JP2008045069A - Cyclic olefin addition copolymer, process for producing the same, and use thereof - Google Patents

Abstract

【効果】本発明によれば、優れた低複屈折性と透明性、耐熱性、低吸水性を有し、有機溶媒への高い溶解性及び溶融成形加工性を示す新規な環状オレフィン系付加共重合体、および該環状オレフィン系付加共重合体を高い経済性と生産性で製造する製造方法、ならびに該環状オレフィン系付加共重合体を成形して得られる光学部材および光学フィルムを提供することができる。
【選択図】なしThe cyclic olefin addition copolymer of the present invention has a structural unit (1) represented by the following formula (1) and a structural unit (2) represented by the following formula (2). It is a feature.

[Effect] According to the present invention, a novel cyclic olefin-based addition copolymer having excellent low birefringence, transparency, heat resistance, low water absorption, high solubility in organic solvents and melt molding processability. To provide a polymer, a production method for producing the cyclic olefin addition copolymer with high economic efficiency and productivity, and an optical member and an optical film obtained by molding the cyclic olefin addition copolymer. it can.
[Selection figure] None

Description

  The present invention relates to a cyclic olefin addition copolymer, a method for producing the same, and an application. Specifically, the present invention provides excellent transparency, heat resistance, low water absorption, and low water absorption obtained by addition copolymerization of a cyclic olefin compound having a specific structure such as a fluorene skeleton and other cyclic olefin compounds. Novel cyclic olefin addition copolymer showing birefringence, high solubility in organic solvents and melt molding processability, a method for producing the cyclic olefin addition copolymer with high productivity and economy, and The present invention relates to an optical member and an optical film obtained by molding a cyclic olefin addition copolymer.

  Of course, optical materials such as lenses, backlights, light guide plates, and optical films are required to have excellent transparency, but in recent years, they have other heat resistance, low water absorption, low dielectric constant, and flexibility. The demands for sex and toughness are increasing.

  For example, polyester resins, acrylic resins, polycarbonate resins, polyarylate resins, polyethersulfone resins, and the like are known as transparent resins used for optical materials, but these resins have heat resistance, water absorption, and transparency. Properties such as sex were not sufficient.

  As resins having excellent transparency and heat resistance, many hydrogenated products or addition polymers of ring-opening polymers of cyclic olefin compounds have been proposed. Since the main chain is composed of alicyclic hydrocarbons, they are useful because they have less absorption in the short wavelength region than aromatic resins. Many cyclic olefin ring-opening polymers and hydrogenated products thereof have been proposed as useful optical materials for producing lenses, optical disks and the like (for example, Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, Patent Document 6), the cyclic olefin-based ring-opening (co) polymers and hydrogenated products thereof disclosed therein have excellent heat resistance and low water absorption (humidity) and are transparent. It also has excellent optical properties such as injection molding and moldability such as injection molding. In addition, a ring-opening polymer of a cyclic olefin monomer in which a polar group is introduced into the molecule and a hydrogenated product thereof have been proposed (for example, Patent Document 7 and Patent Document 8). It is disclosed that it has excellent affinity with other materials and excellent post-processability such as adhesion. However, since cyclic olefin-based ring-opened polymers have double bonds in the main chain after the polymerization reaction, a hydrogenation step is required to improve the heat resistance deterioration, which causes problems in industrial productivity and economy. I'm leaving.

  On the other hand, it is known that a resin excellent in heat resistance and transparency can be obtained by addition polymerization of a cyclic olefin compound. The addition polymer of a cyclic olefin compound is excellent in heat deterioration resistance because there is no double bond in the main chain after the polymerization reaction, and is excellent in industrial productivity and economy because no hydrogenation is required.

  As examples of addition polymers of cyclic olefin compounds, many addition copolymers of cyclic olefin compounds and α-olefins have been reported (for example, Patent Document 9 and Patent Document 10). However, in these copolymers, a chain of structural units derived from an α-olefin such as ethylene may crystallize, which is not necessarily sufficient for use in optical materials such as a decrease in transparency. In addition, since the difference in polymerization reactivity between the cyclic olefin and the α-olefin is large, the composition of the copolymer is distributed, and the transparency may be lowered.

In addition, cyclic olefin addition polymers formed only from structural units derived from cyclic olefin compounds can be produced using titanium catalysts, zirconium catalysts, cobalt catalysts, nickel catalysts, palladium catalysts, etc., and have excellent heat resistance. It is known as a resin exhibiting properties and transparency. Here, the stereoregularity of the polymer produced by the selection of the catalyst to be used (atactic / erythro-disyndiotactic / erythro-diisotactic etc.) and the mode of addition polymerization (addition at the 2,3-position and 2, It has been known so far that the addition at the 7-position) and the controllability of the molecular weight are different. For example, it has been reported that a norbornene polymer polymerized using a zirconium-based metallocene catalyst is infusible and insoluble in common solvents (Non-Patent Document 1). Further, the norbornene addition polymer polymerized using a nickel-based catalyst shows good solubility in hydrocarbon solvents such as cyclohexane (Patent Document 11), but is reported to be inferior in mechanical strength and brittle. (Patent Document 12).

  On the other hand, it has been reported that by using a specific catalyst containing a palladium compound, a cyclic olefin-based addition polymer having high polymerization activity and excellent transparency, heat resistance and mechanical strength can be produced (patent) Literature 12, Patent Literature 13, Patent Literature 14). Patent Document 15 discloses that a cyclic olefin copolymer having a hydrolyzable silyl group-containing cyclic olefin and obtained using a catalyst containing a palladium compound exhibits excellent heat resistance and dimensional stability. Yes. However, while the addition polymers described therein exhibit very high heat resistance, they cannot be hot melt molded, and the molding method is limited to the solution casting method (cast method). The casting method uses a large amount of solvent and requires removal and recovery steps of the solvent, so that there are industrial problems such as an increase in equipment size, low productivity and high cost.

  In order to reduce the glass transition temperature in order to enable melt molding of the cyclic olefin addition polymer, it has been proposed to use a cyclic olefin compound having an alkyl substituent as a monomer. For example, Patent Document 16 describes an addition copolymer using 5-hexyl-2-norbornene. Patent Document 11 and Non-Patent Document 2 describe that norbornene having a long-chain alkyl group is used as a monomer, and the glass transition temperature of the addition copolymer can be controlled by the chain length and ratio. However, these prior arts do not describe the influence of the polymerization catalyst on the mechanical strength of the resulting molded article. Moreover, the polymerization catalyst used in these is not satisfactory in its activity, and requires a step of removing unreacted monomers and catalyst remaining after the reaction.

Furthermore, since the cyclic olefin having a long-chain alkyl group has a lower polymerization reactivity than norbornene, the copolymer composition is distributed during the copolymerization of the both. Non-Patent Document 2 does not mention the difference in monomer reactivity or composition distribution. The distribution becomes conspicuous at a high conversion rate, and the transparency and strength of the resulting molded product may be impaired. Therefore, it is a problem to achieve both high conversion rate and high transparency. In other words, despite the desire for a method for producing a cyclic olefin copolymer that is excellent in economic efficiency and productivity, exhibits good heat resistance and melt molding processability, and obtains high transparency at a high conversion rate, to date Not reported to.
Japanese Unexamined Patent Publication No. 63-21878 JP-A-1-138257 JP-A-1-168725 Japanese Patent Laid-Open No. 2-102221 JP-A-2-133413 Japanese Patent Laid-Open No. 4-170425 JP 50-111200 A JP-A-1-132626 JP 61-292601 A US Pat. No. 2,883,372 Japanese National Patent Publication No. 9-508649 JP 2006-52347 A JP 2005-162990 A JP 2005-213435 A Japanese Patent Laid-Open No. 2005-48060 JP-A-8-198919 Macromol. Chem. Macromol. Symp., Vol. 47, 831 (1991) Proc. Am. Chem. Soc. Div. Polym. Mater .: Sci. Eng. Vol. 75, 56 (1997)

  The present invention provides a cyclic olefin addition copolymer having excellent low birefringence, transparency and heat resistance, low water absorption, high solubility in organic solvents and melt molding processability, and the cyclic olefin addition copolymer. An object of the present invention is to provide an optical material such as an optical film obtained by molding a polymer, and a method for producing the cyclic olefin addition copolymer with high productivity.

The cyclic olefin addition copolymer of the present invention is
It has a structural unit (1) represented by the following formula (1) and a structural unit (2) represented by the following formula (2).

(In the formula (1), A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group, or a halogenated hydrocarbon. And a hydrolyzable silyl group or a group represented by — (CH ₂ ) _q —X, wherein A ¹ and A ² or A ³ and A ⁴ are bonded to each other to form an alkylidene group. A ¹ and A ² , A ³ and A ^4, or A ² and A ³ may be bonded to each other to form a carbocyclic or heterocyclic ring (these carbocyclic or heterocyclic rings may have a monocyclic structure). And a carbocyclic or heterocyclic ring formed may be an aromatic ring or a non-aromatic ring, and p is 0 or 1.

In the formula — (CH ₂ ) _q —X, q is an integer of 0 to ⁵ , and X is —COOA ⁵ , —O.
Shows the COA ^6, or -OA ^7, A ^5, A ⁶ and A ⁷ are each independently 1 to 10 carbon atoms
And a substituent containing a hydrocarbon group, a halogenated hydrocarbon group, or an oxetanyl group. ),

(In the formula (2), m and n are each independently an integer of 0 to 2,
B ¹ , B ² , B ³ , B ⁴ , B ⁵ , B ⁶ , B ⁷ , and B ⁸ are each independently a hydrogen atom; a halogen atom; a linkage containing an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a group; and an atom or group selected from the group consisting of polar groups;
s, t, and u are each independently an integer of 0 to 3. )
Such a cyclic olefin addition copolymer of the present invention preferably has 99 to 30 mol% of the structural unit (1) and 1 to 70 mol% of the structural unit (2).

The cyclic olefin addition copolymer of the present invention preferably has a glass transition temperature of 100 to 400 ° C. and a number average molecular weight in the range of 20,000 to 500,000.
The method for producing the cyclic olefin-based addition copolymer of the present invention includes:
A monomer (1m) represented by the following formula (1m) and a monomer (2m) represented by the following formula (2m),
It is characterized by addition copolymerization in the presence of a catalyst obtained using the following (a), (b) and (d), or a catalyst obtained using the following (c) and (d).

(In the formula (1m), A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group, or a halogenated hydrocarbon. And a hydrolyzable silyl group or a group represented by — (CH ₂ ) _q —X, where A ¹
And A ² or A ³ and A ⁴ may be bonded to each other to form an alkylidene group, and A ¹ and A ² , A ³ and A ⁴ or A ² and A ³ are bonded to each other. A carbocycle or a heterocycle (these carbocycle or heterocycle may be a monocyclic structure or a polycyclic structure in which other rings are condensed) may be formed. The formed carbocyclic or heterocyclic ring may be an aromatic ring or a non-aromatic ring. p is 0 or 1.

In the formula — (CH ₂ ) _q —X, q is an integer of 0 to ⁵ , and X is —COOA ⁵ , —O.
Shows the COA ^6, or -OA ^7, A ^5, A ⁶ and A ⁷ are each independently 1 to 10 carbon atoms
And a substituent containing a hydrocarbon group, a halogenated hydrocarbon group, or an oxetanyl group. )
,

(In the formula (2m), m and n are each independently an integer of 0 to 2,
B ¹ , B ² , B ³ , B ⁴ , B ⁵ , B ⁶ , B ⁷ and B ⁸ are each independently a hydrogen atom; a halogen atom; a linking group containing an oxygen atom, nitrogen atom, sulfur atom or silicon atom A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have an atom; and an atom or group selected from the group consisting of polar groups,
s, t, and u are each independently an integer of 0 to 3. ),
(A) an organic acid salt of palladium or a β-diketonate compound of palladium,
(B) a phosphine compound represented by the following formula (b),
P (R ¹ ) ₂ (R ² ) (b)
[In Formula (b), R ¹ is a substituent selected from a cyclopentyl group, a cyclohexyl group, and an isopropyl group, and R ² represents a hydrocarbon group having 3 to 10 carbon atoms. ]
(C) a phosphine complex of divalent palladium represented by the following formula (c):
Pd [P (R ¹ ) ₂ (R ² )] _n X ₂ (c)
[In the formula (c), R ¹ is a substituent selected from a cyclopentyl group, a cyclohexyl group, and an isopropyl group, R ² represents a hydrocarbon group having 3 to 10 carbon atoms, and X is an organic acid anion or β-di- It is a ketonate anion, and n represents 1 or 2. ]
(D) An ionic boron compound.

  The optical member or optical film of the present invention is characterized by comprising the above-mentioned cyclic olefin addition copolymer of the present invention.

  According to the present invention, a novel cyclic olefin-based addition copolymer having excellent low birefringence and transparency, heat resistance, low water absorption, high solubility in organic solvents and melt molding processability, And a production method for producing the cyclic olefin-based addition copolymer with high economic efficiency and productivity, and an optical member and an optical film obtained by molding the cyclic olefin-based addition copolymer.

Hereinafter, the present invention will be specifically described.
Method for Producing Cyclic Olefin Addition Copolymer The cyclic olefin addition copolymer according to the present invention includes a structural unit (1) represented by the above formula (1) and a structural unit represented by the above formula (2). (2)

Here, the structural unit (1) is usually derived from a monomer (1m) represented by the following formula (1m), and the structural unit (2) is a monomer represented by the following formula (2m). Derived from (2m).

(In the formula (1m), A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group, or a halogenated hydrocarbon. And a hydrolyzable silyl group or a group represented by — (CH ₂ ) _q —X, where A ¹
And A ² or A ³ and A ⁴ may be bonded to each other to form an alkylidene group, and A ¹ and A ² , A ³ and A ⁴ or A ² and A ³ are bonded to each other. A carbocycle or a heterocycle (these carbocycle or heterocycle may be a monocyclic structure or a polycyclic structure in which other rings are condensed) may be formed. The formed carbocyclic or heterocyclic ring may be an aromatic ring or a non-aromatic ring. p is 0 or 1.

In the formula — (CH ₂ ) _q —X, q is an integer of 0 to ⁵ , and X is —COOA ⁵ , —O.
Shows the COA ^6, or -OA ^7, A ^5, A ⁶ and A ⁷ are each independently 1 to 10 carbon atoms
And a substituent containing a hydrocarbon group, a halogenated hydrocarbon group, or an oxetanyl group. )

(In the formula (2m), m and n are each independently an integer of 0 to 2,
B ¹ , B ² , B ³ , B ⁴ , B ⁵ , B ⁶ , B ⁷ and B ⁸ are each independently a hydrogen atom; a halogen atom; a linking group containing an oxygen atom, nitrogen atom, sulfur atom or silicon atom A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have an atom; and an atom or group selected from the group consisting of polar groups,
s, t, and u are each independently an integer of 0 to 3. )
In the method for producing a cyclic olefin addition copolymer of the present invention, a monomer composition containing at least one monomer (1m) and at least one monomer (2m) is subjected to addition copolymerization. .
<Monomer>
The monomers (1m) and (2m) used in the present invention are compounds represented by the above formulas (1m) and (2m), respectively, and correspond to the structural units (1) and (2).

In the present invention, bicyclo [2.2.1] hept-2-ene and 5-alkylbicyclo [2.2.1] hept-2-ene having 1 to 20 carbon atoms are used as the monomer (1m). Preferably used. Regarding A ¹ , A ² , A ³ , and A ⁴ of the monomer (1m) in formula (1m), examples of the alkyl group having 1 to 20 carbon atoms include 1-methyl group, 1-ethyl group, 1- Propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, 1-undecyl group, 1-dodecyl group, 2- Examples include those having a linear or branched alkyl group such as a decyl group and an 8-methyl-1-nonyl group. Among them, a 1-butyl group, a 1-hexyl group, a 1-octyl group, a 1-decyl group, 1 -A dodecyl group is preferable.

  Specific examples of such a monomer (1m) include 5-methyl-bicyclo [2.2.1] hept-2-ene and 5-ethyl-bicyclo [2.2.1] hept-2-ene. Ene, 5-propyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-pentylbicyclo [2.2.1] hepta 2-ene, 5-hexylbicyclo [2.2.1] hept-2-ene, 5-heptylbicyclo [2.2.1] hept-2-ene, 5-octylbicyclo [2.2.1] Hept-2-ene, 5-nonylbicyclo [2.2.1] hept-2-ene, 5-decylbicyclo [2.2.1] hept-2-ene, 5-undecylbicyclo [2.2. 1] Hept-2-ene, 5-dodecylbicyclo [2.2.1] hept-2-ene Any linear alkyl group, 2- (bicyclo [2.2.1] hept-2-en-5-yl) decene, 8-methyl-1- (bicyclo [2.2.1] hepta- Examples thereof include those having a branched alkyl group such as 2-en-5-yl) nonane.

Furthermore, as the monomer (1m), 5-vinyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5- ( 1'-butenyl) -bicyclo [2.2.1] hept-2-ene, 5,6-dimethyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-6-ethyl-bicyclo [ 2.2.1] hept-2-ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5- Methoxy-bicyclo [2.2.1] hept-2-ene, 5-ethoxy-bicyclo [2.2.1] hept-2-ene, 5-fluoro-bicyclo [2.2.1] hept-2- Ene, 5-chloro-bicyclo [2.2.1] hept-2-ene, bicyclo [2.2. 1] methyl hept-2-ene-5-carboxylate, bicyclo [2.2.1] t-butyl hept-2-ene-5-carboxylate, bicyclo [2.2.1]
] Hept-2-ene-5-spiro-N-cyclohexylsuccinimide, bicyclo [2.2.1] hept-2-ene-5,6-N-cyclohexylcarboxylic acid imide, bicyclo [2.2.1] hepta 2-ene-5,6-carboxylic anhydride, tricyclo [5.2.1.0 ^{2, 6]} deca-8-ene, tricyclo [5.2.1.0 ^{2, 6]} deca -3,8 -Diene, tetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene, 9-methyl-tetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4 -Ene, 9-ethyl-tetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene, 9-methoxycarbonyl-tetracyclo [6.2.1.1 ^3,6 0 ^{2, 7]} dodeca-4-ene, 9-methyl-9-methoxycarbonyl - tetracyclo [6.2.1.1 ^3,6 0 ^2,7] de Mosquito-4-ene, 9-methyl-9-ethoxycarbonyl - tetracyclo [6.2.1.1 ^3,6 0 ^2,7] such dodeca-4-ene.

In the formula (1m), A ¹ and A ² or A ³ and A ⁴ may be bonded to each other to form an alkylidene group, and A ¹ and A ² , A ³ and A ^4, or A ² and A ^{4 3} may be bonded to each other to form a carbocyclic or heterocyclic ring. The formed carbocyclic or heterocyclic ring may be an aromatic ring or a non-aromatic ring. For example, the A ¹ and A ^4, integrated alkylene group may form a cycloalkylene group or an arylene group, further, A ¹ and A ² or A ¹ and A ⁴ are bonded to each other acid A group derived from an anhydride, lactone or imide may be formed.

In the present invention, as the monomer (1m), one or more of A ¹ , A ² , A ³ , A ^{4 in} the above formula (1m), preferably one of them is a hydrolyzable silyl group or A polar group represented by — (CH ₂ ) _q — is also preferred. Here, the polar group represented by — (CH ₂ ) _q — is specifically a group selected from an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkenylcarbonyloxy group, an acid anhydride group, and an oxetanyl group. Is mentioned. -(CH ₂
) Specific examples of the monomer (1m) having a polar group represented by _q- include, for example, methyl bicyclo [2.2.1] hept-5-ene-2-carboxylate, 2-methylbicyclo [ 2.2.1] methyl hepta-5-ene-2-carboxylate, 2-methylbicyclo [2.2.1] t-butyl hept-5-ene-2-carboxylate, tetracyclo [6.2.1] .1 ^3,6 . 0 ^2,7 ] Dodeca-9-ene-4-carboxylate, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-9-ene-4-carboxylate, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] t-butyl dodec-9-ene-4-carboxylate, acetic acid (bicyclo [2.2.1] hept-5-en-2-yl), acetic acid (bicyclo [2.2.1] Hept-5-en-2-methyl-2-yl), acetic acid (tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodec-9-en-4-yl), bicyclo [2. 2.1] hept-5-ene-2,3-carboxylic anhydride, 5-[(3-ethyl-3-octacenyl) methoxy] bicyclo [2.2.1] hept-2-ene, 5-[( 3-oxetanyl) methoxy] bicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-ethyl-3-oxetanyl) methyl and the like Can be mentioned.

Moreover, as a specific example of the monomer (1m) having a hydrolyzable silyl group,
5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-triethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-methyldimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-methyldiethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-methyldichlorosilyl-bicyclo [2.2.1] hept-2-ene,
9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-triethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-methyldimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-ethyldimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-cyclohexyldimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-phenyldimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-dimethylmethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-trichlorosilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-dichloromethylsilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-chlorodimethylsilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-chlorodimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-dichloromethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-chloromethylmethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . ^02,7 ] dodec-4-ene and the like.

In this invention, a monomer (1m) may be used individually by 1 type, and may be used in combination of 2 or more type.
In the present invention, the compound represented by the formula (2m) is used as the monomer (2m). Specific examples of the hydrocarbon group having 1 to 30 carbon atoms of B ¹ , B ² , B ³ , B ⁴ , B ⁵ , B ⁶ , B ⁷ and B ^{8 in} the formula (2m) include a methyl group and an ethyl group Alkyl groups such as propyl groups; cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups; alkenyl groups such as vinyl groups and allyl groups; alkylidene groups such as ethylidene groups and propylidene groups; aromatic groups such as phenyl groups; And those in which part or all of the hydrogen atoms in the group are substituted by halogen atoms, phenylsulfonyl groups, and the like. Here, specific examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

The substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms may be directly bonded to a carbon atom such as an aromatic ring which is a skeleton to which the group is bonded, or bonded via a linkage. It may be. Here, the linking group is a group containing or not containing an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. Specific examples thereof include a divalent hydrocarbon group having 1 to 10 carbon atoms (for example,- An alkylene group represented by (CH ₂ ) _k — (where k is an integer of 1 to 10), a carbonyl group (—CO—), a carbonyloxy group (—COO—), a sulfone group (—SO ₂ —). ), Ether bond (—O—), thioether bond (—S—), imino group (—
NH-), amide bond (-NHCO-), siloxane bond (-Si (R ₂₎ O-: wherein R
Is an alkyl group such as a methyl group or an ethyl group), or a combination of two or more of these groups.

  Examples of polar groups include hydroxyl groups, alkoxy groups having 1 to 10 carbon atoms, ester groups, alkoxycarbonyl groups, aryloxycarbonyl groups, cyano groups, amide groups, imide groups, triorganosiloxy groups, triorganosilyl groups, amino groups. Group, acyl group, alkoxysilyl group, sulfonyl group, carboxyl group and the like. More specifically, examples of the alkoxy group include a methoxy group and an ethoxy group; examples of the ester group include a fatty acid ester group such as an acetate ester group and a propionate ester group, and a benzoate ester group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group; examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a naphthyloxycarbonyl group, and a fluorenyloxycarbonyl group. The triorganosiloxy group includes, for example, a trimethylsiloxy group and a triethylsiloxy group; the triorganosilyl group includes, for example, a trimethylsilyl group and a triethylsilyl group; Examples of the group include primary amino groups, alkoxysilyl The group for example a trimethoxysilyl group, triethoxysilyl group, and the like.

As such a monomer (2m), in general formula (2m), m = 0 or 1, n = 0 or 1, s and t are each independently 1, u = 0 or 1, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are all hydrogen atoms, the monomer is easily available, has high heat resistance and high solubility, and has high water absorption. It is preferable at the point from which a low cyclic olefin type addition copolymer is obtained. Among these, m = 0 or 1, n = 0, and u = 0 or 1 are more preferable, and m = n = 0 and u = 0 are particularly preferable.

Examples of these groups and preferred structures in the compounds are the same for the structural units corresponding to the monomers.
In the monomer (2m), as the stereoisomer at the site where the spiroaromatic structure and the cyclo ring structure are linked, there are an exo isomer and an endo isomer, but these compositions are not particularly limited and are desired. However, the exo form is preferred from the addition copolymerization activity.

  In addition, since the monomer (2m) imparts “negative birefringence” to the addition copolymer, the monomer (1m) and the monomer (1m) at an appropriate ratio give “positive birefringence” to the addition copolymer. It is also possible to obtain a copolymer that does not substantially generate birefringence. The positive / negative birefringence referred to here is determined from the change in refractive index that occurs when the film is uniaxially stretched, and the refractive index in the stretching direction is larger than the refractive index in the direction perpendicular to the stretching direction. The property is defined as “positive birefringence”, and the property of decreasing the refractive index in the stretching direction is defined as “negative birefringence”.

As for the substituent on the aromatic ring, the wavelength dependence of birefringence can be increased by introducing a functional group having a large polarization (for example, an ester group, an alkoxy group, etc.).
As the monomer (2m), for example, norbornene dimethanol obtained by reducing 5-norbornene-2,3-dicarboxylic acid anhydride, which is a Diels-Alder reaction product of maleic anhydride and cyclopentadiene, is appropriately removed. Examples include spiro compounds synthesized by reacting with a fluorene derivative anion after modification with a leaving group (tosyl group, halogen atom, etc.). Specific examples of the monomer (2m) preferably used in the present invention include the following compounds.
Example of monomer (2m) represented by m = n = 0

(1) Spiro [fluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(2) Spiro [2,7-difluorofluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(3) Spiro [2,7-dichlorofluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(4) Spiro [2,7-dibromofluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(5) Spiro [2-methoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(6) Spiro [2-ethoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(7) Spiro [2-phenoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(8) Spiro [2,7-dimethoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene]
,

(9) Spiro [2,7-diethoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene]
,

(10) Spiro [2,7-diphenoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(11) Spiro [3,6-dimethoxyfluorene-9,8′-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(12) Spiro [9,10-dihydroanthracene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(13) Spiro [fluorene-9,8 '-[2] methyltricyclo [4.3.0.1 ^2.5 ] [3] decene],

(14) Spiro [fluorene-9,8 '-[10] methyltricyclo [4.3.0.1 ^2.5 ] [3] decene],
Example of monomer (2m) represented by m = 1 and n = 0

(15) spiro [fluorene -9,11'- pentacyclo ^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} [4] pentadecene,

(16) Spiro [2,7-difluorofluorene-9,11′-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(17) Spiro [2,7-dichlorofluorene-9,11'-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(18) Spiro [2,7-dibromofluorene-9,11′-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(19) spiro [2-methoxy fluorene -9,11'- pentacyclo ^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} [4] pentadecene,

(20) spiro [2-ethoxy-fluoren -9,11'- pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13]
[4] pentadecene],

(21) Spiro [2-phenoxyfluorene-9,11′-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(22) Spiro [2,7-dimethoxyfluorene-9,11′-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(23) Spiro [2,7-diethoxyfluorene-9,11′-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(24) spiro [2,7-phenoxy fluorene -9,11'- pentacyclo ^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} [4] pentadecene,

(25) spiro [3,6-dimethoxy-fluoren -9,11'- pentacyclo ^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} [4] pentadecene,

(26) spiro [9,10-dihydro-anthracene -9,11'- pentacyclo ^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} [4] pentadecene.
Example of monomer (2m) represented by m = 1 and n = 1

(27) Spiro [fluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(28) spiro [2,7-difluoro-fluorene -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene,

(29) Spiro [2,7-dichlorofluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(30) spiro [2,7-dibromofluorene -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene,

(31) spiro [2-methoxy fluorene -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene,

(32) spiro [2-ethoxy-fluoren -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene,

(33) spiro [2-phenoxyethyl fluorene -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene,

(34) spiro [2,7-dimethoxy-fluoren -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene,

(35) spiro [2,7-diethoxy-fluoren -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene,

(36) Spiro [2,7-diphenoxyfluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(37) spiro [3,6-dimethoxy-fluoren -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene,

(38) spiro [9,10-Hilo mud anthracene -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene].
An example of a norbornene monomer represented by m = 0 and n = 1

(39) Spiro [fluorene-9,10'-tetracyclo [7.4.0.0 ^8.12 .1 ^2.5 ] [3] tetradecene],

(40) Spiro [fluorene-9,10 '-[7] methyltetracyclo [7.4.0.0 ^8.12 .1 ^2.5 ] [3] tetradecene],

(41) spiro [fluorene-9,10 '- [1] methyl tetracyclo ^{[7.4.0.0 8.12 .1 2.5] [3} ] tetradecene.
In this invention, a monomer (2m) may be used individually by 1 type, and may be used in combination of 2 or more type. Further, as the monomer (2m), it is preferable to use a monomer in which m = 0, n = 0, and u = 0 in the formula (2).

  The cyclic olefin addition copolymer according to the present invention may have a structural unit derived from a monomer other than the monomers (1m) and (2m) if desired. Examples of monomers other than the monomers (1m) and (2m) include cyclic olefin compounds other than those represented by the formula (1m) or the formula (2m). The cyclic olefin addition copolymer according to the present invention particularly preferably does not have a structural unit derived from another monomer other than the monomers (1m) and (2m).

In the method for producing a cyclic olefin addition copolymer according to the present invention, the monomer (1 m) and the monomer (2 m) are preferably used in a molar ratio of (1 m) / (2 m), preferably 99 / It is preferable to perform addition copolymerization using a monomer composition containing 1 to 30/70, more preferably 95/5 to 50/50, and even more preferably 95/5 to 70/30.
<Polymerization catalyst>
In the method for producing a cyclic olefin addition copolymer of the present invention, a catalyst obtained using the following (a), (b) and (d), or a catalyst obtained using (c) and (d): Used.

(A) an organic acid salt of palladium or a β-diketonate compound of palladium,
(B) a phosphine compound represented by the following formula (b),
P (R ¹ ) ₂ (R ² ) (b)
[In Formula (b), R ¹ is a substituent selected from a cyclopentyl group, a cyclohexyl group, and an isopropyl group, and R ² represents a hydrocarbon group having 3 to 10 carbon atoms. ]
(C) a phosphine complex of divalent palladium represented by the following formula (c):
Pd [P (R ¹ ) ₂ (R ² )] _n X ₂ (c)
[In the formula (c), R ¹ is a substituent selected from a cyclopentyl group, a cyclohexyl group, and an isopropyl group, R ² represents a hydrocarbon group having 3 to 10 carbon atoms, and X is an organic acid anion or β-di- It is a ketonate anion, and n represents 1 or 2. ]
(D) An ionic boron compound.

  By using a palladium-based catalyst containing the catalyst component, a molded article having excellent mechanical strength can be obtained. Furthermore, since it exhibits a very high polymerization activity, an addition copolymer can be produced at a high conversion rate exceeding 95% by using an extremely small amount of palladium compound, and it remains in the resulting addition copolymer. Monomer and metal component can be suppressed sufficiently low.

(A) Palladium organic acid salt or palladium β-diketonate compound is, for example, divalent palladium carboxylate, sulfonate, β-diketonate compound, specifically,
1) Palladium acetate, palladium chloroacetate, palladium fluoroacetate, palladium trifluoroacetate, palladium propionate, palladium 3,3,3-trifluoropropionate, palladium butyrate, palladium 3-methylbutyrate, palladium pentanoate, palladium hexanoate , Palladium 2-ethylhexanoate, palladium octoate, palladium dodecanoate, palladium 2-methylpropenoate, palladium octadec-9-enoate, palladium cyclohexanecarboxylate, palladium benzoate, palladium 2-methylbenzoate, 4-methyl C1-C15 organic monocarboxylates, such as palladium benzoate and palladium naphthalenecarboxylate.
2) C1-C20 organic sulfonates such as palladium methanesulfonate, palladium trifluoromethanesulfonate, palladium p-toluenesulfonate, palladium benzenesulfonate, palladium naphthalenesulfonate, palladium dodecylbenzenesulfonate,
3) β-diketonate compounds having 5 to 15 carbon atoms such as 2,4-pentadione (acetylacetonate) of palladium, methyl acetoacetate, ethyl acetoacetate, hexafluoroacetylacetone,
Are preferred. Among these, palladium acetate, palladium propionate, palladium 2-ethylhexanoate, and palladium bis (acetylacetonate) are preferable, and palladium acetate is most preferable.

  (B) Specific examples of the phosphine compound include tricyclopentylphosphine, dicyclopentyl (cyclohexyl) phosphine, dicyclopentyl (3-methylcyclohexyl) phosphine, dicyclopentyl (isopropyl) phosphine, dicyclopentyl (s-butyl) phosphine, dicyclopentyl. (T-butyl) phosphine, dicyclopentyl (2-methylphenyl) phosphine, tricyclohexylphosphine, dicyclohexyl (cyclopentyl) phosphine, dicyclohexyl (3-methylcyclohexyl) phosphine, dicyclohexyl (isopropyl) phosphine, dicyclohexyl (2-methylphenyl) phosphine And triisopropylphosphine. Of these, tricyclopentylphosphine and tricyclohexylphosphine are preferably used.

  (C) The phosphine complex of divalent palladium is advantageous in the solution polymerization process because it shows better solubility in a hydrocarbon solvent as compared with the palladium compound mentioned in (a). Moreover, it is advantageous and preferable in that the generation efficiency of active species is high and the induction period is hardly observed.

As the phosphine complex of palladium represented by the formula (c),
(Tricyclopentylphosphine) palladium di (acetate),
[Bis (tricyclopentylphosphine)] palladium di (acetate),
[Dicyclopentyl (t-butyl) phosphine] palladium di (acetate),
[Dicyclopentyl (cyclohexyl) phosphine] palladium di (acetate),
[Dicyclopentyl (2-methylphenyl) phosphine] palladium di (acetate), (tricyclopentylphosphine) palladium bis (trifluoroacetate),
Bis (tricyclopentylphosphine) palladium bis (trifluoroacetate),
[Dicyclopentyl (cyclohexyl) phosphine] palladium bis (trifluoroacetate),
(Tricyclopentylphosphine) palladium di (propionate),
Bis (tricyclopentylphosphine) palladium di (propionate),
(Tricyclopentylphosphine) palladium bis (2-ethylhexanoate),
Bis (tricyclopentylphosphine) palladium bis (2-ethylhexanoate), (tricyclopentylphosphine) palladium bis (acetylacetonate),
Bis (tricyclopentylphosphine) palladium bis (acetylacetonate),
[Dicyclopentyl (cyclohexyl) phosphine] palladium bis (acetylacetonate),
(Tricyclopentylphosphine) palladium bis (trifluoromethanesulfonate),
Bis (tricyclopentylphosphine) palladium bis (trifluoromethanesulfonate),
(Tricyclohexylphosphine) palladium di (acetate),
[Bis (tricyclohexylphosphine)] palladium di (acetate),
[Dicyclohexyl (t-butyl) phosphine] palladium di (acetate),
[Dicyclohexyl (cyclopentyl) phosphine] palladium di (acetate),
[Dicyclohexyl (2-methylphenyl) phosphine] palladium di (acetate), (tricyclohexylphosphine) palladium bis (trifluoroacetate),
Bis (tricyclohexylphosphine) palladium bis (trifluoroacetate),
[Dicyclohexyl (cyclopentyl) phosphine] palladium bis (trifluoroacetate),
(Tricyclohexylphosphine) palladium di (propionate),
Bis (tricyclohexylphosphine) palladium di (propionate),
(Tricyclohexylphosphine) palladium bis (2-ethylhexanoate),
Bis (tricyclohexylphosphine) palladium bis (2-ethylhexanoate), (tricyclohexylphosphine) palladium bis (acetylacetonate),
Bis (tricyclohexylphosphine) palladium bis (acetylacetonate),
[Dicyclohexyl (cyclopentyl) phosphine] palladium bis (acetylacetonate),
(Tricyclohexylphosphine) palladium bis (trifluoromethanesulfonate),
Examples thereof include, but are not limited to, bis (tricyclohexylphosphine) palladium bis (trifluoromethanesulfonate), and the like. Among them, (tricyclopentylphosphine) palladium di (acetate),
(Tricyclopentylphosphine) palladium bis (trifluoroacetate),
(Tricyclopentylphosphine) palladium di (propionate),
(Tricyclopentylphosphine) palladium bis (2-ethylhexanoate),
(Tricyclopentylphosphine) palladium bis (acetylacetonate),
(Tricyclopentylphosphine) palladium bis (trifluoromethanesulfonate),
(Tricyclohexylphosphine) palladium di (acetate),
(Tricyclohexylphosphine) palladium bis (trifluoroacetate),
(Tricyclohexylphosphine) palladium di (propionate),
(Tricyclohexylphosphine) palladium bis (2-ethylhexanoate),
(Tricyclohexylphosphine) palladium bis (acetylacetonate),
(Tricyclohexylphosphine) palladium bis (trifluoromethanesulfonate),
(Tricyclopentylphosphine) palladium di (acetate), (tricyclopentylphosphine) palladium bis (acetylacetonate), (tricyclohexylphosphine) palladium di (acetate), (tricyclohexylphosphine) palladium bis (acetylacetonate) Is most preferred. For the synthesis of these complexes, known methods may be used as appropriate, and they may be used after purification or isolation, or may be used without isolation after synthesis. For example, you may synthesize | combine by making a suitable palladium compound and catalyst component (b) phosphine compound react in the temperature range of 0-70 degreeC in an aromatic hydrocarbon solvent or a halogenated hydrocarbon solvent.
(D) As the ionic boron compound, a compound represented by the following formula (d) is used.

[R ^{3] +} [M (R ^{₄₎ 4] -} ... (d)
[In the formula (d), R ³ represents an organic cation having 4 to 25 carbon atoms selected from a carbenium cation, a phosphonium cation, an ammonium cation or an anilinium cation, M represents a boron atom or an aluminum atom, and R ⁴ Represents a fluorine atom-substituted or fluorinated alkyl-substituted phenyl group. ]

As a specific example,
Triphenylcarbenium tetrakis (pentafluorophenyl) borate,
Tri (p-tolyl) carbenium tetrakis (pentafluorophenyl) borate,
Triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,
Tri (p-tolyl) carbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,
Triphenylcarbenium tetrakis (2,4,6-trifluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Diphenylphosphonium tetrakis (pentafluorophenyl) borate,
Tributylammonium tetrakis (pentafluorophenyl) borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
N, N-diethylanilinium tetrakis (pentafluorophenyl) borate,
And so on. Among these, an ionic boron compound in which the cation is a carbenium cation and the anion is a tetrakis (pentafluorophenyl) borate anion or a tetrakis (perfluoroalkylphenyl) borate anion is preferable, and triphenylcarbenium tetrakis (pentafluorophenyl). Borate and triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate are most preferred.

  (A) An organic acid salt of palladium or a β-diketonate compound of palladium, or (c) a phosphine complex of divalent palladium is 0.0005 to 0.02 mmol, preferably 0 as a palladium atom per mole of monomer. Since a high conversion can be obtained only by using within the range of 0.001 to 0.01 mmol, more preferably 0.001 to 0.005 mmol, high economy and productivity are exhibited. In addition, since the metal component remaining in the addition copolymer can be kept low, it is possible to obtain a molded body with little coloration and excellent transparency, and the deashing step may be omitted. In addition, regarding (b) the phosphine compound, it is usually used in the range of 0.1 to 5 mol, preferably 0.5 to 2 mol, with respect to 1 mol of palladium atom contained in the catalyst component (a) Most suitable for high polymerization activity. Moreover, regarding the said catalyst component (c) ionic boron compound, it is 0.5-10 mol normally with respect to 1 mol of palladium atoms contained in a catalyst component (a), Preferably it is 0.7-5.0 mol. More preferably, it is used in the range of 1.0 to 2.0 mol. With respect to each of the catalyst components (a) to (d) above, in the present invention, there is no particular limitation on the adjustment method and use method of the addition order, etc., and a mixture of a monomer and a solvent used for the polymerization reaction in the present invention May be added simultaneously or sequentially.

<Addition copolymerization>
In the present invention, the polymerization system may be a batch system, and for example, a tubular continuous reactor equipped with a suitable monomer feed port may be used. The polymerization reaction is performed under a nitrogen or argon atmosphere if necessary, but may be performed in air. The reaction temperature is 0 to 150 ° C, more preferably 10 to 100 ° C, and more preferably 20 to 80 ° C. Solvents used are not particularly limited, but cycloaliphatic hydrocarbon solvents such as cyclohexane, cyclopentane, and methylcyclopentane, aliphatic hydrocarbon solvents such as hexane, heptane, and octane, toluene, benzene, xylene, ethylbenzene, mesitylene, and the like. Aromatic hydrocarbon solvents, halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethylene, 1,1-dichloroethylene, tetrachloroethylene, chlorobenzene and dichlorobenzene can be used alone or in combination of two or more. Of these, alicyclic hydrocarbon solvents and aromatic hydrocarbon solvents are preferred. These solvents are usually used in the range of 0 to 2,000 parts by weight with respect to 100 parts by weight of the total monomers.

In the method for producing an addition copolymer according to the present invention, by performing addition copolymerization in the presence of a molecular weight regulator, the molecular weight of the resulting copolymer can be arbitrarily controlled, and as a result, melt molding is performed. It is possible to control the flow characteristics in The molecular weight regulator is preferably ethylene,
Α-olefin compounds such as propylene, 1-butene, 1-hexene, 1-octene, trimethylvinylsilane, trimethoxyvinylsilane or substituted α-olefin compounds, monocyclic monoolefin compounds such as cyclopentene, styrene, α-methylstyrene, etc. Aromatic vinyl compounds are used. Among these molecular weight regulators, it is preferable to use an α-olefin compound or a monocyclic monoolefin compound, and ethylene is most preferable. The amount of molecular weight regulator used varies depending on the target molecular weight of the cyclic olefin addition copolymer, the selection of catalyst components, the selection of polymerization temperature conditions, etc. It is preferable to use an amount of 0.001 to 0.5 times. Moreover, these molecular weight regulators may be used individually by 1 type, and may be used in combination of 2 or more type.

Since the palladium-based polymerization catalyst used in the production method of the cyclic olefin-based addition copolymerization of the present invention is very high in activity, the conversion rate should be 96% or more, preferably 99% or more only by using a small amount of catalyst. it can. As a result, a process for removing the remaining monomer and metal component is not necessarily required. When removing monomers and metal components as necessary, a known method may be used as appropriate. For example, a polymerization reaction solution may be used as an oxycarboxylic acid such as lactic acid, glycolic acid, oxypropionic acid, oxybutyric acid, or triethanol. Extraction and separation using a solution selected from aqueous solutions such as amine, dialkylethanolamine, ethylenediaminetetraacetate, methanol solution and ethanol solution, or using adsorbents such as diatomaceous earth, silica, alumina, activated carbon, and celite. Metal components can be removed by adsorption and filtration separation with a filter. Alternatively, the polymerization reaction solution can be coagulated using alcohols such as methanol, ethanol and propanol, and ketones such as acetone and methyl ethyl ketone. The metal component contained in the cyclic olefin addition copolymer according to the present invention can be preferably 10 ppm or less, more preferably 5 ppm or less as Pd atoms.
Cyclic Olefin-Based Addition Copolymer The cyclic olefin-based addition copolymer according to the present invention is preferably obtained by the above-described method, and the structural unit (1) represented by the following formula (1) and the following formula (2) It has the structural unit (2) represented by these.

(In the formula (1), A ¹ , A ² , A ³ , A ⁴ and p are the same as those in the formula (1m).)

(In the formula (2), m, n, s, t, u, B ¹ , B ² , B ³ , B ⁴ , B ⁵ , B ⁶ , B ⁷ , and B ⁸ are the same as the formula (2m). .)
Here, the structural unit (1) includes bicyclo [2.2.1] hept-2-ene, 5-alkylbicyclo [2.2.1] hept-2-ene having 1 to 20 carbon atoms, and the like. The structural unit (2) is derived from the monomer (1m), and the structural unit (2) is derived from the monomer (2m) which is a spiro-type norbornene compound.

Examples of the structural unit (1) include structural units derived by addition copolymerization of the above-described monomer (1m).
When the cyclic olefin-based addition copolymer of the present invention is used for the purpose of producing a film (including a sheet), bicyclo [2.2. 1] Two or more selected from the group consisting of hepta-2-ene and 5-alkylbicyclo [2.2.1] hept-2-ene, or two or more 5-alkylbicyclo [2.2.1] It preferably has a structural unit derived from hept-2-ene. As the number of carbon atoms of the alkyl group of 5-alkylbicyclo [2.2.1] hept-2-ene increases, the flexibility (elongation) of the resulting film or sheet tends to increase, and the glass transition temperature tends to decrease. . Furthermore, 5-alkylbicyclo [2.2.1] hepta in a molar ratio of bicyclo [2.2.1] hept-2-ene and 5-alkylbicyclo [2.2.1] hept-2-ene. As the ratio of 2-ene increases, the flexibility (elongation) of the obtained film or sheet increases, and the glass transition temperature tends to decrease.

Examples of the structural unit (2) include structural units derived from addition copolymerization of the above-described monomer (2m).
As such a structural unit (2), in the formula (2), m = 0 or 1, n = 0 or 1, s and t are each independently 1, u = 0 or 1, In addition, it is preferable that all of B ^{1 to} B ⁸ are hydrogen atoms from the viewpoint that a monomer can be easily obtained, a cyclic olefin addition copolymer having high heat resistance, high solubility, and low water absorption can be obtained. . Among these, m = 0 or 1, n = 0, and u = 0 or 1 are more preferable, and m = n = 0 and u = 0 are particularly preferable.

  The cyclic olefin addition copolymer according to the present invention preferably has 99 to 30 mol% of the structural unit (1) and 1 to 70 mol% of the structural unit (2), more preferably the structural unit (1 ) Is 95 to 50 mol%, the structural unit (2) is 5 to 50 mol%, and more preferably, the structural unit (1) is 95 to 70 mol% and the structural unit (2) is 5 to 30 mol%. It is preferable to have a ratio.

The glass transition temperature (Tg) of the cyclic olefin-based addition copolymer according to the present invention is derived from the storage elastic modulus (E ′) and loss elastic modulus (E ″) measured by dynamic viscoelasticity Tan δ = E It is determined from the temperature dispersion peak temperature of “/ E ′”, and is usually 100 to 400 ° C., preferably 100 to 250 ° C., more preferably 130 to 240 ° C., depending on the application. When this glass transition temperature is less than 100 ° C., it is not suitable for applications requiring heat resistance, whereas when it exceeds 250 ° C., melt molding becomes difficult.

  The cyclic olefin-based addition copolymer of the present invention exhibits good melt moldability when the glass transition temperature is 250 ° C. or lower. Therefore, a melt molding method such as extrusion molding or a cast molding method (solution casting method). It is suitable for molding various optical members, and when it has a glass transition temperature higher than that, it is inferior in melt moldability but is soluble in a solvent. It is suitable for. For this reason, when using the cyclic olefin type addition copolymer of this invention for a melt molding use, it is preferable that a glass transition temperature is 250 degrees C or less.

  The glass transition temperature of the cyclic olefin addition copolymer of the present invention can be controlled by the type of the structural unit (1) and the composition ratio of the structural unit (1) to the structural unit (2). The cyclic olefin addition copolymer of the present invention having a melt moldability having a glass transition temperature of 250 ° C. or lower is, for example, bicyclo [2.2.1] hept-2-ene and a 5-alkyl having 1 to 20 carbon atoms. A mixture of bicyclo [2.2.1] hept-2-ene or a mixture of 5-alkylbicyclo [2.2.1] hept-2-ene having 1 to 20 carbon atoms, specifically 4 to 4 carbon atoms 5-alkylbicyclo [2.2.1] hept-2-ene having 6 alkyl groups and 5-alkylbicyclo [2.2.1] hept-2-ene having an alkyl group having 8 to 12 carbon atoms; Is used as the monomer (1) for deriving the structural unit (1), and the molar ratio of the structural unit (1) / the structural unit (2) is controlled to be in the range of 95 to 70/5 to 30. Can be obtained.

  In particular, when the structural unit (1) is derived from 5-alkylbicyclo [2.2.1] hept-2-ene, the flexibility (elongation) of the film or sheet obtained when the proportion of the structural unit (2) decreases. ) Increases and the glass transition temperature decreases, but the positive birefringence tends to increase.

  The cyclic olefin-based addition copolymer of the present invention can have an appropriate birefringence such as a positive or negative birefringence or a birefringence that does not exhibit birefringence depending on the composition. For this reason, from the cyclic olefin type addition copolymer of this invention, the optical film which has a desired retardation value can be manufactured, and it can use suitably for various optical uses.

  In addition, the molecular weight of the cyclic olefin addition copolymer according to the present invention is a polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatogram (GPC) of 20,000 to 500,000, preferably 30 ,. It is desirable that it is 000-200,000, More preferably, it is 30,000-100,000. When the number average molecular weight is less than 20,000, when it is formed into a film or sheet, the mechanical strength is lowered and it may be easily broken. On the other hand, when the number average molecular weight exceeds 500,000, the melt viscosity becomes too high, so that molding becomes difficult or the flatness of the molded product is often impaired. The molecular weight of the cyclic olefin-based addition copolymer can be adjusted by performing polymerization in the presence of an appropriate molecular weight regulator.

  The cyclic olefin-based addition copolymer of the present invention is excellent in transparency, and the transmittance at a wavelength of 400 nm is usually 85% or more, preferably 88% or more, as measured with a film having a thickness of 100 μm. The haze value is usually 2.0% or less, preferably 1.0% or less.

Since the cyclic olefin addition copolymer of the present invention exhibits high solubility in an organic solvent and melt molding processability, a desired molded body can be produced by cast molding or melt extrusion molding. Particularly in melt extrusion molding, molded articles such as films and sheets can be produced with high economic efficiency and productivity, and the obtained molded articles such as films and sheets have excellent low birefringence and transparency, heat resistance and low water absorption. Have sex.
<Additives>
The cyclic olefin-based addition copolymer of the present invention can be used by adding various additives depending on the purpose, such as improvement in oxidation stability, light resistance or processability.

  For example, an antioxidant selected from a phenolic antioxidant, a lactone antioxidant, a phosphorus antioxidant and a sulfur antioxidant can be blended in order to improve oxidation stability and prevent coloring and deterioration. The antioxidant can be blended at a ratio of 0.001 to 5 parts by weight per 100 parts by weight of the copolymer. Specific examples of antioxidants include

1) 2,6-di-t-butyl-4-methylphenol, 4,4′-thiobis- (6-t-
Butyl-3-methyl-phenyl), 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), tetrakis [methylene-3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate] methane, 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearate, 2,5-di-t-butylhydroquinone, Phenolic antioxidants or hydroquinone antioxidants such as pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] propionate,

2) Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t -Butyl-5-methylphenyl) 4,4'-biphenylenediphosphonite, 3
, 5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (4-methoxy-3,5-diphenyl) phos Phosphorous secondary antioxidants such as phyto and tris (nonylphenyl) phosphite

3) Sulfur-based secondary antioxidants such as dilauryl-3,3'-thiodipropionate and 2-mercaptobenzimidazole.

Moreover, a flame retardant can also be mix | blended with the cyclic olefin type addition copolymer of this invention. A well-known thing can be used as a flame retardant, For example, a halogen flame retardant, an antimony flame retardant, a phosphate ester flame retardant, a metal hydroxide etc. can be mentioned. Among these, phosphate ester-based flame retardants that are effective with a small amount of blending and can minimize deterioration of water absorption, low dielectric properties, and transparency are preferable. 1,3-bis (phenylphosphoryl) benzene, 1,3 -Bis (diphenylphosphoryl) benzene, 1,3-bis [di (alkylphenyl) phosphoryl] benzene, 1,3-bis [di (2 ', 6'-dimethylphenyl) phosphoryl] benzene, 1,3-bis [ Di (2 ′, 6′-diethylphenyl) phosphoryl] benzene, 1,3
-Bis [di (2 ', 6'-diisopropylphenyl) phosphoryl] benzene, 1,3-bis [di (2', 6'-dibutylphenyl) phosphoryl] benzene, 1,3-bis [di (2'- t-butylphenyl) phosphoryl] benzene, 1,3-bis [di (2′-isopropylphenyl) phosphoryl] benzene 1,3-bis [di (2′-methylphenyl) phosphoryl] benzene, 1,4-bis ( Diphenylphosphoryl) benzene, 1,4-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl] benzene, 1,4-bis [di (2 ′, 6′-diethylphenyl) phosphoryl] benzene, 1,4 -Bis [di (2 ', 6'-diisopropylphenyl) phosphoryl] benzene, 1,4-bis [di (2'-t-butylphenyl) phosphoryl] benzene, 1,4-bis [di (2' Isopropylphenyl) phosphoryl] benzene, 1,4-bis [di (2'-methyl phenyl) phosphoryl] benzene, 4,4
More preferred are condensed phosphate ester flame retardants such as' -bis [di (2 ", 6" -dimethylphenyl) phosphorylphenyl] dimethylmethane. The blending amount depends on the choice of flame retardant and the required degree of flame retardancy, but is preferably 0.5 to 40 parts by weight, more preferably 2 to 30 parts by weight, based on 100 parts by weight of the cyclic olefin copolymer. -20 parts by weight is most preferred. When the amount is less than 0.5 parts by weight, the effect is insufficient. On the other hand, when the amount exceeds 40 parts by weight, transparency is impaired, electrical characteristics such as dielectric constant are deteriorated, and water absorption is increased. Or heat resistance may deteriorate.

If necessary, the cyclic olefin addition copolymer of the present invention may further contain a known lubricant, ultraviolet absorber, leveling agent, dye, and the like.
<Molded body>
The cyclic olefin-based addition copolymer of the present invention can be obtained by hot melt molding such as injection molding, extrusion molding, compression molding or the like, or cast molding using a solvent, depending on the characteristics and desired molding properties. These can be appropriately molded into various molded bodies.

  Since the cyclic olefin addition copolymer of the present invention has excellent low birefringence, transparency, heat resistance, and low water absorption, it is particularly useful in the fields of various optical members (optical parts) and electrical and electronic materials. Specifically, for example, optical films (display films, retardation films, polarizing films, transparent conductive films, wave plates, antireflection films, optical pickup films, etc.), optical sheets, optical fibers, Light guide plate, light diffusion plate, optical card, optical mirror, IC / LSI / LED sealing material, optical disc, magneto-optical disc, optical lens (Fθ lens, pickup lens, laser printer lens, camera lens, etc.), spectacle lens The use of is mentioned.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

In Examples and Comparative Examples, the properties of copolymers and films were measured or evaluated by the following methods.
(1) Molecular weight:
Using a Shodex GPC-101 gel permeation chromatography (GPC) apparatus manufactured by Showa Denko, THF was measured as a solvent, and the molecular weight was determined using standard polystyrene equivalent values.

(2) Copolymer composition:
10 mg of the copolymer was placed in a 5 mm tube and dissolved in a deuterated benzene solvent, and diluted to a liquid surface height of 4 cm, and 270 MHz by ¹ H-NMR (manufactured by JEOL Ltd., EX-270).
The composition ratio of each structural unit was determined from the proton absorption ratio.

  Further, a part of the polymerization reaction solution was sampled, and the supernatant obtained by coagulating the polymer with excess isopropanol was gas chromatogram (GC-14B manufactured by Shimadzu Corporation) apparatus, capillary column (film thickness 1 μm, inner diameter 0.25 mm, length 60 m). And the total monomer composition was calculated by quantifying the residual monomer.

(3) Residual monomer measurement by gas chromatograph:
Residual monomer was measured with a gas chromatograph GC-2010 manufactured by Shimadzu Corporation.
(4) Glass transition temperature:
Derived from storage elastic modulus (E ') and loss elastic modulus (E ") in tensile mode with a measurement frequency of 1 Hz, a heating rate of 5 ° C / min, using a viscoelasticity measuring device manufactured by TA Instruments Japan It was determined from the temperature dispersion of Tan δ (= E ″ / E ′).

(5) Spectral light transmittance and haze:
The light transmittance at a wavelength of 400 nm was measured with a visible / ultraviolet spectrophotometer (Hitachi U-2010 Spectro Photo Meter) using a film having a thickness of 100 μm.

About haze, it measured according to JISK7105 using Haze-Gard plus (product made from BYK-Gardner).
(6) Optical anisotropy (Re (0), Re (45)):
Using a film with a thickness of 100 μm, measured by a rotary analyzer type automatic ellipsometer manufactured by Mizoji Optical Co., Ltd. using a He—Ne laser (λ = 632.8 nm) as a light source at incident angles of 0 ° and 45 °. did.

(7) Breaking strength, elongation and breaking energy:
The test piece was measured at a tensile speed of 3 mm / min according to JIS K7113.
(8) Water absorption rate:
The film was immersed in 23 ° C. water for 24 hours, and the water absorption was determined from the change in weight before and after the immersion.

[Synthesis Example 1]
<Synthesis of spiro [fluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene] (exo form, see formula (A) below)>
Fluorene (18.76 g, 0.1128 mol) and dehydrated THF (100 ml) were added to a 500 ml flask equipped with a dropping funnel, and stirred well with a stirrer to dissolve. Next, 141 ml of a 1.6 mol / l hexane solution of n-butyllithium was added dropwise while maintaining at −78 ° C., and the mixture was stirred for 1 hour. Here, 26.10 g (0.0564 mol) of 2,3-bis- (toluene-4-sulfonyloxy) -5-norbornene represented by the following formula (B) dissolved in 500 ml of THF was gradually added dropwise.

After completion of dropping, the mixture was stirred for 1 hour, and then allowed to react until the temperature returned to room temperature (about 3 hours). After adding saline, the reaction solution was washed with distilled water and dried over sodium sulfate. Subsequently, the solvent is removed by heating under reduced pressure, and the obtained crystal is recrystallized from methanol to give a spiro [fluorene-9,8′-tricyclo [ 4.3.0.1 ^2.5 ] [3] decene] (exo isomer) (10.09 g) was obtained.

[Example 1]
In a 1 L stainless steel reactor in a nitrogen atmosphere, 216 g of toluene, 41 g (0.27 mol) of 5-butylbicyclo [2.2.1] hept-2-ene and 5-decylbicyclo [2.2
. 1] 30.8 g (0.13 mol) of hepta-2-ene and the spiro obtained in Synthesis Example 1 [
Fluorene-9,8′-tricyclo [4.3.0.1 ^2.5 ] [3] decene] (exo form) 10 wt% toluene solution 130.5 g (0.045 mol) was charged, and ethylene was introduced with stirring until 0.010 MPa. did.

The temperature inside the container was raised to 30 ° C., and 4.6 × 10 ⁻³ mmol of a toluene solution of (tricyclopentylphosphine) palladium di (acetate) and a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate to 2. Polymerization was started by adding 3 × 10 ⁻³ mmol.

As a result of performing the polymerization for a total of 12 hours, the conversion was 99% from the determination of the unreacted monomer, and spiro [fluorene-9,8′-tricyclo [4.3.0.1 ^2.5 ] [3] decene] in the copolymer. The (exo form) content was calculated to be 9 mol% from the proton absorption ratio by ¹ H-NMR (manufactured by JEOL Ltd., EX-270).

  The contents of 5-butylbicyclo [2.2.1] hept-2-ene and 5-decylbicyclo [2.2.1] hept-2-ene in the copolymer are 61 respectively based on the polymerization conversion rate and the charging ratio. Estimated mol% and 29 mol%. The reaction solution diluted with toluene was coagulated with 2 L of isopropyl alcohol, and then heated and dried under vacuum to obtain 82 g of copolymer A. Copolymer A had Mn of 62,000 and Mw of 246,000.

To 100 parts by weight of this copolymer A, pentaerythrityltetox [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4-di-t-butylphenyl) Each 0.5 parts by weight of phosphite was mixed, and then a film A having a thickness of 100 μm was obtained at 250 ° C. by a vacuum press. The glass transition temperature of the film A was 232 ° C., and as shown in Table 1, it was confirmed that the retardation value as an index of birefringence was very small and the material was a low birefringence material. Further, the copolymer was excellent in heat resistance, transparency and low water absorption, had a large breaking energy as an index of elongation, particularly the strength of the film, and was excellent in melt moldability.

[Example 2]
In a 1 L stainless steel reactor in a nitrogen atmosphere, 606 g of toluene, 81.3 g (0.65 mol) of bicyclo [2.2.1] hept-2-ene in a 75 wt% toluene solution, 5-butylbicyclo [2 2.1] 74.3 g (0.495 mol) of hepta-2-ene and spiro [fluorene-9,8′-tricyclo [4.3.0.1 ^2.5 ] [3] decene] (exo form) 32.7 wt% toluene solution 145.5 g (0.145 mol) was charged, and ethylene was introduced to 0.010 MPa while stirring.

The temperature inside the container was raised to 50 ° C., 14.6 × 10 ⁻³ mmol of a toluene solution of (tricyclopentylphosphine) palladium di (acetate) and 7.7 of a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate. Polymerization was started by adding 3 × 10 ⁻³ mmol.

In the course of the polymerization, 20.4 g (0.163 mol) of bicyclo [2.2.1] hept-2-ene in a 75% by weight toluene solution was dividedly charged in four portions. As a result of continuing the polymerization for 12 hours from the start of the polymerization, the conversion was 99% from the determination of the unreacted monomer, and spiro [fluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] in the copolymer. ] decene] (exo form) content by ¹ H
-It was calculated as 10 mol% from the proton absorption ratio by NMR (manufactured by JEOL Ltd., EX-270).

  The contents of bicyclo [2.2.1] hept-2-ene and 5-butylbicyclo [2.2.1] hept-2-ene in the copolymer are 56 mol% from the polymerization conversion rate and the charging ratio, respectively. It was estimated to be 34 mol%. The reaction solution diluted with toluene was coagulated with 2 L of isopropyl alcohol, and then heated and dried under vacuum to obtain 215 g of copolymer B. Copolymer B had Mn of 54,000 and Mw of 280,000.

To 100 parts by weight of this copolymer B, pentaerythrityltetox [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4-di-t-butylphenyl) 0.5 parts by weight of phosphite and toluene are added to make a solution with a solid content concentration of 20 wt%, cast on a PET film, dried at 100 ° C. for 1 hour, 150 ° C. for 1 hour, and then dried at 180 ° C. for 2 hours. Thus, a film B having a thickness of 100 μm was obtained. The glass transition temperature of the film B was 288 ° C., and it was confirmed that the film B was particularly excellent in heat resistance. Further, as shown in Table 1, it can be confirmed that the retardation value, which is an index of birefringence, is a very small low birefringence material, and in addition to heat resistance and low birefringence, transparency and low water absorption. It is also an excellent film.

However, since the glass transition temperature of the copolymer B is as high as 288 ° C., melt molding is difficult, and the film must be formed by a solvent casting method.
[Comparative Example 1]
In a 1 L stainless steel reactor, under a nitrogen atmosphere, 600 g of toluene, 114 g (0.76 mol) of 5-butylbicyclo [2.2.1] hept-2-ene and 5-decylbicyclo [2
. 2.1] 86 g (0.37 mol) of hepta-2-ene was charged, and ethylene was introduced to 0.010 MPa while stirring.

The temperature inside the container was raised to 30 ° C., and a toluene solution of (tricyclopentylphosphine) palladium di (acetate) 4.51 × 10 ⁻³ mmol and a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 4. Polymerization was initiated by adding 51 × 10 ⁻³ mmol. As a result of carrying out the polymerization for a total of 12 hours, the conversion was 99% based on the determination of the unreacted monomer, and the 5-decylbicyclo [2.2.1] hept-2-ene content in the copolymer was 36 mol%. It was calculated. The reaction solution diluted with toluene was coagulated with 2 L of isopropyl alcohol, and then heated and dried under vacuum to obtain 198 g of copolymer C. Copolymer C had Mn of 46,000 and Mw of 276,000.

To 100 parts by weight of this copolymer C, pentaerythrityltetox [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4-di-t-butylphenyl) Each 0.5 parts by weight of phosphite was mixed, and then a film C having a thickness of 100 μm was obtained at 250 ° C. by a vacuum press. Film C has a glass transition temperature of 205 ° C., and as shown in Table 1, it has excellent heat resistance, transparency and low water absorption, and has a very high breaking energy, which is an index of elongation, particularly the strength of the film. Although the copolymer was excellent in moldability, it was a film having a large retardation which is an index of birefringence.

[Comparative Example 2]
In a 1 L stainless steel reactor, under a nitrogen atmosphere, 600 g of toluene, 99 g (0.66 mol) of 5-butylbicyclo [2.2.1] hept-2-ene and a bicyclo [2.2 .1] 143.7 g (1.07 mol) of hepta-2-ene was charged, and ethylene was introduced to 0.015 MPa while stirring. The temperature inside the container was raised to 50 ° C., and a toluene solution of (tricyclopentylphosphine) palladium di (acetate) was added to 3.
Polymerization was initiated by adding 3.85 × 10 ⁻³ mmol of a toluene solution of 85 × 10 ⁻³ mmol and triphenylcarbenium tetrakis (pentafluorophenyl) borate. As a result of carrying out the polymerization for a total of 10 hours, the conversion was 99% from the determination of the unreacted monomer, and the 5-butylbicyclo [2.2.1] hept-2-ene content in the copolymer was 38 mol%. , And calculated. The reaction solution diluted with toluene was coagulated with 2 L of isopropyl alcohol and then heat-dried under vacuum to obtain 198 g of copolymer D. Copolymer D had Mn of 46,000 and Mw of 204,000.

To 100 parts by weight of this copolymer D, pentaerythrityl tetokis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4-di-t-butylphenyl) After mixing 0.5 parts by weight of each phosphite, toluene was added to make a solution with a solid content concentration of 20 wt%, cast on a PET film, dried at 100 ° C. for 1 hour, 150 ° C. for 1 hour, and then at 180 ° C. A film D having a thickness of 100 μm was obtained by drying for 2 hours. The glass transition temperature of Film D was 272 ° C.

  Since this copolymer has a very high glass transition temperature of 272 ° C., it is difficult to melt-mold, and a film was formed by a solvent casting method. As shown in Table 1, the copolymer has particularly excellent heat resistance, The film was excellent in transparency and low water absorption, but this film also had a large retardation.

The cyclic olefin-based addition copolymer of the present invention has excellent low birefringence, transparency and heat resistance, low water absorption and dielectric constant, and is suitably used for optical materials, electrical / electronic parts, medical equipment and the like. be able to.

  As optical materials, liquid crystal display elements, organic EL elements, plasma displays and electronic paper, display color filter substrates, nanoimprint substrates, transparent conductive films and transparent conductive films laminated with ITO or conductive resin layers, touch panels, light guide plates, Protective film, deflection film, retardation film, near-infrared cut film, light diffusion film, antireflection film, high reflection film, transflective film, ND filter, dichroic filter, electromagnetic wave shielding film, beam splitter, filter for optical communication It can be used for optical lenses such as camera lenses, pickup lenses, F-θ lenses and prisms, optical recording substrates such as MD, CD, and DVD. As medical equipment, it is used for medicine packaging materials, sterilization containers, syringes, pipes, tubes, ampoules and the like. As electronic / electrical parts, they are used for containers, trays, carrier tapes, separation films, insulating films, printed circuit board materials, and the like.

Claims (6)

A cyclic olefin-based addition copolymer comprising a structural unit (1) represented by the following formula (1) and a structural unit (2) represented by the following formula (2);

(In the formula (1), A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group, or a halogenated hydrocarbon. And a hydrolyzable silyl group or a group represented by — (CH ₂ ) _q —X, wherein A ¹ and A ² or A ³ and A ⁴ are bonded to each other to form an alkylidene group. A ¹ and A ² , A ³ and A ^4, or A ² and A ³ may be bonded to each other to form a carbocyclic or heterocyclic ring (these carbocyclic or heterocyclic rings may have a monocyclic structure). And a carbocyclic or heterocyclic ring formed may be an aromatic ring or a non-aromatic ring, and p is 0 or 1.
In the formula — (CH ₂ ) _q —X, q is an integer of 0 to ⁵ , and X is —COOA ⁵ , —O.
Shows the COA ^6, or -OA ^7, A ^5, A ⁶ and A ⁷ are each independently 1 to 10 carbon atoms
And a substituent containing a hydrocarbon group, a halogenated hydrocarbon group, or an oxetanyl group. ),

(In the formula (2), m and n are each independently an integer of 0 to 2,
B ¹ , B ² , B ³ , B ⁴ , B ⁵ , B ⁶ , B ⁷ , and B ⁸ are each independently a hydrogen atom; a halogen atom; a linkage containing an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a group; and an atom or group selected from the group consisting of polar groups;
s, t, and u are each independently an integer of 0 to 3. ).   2. The cyclic olefin addition copolymer according to claim 1, comprising 99 to 30 mol% of the structural unit (1) and 1 to 70 mol% of the structural unit (2).   The cyclic olefin addition copolymer according to claim 1 or 2, which has a glass transition temperature of 100 to 400 ° C and a number average molecular weight of 20,000 to 500,000. A monomer (1m) represented by the following formula (1m) and a monomer (2m) represented by the following formula (2m),
A cyclic olefin characterized by addition copolymerization in the presence of a catalyst obtained using the following (a), (b) and (d), or a catalyst obtained using the following (c) and (d): A method for producing a system addition copolymer;

(In the formula (1m), A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group, or a halogenated hydrocarbon. And a hydrolyzable silyl group or a group represented by — (CH ₂ ) _q —X, where A ¹
And A ² or A ³ and A ⁴ may be bonded to each other to form an alkylidene group, and A ¹ and A ² , A ³ and A ⁴ or A ² and A ³ are bonded to each other. A carbocycle or a heterocycle (these carbocycle or heterocycle may be a monocyclic structure or a polycyclic structure in which other rings are condensed) may be formed. The formed carbocyclic or heterocyclic ring may be an aromatic ring or a non-aromatic ring. p is 0 or 1.
In the formula — (CH ₂ ) _q —X, q is an integer of 0 to ⁵ , and X is —COOA ⁵ , —O.
Shows the COA ^6, or -OA ^7, A ^5, A ⁶ and A ⁷ are each independently 1 to 10 carbon atoms
And a substituent containing a hydrocarbon group, a halogenated hydrocarbon group, or an oxetanyl group. ),

(In the formula (2m), m and n are each independently an integer of 0 to 2,
B ¹ , B ² , B ³ , B ⁴ , B ⁵ , B ⁶ , B ⁷ and B ⁸ are each independently a hydrogen atom; a halogen atom; a linking group containing an oxygen atom, nitrogen atom, sulfur atom or silicon atom A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have an atom; and an atom or group selected from the group consisting of polar groups,
s, t, and u are each independently an integer of 0 to 3. ),
(A) an organic acid salt of palladium or a β-diketonate compound of palladium,
(B) a phosphine compound represented by the following formula (b),
P (R ¹ ) ₂ (R ² ) (b)
[In Formula (b), R ¹ is a substituent selected from a cyclopentyl group, a cyclohexyl group, and an isopropyl group, and R ² represents a hydrocarbon group having 3 to 10 carbon atoms. ]
(C) a phosphine complex of divalent palladium represented by the following formula (c):
Pd [P (R ¹ ) ₂ (R ² )] _n X ₂ (c)
[In the formula (c), R ¹ is a substituent selected from a cyclopentyl group, a cyclohexyl group, and an isopropyl group, R ² represents a hydrocarbon group having 3 to 10 carbon atoms, and X is an organic acid anion or β-di- It is a ketonate anion, and n represents 1 or 2. ]
(D) An ionic boron compound.   An optical member comprising the cyclic olefin-based addition copolymer according to any one of claims 1 to 3.   An optical film comprising the cyclic olefin-based addition copolymer according to any one of claims 1 to 3.