JP2006305816A - Norbornene-based polymer film and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a norbornene-based polymer film excellent in production efficiency, and the norbornene-based polymer film excellent in optical characteristics. <P>SOLUTION: In the manufacturing method of the norbornene-based polymer film, a monomer component containing at least one norbornene-based monomer is subjected to addition polymerization in the presence of the following catalyst (A) and the following cocatalyst (B) and a solution, which is prepared by dissolving or dispersing the obtained norbornene-based polymer in a solvent, is molded by a cast molding method. The catalyst (A) is a complex obtained by coordinating at least a cyclopentadienyl ligand on one transition metal selected from group VIII-X elements and the cocatalyst (B) is at least one compound selected from an organoaluminum compound (a), an ionic compound (b) capable of producing a cationic transition metal compound upon the reaction with the catalyst (A) and a compound (c) for accelerating the dissociation of the ligand of the complex which forms the catalyst (A). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a norbornene-based polymer film and a norbornene-based polymer film obtained by this method. More specifically, the present invention has excellent production efficiency including a step of synthesizing a norbornene-based polymer using a novel catalyst. The present invention relates to a method for producing a norbornene polymer film and a norbornene polymer film excellent in optical properties obtained by this method.

  Conventionally, a cyclic olefin addition polymer typified by a norbornene polymer is suitably used for applications such as an optical film as an organic material having excellent heat resistance and transparency. The cyclic olefin addition polymer has been obtained by addition polymerization of a cyclic olefin monomer using a catalyst containing a transition metal compound such as Ni, Pd, Ti, Zr, and Cr.

  However, conventionally used catalysts are not sufficient in terms of polymerization activity. In addition, when the cyclic olefin addition polymer is used for optical applications, it is difficult to obtain sufficient optical characteristics unless it is decontacted. However, if a catalyst having insufficient polymerization activity is used, The amount of catalyst to be used increases, and it may be difficult to remove the catalyst sufficiently.

  Accordingly, there has been a demand for a method for producing an optical film using a catalyst that can efficiently produce a cyclic olefin addition polymer having high polymerization activity and excellent optical properties.

  The subject of this invention is providing the manufacturing method of the norbornene-type polymer film excellent in production efficiency, and providing the norbornene-type polymer film excellent in the optical characteristic.

According to the present invention, the following norbornene-based polymer film production method and norbornene-based polymer film are provided, and the above-described object of the present invention is achieved.
(1)
In the presence of the following catalyst (A) and the following cocatalyst (B), a monomer component containing at least one norbornene monomer is subjected to addition polymerization, and the resulting norbornene polymer is used as a solvent. A method for producing a norbornene-based polymer film, wherein the film is formed by a casting method using a dissolved or dispersed liquid;
Catalyst (A): Complex in which at least a cyclopentadienyl-based ligand is coordinated to a kind of transition metal selected from Group 8 element, Group 9 element and Group 10 element of the periodic table. ): An organoaluminum compound (a), an ionic compound (b) that can react with the catalyst (A) to form a cationic transition metal compound, and a compound that promotes dissociation of the ligand of the complex that forms the catalyst (A) At least one compound selected from (c).
(2)
The method for producing a norbornene polymer film according to (1), wherein the catalyst (A) is a complex represented by the following formula (i).

ML _n K ¹ _X K ² _Y K ³ _Z (i)
(In the formula, M is a kind of transition metal selected from Group 8 element, Group 9 element and Group 10 element of the periodic table, and L is a cyclometal selected from cyclopentadienyl and its derivatives. A pentadienyl-based ligand, wherein K ¹ , K ² and K ³ are different negative or neutral ligands, n is an integer of 1 to 3, and X, Y, Z Is an integer from 0 to 7.)
(3)
The catalyst (A) and the cocatalyst (B) are premixed and contacted for 1 minute or longer, and then the mixture is added to the reaction system to perform addition polymerization of the monomer component (1) or The manufacturing method of the norbornene-type polymer film as described in (2).
(4)
A film is formed by a cast molding method using a liquid in which a rubbery polymer and / or a thermoplastic resin other than the norbornene polymer is co-dissolved or co-dispersed in a solvent together with the norbornene polymer. (1) The manufacturing method of the norbornene-type polymer film in any one of (3).
(5)
The method for producing a norbornene polymer film according to any one of (1) to (4), wherein the molded film is heated at a temperature of 30 to 250 ° C. under reduced pressure and / or a nitrogen stream.
(6)
A norbornene-based polymer film obtained by the method according to any one of (1) to (5).

The method for producing a norbornene polymer film according to the present invention can efficiently produce a norbornene polymer film.
The norbornene polymer film according to the present invention is excellent in optical properties.

Hereinafter, the method for producing a norbornene polymer film and the norbornene polymer film according to the present invention will be described in detail.
First, the catalyst (A) and the promoter (B) used in the present invention will be described.

[Catalyst (A)]
In the catalyst (A) used in the present invention, at least a cyclopentadienyl-based ligand is coordinated to a kind of transition metal selected from Group 8 element, Group 9 element and Group 10 element of the Periodic Table. It is preferable that it is a transition metal complex represented by the following formula (i).

ML _n K ¹ _X K ² _Y K ³ _Z (i)
In the formula, M is a kind of transition metal selected from Group 8 element, Group 9 element and Group 10 element of the Periodic Table. Specific examples of M include iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), and platinum (Pt). Among these, preferred elements from the viewpoint of increasing the polymerization activity of the catalyst are cobalt, nickel, palladium and platinum, and it is particularly preferable to use nickel and palladium.

L is a cyclopentadienyl-based ligand selected from cyclopentadienyl and its derivatives.
Specific examples of when L is a cyclopentadienyl derivative include substituted cyclopentadienyl, indenyl, fluorenyl, etc., in which hydrogen of cyclopentadienyl is substituted with a substituent as described later. Derivatives in which hydrogen of indenyl and fluorenyl are substituted with similar substituents are also exemplified as cyclopentadienyl derivatives.

  Examples of the substituted cyclopentadienyl include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a phenyl group, a benzyl group, and a neopentyl group. A hydrocarbon-substituted silyl group such as a trimethylsilyl group.

Examples of the substituent of the substituted cyclopentadienyl include a substituent having a hetero atom, for example, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a halogen atom and the like and exhibiting polarity. Examples thereof include RO group, RCO group, ROCO group, RCOO group, R ₂ N group, R ₂ NCO group, NC group, RS group, RCS group, RSO group, R ₂ S group and the like. Here, R represents a hydrocarbon group having 1 to 12 carbon atoms, and when a plurality of R are present, they may be the same or different. Specific examples of R include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, hexyl group, alkyl group such as octyl group, aryl group such as phenyl, benzyl group, etc. And an aralkyl group. Of these, an alkyl group having 1 to 4 carbon atoms is particularly preferable.

  Examples of the substituent of the substituted cyclopentadienyl further include a methoxy group, an ethoxy group, a t-butoxy group, an acetyl group, a propionyl group, a dimethylamino group, a diethylamino group, a nitrile group, a dimethylaminocarbonyl group, and a diethylaminocarbonyl group. It is done.

  Preferred examples of L are cyclopentadienyl, cyclopentadienyl having 1 to 5 methyl groups, phenylcyclopentadienyl, benzylcyclopentadienyl, and indenyl.

K ¹ , K ² , and K ³ are different negative or neutral ligands.
Examples where K ¹ , K ² and K ³ are negative ligands are given below.
Hydrogen atom; oxygen atom; halogen atom such as fluorine, chlorine, bromine, iodine; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, octyl group, 2- An alkyl group having a straight chain or branched chain having 1 to 20 carbon atoms such as an ethylhexyl group; an aryl group having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a xylyl group or a benzyl group; an alkylaryl group or an arylalkyl group; ;
Hydroxyl group: C1-C20 alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group; C6-C20 such as phenoxy group, methylphenoxy group, 2,6-dimethylphenoxy group, naphthyloxy group Aryloxy group; dimethylamino group, diethylamino group, di (n-propyl) amino group, di (isopropyl) amino group, di (n-butyl) amino group, di (t-butyl) amino group, di (isobutyl) amino A dialkylamino group or a diarylamino group having an alkyl substituent of 1 to 20 carbon atoms such as a group, a diphenylamino group, a methylphenylamino group;
π-allyl group; substituted aryl group having 3 to 20 carbon atoms; acetylacetonate group; substituted acetylacetonate group having 5 to 20 carbon atoms; hydrocarbon-substituted silyl group such as trimethylsilyl group; carbonyl group;

Examples where K ¹ , K ² and K ³ are neutral ligands are given below.
Nitrogen molecule; ethylene; ethers such as diethyl ether and tetrahydrofuran; nitriles such as acetonitrile and benzonitrile; esters such as ethyl benzoate; amines such as triethylamine, 2,2-bipyridine and phenanthroline; trimethylphosphine and Trialkylphosphines such as triethylphosphine, and triarylphosphines such as triphenylphosphine;
Silicon substituted hydrocarbon groups such as (trimethylsilyl) methyl; Lewis bases such as sulfoxides, isocyanides, phosphonic acids, thiocyanates; aromatic hydrocarbons such as benzene, toluene and xylene, cycloheptatriene, cyclooctadiene, cycloocta Cyclic unsaturated hydrocarbons such as triene, cyclooctatetraene or derivatives thereof.

In the formula (1), K ¹ , K ² , and K ³ may all be negative ligands, all may be neutral ligands, or any of them may be negatively coordinated. The remainder may be a neutral ligand.

n is an integer of 1 to 3, and X, Y, and Z are integers of 0 to 7.
The catalyst (A) is represented by the following formula (i)
Specific examples of the catalyst (A) represented by the general formula (i) include cyclopentadienyl (methyl) (triphenylphosphine) nickel, methylcyclopentadienyl (methyl) (triphenylphosphine) nickel, and pentamethyl. Cyclopentadienyl (methyl) (triphenylphosphine) nickel, indenyl (methyl) (triphenylphosphine) nickel, fluorenyl (methyl) (triphenylphosphine) nickel, cyclopentadienyl (methyl) (tricyclohexylphosphine) nickel, Pentamethylcyclopentadienyl (methyl) (tricyclohexylphosphine) nickel, indenyl (methyl) (tricyclohexylphosphine) nickel, fluorenyl (methyl) (tricyclohexylphosphine) nickel, Pentadienyl (π-allyl) palladium, methylcyclopentadienyl (π-allyl) palladium, pentamethylcyclopentadienyl (π-allyl) palladium, indenyl (π-allyl) palladium, fluorenyl (π-allyl) palladium, etc. Can be mentioned.

Such a transition metal complex represented by the above formula (i) can be produced, for example, by the method described in Yamazaki. H et al., Bull. Chem. Soc. Jpn., 1964, 37, 907.
[Cocatalyst (B)]
The co-catalyst (B) used in the present invention comprises an organoaluminum compound (a), an ionic compound (b) capable of reacting with the catalyst (A) to form a cationic transition metal compound, and a complex forming the catalyst (A) At least one compound selected from the compound (c) that promotes dissociation of the ligand. These may be used alone or in combination.

Organoaluminum compound (a)
The organoaluminum compound (a) is an aluminum compound having a hydrocarbon group, and examples thereof include organoaluminum, halogenated organoaluminum, hydrogenated organoaluminum, and organoaluminumoxy compounds.

Among these, examples of the organic aluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum. Examples of the halogenated organoaluminum include dimethylaluminum chloride, diethylaluminum chloride, sesquiethylaluminum chloride, and ethylaluminum dichloride. Examples of the organic aluminum hydride include diethylaluminum hydride and sesquiethylaluminum hydride. The organoaluminum oxy compound is also called aluminoxane and is a linear or cyclic polymer represented by the general formula (—Al (R ′) O—) ₁ . Here, R ′ is a hydrocarbon group having 1 to 10 carbon atoms, including those partially substituted with halogen atoms and / or R′O groups. l is the degree of polymerization and is 5 or more, preferably 10 or more. Examples of R ′ include a methyl group, an ethyl group, a propyl group, and an isobutyl group.

Preferred as the organoaluminum compound (a) are halogenated organoaluminum and organoaluminum oxy compounds, and particularly preferred are diethylaluminum chloride, sesquiethylaluminum chloride, methylaluminoxane, ethylaluminoxane, and ethylchloroaluminoxane.

Ionic compound (b)
Examples of the ionic compound (b) capable of forming a cationic complex by reacting with the catalyst (A) include an ionic compound in which a non-coordinating anion exemplified below and a cation exemplified below are combined.

  Non-coordinating anions include, for example, tetra (phenyl) borate, tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluoro) Phenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (triyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride -7,8-dicarbaound decaborate and the like.

  Examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal.

  Specific examples of the carbonium cation include tri-substituted carbonium cations such as a triphenyl carbonium cation and a tri-substituted phenyl carbonium cation. Specific examples of the tri-substituted phenyl carbonium cation include a tri (methylphenyl) carbonium cation and a tri (dimethylphenyl) carbonium cation.

  Specific examples of the ammonium cation include a trialkylammonium cation, a triethylammonium cation, a tripropylammonium cation, a tributylammonium cation, a trialkylammonium cation such as a tri (n-butyl) ammonium cation, an N, N-diethylanilinium cation, an N N, N-dialkylanilinium cations such as N, N-2,4,6-pentamethylanilinium cation, dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

  Preferred examples of the ionic compound (b) include trityltetra (pentafluorophenyl) borate, triphenylcarboniumtetra (fluorophenyl) borate, N, N-dimethylaniliniumtetra (pentafluorophenyl) borate, 1,1 ′. -Dimethylferrocenium tetra (pentafluorophenyl) borate and the like.

Compound (c)
Examples of the compound (c) that promotes dissociation of the ligand of the complex forming the catalyst (A) include tris (pentafluorophenyl) boron, tris (monofluorophenyl) boron, tris (difluorophenyl) boron, triphenylboron, Examples thereof include biscyclooctadiene nickel.

In the present invention, as the catalyst (A), in the formula (i), M is nickel (Ni) or palladium (Pd), L is cyclopentadienyl or indenyl, and the other ligand is CH _3. (Methyl) and PPh ₃ (triphenylphosphine), Cl (chlorine) and PPh ₃ , or C ₃ H ₅ (allyl), and a tris (
Using pentafluorophenyl) boron [B (C ₆ F ₅ ) ₃ ], trityltetra (pentafluorophenyl) borate {[Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]} or methylaluminoxane (MAO) It is one of preferred embodiments to produce a norbornene polymer.

Further, in the above formula (i) as the catalyst (A), M is nickel (Ni) or palladium (Pd), L is cyclopentadienyl, and other ligands are CH ₃ (methyl) and P
Using a complex which is Ph ₃ (triphenylphosphine) or C ₃ H ₅ (allyl), B (C ₆ F ₅ ) ₃ or [Ph ₃ C] [B (C ₆ One preferred embodiment is to produce a norbornene-based polymer using F ₅ ) ₄ ].

Next, the norbornene monomer used in the present invention will be described.
[Norbornene monomer]
In the present invention, as the norbornene-based monomer, for example, a compound represented by the following formula (ii) or the following formula (iii) is used.

In the above formula (ii), m, p, q and r are each independently an integer of 0 or more, preferably 0, 1 or 2.
R ^{1 to} R ⁴ each independently have a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; and a linking group that may contain an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. Or an unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group.

Examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group, and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; vinyl groups, allyl groups, propenyl groups, and the like. An alkenyl group etc. are mentioned. The hydrocarbon group may be directly bonded to the ring structure or may be bonded via a linkage.

As such a linking group, a divalent hydrocarbon group having 1 to 10 carbon atoms (for example,-(
CH ₂ ) _m — (an alkylene group represented by m is an integer of 1 to 10); a linking group containing oxygen, nitrogen, sulfur or silicon (for example, a carbonyl group (—CO—), an oxycarbonyl group (—O (CO)-), sulfone group (—SO ₂ —), ether bond (—O—), thioether bond (
-S-), imino group (-NH-), amide bond (-NHCO-, -CONH-), siloxane bond (-OSi (R ₂ )-(R is an alkyl group such as methyl or ethyl)) and the like. And
A linking group containing a plurality of these may be used.

R ¹ and R ² and / or R ³ and R ⁴ may be integrated to form a divalent hydrocarbon group, and R ¹ or R ² and R ³ or R ⁴ are bonded to each other. May form a carbocycle or a heterocycle, and the carbocycle or heterocycle may be a monocyclic structure or a polycyclic structure.

  Examples of the polar group include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group, etc.), an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), an aryloxycarbonyl group (eg, Phenoxycarbonyl group, naphthyloxycarbonyl group, fluorenyloxycarbonyl group, biphenylyloxycarbonyl group, etc.), cyano group, amide group, imide ring-containing group, triorganosiloxy group (for example, trimethylsiloxy group, triethylsiloxy group) Etc.), triorganosilyl group (eg trimethylsilyl group, triethylsilyl group etc.), amino group (eg primary amino group etc.), acyl group, alkoxysilyl group (eg trimethoxysilyl group, triethoxysilyl group etc.) Etc.), sulfo Etc. Le-containing group and a carboxyl group.

  Specific examples of such a monomer (hereinafter also referred to as “monomer (ii)”) are shown below, but the present invention is not limited to these specific examples. Moreover, monomer (ii) may be used independently or may be used in combination of 2 or more type.

Tricyclo [5.2.1.0 ^2,6 ] -8-decene,
Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- pentadecene,
Pentacyclo ^{[7.4.0.1 2,5 .1 9,12 .0 8,13]} -3- pentadecene,
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,
8 methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 phenoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-
Dodecene,
8-methyl-8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-
Dodecene,
8-methyl -8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10]
-3-dodecene,
8-methyl-8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10]
-3-dodecene,
8-methyl -8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -
3-dodecene,
8-methyl-8-phenoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3
-Dodecene,
Pentacyclo ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} -3- hexadecene,
Heptacyclo ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0 11,16] -4- eicosene,
Heptacyclo ^{[8.8.0.1 4,7 .1 11,18 .1 13,16 .0} 3,8 .0 12,17] -5- heneicosene,
8 ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-phenyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-phenyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-fluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-fluoro-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 difluoromethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 preventor fluoroethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-
Dodecene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-
Dodecene,
8-methyl-8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-
Dodecene,
8,8,9- trifluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10]
-3-dodecene,
8,8,9,9- tetrafluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene,
8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.
1 ^2,5 .1, ^7,10 ] -3-dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.
1 ^2,5 .1, ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene,
8,8,9- trifluoro-9-trifluoromethoxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.
1 ^2,5 .1, ^7,10 ] -3-dodecene,
8-Fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-8-heptafluoro-iso- propyl-9-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-Chloro -8,9,9- trifluoro tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3
-Dodecene,
8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
, And the like 8-methyl-8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [44.0.1 ^2,5 .1 ^7,10] -3-dodecene.

In said formula (iii), R < ⁵ > -R < ⁸ > is synonymous with R < ¹ > -R < ⁴ > in said formula (ii).
R ⁵ and R ⁶ and / or R ⁷ and R ⁸ may be integrated to form a divalent hydrocarbon group, and R ⁵ or R ⁶ and R ⁷ or R ⁸ are bonded to each other. May form a carbocycle or a heterocycle, and the carbocycle or heterocycle may be a monocyclic structure or a polycyclic structure.

Specific examples of such a monomer (hereinafter also referred to as “monomer (iii)”) are shown below.
The present invention is not limited to these specific examples. Monomer (iii) may be used alone or in combination of two or more.

Bicyclo [2.2.1] hept-2-ene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
5-phenylbicyclo [2.2.1] hept-2-ene,
5- (2-naphthyl) bicyclo [2.2.1] hept-2-ene (both α and β types are acceptable),
5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,
5,5-difluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2-ene,
5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethysole) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,
5- (4-phenylphenyl) bicyclo [2.2.1] hept-2-ene 4- (bicyclo [2.2.1] hept-5-en-2-yl) phenylsulfonylbenzene,
And tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene.

Of these, R ^{5 to} R ⁸ in the general formula (iii) are all hydrogen atoms, or any one is a hydrocarbon group having 1 to 30 carbon atoms and the other is a hydrogen atom, or any two are The monomer (iii) linked by an alkylene group having 3 to 5 carbon atoms is preferable in that it has a large effect of improving the toughness of the resulting optical film, and in particular, R ^{5 to} R ⁸ are all hydrogen atoms, Alternatively, a monomer in which any one of them is a methyl group, an ethyl group or a phenyl group and the others are all hydrogen atoms is preferable from the viewpoint of heat resistance. Furthermore, bicyclo [2.2.1] hept-2-ene, 5-phenylbicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^2,5 ] deca-3, 7-diene is preferred in that its synthesis is easy.

In the present invention, the monomer used for the production of the norbornene-based polymer is also a monomer other than the monomers (ii) and (iii), for example, cyclobutene, cyclopentene, cycloheptene, cyclooctene, tricyclo [5. 2.1.0 ^2,6 ] -3-decene, cycloolefin such as dicyclopentadiene, and the like may be used.

〔polymerization〕
In the present invention, the polymerization of the norbornene-based monomer using the catalyst (A) and the cocatalyst (B) may be carried out in bulk or in a solution. When polymerization is carried out in solution, it is necessary to use a solvent that does not adversely affect the catalyst activity. Solvents that can be used include aliphatic hydrocarbons such as pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated carbons such as dichloromethane, chloroform, and chlorobenzene. Hydrogen; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; and ethers such as diethyl ether, dioxane and tetrahydrofuran. These solvents may be used as a mixture.

  When performing the polymerization, the norbornene monomer to be polymerized and the catalyst (A) and the cocatalyst (B) are mixed, but the mixing order is not particularly limited. The catalyst (A) component and the cocatalyst (B) may be mixed in advance to obtain a reaction composition, which may be added to a solution containing a monomer to be polymerized. Further, the promoter (B) may be added to the solution containing the monomer to be polymerized and the catalyst (A), and the catalyst (A) is added to the mixed solution of the monomer to be polymerized and the promoter (B). It may be added.

  In the present invention, it is preferable that the catalyst (A) and the cocatalyst (B) are mixed in advance and contacted for 1 minute or longer, preferably about 30 minutes to 1 hour, and then added to the reaction system. By performing such an operation, it becomes possible to express higher polymerization activity.

  The ratio of the catalyst (A) and the cocatalyst (B) used in the method of the present invention is not uniquely determined because it varies depending on various conditions, but is usually (A) / (B) (molar ratio). It is 1 / 0.1 to 1 / 10,000, preferably 1 / 0.5 to 1 / 5,000, and more preferably 1/1 to 1 / 2,000.

The polymerization temperature is not particularly limited, but is generally -100 ° C to 150 ° C, preferably -50 ° C to 120 ° C. If the temperature is too low, the polymerization rate becomes slow, and if the temperature is too high, the activity of the catalyst decreases. By selecting the polymerization temperature within the above range, the polymerization rate, molecular weight and the like can be adjusted.

The polymerization time is not particularly limited, and is, for example, 1 minute to 100 hours.
[Norbornene polymer]
The norbornene polymer thus obtained has an intrinsic viscosity (η _inh ) measured in chloroform (30 ° C.) of 0.2 to 5 dl / g, preferably 0.3 to 4 dl / g, particularly preferably. Is 0.5-3 dl / g. When the above range is exceeded, the solution viscosity becomes too high, and the workability may deteriorate, and when it is lower than the above range, the film strength may decrease.

As the molecular weight of the norbornene-based polymer, the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is usually 8,000 to
1,000,000, preferably 10,000 to 500,000, particularly preferably 20,000
0 to 100,000, and the weight average molecular weight (Mw) is usually 20,000 to 3,000.
The range is 000,000, preferably 30,000 to 1,000,000, particularly preferably 40,000 to 500,000. The molecular weight distribution is such that the above Mw / Mn is usually 1.
5-10, preferably 2-8, particularly preferably 2.5-5.

The saturated water absorption at 23 ° C. of the norbornene polymer is usually 0.001 to 1% by weight, preferably 0.01 to 0.7% by weight, and more preferably 0.1 to 0.5% by weight. When the saturated water absorption is within this range, various optical characteristics such as transparency, retardation, uniformity of retardation, and dimensional accuracy are maintained even under conditions such as high temperature and high humidity, and adhesion to other materials. In addition, since it is excellent in adhesiveness, peeling does not occur during use, and since compatibility with additives such as antioxidants is good, the degree of freedom of addition is increased. The saturated water absorption rate is ASTM D57.
This is a value obtained by immersing in 23 ° C. water for 1 week and measuring the increased weight.

The SP value (solubility parameter) of the norbornene polymer is preferably 10 to 30 (MPa ^1/2 ), more preferably 12 to 25 (MPa ^1/2 ), and particularly preferably 15 to 20 (MPa ^1/2 ). It is. When the SP value is in the above range, the norbornene polymer can be dissolved well in a general-purpose solvent, a stable film can be produced, and the properties of the obtained film become uniform, and the adhesiveness and adhesion to the substrate. The water absorption rate can be controlled appropriately.

  The glass transition temperature (Tg) of the norbornene-based polymer varies depending on the type of the constituent unit of the norbornene-based polymer, the composition ratio, the presence or absence of additives, etc., but is usually 80 to 350 ° C., preferably 100 to 250 ° C. Preferably it is 120-200 degreeC. When Tg is lower than the above range, the heat distortion temperature is lowered, there is a possibility that a problem occurs in heat resistance, and the change in the optical characteristics depending on the temperature of the obtained optical film may be increased. Moreover, when Tg is higher than the above range, there is a high possibility that the resin is thermally deteriorated when heated to the vicinity of Tg for processing such as stretching.

  Norbornene-based polymers include known thermoplastic resins, thermoplastic elastomers, rubber polymers, organic fine particles, inorganic fine particles, antioxidants, ultraviolet absorbers, mold release agents, as long as transparency and heat resistance are not impaired. Flame retardants, antibacterial agents, wood powder, coupling agents, petroleum resins, plasticizers, colorants, lubricants, antistatic agents, silicone oils, foaming agents and the like may be blended.

[Method for producing film]
The norbornene-based polymer film according to the present invention can be obtained by forming a film of the norbornene-based polymer obtained as described above by a solution casting method (solution casting method).

  As the solution casting method, for example, a norbornene-based polymer is dissolved or dispersed in an appropriate solvent to obtain a liquid having an appropriate concentration, and this is poured onto an appropriate substrate or applied and dried to obtain a resin. The method of peeling a film | membrane from a base material is mentioned.

  The concentration of the norbornene polymer component in the norbornene polymer solution or dispersion (hereinafter collectively referred to as “resin solution”) is usually 0.1 to 90% by weight, preferably 1 to 50% by weight. More preferably, it is 5 to 35% by weight. If the concentration of the norbornene-based polymer component is lower than the above range, a film having a sufficient thickness may not be obtained, and good surface smoothness may be caused by foaming caused by evaporation of the solvent. The film which has it may not be obtained. On the other hand, when the concentration of the norbornene polymer component exceeds the above range, the viscosity of the resin solution becomes too high, and a film having a uniform thickness and surface state may not be obtained.

  The resin solution has a viscosity at room temperature of usually 1 to 1,000,000 mPa · s, preferably 10 to 100,000 mPa · s, more preferably 100 to 50,000 mPa · s, and particularly preferably 1,000. ~ 40,000 mPa · s.

  Examples of the solvent used for preparing the resin solution include aromatic solvents such as benzene, toluene and xylene; cellosolve solvents such as methyl cellosolve, ethyl cellosolve and 1-methoxy-2-propanol; diacetone alcohol, acetone, Ketone solvents such as cyclohexanone, methyl ethyl ketone, 4-methyl-2-pentanone, cyclohexanone, ethyl cyclohexanone, 1,2-dimethylcyclohexane; ester solvents such as methyl lactate and ethyl lactate; 2,2,3,3-tetrafluoro Examples include halogen-containing solvents such as -1-propanol, methylene chloride, and chloroform; ether solvents such as tetrahydrofuran and dioxane; and alcohol solvents such as 1-pentanol and 1-butanol.

  The temperature for dissolving or dispersing the norbornene polymer with a solvent may be room temperature or high temperature. By stirring sufficiently, a uniform resin solution can be obtained. In addition, a means for removing bubbles remaining in the resin solution by, for example, heating and standing the resin solution as required is taken. In addition, when coloring as needed, coloring agents, such as dye and a pigment, can also be suitably added to a resin solution. Further, a leveling agent may be added to improve the surface smoothness of the film. Such a leveling agent is not particularly limited as long as it is a general leveling agent. For example, a fluorine nonionic surfactant, a special acrylic resin leveling agent, a silicone leveling agent, and the like can be used.

  Examples of the substrate used in the solution casting method include metal drums, steel belts, polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and belts made of polytetrafluoroethylene.

  When a polyester film is used as the substrate, a surface-treated film may be used. As a surface treatment method, a commonly used hydrophilic treatment method, for example, a method of laminating an acrylic resin or a sulfonate group-containing resin by coating or lamination, or a film by plasma treatment or corona discharge treatment, etc. And the like, and the like.

As a method for applying the resin solution to the substrate, a method using a die, a coater, a brush or the like, a spray method, a roll coating method, a spin coating method, a dipping method, a gravure method, or the like can be used. Moreover, in order to obtain an optical film having a desired thickness, the resin solution may be repeatedly applied.

  The method for evaporating the solvent from the resin solution applied to the substrate is not particularly limited, and a generally used method, for example, a method of passing through a drying furnace with a large number of rollers, is used. However, if bubbles are generated as the solvent evaporates, the properties of the resulting optical film are significantly reduced.In order to avoid the generation of bubbles, the solvent is evaporated in a plurality of steps. It is preferable to control the temperature and the air volume in the process.

  In this invention, it is preferable to heat the film after shaping | molding at 30-250 degreeC, Preferably it is 50-200 degreeC. This heating is performed under reduced pressure, preferably under reduced pressure of 10 to 759 mmHg, and is also preferably performed under a nitrogen stream.

  The amount of the solvent remaining in the norbornene polymer film is usually 20% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less, and particularly preferably 0.5% by weight or less. When the residual solvent amount exceeds the above range, the dimensional change with time may increase when the resin film is actually used, and the glass transition temperature is lowered by the residual solvent, resulting in heat resistance. May decrease.

  Moreover, in order to perform the extending | stretching process mentioned later suitably, it may be necessary to adjust suitably the quantity of the solvent which remains in a norbornene-type polymer film within the said range. Specifically, in order to stably and uniformly express the retardation due to the stretching treatment, the amount of the remaining solvent is usually 20 to 0.1% by weight, preferably 5 to 0.1% by weight, more preferably It may be 1 to 0.1% by weight. By controlling the amount of the solvent within such a range, the stretching process can be easily performed, and the phase difference can be easily controlled.

  The thickness of the norbornene polymer film thus obtained is usually 5 to 1,000 μm, preferably 15 to 500 μm, more preferably 25 to 300 μm, and particularly preferably 40 to 150 μm. When this thickness is smaller than the above range, handling of the norbornene polymer film becomes practically difficult. On the other hand, when the thickness exceeds the above range, it is difficult to wind the norbornene polymer film into a roll.

  The thickness distribution in the norbornene-based polymer film is usually within ± 20%, preferably within ± 10%, more preferably within ± 5%, particularly preferably within ± 3%, and 1 cm relative to the average value. The variation rate of the thickness per round is usually 10% or less, preferably 5% or less, more preferably 1% or less, and particularly preferably 0.5% or less. By forming the norbornene-based polymer film under such a thickness condition, when the resin film is stretched, it is possible to prevent the occurrence of transmission light retardation unevenness.

  The film obtained by the production method of the present invention may be further stretched. Specifically, it can be produced by a known uniaxial stretching method, biaxial stretching method, or Z-axis stretching method. That is, the horizontal uniaxial stretching method by the tenter method, the compression stretching method between rolls, the longitudinal uniaxial stretching method using rolls having different circumferential speeds, the biaxial stretching method in which the horizontal uniaxial and the longitudinal uniaxial are combined, the stretching method by the inflation method Etc. can be used.

In the case of the uniaxial stretching method, the stretching speed is usually 1 to 5,000% / min, preferably 50 to
It is 1,000% / min, and more preferably 100 to 1,000% / min.
In the case of the biaxial stretching method, stretching may be performed in two directions at the same time, or the stretching may be performed in a direction different from the first stretching direction after uniaxial stretching. At this time, the intersecting angle of the two stretching axes for controlling the shape of the refractive index ellipsoid is not particularly limited because it is determined by desired characteristics, but is usually in the range of 120 to 60 degrees. The stretching speed may be the same or different in each stretching direction, and is usually 1 to 5,000% / min, preferably 50 to 1,000% / min, and more preferably Is 100 to 1,000% / min, particularly preferably 100 to 1,000% / min.
500% / min.

  The stretching temperature is not particularly limited, but is usually Tg ± 30 ° C., preferably Tg ± 15 ° C., more preferably Tg−5 to Tg + 15 ° C., based on the glass transition temperature Tg of the norbornene polymer. Range. Within the above range, it is possible to suppress the occurrence of phase difference unevenness, and it is preferable because the control of the refractive index ellipsoid becomes easy.

  The draw ratio is not particularly limited because it is determined by desired properties, but is usually 1.01 to 10 times, preferably 1.03 to 5 times, and more preferably 1.03 to 3 times. When the draw ratio is 10 times or more, it may be difficult to control the phase difference.

  Although the stretched film may be cooled as it is, it is heat set by holding it in a temperature atmosphere of Tg-20 ° C. to Tg for at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 minute to 60 minutes. It is preferable to do. As a result, a stable retardation film can be obtained with little change over time in the retardation of transmitted light.

Films obtained by the production method of the present invention include various types such as mobile phones, digital information terminals, pagers, navigation, in-vehicle liquid crystal displays, liquid crystal monitors, light control panels, OA equipment displays, AV equipment displays, etc. It can be used for a liquid crystal display element, an electroluminescence display element, a touch panel, or the like. It is also useful as a wave plate used in an optical disk recording / reproducing apparatus such as a CD, CD-R, MD, MO, and DVD.
[Example]
Examples of the present invention are shown below. In addition, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the polymer obtained in each Example were obtained by GPC using polystyrene as a standard substance. The composition ratio of norbornene to norbornene carboxylic acid methyl ester in the copolymer was the peak [δ: 3.5 obtained by ¹ H-NMR.
-3.9 “-COOMe unit of norbornene carboxylic acid methyl ester” and δ: 0.8-3.0 (“—CH _{2 of} norbornene and norbornene carboxylic acid methyl ester”
-"And" -CH = "units)]].

Moreover, each physical property evaluation of the film was performed on the following conditions.
Tensile strength and elongation (TS, TE) :
Measured according to ASTM D638.
Total light transmittance (Tt):
Measured according to ASTM D1003.
Yellowness (YI):
It measured according to JIS K7103.
Glass transition temperature (Tg):
It was measured at the peak temperature of temperature dispersion of Tan δ (ratio of storage elastic modulus (E ′) to loss elastic modulus (E ″) (E ″ / E ′)) measured by dynamic viscoelasticity. Measurement uses Leovibron DDV-01FP (manufactured by Orientec), measurement frequency: 10 Hz, heating rate: 4 ° C./min, excitation mode: single waveform, excitation amplitude: 2.5 μm peak of Tan δ The temperature was measured.
Resistivity (ρ) (Ω · cm):
Measured according to ASTM D257.
Light resistance:
Discoloration (ΔE) after 500 hours was measured with a fade meter (63 ° C., no rain).

Cyclopentadienyl (methyl) (triphenylphosphine) nickel was synthesized according to the synthesis method of Yamazaki et al. (Yamazaki. H et al., Bull. Chem. Soc. Jpn., 1964, 37, 907).
Production of norbornene polymer [Example 1]
20 μmol of cyclopentadienyl (methyl) (triphenylphosphine) nickel [C ₅ H ₅ NiCH ₃ (PPh ₃ )] and tris (pentafluorophenyl) boron [B (C ₆ F ₅₎ ) ₃ ] was added in an amount of 20 μmol, and 5 mL of toluene was further added to dissolve them. Next, 5 ml of a toluene solution containing 1.41 g (0.015 mol) of norbornene and 0.77 g (0.005 mol) of norbornenecarboxylic acid methyl ester was added to this container, and a polymerization reaction was performed at room temperature for 15 minutes.

After completion of the reaction, the contents of the container were poured into a large amount of methanol to precipitate a polymer, filtered and washed, and then dried under reduced pressure at 60 ° C. for 5 hours to obtain 1.04 g of polymer. The obtained polymer was easily dissolved in a solvent such as THF, chloroform, or dichloromethane. When this polymer was measured by GPC, the molecular weight was Mw = 735,500, Mn = 4.
06,800, molecular weight distribution (Mw / Mn) = 1.81. Moreover, the composition ratio of norbornene / norbornenecarboxylic acid methyl ester in the copolymer was confirmed to be 84.8 / 15.2 by molar ratio by ¹ H-NMR spectrum. Hereinafter, this copolymer is referred to as a copolymer (p-1).
[Example 2]
The amount of norbornene was 0.47 g (0.005 mol), the amount of norbornenecarboxylic acid methyl ester was 1.53 g (0.010 mol), and the polymerization reaction time was 30 minutes. Except this, the polymerization reaction was carried out in the same manner as in Example 1.
As a result, 0.59 g of polymer was obtained. Molecular weight Mw = 362,000, Mn = 1
93,200, molecular weight distribution (Mw / Mn) = 1.87, norbornene /
It was confirmed that the composition ratio of norbornenecarboxylic acid methyl ester was 67.9 / 32.1 in terms of molar ratio. Hereinafter, this copolymer is referred to as a copolymer (p-2).
[Example 3]
The amount of norbornene was 0.47 g (0.005 mol), the amount of norbornenecarboxylic acid methyl ester was 2.23 g (0.015 mol), and the polymerization reaction time was 30 minutes. Except this, the polymerization reaction was carried out in the same manner as in Example 1.

As a result, 0.13 g of polymer was obtained. The molecular weight is Mw = 242,200, Mn =
124,600, molecular weight distribution (Mw / Mn) = 1.94, and it was confirmed that the composition ratio of norbornene / norbornenecarboxylic acid methyl ester in the polymer was 43.5 / 56.5 in molar ratio. . Hereinafter, this copolymer is referred to as a copolymer (p-3).
[Comparative Example 1]
The polymerization reaction was performed in the same manner as in Example 1 except that palladium acetate [Pd (OCOCH ₃ ) ₂ ] was used instead of C ₅ H ₅ NiCH ₃ (PPh ₃ ).
As a result, the polymer yield was 0.10 g, which was significantly lower than that of Example 1. The molecular weight was Mw = 173,100, Mn = 76,000, and the molecular weight distribution (Mw / Mn) = 2.23. Further, the composition ratio of norbornene / norbornene carboxylic acid methyl ester in the polymer was 95.2 / 4.8 in molar ratio, and the copolymerizability of norbornene carboxylic acid methyl ester was remarkably lowered. Hereinafter, this copolymer is referred to as a copolymer (r-1).
[Examples 4 to 7]
A solution of the copolymers (p-1, p-2, p-3) obtained in Examples 1 to 3 in dichloromethane (
A 20% density) was passed through a die to obtain an undried film having a uniform thickness, which was dried at 150 ° C. to produce a film having a thickness of 100 μm. The width of this film tank: 100 cm was processed under the dry conditions shown in Table 1, and the physical properties of the obtained films (f-1 to f-4) were measured. In Examples 4 to 6, nitrogen was flowed at 10 cm ³ / min instead of reducing the pressure in Example 7.
[Example 8]
A 200 μm-thick film was produced from a toluene solution (concentration 25%) of copolymer (p-1) / thermoplastic elastomer = 90/10 (wt%) (f-5). This film tank was processed at a width of 100 cm under the conditions shown in Table 1 and measured for physical properties. Note that Septon 2002 (trade name, manufactured by Kuraray Co., Ltd.) was used as the thermoplastic elastomer.
[Comparative Example 2]
Film production was attempted by the same method as in Example 4 using the copolymer (r-1). However, since the copolymer (r-1) was not dissolved in an organic solvent such as dichloromethane, toluene, cyclohexane, or tetrahydrofuran, it could not be formed into a film by a solvent casting method.

Claims (6)

In the presence of the following catalyst (A) and the following cocatalyst (B), a monomer component containing at least one norbornene monomer is subjected to addition polymerization, and the resulting norbornene polymer is used as a solvent. A method for producing a norbornene-based polymer film, wherein the film is formed by a casting method using a dissolved or dispersed liquid;
Catalyst (A): Complex in which at least a cyclopentadienyl-based ligand is coordinated to a kind of transition metal selected from Group 8 element, Group 9 element and Group 10 element of the periodic table. ): An organoaluminum compound (a), an ionic compound (b) that can react with the catalyst (A) to form a cationic transition metal compound, and a compound that promotes dissociation of the ligand of the complex that forms the catalyst (A) At least one compound selected from (c). The method for producing a norbornene polymer film according to claim 1, wherein the catalyst (A) is a complex represented by the following formula (i):
ML _n K ¹ _X K ² _Y K ³ _Z (i)
(In the formula, M is a kind of transition metal selected from Group 8 element, Group 9 element and Group 10 element of the periodic table, and L is a cyclometal selected from cyclopentadienyl and its derivatives. A pentadienyl-based ligand, wherein K ¹ , K ² and K ³ are different negative or neutral ligands, n is an integer of 1 to 3, and X, Y, Z Is an integer from 0 to 7.)   The catalyst (A) and the co-catalyst (B) are mixed in advance and contacted for 1 minute or longer, and then the mixture is added to the reaction system to perform addition polymerization of the monomer component. Or the manufacturing method of the norbornene-type polymer film of 2.   A film is formed by a cast molding method using a liquid in which a rubbery polymer and / or a thermoplastic resin other than the norbornene polymer is co-dissolved or co-dispersed in a solvent together with the norbornene polymer. The manufacturing method of the norbornene-type polymer film in any one of Claims 1 thru | or 3.   The method for producing a norbornene polymer film according to any one of claims 1 to 4, wherein the molded film is heated at a temperature of 30 to 250 ° C under reduced pressure and / or a nitrogen stream. A norbornene-based polymer film obtained by the method according to claim 1.