, but the alicyclic copolymer obtained is the same as the above, and therefore the description thereof is omitted here.

The reaction ratio of the alicyclic bis-epoxy compound and the alicyclic compound is preferably 1:10 to 10: 1 (m).
ol ratio). If the reaction ratio is out of these ranges, a large amount of unreacted raw material monomer may remain, or the reactivity or heat resistance of the copolymer may decrease. The reaction ratio is more preferably 3: 7 to 7: 3, and further preferably 4 :.
6 to 6: 4.

The reaction temperature between the alicyclic bis-epoxy compound and the alicyclic compound is not particularly limited, but is, for example, 40 to
150 ° C is preferred. When the reaction temperature is lower than 40 ° C,
Reactivity may be significantly reduced. On the other hand, if the temperature exceeds 150 ° C, the reaction may be controlled or the solvent species used for the polymerization may be excessively limited. The reaction temperature is more preferably 50 to 120 ° C, further preferably 60 to 9 ° C.
It is 0 ° C.

The reaction time between the alicyclic bis-epoxy compound and the alicyclic compound is not particularly limited, but for example, 1 to 1
20 hours is preferred. When the reaction time is less than 1 hour,
Reactivity may be significantly reduced, while if it exceeds 120 hours, it may be difficult to control these reactions or it may be economically disadvantageous. The reaction time is
The time is more preferably 6 to 72 hours, further preferably 12 to 48 hours.

FIG. 1 shows an example of the relationship between the reaction time (h) of the starting monomer, the number average molecular weight (Mn) and the yield (%) of the copolymer in the reactions of Examples 1 and 10 to 13. Show. ● represents the relationship between the reaction time (h) and the number average molecular weight (Mn), and ■ represents the relationship between the reaction time (h) and the yield (%). From this figure, the yield and molecular weight increase with reaction time,
It is understood that the reaction time peaks in about 24 hours, that is, in the case of Example 1, and then decreases with time. In this figure, the decrease in yield and molecular weight over 24 hours means that the reaction system is greatly affected by water as the raw material monomer concentration decreases, and as a result, It is thought that this is because the ester portion of the combined product is hydrolyzed. However, when the raw material monomer and the type of solvent are changed, the reaction time at which the yield and the molecular weight are at the peak may be changed.

A catalyst is preferably used in the polyaddition reaction of the alicyclic bis-epoxy compound and the alicyclic compound. As such a catalyst, a quaternary onium salt,
There may be mentioned at least one catalyst selected from the group consisting of tertiary amines and tertiary phosphines. More specifically, tetrabutylammonium bromide (TBA
B), tetrabutylammonium chloride (TBA
C), tetrabutylphosphonium bromide (TBP
B), tetrabutylphosphonium chloride (TBP
C), tetrabutylammonium iodide (TBA
I), tetraphenylphosphonium bromide (TPP
B), tetraphenylphosphonium chloride (TPP
C), tetraphenylphosphonium iodide (TPP
Quaternary onium salts such as I); triphenylphosphine (T
PP) such as tertiary phosphines; 4- (N, N-dimethylamino) pyridine (DMAP), and tertiary amines such as 1,8-diazabicyclo- [5,4,0] -undecene-7 (DBU). One kind may be used alone, or two or more kinds may be used in combination. Of these, quaternary onium salts are preferable, and above all, TPPC and TBP having Cl ⁻ as a counter anion.
C, TBAC and the like are more preferable because a high molecular weight copolymer can be obtained.

The amount of the catalyst added is not particularly limited, but is preferably 0.01 to 30 per 100 parts by weight of the total amount of the alicyclic bisepoxy compound and the alicyclic compound.
Add parts by weight. If the addition amount is less than 0.01 parts by weight, the reactivity may be significantly reduced, while if it exceeds 30 parts by weight, control of the reaction and purification operation after the reaction may be difficult. The addition amount of the catalyst is more preferably 0.05 to 20 parts by weight, and further preferably 0.
It is 1 to 10 parts by weight.

The alicyclic bis-epoxy compound and the alicyclic compound are preferably subjected to polyaddition reaction in a solvent. By carrying out the polyaddition reaction in a solvent, the raw material monomers react uniformly with each other, and the molecular weight distribution of the copolymer becomes narrow. Preferred types of solvents include dioxane, toluene, diglyme, o-dichlorobenzene, chlorobenzene, anisole, N, N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, ethyl acetate, N, N '.
-Dimethylacetamide, methyl ethyl ketone, chloroform, dichloromethane, amyl acetate, acetonitrile, nitrobenzene, cyanobenzene and the like may be used alone or in combination of two or more. Of these, chlorobenzene, N, N-dimethylformamide,
N-methylpyrrolidone is more preferable because it improves the reaction rate of the alicyclic copolymer.

The amount of the solvent used is not particularly limited, but is preferably 10 per 100 parts by weight of the raw material monomer.
Use ~ 1,000 parts by weight. If the amount used is less than 10 parts by weight, the reactivity may be significantly reduced and an unnecessary polymer may be formed as a by-product. On the other hand, if it exceeds 1,000 parts by weight,
Control of the reaction and purification operation after the reaction may be difficult in some cases. The amount of the solvent used is more preferably 50 to 800 parts by weight, further preferably 100 to 500 parts by weight.

[Optical Resin] The optical resin of the present invention comprises the above alicyclic copolymer. The optical resin of the present invention includes an antioxidant within a range not departing from the object of the present invention,
UV absorber, plasticizer, surfactant, antistatic agent, silane coupling agent, inorganic filler, pigment, dye, metal particle, dopant, reactive diluent, thermosetting agent, photocuring agent,
One kind or a combination of two or more kinds of various oligomers and polymers can be added. The optical resin of the present invention is excellent in optical characteristics such as low refractive index or has high heat resistance, and therefore, for example, clad material or core material for optical transmission fiber, photosensitive material, optical lens material, optical waveguide material. , Materials for optical films, materials for compact discs,
It can be used for optical applications such as materials for light antireflection films and sealing materials for electric and electronic parts.

For example, the optical resin of the present invention can be used in the optical transmission fiber shown in FIG. The optical resin of the present invention is used for the cladding layers 12 and 1 of the optical transmission fiber 10.
In this case, the refractive index (n _D ) of the optical resin is preferably 1.50 or less in order to reduce the optical loss during transmission. Therefore, it is preferable to introduce fluorine when forming the optical resin. Incidentally, FIG.
In the above, the optical transmission fiber 10 in which the flare 16 is provided and connected is illustrated, but various configurations can be changed as appropriate.

The optical resin of the present invention can also be used in the optical waveguide shown in FIG. The optical resin of the present invention is used for the clad layer 22 of the optical waveguide 20,
Light with a wavelength of 1,300 to 1,600 nm (arrows A and B)
, The refractive index of the optical resin is 1.40 to
It is preferably set to 1.648. And the optical waveguide 2
In order to set the optical loss at 0 to 0.1 dB / cm or less, it is more preferable to make the refractive index of the cladding layer 22 0.002 to 0.5 smaller than the refractive index of the core portion 24. Although FIG. 3 illustrates the optical waveguide 20 as an optical switch, various configurations can be changed as appropriate.

The form of the optical resin of the present invention is not particularly limited, but it is preferably liquid so that a film can be uniformly formed on the substrate or the core of the optical transmission fiber. In the case of a liquid optical resin, its viscosity can be adjusted to, for example, 10 by adding an organic solvent or a viscosity modifier (including a copolymerizable monomer).
It is preferable to adjust to 100,000 mPa · s (measurement temperature 25 ° C.). As an organic solvent and viscosity modifier,
For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; cyclic ethers such as tetrahydrofuran and dioxane; N, N-
Examples thereof include amides such as dimethylformamide and N, N-dimethylacetamide; aromatic hydrocarbons such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride.

In the case of a liquid optical resin, it is preferable to use it by coating so as to form a uniform film on the substrate or the core of the optical transmission fiber. As a coating method, it is preferable to adopt a dipping method, a roll coating method, a spin coating method, a gravure coating method, or the like.

Further, 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 light. By heat-curing and photo-curing as described above, it is possible to remarkably improve the adhesion to the substrate and the heat resistance. Therefore, for example, the heating condition is preferably 50 to 120 ° C. and 1 to 180 minutes. The light irradiation condition is 100 to 100.
It is preferably 0 mJ / cm ² .

[0053]

EXAMPLES Examples of the present invention will be described in detail below.
The scope of the invention is not limited to the description of these examples.
IR spectra and NMR of alicyclic bis-epoxy compounds (Production Examples 1, 4 and 6), alicyclic compounds (Production Examples 2, 3 and 5) and alicyclic copolymers (Examples 1 to 34).
The instruments used for measuring the spectrum, molecular weight and melting point are as follows.

(1) IR spectrum Infrared spectrophotometer (manufactured by JASCO Corporation, FT / IR42
0) was used. (2) NMR spectrum Nuclear magnetic resonance apparatus (JMN-α-5, manufactured by JEOL Ltd.)
00) was used. (3) Number average molecular weight (Mn), weight average molecular weight (Mw)
And molecular weight distribution (Mw / Mn) Gel permeation chromatography (GPC) (Tosoh Corporation)
HLC-8020 system, column: TSK ge
G1000H (Developing solvent: Tetrahydrofuran (T
HF), Examples 1-15) or TSK GEL SUPE
RRAW 3000 + 2500 × 3 (developing solvent: dimethylformamide (DMF), Examples 16 to 34) was used. (4) Melting point Yanako MP-500D manufactured by Yanagimoto Seisakusho Co., Ltd. was used.

Production Example 1 1,3-Adamantane diglycidyl ester (1,3-
Synthesis of ADGE) In a 100 mL eggplant flask, 3.36 g (15 mmo) of 1,3-adamantanedicarboxylic acid (1,3-ADCA).
l), 7.33 g (22.5 mmol) of cesium carbonate,
Tetrabutylammonium bromide (TBAB) (5m
ol%) and N-methyl-2-pyrrolidone (NMP) 5
0 ml was weighed and stirred at 50 ° C. for 3 hours. afterwards,
6.16 g (45 mmol) of epibromohydrin was added and reacted for 15 hours. After completion of the reaction, the mixture was diluted with a large amount of ethyl acetate, washed with distilled water three times, and the organic layer was dried over anhydrous magnesium sulfate. After filtering the desiccant, the organic layer was distilled off under reduced pressure, and the resulting viscous liquid was subjected to silica gel column chromatography (ethyl acetate: n-hexane = 1: 1, R
f = 0.50) to obtain 28% of 1.42 g of viscous liquid.
It was obtained in a yield of.

It was confirmed by IR and ¹ H-NMR measurement that this viscous liquid was 1,3-ADGE (the above formula (5)). The respective spectrum data are shown below. IR (neat, cm- ¹ ): 2937, 2911, ¹
728,908 ¹ H-NMR (500 MHz, DMSO-d ₆ , TM
S) δ (ppm): 1.66 to 1.74, 1.83 to
1.96, 2.08, 2.14 to 2.23, 2.65,
2.84, 3.17 to 3.24, 3.93, 4.41

Production Example 2 Synthesis of 1,3-adamantane dipentafluorophenyl ester (1,3-ADPE) 1,3-ADCA3.36 was placed in a 100 mL round bottom flask.
g (15 mmol) and 12.48 g (1
(05 mmol) was weighed and stirred at 50 ° C. for 2 hours.
After completion of the reaction, excess thionyl chloride was distilled off under reduced pressure, and the obtained white solid was dried under reduced pressure. Then, as a reaction solvent, T
HF 40mL, Triethylamine (TEA) 4.55
g (15 mmol) was added, and under ice cooling, THF 10 mL
6.13 g of pentafluorophenol dissolved in
6 mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, salts were filtered off, THF was concentrated, diluted with ethyl acetate, washed with distilled water three times, and the organic layer was dried over anhydrous magnesium sulfate. After filtering the desiccant, the organic layer was evaporated under reduced pressure, and the resulting light brown liquid was subjected to silica gel column chromatography (ethyl acetate: n-hexane = 1: 1, Rf
= 0.57) to obtain 6.15 g of a white powder in a yield of 74%.

It was confirmed by measuring IR and ¹ H-NMR that this white powder was 1,3-ADPE (the above formula (8)). The respective spectrum data are shown below. IR (KBr, cm ^-1 ): 2948, 2866, 17
28 ¹ H-NMR (200 MHz, CDCl ₃ , TMS) δ
(Ppm): 1.78 to 1.96, 1.98 to 2.2
3,2.28-2.50

Production Example 3 Synthesis of 1,3-bis (4-hydroxyphenyl) adamantane (1,3-BHPAD) In a 200 mL flask, 5.15 g (17.5 mmol) of 1,3-dibromoadamantane and 51.7 of phenol were added.
6 g (0.550 mol) and aluminum chloride 1.1
0 g (5.80 mmol) was weighed out. Then, a cooling tube and a NaOH trap were attached, and the reaction was carried out at 80 ° C. for 16 hours. After completion of the reaction, the reaction mixture was cooled, warm water was poured into the black residue and the mixture was stirred, and then the precipitated solid was collected.
This operation was repeated 3 times, the white solid was collected and dried under reduced pressure. Then, the obtained solid was recrystallized once with methanol to obtain 2.10 g of white crystals in a yield of 38%. The melting point of this white crystal was 202 to 203 ° C.

It was confirmed by IR and ¹ H-NMR measurement that this white crystal was 1,3-BHPAD (the above formula (10)). The respective spectrum data are shown below. IR (film, cm ^-1 ): 3394, 1613, ¹
595 ¹ H-NMR (500 MHz, DMSO-d ₆ , TM
S) δ (ppm): 1.68, 1.70 to 1.85,
2.18, 6.67, 7.16, 9.11.

Production Example 4 Synthesis of 1,3-bis (4-glycidylphenyl) adamantane (1,3-BGPAD) 1,3-B synthesized in Production Example 3 in a 100 mL flask.
HPAD 0.96 g (3 mmol), cesium carbonate 1.
95 g (6 mmol), TBAB 0.097 g (5 mo
1%) and 10 mL of NMP were weighed and stirred at 50 ° C. for 3 hours. After that, 1.64 g of epibromohydrin (1
2 mmol) was added and the reaction was carried out at 50 ° C. for 24 hours.
After the reaction was completed, the cesium salt was filtered off, diluted with ethyl acetate, washed with distilled water three times, and dried over anhydrous magnesium sulfate. After filtering the drying agent, ethyl acetate was distilled off under reduced pressure. The obtained viscous liquid was purified by silica gel column chromatography (acetone: n-hexane = 1: 3) to obtain 0.340 g of a white powder solid in a yield of 26%. The melting point of this white powder solid was 102 to 103 ° C.

This white powder solid is 1,3-BGPAD
It was confirmed by measuring IR, ¹ H-NMR and ¹³ C-NMR (the above formula (6)). The respective spectrum data are shown below. IR (KBr, cm ^-1 ): 2911, 2847, 16
09,1511,914 ¹ H-NMR (500 MHz,
CDCl ₃ , TMS) δ (ppm): 1.78, 1.8
6 to 1.93, 1.96, 2.29, 2.72 to 2.7
6, 3.31 to 3.36, 3.93 to 3.98, 4.1
6-4.21, 6.88, 7.30 ¹³ C-NMR (125 MHz, CDCl ₃ , TMS)
δ (ppm): 22.9, 35.8, 36.7, 42.
4,44.7,49.3,50.2,68.7,11
4.2, 125.9, 143.5, 156.4

Production Example 5 Synthesis of 2,2'-bis (4-hydroxyphenyl) adamantane (2,2'-BHPAD) In a 300 mL flask, 22.5 g of 2-adamantanone was added.
(0.15 mol), phenol 43.34 g (0.4
5 mol) and zinc chloride 2.70 g (5.80 mmo)
l) was weighed out. Then, a NaOH trap was attached, and the reaction was carried out at 60 ° C. for 6 hours while bubbling hydrochloric acid gas. After completion of the reaction, the reaction mixture was cooled, ethanol (50 mL) and distilled water (75 mL) were poured into the brown residue, and the precipitated white solid was collected and dried under reduced pressure. Then, recrystallize once with toluene to give white crystals 3.02 g
Was obtained in a yield of 5%. The melting point of this white crystal is 315-3
It was 17 ° C.

It was confirmed by IR and ¹ H-NMR measurement that this white crystal was 2,2'-BHPAD (the above formula (11)). The respective spectrum data are shown below. IR (KBr, cm ^-1 ): 3464, 3409, 16
09,1592 ¹ H-NMR (500 MHz, DMSO-d ₆ , TM
S) δ (ppm): 1.45 to 2.20, 6.58,
7.16, 9.03

Production Example 6 Synthesis of 2,2'-bis (4-glycidylphenyl) adamantane (2,2'-BGPAD) 2,2'-synthesized in Production Example 5 in a 100 mL flask.
BHPAD 0.96 g (3 mmol), cesium carbonate 1.95 g (6 mmol), TBAB 0.097 g (5
mol%) and 10 mL of NMP, and weigh 3 at 50 ° C.
Stir for hours. Then 1.64 g of epibromohydrin
(12 mmol) was added and the reaction was carried out at 50 ° C. for 24 hours. After the reaction was completed, the cesium salt was filtered off, diluted with ethyl acetate, washed with distilled water three times, and dried over anhydrous magnesium sulfate. After filtering the drying agent, ethyl acetate was distilled off under reduced pressure.
The resulting viscous liquid was purified by silica gel column chromatography (acetone: n-hexane = 1: 2) to obtain 1.13 g of a white powder solid in a yield of 88%. The melting point of this white powder solid was 159 to 160 ° C.

This white powder solid is 2,2'-BGPAD
It was confirmed by measuring IR, ¹ H-NMR and ¹³ C-NMR that it was (the above formula (7)). The respective spectrum data are shown below. IR (KBr, cm ^-1 ): 2932, 2872, 16
06,1507,910 ¹ H-NMR (500 MHz,
CDCl ₃ , TMS) δ (ppm): 1.66 to 2.0
6,2.68 to 2.72,2.82 to 2.88,3.1
6, 3.22 to 3.32, 4.05 to 4.12, 6.7
7, 7.30 ¹³ C-NMR (125 MHz, CDCl ₃ , TMS)
δ (ppm): 27.5, 32.1, 33.3, 44.
8, 49.4, 50.1, 68.6, 114.5, 12
6.7, 141.6, 155.5

Example 1 Tetrabutylphosphonium chloride (TBP) was used as a catalyst in an ampoule tube in a dryback (<10% humidity).
C) 0.015 g (5 mol%) was weighed out and dried under reduced pressure at 60 ° C. for 5 hours. Then, in the ampoule tube, 0.13-g (0.
5 mmol), 1,3-ADPE synthesized in Production Example 2
0.278 g (0.5 mmol) and 0.5 mL (1 mol / L) of chlorobenzene (CB) were weighed out and connected to a two-way cock to make a sealed state, followed by degassing by the following operation. The ampoule tube was placed in liquid nitrogen, the sample was frozen and then depressurized, the ampoule tube was placed in water, and the sample was thawed and then replaced with high-purity nitrogen. The above-mentioned deaeration operation was repeated twice, and then frozen again, and the ampoule tube was sealed under a reduced pressure. After thawing the sample, the reaction was performed in an oil bath at 100 ° C. for 24 hours. After the reaction is completed, the reaction solution is THF
The product was diluted with and purified by reprecipitation once using THF as a good solvent and methanol as a poor solvent. Then, it was dried under reduced pressure to give 89% of 0.399 g of a light brown polymer (P-1a).
It was obtained in a yield of. The number average molecular weight (Mn) and molecular weight distribution (Mn / Mw) of this polymer were measured by the above methods.
The results are shown in Table 1.

Further, it is confirmed that this polymer has a repeating unit represented by the following formula (14): IR, ¹ H-NM
R, ¹³ C-NMR and ¹⁹ F-NMR were measured and confirmed. The respective spectrum data are shown below. IR (film, cm ^-1 ): 2939, 2912, 2
860, 1735, 1606, 1507 ¹ H-NMR (500 MHz, CDCl ₃ ) δ (pp
m): 1.62 to 2.30, 4.15 to 4.55, 5.
23 to 5.40 ¹³ C-NMR (125 MHz, CDCl ₃ , TMS)
δ (ppm): 27.6, 35.2, 37.7, 37.
8, 41.0, 61.5, 64.7, 69.0, 13
6.5-137.3, 138.4-139.3, 14
0.5-140.8, 142.4-142.8, 17
5.5, 175.8 ¹⁹ F-NMR (470 MHz, CDCl ₃ , C
₆ F ₆ ):-161.82 to -161.25, -16
1.23 to -160.83, -155.33 to -15
5.00

[0069]

[Chemical 10]

Examples 2 to 7 In Example 1, no solvent was used in place of chlorobenzene, tetrabutylammonium chloride (TBAC) was used in Example 2, tetrabutylammonium bromide (TBAB) was used in Example 3, and tetrabutylammonium bromide (TBAB) was used in Example 4. Butylphosphonium chloride (TBPC), tetrabutylphosphonium bromide (TBPB) in Example 5, tetraphenylphosphonium chloride (TPPC) in Example 6, and tetraphenylphosphonium bromide (TP) in Example 7.
The same reaction and treatment as in Example 1 were carried out except that PB) was used to obtain the same polymer as in Example 1. Table 1 shows the yield of the polymer obtained in each example and the measurement results of Mn and Mn / Mw.

Examples 8 to 9 The same as Example 1 except that toluene (Tol) was used in Example 8 and o-dichlorobenzene (ODCB) was used in Example 9 instead of chlorobenzene. The reaction and treatment were carried out to obtain the same polymer as in Example 1. Table 1 shows the yield of the polymer obtained in each example and the measurement results of Mn and Mn / Mw.

Examples 10 to 13 In Example 1, the reaction time was changed from 24 hours to Example 1.
0 was 6 hours, Example 11 was 12 hours, Example 12 was 36 hours, and Example 13 was 48 hours, except that the same reaction and treatment as in Example 1 were carried out to obtain the same polymer as Example 1. It was Table 1 shows the yield of the polymer obtained in each example and the measurement results of Mn and Mn / Mw.

Example 14 The same reaction and treatment as in Example 1 were carried out except that 1,3-BGPAD synthesized in Production Example 4 was used in place of 1,3-ADGE in Example 1, and white was obtained. The powder polymer (P-1b) was obtained with a yield of 82%. M of this polymer
Table 1 shows the measurement results of n and Mn / Mw.

Further, IR, ¹ H-NM indicates that this polymer has a repeating unit represented by the following formula (15).
R, ¹³ C-NMR and ¹⁹ F-NMR were measured and confirmed. The respective spectrum data are shown below. IR (film, cm ^-1 ): 2911, 2854, ¹
733, 1609, 1514 ¹ H-NMR (500 MHz, CDCl ₃ , TMS) δ
(Ppm): 1.70 to 2.34, 4.12 to 4.2
8, 4.39 to 4.50, 5.35 to 5.48, 6.7
8-6.91, 7.21-7.35 ¹³ C-NMR (125 MHz, CDCl ₃ , TMS)
δ (ppm): 27.6, 30.3, 35.2, 36.
7, 37.6, 39.2, 41.1, 42.4, 49.
3,65.4,70.4,73.3,114.2,12
5.9, 136.2 to 137.2, 140.3 to 14
1.0, 142.5-143.0, 142.5-14
3.0, 143.8, 156.1, 175.9 ¹⁹ F-NMR (470 MHz, CDCl ₃ , C
₆ F ₆ ): -161.82 to -161.57, -16
1.53 to 161.30, -155.2 to -15
4.97

[0075]

[Chemical 11]

Example 15 In Example 1, except that 2,3′-BGPAD synthesized in Production Example 6 was used instead of 1,3-ADGE.
The same reaction and treatment as in Example 1 were carried out to obtain a white powder polymer (P-1c) in a yield of 84%. Table 1 shows the measurement results of Mn and Mn / Mw of this polymer.

Further, it is confirmed that this polymer has a repeating unit represented by the following formula (16): IR, ¹ H-NM
R, ¹³ C-NMR and ¹⁹ F-NMR were measured and confirmed. The respective spectrum data are shown below. IR (film, cm ^-1 ): 2935, 2911, 2
858, 1734, 1607, 1515 ¹ H-NMR (500 MHz, CDCl ₃ , TMS) δ
(Ppm): 1.58 to 2.30, 3.08 to 3.2
0, 4.00 to 4.20, 4.32 to 4.48, 5.2
8-5.42, 6.68-6.84, 7.20-7.3
8 ¹³ C-NMR (125 MHz, CDCl ₃ , TMS)
δ (ppm): 27.5, 30.3, 32.1, 33.
2, 35.1, 37.6, 38.0, 39.1, 41.
0, 49.4, 114.5, 126.7, 126.2-
137.5, 138.0-139.5, 140.2-1
40.9, 141.7, 142.5 to 142.9, 15
5.2, 175.8 ¹⁹ F-NMR (470 MHz, CDCl ₃ , C
₆ F ₆ ): -161.63 to -161.92, -16
1.35 to -161.62, 154.30 to -15
5.25

[0078]

[Chemical 12]

[0079]

[Table 1]

Example 16 0.008 g (2.55 mol%) of TBAB as a catalyst in an ampoule tube in a dry back (<10% humidity)
The sample was weighed and dried under reduced pressure at 60 ° C for 5 hours. Then, in the ampoule tube, 1,3-AD synthesized in Production Example 1
GE 0.168 g (0.5 mmol), 1,3-adamantanedicarboxylic acid (1,3-ADCA) 0.112 g
(0.5 mmol) and 0.25 mL of DMF (2 mol
/ L) was weighed out, and a two-way cock was connected to make a sealed state, and then degassing was performed by the following operation. The ampoule tube was placed in liquid nitrogen, the sample was frozen and then depressurized, the ampoule tube was placed in water, and the sample was thawed and then replaced with high-purity nitrogen. The above-mentioned deaeration operation was repeated twice, and then frozen again, and the ampoule tube was sealed under a reduced pressure. After thawing the sample, the reaction was carried out for 12 hours in an oil bath at 60 ° C. After the reaction is complete, dilute the reaction solution with THF and use TH
F, reprecipitation purification was performed once using a mixed solvent of ethanol: n-hexane = 1: 3 as a poor solvent. Then, 0.224 g of the white polymer (P-1d) was dried under reduced pressure to give 7
Obtained in a yield of 7%. The number average molecular weight of this polymer (M
Table 2 shows the measurement results of n) and the molecular weight distribution (Mn / Mw).

Further, it was confirmed by IR and ¹ H-NMR measurement that this polymer had a repeating unit represented by the following formula (17) in which the epoxy group was β-cleaved. The respective spectrum data are shown below. In this example, a polymer in which the epoxy group was α-cleaved was also obtained. The rate of cleavage was α: β = 3: 7. IR (film, cm ^-1 ): 3482, 937, 2
911,2859,1734,1607,1515 ¹ H-NMR (500 MHz, CDCl ₃ , TMS) δ
(Ppm): 1.45 to 2.14, 3.40 to 3.54
(Α cleavage), 3.80 to 3.90 (β cleavage), 3.91
~ 4.10 (β cleavage), 4.24 to 4.38 (α cleavage), 4.84 to 5.40

[0082]

[Chemical 13]

Examples 17 to 19 In Example 16, the reaction temperature was changed from 60 ° C. to Example 1
The same reaction and treatment as in Example 16 were carried out except that the temperature was 50 ° C. in Example 7, 70 ° C. in Example 18, and 80 ° C. in Example 19 to obtain the same polymer as in Example 16. Table 2 shows the yield of the polymer obtained in each example and the measurement results of Mn and Mn / Mw.

Examples 20 to 22 In Example 16, the reaction time was changed from 12 hours to 24 hours in Example 20, 36 hours in Example 21, and Example 2
In Example 2, the same reaction and treatment as in Example 16 were carried out except that the time was 48 hours to obtain the same polymer as in Example 16. Yield of polymer obtained in each Example, and Mn and Mn
Table 2 shows the measurement results of / Mw.

[0085]

[Table 2]

Example 23 0.011 g (5 mol%) of TBPC as a catalyst was weighed out as a catalyst in an ampoule tube in a dryac (<10% humidity), and dried under reduced pressure at 60 ° C. for 5 hours. Then, 1,3-BGPAD synthesized in Production Example 4 was placed in the ampoule tube.
0.130 g (0.3 mmol), 1,3-BHPAD 0.096 g (0.3 mmol) synthesized in Production Example 3 and NMP 0.5 mL (1 mol / L) were weighed out, and a two-way cock was connected to form a closed state. After that, degassing was performed by the following operation. The ampoule tube was placed in liquid nitrogen, the sample was frozen and then depressurized, the ampoule tube was placed in water, and the sample was thawed and then replaced with high-purity nitrogen. The above-mentioned deaeration operation was repeated twice, and then frozen again, and the ampoule tube was sealed under a reduced pressure. After thawing the sample, the reaction was carried out in an oil bath at 120 ° C. for 48 hours. After the reaction is completed, the reaction solution is THF
The product was diluted with and purified by reprecipitation once using THF as a good solvent and methanol as a poor solvent. Then, 0.219 g of a white polymer (P-1e) was obtained with a yield of 97% by drying under reduced pressure. Table 3 shows the measurement results of the number average molecular weight (Mn) and the molecular weight distribution (Mn / Mw) of this polymer.

Further, it was confirmed that this polymer had a repeating unit represented by the following formula (18): IR, ¹ H-NM
It was confirmed by measuring R and ¹³ C-NMR. The respective spectrum data are shown below. IR (film, cm ^-1 ): 3382, 2901, 2
847,1609,1579 ¹ H-NMR (500 MHz, CDCl ₃ ) δ (pp
m): 1.66 to 2.35, 2.25 to 2.75, 4.
02-4.20, 4.30-4.40, 6.80-6.
94, 7.22 to 7.37 ¹³ C-NMR (125 MHz, CDCl ₃ , TMS)
δ (ppm): 29.6, 35.8, 36.7, 42.
4, 49.3, 68.7, 68.8, 114.2, 12
5.9, 143.6, 156.3

[0088]

[Chemical 14]

Examples 24 to 27 In Example 23, the reaction temperature was 90 ° C. and the reaction time was 24 hours. In Example 24, TBAC and Example 25 were used.
Except that TBAB was used in Example 26, TBPC was used in Example 26, and TBPB was used in Example 27, and the same reaction and treatment as in Example 1 were carried out to obtain the same polymer as that in Example 1. Yield of the polymer obtained in each example, and Mn and Mn / Mw
The measurement results of are shown in Table 3.

Examples 28 to 30 In Example 23, the reaction time was 24 hours, and the reaction temperature was 100 ° C. in Example 28 and 110 in Example 29.
C., Example 23 except 120 ° C.
The same reaction and treatment as in Example 23 were carried out to obtain the same polymer as that in Example 23. Table 3 shows the yields of the polymers obtained in each example and the measurement results of Mn and Mn / Mw.

Examples 31 to 32 In Example 23, the reaction and reaction were the same as in Example 23 except that the reaction temperature was 120 ° C. and the reaction time was 12 hours in Example 31 and 36 hours in Example 32. Treatment was carried out to obtain the same polymer as in Example 23. Table 3 shows the yields of the polymers obtained in each example and the measurement results of Mn and Mn / Mw.

Example 33 In Example 23, instead of 1,3-BHPAD,
The reaction and treatment were performed in the same manner as in Example 23, except that the 2,2′-BHPAD synthesized in Production Example 5 was used and the reaction time was 24 hours. The yield of the white polymer (P-1f) was 89%. Got with. Table 3 shows the measurement results of the number average molecular weight (Mn) and the molecular weight distribution (Mn / Mw) of this polymer.

Further, it was confirmed that this polymer had a repeating unit represented by the following formula (19) by IR, ¹ H-NM
It was confirmed by measuring R and ¹³ C-NMR. The respective spectrum data are shown below. IR (film, cm ^-1 ): 3400, 2911, 2
850,1608,1579 ¹ H-NMR (500 MHz, CDCl ₃ ) δ (pp
m): 1.62 to 2.34, 3.10 to 3.20, 2.
51-2.70, 3.95-4.15, 4.22-4.
37,6.71 to 6.92,7.20 to 7.36 ¹³ C-NMR (125 MHz, CDCl ₃ , TMS)
δ (ppm): 27.5, 29.6, 32.0, 33.
3,35.8,36.7,38.0,42.4,44.
8, 49.3, 68.5, 68.7, 114.1, 11
4.5, 125.9, 126.7, 141.6, 14
3.5, 155.4, 156.3

[0094]

[Chemical 15]

Example 34 In Example 23, 2,2′-BGPAD and 1,3-BH synthesized in Production Example 6 were used instead of 1,3-BGPAD.
2,2′-BHP synthesized in Production Example 5 instead of PAD
The same reaction as in Example 23 was performed except that each AD was used and the reaction time was 24 hours. After the reaction was completed, the precipitated solid was collected, methanol was added, and the mixture was stirred at 50 ° C. for 2 hours. Then, the insoluble white solid was suction filtered and dried under reduced pressure to obtain a white polymer (P-1g) in a yield of 94%.
Since this polymer was insoluble in various organic solvents, the number average molecular weight (Mn) and the molecular weight distribution (Mn / Mw) could not be measured.

Further, it was confirmed by IR measurement that this polymer had a repeating unit represented by the following formula (20). IR spectrum data is shown below. IR (KBr, cm ^-1 ): 3448, 2910, 28
53,1605,1506

[0097]

[Chemical 16]

[0098]

[Table 3]

Examples 1, 14-16, 23, 33 and 3
The refractive index (n _D ), glass point transfer temperature (Tg) and decomposition start temperature (Td _5% ) of the alicyclic copolymer synthesized in Example 4 were measured under the following conditions, and the optical characteristics of each copolymer and The heat resistance was evaluated. Further, the fluorine content of each of the copolymers of Examples 1, 14 and 15 was measured by the alizarin complexon method.
The results are shown in Table 4. The refractive index of the copolymer synthesized in Example 34 could not be measured because it was insoluble in various organic solvents.

(1) As a refractive index casting solvent, methyl cellosolve acetate
2 mL was added to the sample bottle, in which the film thickness was about 1.
The alicyclic copolymer previously prepared was added to a concentration such that a thin film of 0 μm was formed, and the mixture was stirred until it was completely dissolved. After that, it was dropped on a silicon plate and coated using a spinner (manufactured by Asanuma Seisakusho Co., Ltd.). 170 this
A thin film was formed by drying at 30 ° C. for 30 minutes. The refractive index of the obtained thin film was measured by an ellipsometer (L11 manufactured by Gardner Co., Ltd.).
5B type) and measured 5 times with a laser having a wavelength of 0.6328 μm to remove the maximum refractive index and the minimum refractive index 3
It was determined as the average value of the measurements.

(2) Glass transition temperature (Tg) About 3 mg of an alicyclic copolymer was weighed into an aluminum pan and the pan was sealed, and then the differential scanning calorimeter (DSC) (manufactured by Seiko Instruments Inc., EXSTAR600).
0 / DSC6200) in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min and a temperature rising setting of room temperature to 200 ° C. to perform DSC measurement.
g was determined.

(3) Decomposition start temperature (Td _5% ) About 3 mg of the alicyclic copolymer was weighed into an aluminum pan, and a differential thermogravimetric simultaneous measurement device (manufactured by Seiko Instruments Inc., EXSTAR 6000 / TG / DTA) was used.
6200) in a nitrogen atmosphere at a heating rate of 10 ° C.
/ Min, temperature setting is room temperature to 600 ℃, thermobalance-
Differential scanning calorimetry (TG-DTA) was performed. TG / DT
The Td _5% was determined from the weight loss of the TG curve obtained from the A measurement. The Td of _5% is the temperature when the alicyclic copolymer is decomposed and the total weight of 5% is reduced.

[0103]

[Table 4]

[0104]

According to the present invention, there are provided an alicyclic copolymer having excellent heat resistance and / or optical properties, a method for producing the same, and an optical resin using such an alicyclic copolymer. it can.

[Brief description of drawings]

FIG. 1 is a diagram showing a relationship between a reaction time (h) of a raw material monomer, a yield (%) of a copolymer and a number average molecular weight (Mn) in the reactions of Examples 1 and 10 to 13.

FIG. 2 is a diagram showing an optical transmission fiber using the optical resin of the present invention.

FIG. 3 is a diagram showing an optical waveguide using the optical resin of the present invention.

[Explanation of sign]

10 Fiber for optical transmission 12,14 Clad layer 20 optical waveguide 22 Clad layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 6/12 G02B 6/12 N (72) Inventor Hiroto Kudo 4chome, Rokukakubashi, Kanagawa-ku, Yokohama-shi, Kanagawa No. 11 No. 28 F term (reference) 2H047 QA05 2H050 AA14 AB50Z 4J036 AA05 AD05 AD11 AG06 DA05 DB05 DB07 DB11 DB17 DB21 DB30 DC05 DC38 DC46 DD07 GA02 GA04 JA15

Claims (6)

[Claims] 1. A table represented by the following general formula (1) and / or (2)
Units derived from alicyclic bis-epoxy compounds
And a compound represented by the following general formula (3) and / or (4)
Alicyclic ring-containing copolymer containing structural unit derived from alicyclic compound
body. [Chemical 1] [In the formula, Cy is a divalent alicyclic hydrocarbon having 3 to 10 carbon atoms.
R is a base¹Are mutually independent, fluorine-substituted or non-substituted
A substituted arylene group having 6 to 12 carbon atoms, R ^TwoIs
Mutually independent hydrogen atoms, fluorine-substituted or unsubstituted carbon
Alkyl groups of 1 to 5 or fluorine-substituted or unsubstituted fluorine groups
It is a phenyl group] 2. A number average molecular weight of 2,000 to 300,0.
The alicyclic copolymer according to claim 1, which is 00. 3. The alicyclic copolymer according to claim 1, further comprising a structural unit derived from a crosslinking agent. 4. The following general formula (1) and / or (2)
Alicyclic bis-epoxy compound to be used and the following general formula (3)
And / or polyaddition with an alicyclic compound represented by (4)
A method for producing an alicyclic copolymer to be reacted. [Chemical 2] [In the formula, Cy is a divalent alicyclic hydrocarbon having 3 to 10 carbon atoms.
R is a base¹Are mutually independent, fluorine-substituted or non-substituted
A substituted arylene group having 6 to 12 carbon atoms, R ^TwoIs
Mutually independent hydrogen atoms, fluorine-substituted or unsubstituted carbon
Alkyl groups of 1 to 5 or fluorine-substituted or unsubstituted fluorine groups
It is a phenyl group] 5. A quaternary onium salt, a tertiary amine and a tertiary
The method for producing an alicyclic copolymer according to claim 4, wherein the polyaddition reaction is carried out in the presence of at least one catalyst selected from the group consisting of phosphines. 6. An optical resin containing the alicyclic copolymer according to any one of claims 1 to 3.