JP2011057945A - Alicyclic hydrocarbon copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent thermoplastic resin excellent in low hygroscopicity and heat resistance and useful as an optical material. <P>SOLUTION: The alicyclic hydrocarbon copolymer includes structures represented by general formula (1) and general formula (2). In the general formula, each of R<SP>1</SP>and R<SP>2</SP>is a hydrogen atom or a 1-3C alkyl group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an alicyclic hydrocarbon copolymer. More specifically, the present invention relates to an alicyclic hydrocarbon copolymer that is useful as an optical material and has excellent heat resistance.

  Transparent thermoplastic resins are widely used for optical elements and optical films for displays because of their high moldability, light weight, and mass productivity. Conventionally, polymethyl methacrylate, polycarbonate, and the like have been used as optical polymer materials. However, the former has high hygroscopicity and insufficient heat resistance, and the latter has problems such as high birefringence of molded products. As a result, it is becoming difficult to meet the demand for increasingly sophisticated optical polymer materials.

  A transparent thermoplastic resin obtained by polymerizing an alicyclic hydrocarbon monomer such as a polycyclic olefin has been developed as a polymer material with these drawbacks improved. For example, a hydrogenated product of a ring-opening metathesis polymer of a norbornene monomer (for example, see Patent Document 1), or an addition copolymer of a norbornene monomer and ethylene (for example, see Patent Document 2). As an optical polymer material excellent in transparency, heat resistance, low hygroscopicity, low birefringence, moldability, etc., it is represented by pickup lenses for optical disks such as camera lenses and DVDs. Used for precision optical components.

  Further, in-vehicle camera lenses and pickup lenses for next-generation high-density optical discs require optical polymer materials with higher heat resistance, and a transparent thermoplastic resin having a high glass transition temperature is required. .

  As a cyclic olefin polymer having a high glass transition temperature, a ring-opening metathesis polymer hydrogenated product of a norbornene-based monomer having an increased cohesive force by introducing a polar group such as an ester group has been proposed (for example, Patent Document 3). reference).

  However, since these polar norbornene polymers have high hygroscopicity, there is a problem that they are greatly deformed under high temperature and high humidity, and adversely affect optical properties.

JP 60-26024 A JP 60-168708 A Japanese Patent Laid-Open No. 09-221577

  An object of the present invention is to provide a transparent thermoplastic resin that is excellent in low moisture absorption and heat resistance and useful as an optical material.

The inventor of the present invention has arrived at the present invention as a result of intensive studies to achieve the above object. That is, the present invention
It is an alicyclic hydrocarbon copolymer containing the structural unit represented by General formula (1) and the structural unit represented by General formula (2).

[Wherein, m and n are each independently 1 or 2. ]

[Wherein, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

  According to the present invention, an alicyclic hydrocarbon polymer having high heat resistance can be provided without impairing physical properties such as low hygroscopicity.

  The alicyclic hydrocarbon copolymer of the present invention has at least one structural unit represented by the general formula (1) and at least one structural unit represented by the general formula (2).

  In general formula (1), m and n are each independently 1 or 2. That is, the alicyclic hydrocarbon copolymer of the present invention contains a bicyclic saturated hydrocarbon skeleton composed of a cyclopentane ring or a cyclohexane ring. From the viewpoint of heat resistance, a bicyclic saturated hydrocarbon skeleton in which a cyclopentane ring and a cyclohexane ring are condensed is preferable. That is, a bicyclic saturated hydrocarbon skeleton represented by m = 1 and n = 2 or a bicyclic saturated hydrocarbon skeleton represented by m = 2 and n = 1 is preferable.

In general formula (2), R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. From the viewpoint of heat resistance, R ¹ and R ² are preferably each independently a hydrogen atom or a methyl group.

  The total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the alicyclic hydrocarbon copolymer of the present invention is usually 60 mol% or more, preferably Is 70 mol% or more, more preferably 80 mol% or more. If it is less than 60 mol%, the heat resistance may be insufficient.

  The molar ratio of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) is 1/99 to 99/1 from the viewpoint of achieving both heat resistance and flexibility. Preferably, it is 5/95 to 95/5.

  The alicyclic hydrocarbon copolymer of the present invention includes, for example, at least one bicyclic conjugated diene monomer represented by the general formula (3) and an alkylidene norbornene monomer represented by the general formula (4). It can be produced by polymerizing a mixture containing a monomer in the presence of a cationic polymerization initiator and then hydrogenating the mixture.

  M and n in the general formula (3) are each independently 1 or 2. That is, the bicyclic conjugated diene monomer used in the present invention is a bicyclic conjugated diene composed of a cyclopentene ring or a cyclohexene ring.

  Specific examples of the bicyclic conjugated diene monomer include bicyclo [4,4,0] -1,9-decadiene [m = n = 2 in general formula (3) (the same applies hereinafter), bicyclo [4, 3,0] -2,9-nonadiene (m = 1, n = 2), bicyclo [4,3,0] -1,8-nonadiene (m = 2, n = 1) and bicyclo [3,3 0] -1,7-octadiene (m = n = 1). These bicyclic conjugated diene monomers may be used alone or in combination of two or more.

  Among the bicyclic conjugated diene monomers, bicyclo [4,3,0] -2,9-nonadiene and bicyclo [4,3 can be easily produced and have a high heat resistance polymer. , 0] -1,8-nonadiene is preferred, and bicyclo [4,3,0] -2,9-nonadiene is particularly preferred.

  The bicyclic conjugated diene monomer used in the present invention can be produced by isomerization of a bicyclic nonconjugated diene. For example, bicyclo [4,3,0] -3,7-nonadiene, which is industrially mass-produced, is isomerized with a titanocene dichloride / lithium aluminum hydride catalyst to produce bicyclo [4,3,0]- A mixture of 2,9-nonadiene and bicyclo [4,3,0] -1,8-nonadiene can be easily produced (see, for example, Tetrahedron Letters 1980, Vol. 21, 637-640). The mixing ratio can be controlled by isomerization conditions, and each component can be fractionated by a method such as precision distillation.

  Specific examples of the alkylidene norbornene monomer include 5-methylidene norbornene, 5-ethylidene norbornene, 5-propylidene norbornene, 5-isopropylidene norbornene and 5-iso partylidene norbornene. These alkylidene norbornene monomers may be used alone or in combination of two or more.

  Of the alkylidene norbornene monomers represented by the general formula (4), 5-ethylidene norbornene and 5-propylidene norbornene are preferable, particularly 5 because they are industrially mass-produced and have high cationic polymerizability. -Ethylidene norbornene is preferred.

  In the polymerization, bicyclic conjugated diene monomers and alkylidene norbornene monomers are used for the purpose of improving properties such as molding processability, flexibility, and mechanical strength of the finally obtained hydrogenated copolymer. It is also possible to mix and copolymerize other cationic polymerizable monomers.

  Specific examples of the cationic polymerizable monomer other than the bicyclic conjugated diene monomer and the alkylidene norbornene monomer include propylene, 1-butene, 2-butene, isobutene, 2-methyl-1-butene, 2- C1-C10 monoolefins such as methyl-1-pentene and β-pinene, C4-C10 dienes such as butadiene, isoprene, cyclopentadiene and norbornadiene, carbons such as styrene, α-methylstyrene and vinylnaphthalene Examples thereof include vinyl aromatic compounds having 8 to 12 carbon atoms, cyclic ethers having 2 to 8 carbon atoms such as ethylene oxide, propylene oxide, 1,4-dioxane, trioxane, 1,3-dioxolane, cyclohexene oxide, and tetrahydrofuran. These may be used alone or in combination of two or more.

  In the alicyclic hydrocarbon copolymer of the present invention, the content ratio of the structural unit derived from the cationic polymerizable monomer other than the bicyclic conjugated diene monomer and the alkylidene norbornene monomer is usually less than 40 mol%, Preferably it is less than 30 mol%, More preferably, it is less than 20 mol%. When it exceeds 20 mol%, the glass transition temperature of the copolymer becomes low, so that the heat resistance becomes insufficient.

  The catalyst used in the cationic polymerization is not particularly limited, and a commonly used catalyst such as Lewis acid or proton acid can be used.

  Specific examples of Lewis acids include aluminum chloride, boron trichloride, boron tribromide, boron trifluoride ether complex, metal halides such as titanium tetrachloride, tin tetrachloride and iron trichloride, ethylaluminum dichloride and Examples thereof include alkylaluminum chlorides such as diethylaluminum chloride, alkylaluminums such as triethylaluminum and triisobutylaluminum, and aromatic borons such as triphenylborane and trispentafluorophenylborane.

  Specific examples of the protonic acid include hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, nitric acid and perchloric acid.

  Of these cationic polymerization catalysts, preferred are Lewis acids, more preferred are metal halides or alkylaluminum chlorides, and particularly preferred are alkylaluminum chlorides.

  When a catalyst comprising at least one selected from Lewis acids and proton acids is used as the cationic polymerization catalyst, the amount used is 0.0001 to 1 mol%, preferably 0.001 to 0.1 mol, based on the monomer. Mol%.

  When a Lewis acid is used as the cationic polymerization catalyst, an additive may be used in combination for the purpose of controlling the molecular weight. Specific examples of additives include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium tetrafluoroborate, tetrabutylammonium tetraphenylborate and tetrakispentafluoro Quaternary ammonium salts such as tetrabutylammonium phenylborate, -tert-butyl chloride, 2-methoxy-2-phenylpropane, 2-phenyl-2-propanol, 1,4-bis (α-chloroisopropyl) benzene and Compounds generally known as Kennedy catalysts, such as 1,3,5-tris (α-chloroisopropyl) benzene, triethylamine, pyridine, triphenylphosphine, diethyl ether, acetone, tetrahydrofuran , Dimethyl sulfoxide and N, N- dimethylformamide electron-donating compound such as and the like. The amount of the additive used is not particularly limited as long as it is within a normal range.

  The polymerization can be carried out in the presence or absence of a solvent. There is no restriction | limiting in particular in the solvent used for superposition | polymerization, A normal solvent can be used. Specific examples of the solvent include chlorinated solvents such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and tetrachloroethane, aromatic solvents such as benzene, toluene, xylene, chlorobenzene and o-dichlorobenzene, nitromethane. And nitro solvents such as nitrobenzene and aliphatic solvents such as pentane, hexane, heptane, cyclohexane and decahydronaphthalene. These may be used alone or in combination of two or more.

  Among these solvents, from the viewpoint of the solubility of the resulting polymer, a chlorinated solvent and an aromatic solvent are preferable, and methylene chloride or toluene is particularly preferable.

  When a solvent is used, the amount used is not particularly limited, but it is desirable to adjust the total monomer charge concentration to be 1 to 50% by weight.

  The polymerization temperature is preferably between −150 ° C. and 100 ° C. Preferably it is -100 degreeC to 80 degreeC, More preferably, it is -80 degreeC to 60 degreeC.

  The polymerization time is usually 0.1 to 24 hours, although it depends on the catalyst used and the reaction temperature.

  The molecular weight of the alicyclic hydrocarbon copolymer of the present invention is a number average molecular weight (Mn) measured by gel permeation chromatography (GPC), and is usually 3,000 to 500,000, preferably 5,000 to 300,000. When the molecular weight is less than 3000, the film formability and the mechanical strength of the film are insufficient, and when it is greater than 500,000, the melt viscosity becomes high and molding may be difficult. The molecular weight distribution (Mw / Mn) is 10 or less, preferably 5 or less. If the molecular weight distribution is too large, the proportion of low molecular weight components increases, and the film formability and film mechanical strength may be insufficient. The molecular weight can be adjusted by appropriately selecting the conditions such as the charging ratio of the cationic polymerization catalyst and the monomer, the presence / absence of an additive controlling the molecular weight, the reaction temperature, as described above.

  In the hydrogenation reaction, a hydrogenation catalyst is added to a solvent solution of a cationic polymer in a usual manner, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is added thereto at 0 to 200 ° C., preferably 20 It is carried out by acting at ~ 180 ° C. As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.

  Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania.

  Homogeneous catalysts include rhodium acetate, chlorotris (triphenylphosphine) rhodium, chlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, nickel naphthenate / Examples include transition metal catalysts such as triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium.

  The usage-amount of a hydrogenation catalyst is 0.0001-100 weight% normally with respect to the polymer obtained by cationic polymerization.

There is no restriction | limiting in particular in the solvent used for hydrogenation reaction, The solvent which can be used for cationic polymerization can be used as it is. From the viewpoint of solubility, a chlorinated solvent and an aromatic solvent are preferable, and methylene chloride or toluene is particularly preferable.
Although there is no restriction | limiting in particular in the usage-amount of a solvent, It is desirable to adjust so that the preparation density | concentration of the polymer obtained by cationic polymerization may be 1 to 50 weight%.

  The hydrogenation reaction may be carried out by isolating the polymer obtained by cationic polymerization and then redissolving it in a suitable solvent, or by directly adding a hydrogenation catalyst to the reaction solution obtained by cationic polymerization. You may go. The latter is preferable in terms of simple operation.

The hydrogenated polymer obtained by hydrogenation has excellent thermal stability, and its characteristics are not deteriorated even by heating during molding or use as a product. The hydrogenation rate is usually 70% or more, preferably 80% or more, more preferably 90% or more, relative to the number of moles of unsaturated bonds in the polymer. The hydrogenation rate can be determined from an integral value derived from an olefinic proton by ¹ H-NMR spectrum.

  The hydrogenated polymer thus obtained can be isolated as a solid by mixing the reaction solution with a poor solvent and precipitating.

  Specific examples of the poor solvent include polar solvents such as water, methanol, ethanol, isopropanol, acetone, acetonitrile, and ethylene glycol. These poor solvents may be used alone or in combination of two or more, but it is preferable to use in combination of two or more in terms of efficiently removing impurities such as catalyst residues.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. Hereinafter, unless otherwise specified, “%” means “% by weight” and “part” means “part by weight”.

[Measuring method]
The glass transition temperature of the polymer is determined from the inflection point when the temperature is raised from 70 to 250 ° C. at a rate of 10 ° C. per minute using a differential thermal scanning calorimeter (DSC-7 manufactured by PerkinElmer). It was.
The ratio of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) and the hydrogenation rate in the polymer are determined by using ¹ H-NMR (lamda 400 manufactured by JEOL Ltd.). It was calculated from the integral ratio of protons derived from each structural unit.
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer were determined as values in terms of standard polystyrene using gel permeation chromatography (RID-6A manufactured by Shimadzu Corporation). As the column, Shodex GPC AD802-S, AD803-S, AD804-S and AD805-S (manufactured by Tosoh Corporation) were used. Toluene was used as the eluent, RI was used as the detector under conditions of a column temperature of 40 ° C. and a flow rate of 1.0 mL / min.
The light transmittance (%) of the molded body was measured at a wavelength of 830 nm and an optical path length of 2 mm using a spectrophotometer (V-570 manufactured by JASCO Corporation).
The water absorption rate (%) was determined from the weight increase after the molded body was immersed in 25 ° C. water for 24 hours.

[Production Example 1] <Production of bicyclic conjugated diene monomer>
Bicyclo [4,3,0] -2,9-nonadiene and bicyclo [4,3,0] -1,8-nonadiene, which are bicyclic conjugated diene monomers, were converted into tetrahedron letters 1980, Vol. 21, 637-640 was used as a reference for synthesis as follows. In a flask purged with nitrogen, 100 parts of bicyclo [4,3,0] -3,7-nonadiene, 0.8 part of titanocene dichloride and 0.5 part of lithium aluminum hydride were charged. The temperature was slowly raised while stirring, and the reaction was carried out at 165 ° C. for 6 hours. After completion of the reaction, flash distillation was performed at 665 Pa (5 mmHg) to obtain 80 parts of a single yellow transparent liquid. The obtained liquid was subjected to precision distillation under the conditions of 532 Pa (4 mmHg) and an oil bath temperature of 80 ° C. to obtain 50 parts of a colorless and transparent liquid. This liquid was a mixture of bicyclo [4,3,0] -2,9-nonadiene and bicyclo [4,3,0] -1,8-nonadiene having a molar ratio of 88:12 by ¹ H-NMR measurement. It was.

[Example 1]
In a flask substituted with nitrogen, 60 parts of toluene, moles of bicyclo [4,3,0] -2,9-nonadiene and bicyclo [4,3,0] -1,8-nonadiene obtained in Preparation Example 1 above. 10 parts of a 88:12 mixture and 10 parts of 5-ethylidene norbornene were charged. After cooling to 0 ° C. with stirring, 0.6 part of a 17% hexane solution of ethylaluminum dichloride was added and stirred at 0 ° C. for 3 hours to obtain a copolymer solution.

  80 parts of the obtained copolymer solution is put into an autoclave, 0.1 part of chlorohydrocarbonyltris (triphenylphosphine) ruthenium is added, and the mixture is heated and stirred for 4 hours under conditions of a hydrogen gas pressure of 100 kg / cm 2 and a reaction temperature of 150 ° C. The hydrogenation reaction was performed. The obtained hydrogenated polymer solution was cooled and poured into 400 parts of methanol, and the resulting white precipitate was filtered and dried to obtain 14 parts of an alicyclic hydrocarbon copolymer.

The obtained alicyclic hydrocarbon copolymer had a glass transition temperature of 186 ° C. as measured by DSC. As a result of analysis by ¹ H-NMR spectrum, the ratio of the structural unit represented by the general formula (1) to the structural unit represented by the general formula (2) was 62:38. Since no olefinic protons were observed, the hydrogenation rate was substantially 100%. The number average molecular weight (Mn) by GPC measurement was 24800, the weight average molecular weight (Mw) was 54000, and the molecular weight distribution (Mw / Mn) was 2.2.

  This alicyclic hydrocarbon copolymer was compression molded at 230 ° C. to prepare a test piece having a 4 cm square and a thickness of 2 mm. The molded specimen was tough and colorless and transparent, and the light transmittance at 830 nm was 90%. The water absorption after immersion in water at 25 ° C. for 24 hours was 0.01% or less.

[Example 2]
The number of parts of the mixture of bicyclo [4,3,0] -2,9-nonadiene and bicyclo [4,3,0] -1,8-nonadiene in a molar ratio of 88:12 is 13 parts, and 5-ethylidene norbornene 15 parts of alicyclic hydrocarbon copolymer was obtained in the same manner as in Example 1 except that 7 parts was replaced with 7 parts.

The obtained alicyclic hydrocarbon copolymer had a glass transition temperature of 195 ° C. as measured by DSC. As a result of analysis by ¹ H-NMR spectrum, the ratio of the structural unit represented by the general formula (1) to the structural unit represented by the general formula (2) was 74:26. Since no olefinic protons were observed, the hydrogenation rate was substantially 100%. The number average molecular weight (Mn) by GPC measurement was 26600, the weight average molecular weight (Mw) was 62000, and the molecular weight distribution (Mw / Mn) was 2.3.

  Using this alicyclic hydrocarbon copolymer, a test piece having a thickness of 2 mm was prepared in the same manner as in Example 1. The light transmittance at 830 nm was 89%. The water absorption after immersion in water at 25 ° C. for 24 hours was 0.01% or less.

[Example 3]
The number of parts of a mixture of bicyclo [4,3,0] -2,9-nonadiene and bicyclo [4,3,0] -1,8-nonadiene in a molar ratio of 88:12 is 7 parts, and 5-ethylidene norbornene. Was replaced with 13 parts in the same manner as in Example 1 to obtain 13 parts of an alicyclic hydrocarbon copolymer.

The glass transition temperature of the obtained alicyclic hydrocarbon copolymer as measured by DSC was 178 ° C. As a result of analysis by ¹ H-NMR spectrum, the ratio of the structural unit represented by the general formula (1) to the structural unit represented by the general formula (2) was 44:56. Since no olefinic protons were observed, the hydrogenation rate was substantially 100%. The number average molecular weight (Mn) by GPC measurement was 23000, the weight average molecular weight (Mw) was 58200, and the molecular weight distribution (Mw / Mn) was 2.6.

  Using this alicyclic hydrocarbon copolymer, a test piece having a thickness of 2 mm was prepared in the same manner as in Example 1. The light transmittance at 830 nm was 91%. The water absorption after immersion in water at 25 ° C. for 24 hours was 0.01% or less.

[Example 4]
9 parts of a mixture of bicyclo [4,3,0] -2,9-nonadiene and bicyclo [4,3,0] -1,8-nonadiene in a molar ratio of 88:12 is 10 parts of 5-ethylidenenorbornene Was replaced with 9 parts of 5-ethylidene norbornene and 2 parts of isobutene in the same manner as in Example 1 to obtain 13 parts of an alicyclic hydrocarbon copolymer.

The obtained alicyclic hydrocarbon copolymer had a glass transition temperature of 172 ° C. as measured by DSC. As a result of analysis by ¹ H-NMR spectrum, the ratio of the structural unit represented by the general formula (1), the structural unit represented by the general formula (2), and the structural unit derived from isobutene was 56: 36: 8. . Since no olefinic protons were observed, the hydrogenation rate was substantially 100%. The number average molecular weight (Mn) measured by GPC was 19200, the weight average molecular weight (Mw) was 44400, and the molecular weight distribution (Mw / Mn) was 2.3.

  Using this alicyclic hydrocarbon copolymer, a test piece having a thickness of 2 mm was prepared in the same manner as in Example 1. The light transmittance at 830 nm was 90%. The water absorption after immersion in water at 25 ° C. for 24 hours was 0.01% or less.

[Comparative Example 1]
Using a commercially available norbornene polymer [manufactured by Nippon Zeon Co., Ltd., glass transition temperature: 138 ° C.], a test piece having a thickness of 2 mm was prepared in the same manner as in Example 1. The light transmittance at 830 nm was 90%. The water absorption after immersion in water at 25 ° C. for 24 hours was 0.01% or less.

[Comparative Example 2]
Using a commercially available polar norbornene polymer [manufactured by JSR Corporation, glass transition temperature 164 ° C.], a test piece having a thickness of 2 mm was prepared in the same manner as in Example 1. The light transmittance at 830 nm was 90%. The water absorption after immersion in water at 25 ° C. for 24 hours was 0.4%.

  The alicyclic hydrocarbon copolymers obtained in Examples 1 to 4 have high transparency, exhibit a glass transition temperature significantly higher than that of the norbornene polymer of Comparative Example 1, and have excellent heat resistance. I understand. In addition, it can be seen that the polymers obtained in Examples 1 to 4 have significantly lower hygroscopicity than the norbornene polymer of Comparative Example 2, and have superior properties.

  Since the alicyclic hydrocarbon polymer of the present invention has high heat resistance without impairing physical properties such as low hygroscopicity and transparency, it is useful as an optical material. In particular, it is useful as a polymer material for precision optical parts such as a vehicle-mounted camera lens, a next-generation high-density optical disk pickup lens, and a projector lens that require high heat resistance and dimensional stability.

Claims (3)

The alicyclic hydrocarbon copolymer containing the structural unit represented by General formula (1) and the structural unit represented by General formula (2).
[Wherein, m and n are each independently 1 or 2. ]
[Wherein, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]   The structural unit represented by the general formula (1) comprises a structural unit in which m is 1 and n is 2 and / or a structural unit in which m is 2 and n is 1 in the general formula (1). The alicyclic hydrocarbon copolymer according to 1.   The alicyclic ring according to claim 1 or 2, wherein a total content ratio of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) is 60 mol% or more of the total structural units. Formula hydrocarbon copolymer.