JPH10101907A - Liquid composition and cast film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent transparency by casting a liquid composition comprising a solution or dispersion of an aromatic norbornene polymer in a halogenated hydrocarbon solvent on a carrier and removing the solvent by drying. SOLUTION: A norbornene monomer comprising, e.g. 1,4-methano-1,4,4a,9a- tetrahydrofluorene, dissolved in, e.g. toluene, is mixed with a polymerization catalyst comprising, e.g. tri-isobutylaluminum/isobutyl alcohol, and WCl6 is dropped into the mixture. After reaction for a prescribed time, the reaction liquid is transferred into an autoclave and mixed under stirring with a acetylacetonatonickel/tri-isobutylaluminum catalyst. Hydrogen is introduced into the mixture at 80 deg.C to react for about 3hr while maintaining a hydrogen pressure of about 30kg/cm<2> , thus giving an aromatic norbornene polymer having a number-average molecular weight of 1,000 to 100,000. This polymer is dissolved in a halogenated hydrocarbon solvent such as methylene chloride and mixed with a leveling agent, etc., to prepare a liquid composition. This composition is case on a glass plate, thermally dried and then peeled from the glass plate to give a case film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid composition containing an aromatic ring-containing norbornene-based polymer, and a cast film formed by casting the liquid composition by a solution casting method. The cast film of the present invention is excellent in water resistance, moisture resistance, physical strength, heat resistance, transparency and the like, and is useful as a protective film for a polarizer.

[0002]

2. Description of the Related Art A liquid crystal display generally comprises a liquid crystal cell, a polarizer, a reflector or a backlight. The liquid crystal cell is composed of two liquid crystal substrates having a transparent electrode and an alignment film provided on an inward surface of a transparent substrate made of glass or plastic, a spacer, a liquid crystal material, and the like. The two liquid crystal substrates are opposed to each other with a predetermined gap therebetween via a spacer, and a liquid crystal material is injected into the gap and sealed. Polarizers are arranged on both sides of a liquid crystal cell in the case of a normal TN type liquid crystal.

As a polarizer, a thin-film type polarizer (polarizing film) is usually used. A typical example is a polarizing substrate made of a polyvinyl alcohol (PVA) film on which a polarizing element (iodine, dye, etc.) is provided. There is a polarizing film having a structure in which it is adsorbed and dispersed. Specific examples include PVC
There are PVA-based polarizing films such as iodine-based, PVA / dye-based, and PVA / polyvinylene-based. Polarizing film has low mechanical strength in the transmission axis direction, and shrinks due to heat and moisture,
As the polarization function deteriorates, to compensate for these drawbacks,
Protective layers made of various films are laminated on both sides by an adhesive. This laminate is called a polarizing film or a polarizing plate.

The protective film has no birefringence, high light transmittance, good heat resistance and moisture absorption, high mechanical strength, smooth surface and high resolution, temperature and humidity. A large number of performances are required, such as a small shrinkage due to the change in the size and excellent appearance. Conventionally, a cast film of cellulose triacetate (hereinafter abbreviated as TAC) has been mainly used as a protective film. However, the water vapor permeability of the PVA film constituting the polarizing substrate is 25 ° C. at a thickness of 25 μm.
An environment of ^{90% RH, 1000~1200g / m 2} · 2
On the other hand, the TAC film has a water vapor permeability of about 700 g / m ² · 24 hr under the same conditions, whereas the moisture resistance is insufficient. Therefore, TA
A polarizing film having a C film as a protective layer has poor durability under high temperature and high humidity. For example, it deteriorates in 100 hours or less under an environment of 80 ° C. and 90% RH, and its polarizing performance rapidly decreases. I will.

As a technique for solving these problems, it has been reported that a sheet made of a thermoplastic norbornene resin is useful as a protective film for a polarizer (JP-A-4-339821, JP-A-5-33921). 212828
No.). However, the thermoplastic norbornene resins used in the prior art are only soluble in flammable solvents such as cyclohexane, toluene and decalin, and in order to produce cast films, the production facilities must be explosion-proof equipment. There was a problem. In addition, since these solvents have a high boiling point and an affinity for the thermoplastic norbornene-based resin is too high, a long-time high-temperature drying step is required to keep the residual solvent within the specified value. Thus, there is a problem that productivity is poor. As a solvent for a general cast film, a halogenated hydrocarbon solvent such as methylene chloride, which is flame-retardant and has a low boiling point, is used.However, most of the thermoplastic norbornene-based resin is a halogenated hydrocarbon solvent. Did not dissolve or finely disperse. On the other hand, since a film having a smooth surface can be easily obtained by a solvent casting method, it has been desired to solve the above problems.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to produce a cast film having excellent properties such as water resistance, moisture resistance, physical strength, heat resistance and optical transparency by using a thermoplastic norbornene resin. It is an object of the present invention to provide a liquid composition which can be easily produced by a simple production facility, and a cast film obtained by forming the liquid composition into a film by a solution casting method. The present inventors have conducted intensive studies to overcome the problems of the prior art, and as a result, as a thermoplastic norbornene-based resin, a thermoplastic norbornene-based resin having an aromatic ring structure (that is, an aromatic ring-containing norbornene-based resin). (1) a solution casting method using a halogenated hydrocarbon solvent, which is easily dissolved or finely dispersed in a low-boiling and flame-retardant halogenated hydrocarbon solvent such as methylene chloride. (2) The use of halogenated hydrocarbon solvents eliminates the need for explosion-proof equipment and reduces the amount of residual solvent in a short time compared to hydrocarbon solvents. That it can be manufactured, and (3) the resulting cast film is
The inventors have found that the present invention has excellent properties such as water resistance, moisture resistance, physical strength, heat resistance, and transparency, and have completed the present invention.

[0007]

Thus, according to the present invention, there is provided a liquid composition obtained by dissolving or dispersing an aromatic ring-containing norbornene-based polymer in a halogenated hydrocarbon solvent. Further, according to the present invention, there is provided a cast film obtained by casting a liquid composition obtained by dissolving or dispersing an aromatic ring-containing norbornene-based polymer in a halogenated hydrocarbon solvent on a carrier and drying and removing the solvent. You. further,
The present invention provides a cast film, characterized in that a liquid composition obtained by dissolving or dispersing an aromatic ring-containing norbornene polymer in a halogenated hydrocarbon solvent is cast on a support, and then the solvent is removed by drying. It relates to a manufacturing method.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Aromatic ring-containing norbornene-based polymer (1) Polymer and monomer The aromatic ring-containing norbornene-based polymer used in the present invention is a norbornene-based polymer and has at least one polymer in a molecule. There is no particular limitation as long as it has two aromatic rings, but a polymer containing an aromatic ring-containing monomer unit is preferably used. Examples of the aromatic ring-containing monomer include, for example, an aromatic ring-containing norbornene-based monomer and an aromatic vinyl compound. Among these, in order to increase the content of the aromatic ring and the content of the norbornene-based monomer unit, the aromatic ring-containing monomer is used. Norbornene monomers are preferred.

Examples of the aromatic ring-containing norbornene-based polymer having an aromatic ring-containing monomer unit include a ring-opened polymer of an aromatic ring-containing norbornene-based monomer, an aromatic ring-containing norbornene-based monomer and a norbornene-based monomer containing no aromatic ring. And hydrogenated products thereof. Examples of the aromatic ring-containing norbornene-based polymer include (i) an addition polymer of an aromatic ring-containing norbornene-based monomer and an aromatic vinyl compound, (ii) an aromatic ring-containing norbornene-based monomer, and a norbornene-based monomer containing no aromatic ring. An addition polymer of an aromatic vinyl compound, (iii) an addition polymer of an aromatic ring-free norbornene-based monomer and an aromatic vinyl compound, and (i)
v) An addition polymer of an aromatic ring-containing norbornene-based monomer and a vinyl compound (eg, ethylene) other than the aromatic vinyl compound can be used.

In the above-mentioned hydrogenated product, the carbon-carbon double bond in the main chain may be hydrogenated to a hydrogenation rate of 99% or more, but not all aromatic rings are hydrogenated. . The hydrogenation rate of the aromatic ring is appropriately selected depending on the content of the aromatic ring-containing monomer, but is usually 90% or less, preferably 80% or less, and more preferably 70% or less. As the aromatic ring-containing norbornene-based monomer,
There is no particular limitation. For example, JP-A-5-97719, JP-A-7-41550, and JP-A-8-72
No. 210 can be used. That is, as the aromatic ring-containing monomer, typically, a compound represented by the following formula (I) can be used.

[0011]

Embedded image In the formula (I), the meaning of each symbol is as follows. m: 0, 1 or 2. h: 0, 1 or 2. j: 0, 1 or 2. k: 0, 1 or 2. R ^{1 to} R ¹¹ each independently represent a hydrogen atom, a hydrocarbon group,
And an atom or group selected from the group consisting of a polar group such as a halogen atom, an alkoxy group, a hydroxyl group, an ester group (eg, an alkyl ester group), a cyano group, an amide group, an imide group, and a silyl group; Represents a substituted hydrocarbon group. R ^{12 to} R ²⁰ each independently represent a hydrogen atom, a hydrocarbon group,
And an atom or group selected from the group consisting of a polar group such as a halogen atom, an alkoxy group, a hydroxyl group, an ester group (eg, an alkyl ester group), a cyano group, an amide group, an imide group, and a silyl group; Represents a substituted hydrocarbon group. In the formula (I), the carbon atom to which R ¹⁰ and R ¹¹ are bonded and the carbon atom to which R ¹⁴ is bonded or the carbon atom to which R ¹² is bonded are directly or a carbon atom having 1 to 3 carbon atoms. May be bonded via an alkylene group of When j = k = 0, R ¹⁶ and R ¹³ or R ¹⁶
And R ²⁰ may combine with each other to form a monocyclic or polycyclic aromatic ring.

The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As the hydrocarbon group, for example, a group having 1 to 2 carbon atoms
0, preferably 1-10, more preferably 1-6 alkyl groups, having 2-20 carbon atoms, preferably 2-10,
More preferably, it has 2 to 6 alkenyl groups and 2 carbon atoms.
-20, preferably 2-10, more preferably 2-6 alkynyl groups, having 2-20 carbon atoms, preferably 2-20
10, more preferably 2 to 6 alkylidene groups, 3 to 15 carbon atoms, preferably 3 to 8, more preferably 5 to 5
And a cycloalkyl group having 6 and an aromatic hydrocarbon group having 6 to 20, preferably 6 to 16, and more preferably 6 to 10 carbon atoms. Examples of the hydrocarbon group substituted with a polar group include a halogenated alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms.

Examples of such an aromatic ring-containing norbornene-based monomer include, for example, 5-phenyl-bicyclo [2.
2.1] Hept-2-ene (5-phenyl-2-norbornene), 5-methyl-5-phenyl-bicyclo [2.
2.1] Hept-2-ene, 5-benzyl-bicyclo [2.2.1] hept-2-ene, 5-tolyl-bicyclo [2.2.1] hept-2-ene [5- (4 -Methylphenyl) -2-norbornene], 5- (ethylphenyl) -bicyclo [2.2.1] hept-2-ene, 5-
(Isopropylphenyl) -bicyclo [2.2.1] hept-2-ene, 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-benzyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene, 8-
Tolyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-dodecene, 8- (ethylphenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8
-(Isopropylphenyl) -tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-diphenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene, 8- (biphenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
(Β-naphthyl) -tetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 8- (α-naphthyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene, 8- (anthracenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 11
-Phenyl-hexacyclo [6.6.1.1 ^3,6 .
0 ^2,7 . 0 ^9,14] -4-heptadecene, 6- (alpha-naphthyl) - bicyclo [2.2.1] - hept-2-ene, 5
-(Anthracenyl) -bicyclo [2.2.1] -hept-2-ene, 5- (biphenyl) -bicyclo [2.
2.1] -Hept-2-ene, 5- (β-naphthyl)-
Bicyclo [2.2.1] -hept-2-ene, 5,6-
Norbornene-based monomers having an aromatic substituent such as diphenyl-bicyclo [2.2.1] -hept-2-ene, 9- (2-norbornen-5-yl) -carbazole; 1,4-methano-1, 4,4a, 4b, 5,8,8
a, 9a-octahydrofluorenes; 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,
4-methano-8-methyl-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-8-chloro-1,
1,4-methano-1,4,4a, 9a- such as 4,4a, 9a-tetrahydrofluorene and 1,4-methano-8-bromo-1,4,4a, 9a-tetrahydrofluorene
Tetrahydrofluorenes, 1,4-methano-1,4,
4a, 9a-tetrahydrodibenzofurans, 1,4-
Methano-1,4,4a, 9a-tetrahydrocarbazole, 1,4-methano-9-phenyl-1,4,4a, 9
1,4-methano- such as a-tetrahydrocarbazole
1,4,4a, 9a-tetrahydrocarbazoles,
1,4-methano-1, such as 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene,
4,4a, 5,10,10a-hexahydroanthracenes, 7,10-methano-6b, 7,10,10a-tetrahydrofluorancenes, (cyclopentadiene-
Acenaphthylene adduct) to which cyclopentadiene is further added, 11,12-benzo-pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, 11,12-benzo-pentacyclo [6.6.
1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene, 1
4,15-benzo-heptacyclo [8.7.0.1
^2,9 . ^14,7 . 1 ^11,17 . 0 ^3,8 . 0 ^12,16 ] -5-eicosene, cyclopentadiene-acenaphthylene adduct, and the like. These aromatic ring-containing norbornene-based monomers include, in addition to the compounds of the above specific examples, alkyl, alkylidene, and alkenyl-substituted derivatives, and halogen, hydroxyl, and ester groups (eg, alkyl ester groups) of these substituted or unsubstituted compounds. And a polar substituent such as an alkoxy group, a cyano group, an amide group, an imide group or a silyl group.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene and p-methylstyrene.
-Methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene and the like. These aromatic ring-containing monomers can be used alone or in combination of two or more. The content (bonding amount) of the aromatic ring-containing monomer unit in the aromatic ring-containing norbornene-based polymer is
It is appropriately selected according to the purpose of use.
Or more, preferably 30% by weight or more, more preferably 50% by weight.
% By weight or more. By containing the aromatic ring-containing monomer unit, the dispersibility of various compounding agents is improved to a high degree.

Other norbornene monomers containing no aromatic ring include, for example, JP-A-2-227424.
JP, JP-A-2-276842 and JP-A-8-276842
Known monomers disclosed in, for example, JP-A-72210 can be used. The norbornene-based monomer containing no aromatic ring is typically a compound represented by the following formula (II).

[0016]

Embedded image In the formula (II), the meaning of each symbol is as follows. n is 0 or 1. p: 0 or an integer of 1 to 4; s: 0 or 1 q is 0 or 1. r: 0 or 1. R _{1 to} R ₂₀ each independently represent a hydrogen atom, a hydrocarbon group,
And an atom or group selected from the group consisting of polar groups such as a halogen atom, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, and a silyl group, and a hydrocarbon group substituted with these polar groups. . R _{a to} R _d each independently represent a hydrogen atom, a hydrocarbon group,
And an atom or group selected from the group consisting of polar groups such as a halogen atom, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, and a silyl group, and a hydrocarbon group substituted with these polar groups. . In the formula (II), R _{15 to} R ₁₈ may combine with each other to form an unsaturated bond, a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring has a double bond. May be. R ₁₅ and R ₁₆ or R ₁₇ and R ₁₈ may form an alkylidene group. When q or r is 0, each bond is bonded to form a 5-membered ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group include, for example, those having 1 to 2 carbon atoms.
0, preferably 1-10, more preferably 1-6 alkyl groups, having 2-20 carbon atoms, preferably 2-10,
More preferably, it has 2 to 6 alkenyl groups and 2 carbon atoms.
-20, preferably 2-10, more preferably 2-6 alkynyl groups, 3-15 carbon atoms, preferably 3-5 carbon atoms.
8, more preferably 5 to 6 cycloalkyl groups, and 6 to 20 carbon atoms, preferably 6 to 16 and more preferably 6 to 10 aromatic hydrocarbon groups. Examples of the hydrocarbon group substituted with a polar group include a halogenated alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms.

Specific examples of the norbornene monomer having no aromatic ring include, for example, norbornene, its alkyl, alkylidene, aromatic substituted derivatives, and halogen, hydroxyl, ester, alkoxy, and substituted or unsubstituted norbornene. Examples include polar group substituents such as a cyano group, an amide group, an imide group, and a silyl group.
More specifically, for example, 2-norbornene [that is, bicyclo [2.2.1] hept-2-ene], 5-
Methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5
-Cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-hexyl-2-
Norbornene, 5-octyl-2-norbornene, 5-
Octadecyl-2-norbornene and the like can be mentioned.

Further, other specific examples include a monomer obtained by adding one or more cyclopentadiene to norbornene, a derivative or a substitution product thereof similar to the above, and more specifically, for example, 1,4: 5,8 -Dimethano-1,2,3,
4,4a, 5,8,8a-2,3-cyclopentadienonaphthalene, 6-methyl-1,4: 5,8-dimethano-
1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4: 5,10: 6,9-trimethano-
1,2,3,4,4a, 5,5a, 6,9,9a, 1
0,10a-dodecahydro-2,3-cyclopentadienoanthracene and the like; a monomer having a polycyclic structure which is a multimer of cyclopentadiene, and derivatives and substituted products thereof as described above;
More specifically, dicyclopentadiene, 2,3-dihydrodicyclopentadiene, etc .; adducts of cyclopentadiene with tetrahydroindene, etc., and the same derivatives and substitutes thereof as described above, more specifically, 1,4 Methano-1,
4,4a, 4b, 5,8,8a, 9a-octahydrofluorene, 5,8-methano-1,2,3,4,4a,
5,8,8a-octahydro-2,3-cyclopentadienonaphthalene; and the like.

The content (bonding amount) of norbornene-based monomer (aromatic ring-containing and / or other norbornene-based monomer) unit in the aromatic ring-containing norbornene-based polymer is as follows:
It is appropriately selected according to the purpose of use, but is usually at least 30% by weight, preferably at least 50% by weight, more preferably at least 70% by weight. If the content of the norbornene-based monomer is excessively small, characteristics such as electric properties, heat resistance, chemical resistance, and mechanical strength may be insufficient, which is not preferable.

Examples of the vinyl compound other than the aromatic vinyl compound include ethylene, propylene, 1-butene,
1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4, 4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3
-Ethyl-1-hexene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene,
2 to 2 carbon atoms such as 1-octadecene and 1-eicosene
0 ethylene or α-olefin; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene,
3a, 5,6,7a-tetrahydro-4,7-methano-
Cycloolefins such as 1H-indene; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene and 1,7-octadiene; These vinyl compounds can be used alone or in combination of two or more.

(2) Polymerization Method The ring-opening polymer or ring-opening copolymer of the norbornene-based monomer can be obtained by a known polymerization method. As the ring-opening polymerization catalyst, ruthenium, rhodium, palladium,
A catalyst comprising a metal halide, nitrate or acetylacetone compound selected from osmium, iridium, and platinum and a reducing agent; or a metal halide or acetylacetone compound selected from titanium, vanadium, zirconium, tungsten, and molybdenum And a catalyst comprising an organometallic compound such as an organoaluminum compound or an organotin; a shrock type (JP-A-7-179575) or a Grubbs type (J. Am. Che)
m. Soc. , 1986, 733); and a living ring-opening metathesis catalyst.

A third component can be added to the above-mentioned catalyst system to enhance polymerization activity and selectivity of ring-opening polymerization. Specific examples include molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound, halogen-containing compound, molecular iodine, and other Lewis. Acids and the like. As the nitrogen-containing compound, an aliphatic or aromatic tertiary amine is preferable, and specific examples include triethylamine, dimethylaniline, tri-n-butylamine, pyridine, α-picoline and the like.

The ring-opening (co) polymerization can be carried out without using a solvent, but can be carried out in an inert organic solvent. As the solvent, for example, benzene, toluene, aromatic hydrocarbons such as xylene, n-pentane, hexane,
Examples thereof include aliphatic hydrocarbons such as heptane, alicyclic hydrocarbons such as cyclohexane, halogenated hydrocarbons such as styrene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, dichlorobenzene, and trichlorobenzene. The polymerization temperature is usually -50C to 100C, preferably -30C to 80C,
More preferably -20 ~ 60 ℃, the polymerization pressure,
Usually 0 to 50 kg / cm ² , preferably 0 to 20 kg
/ Cm ² .

In order to produce an addition copolymer of a norbornene monomer with an aromatic vinyl compound and / or a vinyl compound other than the aromatic vinyl compound, a known method can be employed. A method of copolymerizing in a hydrogen solvent or in the absence of a solvent in the presence of a catalyst comprising a vanadium compound and an organoaluminum compound, preferably a halogen-containing organoaluminum compound, soluble in a solvent or a norbornene-based monomer. be able to. Examples of the hydrocarbon catalyst include aliphatic hydrocarbons such as hexane, heptane, octane, and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, and xylene. The polymerization temperature is usually
The polymerization temperature is usually 50 to 100 ° C, preferably -30 to 80 ° C, more preferably -20 to 60 ° C, and the polymerization pressure is usually 0 to 50 kg / cm ² , preferably 0 to 20 kg / cm ² .
cm ² .

(3) Hydrogenation Method The hydrogenated polymer (hydrogenated product) of an aromatic ring-containing norbornene-based polymer is prepared by subjecting a ring-opened polymer or a ring-opened copolymer to a hydrogenation catalyst in the usual manner. , Hydrogenation with hydrogen. As a hydrogenation catalyst,
Catalyst comprising a combination of a transition metal compound and an alkyl metal compound, for example, cobalt acetate / triethyl aluminum, nickel acetylacetonate / triisobutyl aluminum, titanocene dichloride / n-butyl lithium, zirconocene dichloride / sec-butyl lithium, tetrabutoxy titanate / A combination of dimethylmagnesium and the like can be given. Further, a Wilkinson complex may be used.

The hydrogenation reaction is usually carried out in an inert organic solvent. As the organic solvent, a hydrocarbon-based solvent is preferable, and a cyclic hydrocarbon-based solvent is more preferable, because the resulting hydrogenated product is excellent in solubility. Examples of such hydrocarbon solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as n-pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decalin; and tetrahydrofuran and ethylene glycol dimethyl ether. Ethers; and the like, and two or more of these can be used as a mixture. Usually, it may be the same as the polymerization reaction solvent, and the reaction may be carried out by adding a hydrogenation catalyst to the polymerization reaction solution as it is.

It is preferable that the aromatic ring-containing norbornene polymer used in the present invention has high weather resistance and light deterioration resistance. Therefore, the ring-opened (co) polymer has an unsaturated bond in the main chain structure. Usually, 95% or more, preferably 98% or more, more preferably 99% or more is preferably saturated. In order to achieve the object of the present invention, it is desirable that at least 20%, preferably 30% or more, preferably 40% or more of the aromatic ring structure remain. The unsaturated bond in the main chain structure and the unsaturated bond in the aromatic ring structure are ¹ H
-It can be distinguished and recognized by analysis by NMR. In order to mainly hydrogenate unsaturated bonds in the main chain structure, at a temperature of -20 ° C to 120 ° C, preferably 0 to 100 ° C, more preferably 20 to 80 ° C, 0.1 to 50 kg
/ Cm ² , preferably 0.5 to 30 kg / cm ² , more preferably 1 to 20 kg / cm ² .

(4) Norbornene Polymer Containing Aromatic Ring The norbornene polymer containing an aromatic ring used in the present invention is not particularly limited except that it has an aromatic ring, and is appropriately selected depending on the purpose of use. However, usually, a thermoplastic polymer is used. The molecular weight of the aromatic ring-containing norbornene-based polymer is not particularly limited and may be appropriately selected depending on the purpose of use.
A polystyrene-equivalent number average molecular weight (Mn) by chromatography (GPC) or a polyisoprene-equivalent number average molecular weight (Mn) by GPC using cyclohexane as a solvent when not dissolved in toluene, usually 50.
0 to 500,000, preferably 1,000 to 100,
000, more preferably from 2,000 to 50,000, most preferably from 5,000 to 35,000.
When the number average molecular weight of the aromatic ring-containing norbornene-based polymer is within this range, the mechanical strength and the moldability are highly balanced and suitable.

The molecular weight distribution of the aromatic ring-containing norbornene-based polymer is not particularly limited, but the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) by the GPC method under the above conditions is not limited. , Usually 4.0 or less, preferably 3.
When the value is 0 or less, more preferably 2.5 or less, the mechanical strength is highly enhanced, which is preferable. The glass transition temperature (Tg) of the aromatic ring-containing norbornene-based polymer is appropriately selected according to the purpose of use, but is usually 50 to 300 ° C, preferably 100 to 250 ° C, and more preferably 120 to 200 ° C.
The range of ° C. is suitable because heat resistance and moldability are highly balanced. These aromatic ring-containing norbornene polymers can be used alone or in combination of two or more.

In the present invention, a rubbery polymer or other thermoplastic resin can be added to the aromatic ring-containing norbornene-based polymer, if necessary. The rubbery polymer is a polymer having a glass transition temperature of 0 ° C. or less,
Conventional rubbery polymers and thermoplastic elastomers are included. Mooney viscosity of rubbery polymer (ML _{1 + 4} , 100
C) is appropriately selected according to the purpose of use, and is usually 5 to 20
0.

Examples of the rubbery polymer include ethylene-α-olefin-based rubbery polymers; ethylene-α-olefin-polyene copolymer rubbers; and ethylene and unsaturated monomers such as ethylene-methyl methacrylate and ethylene-butyl acrylate. Copolymer with carboxylic acid ester; Copolymer of ethylene and fatty acid vinyl such as ethylene-vinyl acetate; Acrylic acid such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate Alkyl ester polymer; polybutadiene, polyisoprene, styrene-butadiene or styrene-isoprene random copolymer, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene- (meth) acrylic acid alkyl ester copolymer Polymer, butadiene- (meth)
Diene rubbers such as alkyl acrylate-acrylonitrile copolymer, butadiene-alkyl (meth) acrylate-acrylonitrile-styrene copolymer; and butylene-isoprene copolymer.

As the thermoplastic elastomer, for example,
Aromatic vinyl-conjugated diene block copolymers such as styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, low Crystalline polybutadiene resin, ethylene-
Examples include propylene elastomer, styrene graft / ethylene-propylene elastomer, thermoplastic polyester elastomer, and ethylene ionomer resin. Among these thermoplastic elastomers, preferred are hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, and the like. Specifically, JP-A-2-133406,
JP-A-2-305814, JP-A-3-72512
And Japanese Patent Application Laid-Open No. 3-74409.

As other thermoplastic resins, for example,
Low density polyethylene, high density polyethylene, linear low density polyethylene, ultra low density polyethylene, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, polystyrene, polyphenylene sulfide, polyphenylene ether, polyamide, polyester, polycarbonate, Cellulose triacetate and the like can be mentioned. These rubbery polymers and other thermoplastic resins can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range that does not impair the object of the present invention.

Liquid Composition The liquid composition of the present invention can be obtained by dissolving or finely dispersing the aromatic ring-containing norbornene-based polymer in a halogenated hydrocarbon solvent. The method of dissolving or dispersing may be in accordance with a conventional method, and the temperature for dissolving or dispersing may be either room temperature or high temperature, and a homogeneously dissolved or uniformly dispersed product can be obtained by sufficiently stirring.

The halogenated hydrocarbon solvent is not particularly limited and may be appropriately selected depending on the production conditions of the cast film and the like. The boiling point is usually 100 ° C. or lower, preferably 70 ° C. or lower, more preferably 50 ° C. or lower. The following are
This is preferable because drying can be performed under a mild temperature condition in a short time in the drying step. Specific examples of the halogenated hydrocarbon solvent include, for example, methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride, etc. Among them, methylene chloride, which is flame-retardant and has a low boiling point, is particularly preferable. These halogenated hydrocarbon solvents can be used alone or in combination of two or more.

In the present invention, the halogenated hydrocarbon solvent may contain, if necessary, aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic hydrocarbons such as cyclohexane; esters such as butyl acetate; Other solvents such as ethers such as tetrahydrofuran and dimethoxyethane; alcohols such as methanol, ethanol and isopropanol; ketones such as methyl ethyl ketone; can be used in combination. These other solvents can be used alone or in combination of two or more, and the mixing amount is appropriately selected within a range not to impair the object of the present invention.

The concentration of the aromatic ring-containing norbornene-based polymer in the halogenated hydrocarbon solvent is appropriately selected depending on the thickness of the film to be produced, but is usually 0.1 to 60 based on the total amount of the liquid composition. % By weight, preferably 1 to 50% by weight,
More preferably, it is in the range of 5 to 45% by weight. When the concentration of the aromatic ring-containing norbornene-based polymer is in this range, the thickness of the film can be easily adjusted, and the film-forming property is excellent and suitable. To the aromatic ring-containing norbornene-based polymer used in the present invention, various additives generally used in the field of the norbornene-based polymer can be added, if desired.

Examples of the compounding agents include antioxidants; ultraviolet absorbers; leveling agents; pigments; dyes; esters of aliphatic alcohols, partial esters and partial ethers of polyhydric alcohols, natural oils, synthetic oils, waxes and the like. Lubricants; flame retardants; antistatic agents; fillers and the like.
These compounding agents can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range not to impair the object of the present invention. The following are some specific examples of the compounding agents. Examples of the stabilizer include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Among these, phenol-based antioxidants are preferable, and alkyl-substituted phenol-based antioxidants are particularly preferable. preferable.

As the phenolic antioxidant, conventionally known ones can be used. For example, 2-t-butyl-6-
(3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-
t-Amyl-6- (1- (3,5-di-t-amyl-2)
-Hydroxyphenyl) ethyl) phenyl acrylate and the like.
Acrylate compounds described in 68643;
2,6-di-t-butyl-4-methylphenol, 2,
6-di-t-butyl-4-ethylphenol, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6 t-butylphenol), 4,4 '
-Butylidene-bis (6-t-butyl-m-cresol), 4,4'-thiobis (3-methyl-6-t-butylphenol), bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane , 3,9-bis (2- (3- (3-t-butyl-4-hydroxy-5-
Methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5) -T-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, tetrakis (methylene-3- (3 ', 5'-
Di-tert-butyl-4'-hydroxyphenyl) propionate) methane [that is, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]], triethylene glycol bis (3- (3-tert-butyl-4-hydroxy-5
Alkyl-substituted phenolic compounds such as -methylphenyl) propionate) and tocopherol; 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4
-Bis-octylthio-1,3,5-triazine, 6-
(4-hydroxy-3,5-dimethylanilino) -2,
4-bis-octylthio-1,3,5-triazine, 6
-(4-hydroxy-3-methyl-5-tert-butylanilino) -2,4-bis-octylthio-1,3,5-triazine, 2-octylthio-4,6-bis- (3,5
-Di-t-butyl-4-oxyanilino) -1,3,5
A phenolic compound containing a triazine group such as triazine;

The phosphorus-based antioxidant is not particularly limited as long as it is commonly used in the general resin industry. For example, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris (Nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-
Di-t-butylphenyl) phosphite, tris (2-
t-butyl-4-methylphenyl) phosphite, tris (cyclohexylphenyl) phosphite, 2,2-
Methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 9,10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide, 1
0- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9 Monophosphite compounds such as -oxa-10-phosphaphenanthrene;
4'-butylidene-bis (3-methyl-6-t-butylphenyl-di-tridecyl phosphite), 4,4'-
Isopropylidene-bis (phenyl-di-alkyl (C
₁₂ -C ₁₅₎ phosphite), 4,4'-isopropylidene - bis (diphenyl monoalkyl (C ₁₂ -C ₁₅₎ phosphite), 1,1,3-tris (2-methyl-4-di - tri Decyl phosphite-5-t-butylphenyl)
Butane, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphite, cyclic neopentanetetraylbis (octadecylphosphite), cyclic neopentanetetraylbis (isodecylphosphite) Phyto), cyclic neopentanetetraylbis (nonylphenyl phosphite), cyclic neopentanetetraylbis (2,4-di-
diphosphites such as t-butylphenylphosphite), cyclic neopentanetetraylbis (2,4-dimethylphenylphosphite), and cyclic neopentanetetraylbis (2,6-di-t-butylphenylphosphite) And the like. Among these, monophosphite compounds are preferred, and tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and the like are particularly preferred.

Examples of the sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3 , 3'-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl)-
2,4,8,10-tetraoxaspiro [5,5] undecane and the like. These antioxidants can be used alone or in combination of two or more. The compounding amount of the antioxidant is usually 0.001 to 100 parts by weight of the aromatic ring-containing norbornene-based polymer.
To 5 parts by weight, preferably 0.01 to 1 part by weight.

Examples of the ultraviolet absorber include, for example,
2,2,6,6-tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4) -Piperidyl) -2- (3,5-di-t
-Butyl-4-hydroxybenzyl) -2-n-butylmalonate, 4- (3- (3,5-di-tert-butyl-4)
-Hydroxyphenyl) propionyloxy) -1-
(2- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl) -2,2
Hindered amine UV absorbers such as 6,6-tetramethylpiperidine; 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5 -Chlorobenzotriazole, 2- (3,5-di-t-butyl-
Benzotriazole ultraviolet absorbers such as 2-hydroxyphenyl) -5-chlorobenzotriazole and 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole; 2,4-di-t-butyl Phenyl-
Bezoate UV absorbers such as 3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate;
And the like. These ultraviolet absorbers can be used alone or in combination of two or more. The amount of the ultraviolet absorber is usually 10 to 100,0.
It is in the range of 00 ppm, preferably 100 to 10,000 ppm.

As the leveling agent for reducing the surface roughness, for example, a coating leveling agent such as a fluorine-based nonionic surfactant, a special acrylic resin-based leveling agent, and a silicone-based leveling agent can be used. Those having good compatibility with the solvent are preferable, and the addition amount is usually 5 to 50,000 ppm, preferably 10 to 2 ppm.
0.00000 ppm. Examples of the antistatic agent include an alkylsulfonic acid sodium salt and / or an alkylsulfonic acid phosphonium salt, and a fatty acid ester hydroxyamine-based compound such as a glycerin ester of stearic acid. These antistatic agents can be used alone or in combination of two or more. The compounding amount of the antistatic agent is usually 0 to 100 parts by weight of the aromatic ring-containing norbornene-based polymer.
-5 parts by weight.

As the organic or inorganic filler, for example, titanium oxide, magnesium oxide, calcium oxide,
Aluminum hydroxide, calcium hydroxide, magnesium hydroxide, magnesium carbonate, calcium carbonate, basic magnesium carbonate, basic calcium carbonate, calcium sulfate, barium sulfate, magnesium sulfate, calcium sulfite, calcium silicate, magnesium silicate, titanate Potassium, calcium titanate, silica, diatomaceous earth, alumina, pumice powder, pumice balloon, talc, clay, glass, dolomite, zinc oxide, carbon black, mica, asbestos, glass fiber, glass flake, glass beads, montmorillonite, bentonite , Graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, polyamide fiber and the like. These fillers can be used alone or in combination of two or more. The blending amount of the filler is appropriately selected according to the purpose of use, but is usually 0.1 to 100 parts by weight of the aromatic ring-containing norbornene-based polymer.
The range is from 01 to 50 parts by weight, preferably from 0.1 to 40 parts by weight, more preferably from 0.5 to 30 parts by weight.

Cast Film The cast film of the present invention can be obtained by casting the above liquid composition on a suitable carrier, and then drying and removing the solvent. As a carrier,
There is no particular limitation, and those used in a general solution casting method are used, for example, a glass plate, a metal drum, a steel belt, a polyester film, a polyvinyl chloride film, a polytetrafluoroethylene belt, polyethylene terephthalate, and a metal. A flat plate such as a foil or a roll may be used.

The method for casting the liquid composition on the carrier is not particularly limited, and a general solution casting method can be used. Specifically, the liquid composition can be cast using a bar coater, a T-die, a T-die with a bar, a doctor knife, a Meier bar, a roll coat, a die coat, or the like. The liquid composition may be cast by spraying, brushing, rolling, spin coating, dipping, or the like. If the desired film thickness cannot be obtained by one coating, the coating can be repeated.

The drying and removal of the solvent is not particularly limited.
It can be made according to a conventional method, but the residual solvent concentration is 5% by weight or less,
When it is preferably 2% by weight or less, more preferably 1% by weight or less, and most preferably 0.5% by weight or less,
Usually, drying is performed in two or more stages. First, as the first stage of drying, the film on a flat plate or a roll is heated from room temperature to
Dry at 100 ° C., preferably at room temperature to 80 ° C., until the residual solvent temperature is 10% by weight or less, preferably 5% by weight or less. In this case, if the drying temperature is too high,
As the solvent evaporates, the film foams. Next, the film is peeled off from the flat plate or roll, and as a second stage of drying, the temperature is raised from room temperature to 60 ° C. or higher, preferably from 70 ° C. to the glass transition temperature (Tg) of the resin,
Dry until the residual solvent concentration is 2% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less.

If the drying temperature is too low, drying does not proceed, and if the temperature is too high, foaming tends to occur. The first stage of drying is performed, and after the drying is completed, the sheet is peeled off from a flat plate or a roll.
Even after the drying in the step or after the drying in the first step, the sheet is cooled once, and the sheet is peeled off from the flat plate or the roll.
Stepwise drying may be performed. The drying of the solvent can be performed under reduced pressure, if necessary.

In the present invention, the cast film obtained as described above may be subjected to the following treatment. That is, after contacting the cast film with a mixed solvent consisting of 25 to 100% by weight of a good solvent with respect to the aromatic ring-containing norbornene-based polymer and 0 to 75% by weight of poor solvent with respect to the aromatic ring-containing norbornene-based polymer, This is a method of contacting a solvent composed of a poor solvent for the norbornene-based polymer. Here, examples of the good solvent for the aromatic ring-containing norbornene-based polymer include methylene chloride, chloroform, cyclohexane, and toluene. Examples of the poor solvent for the aromatic ring-containing norbornene-based polymer include methanol and ethanol. Is mentioned. The temperature when the solution cast film is brought into contact with a mixture of a good solvent and a poor solvent or a poor solvent is usually 25 to 80.
° C, preferably 25 to 60 ° C, and the immersion time is usually 1
About 60 seconds. The thickness of the cast film thus obtained is usually 0.5 μm to 5 mm, preferably 1 μm.
m to 2 mm, more preferably 5 μm to 0.5 mm. When the thickness of the cast film is in this range, drying of the solvent is facilitated and the appearance of the film is also excellent and suitable.

When the cast film produced by the production method of the present invention is used as a protective film for a polarizer, the thickness of the film is usually 5 to 500 μm, preferably 1 to 500 μm.
The range of 0 to 150 μm, more preferably 20 to 100 μm, is suitable because properties such as mechanical strength, transparency, and birefringence are highly balanced. The thickness unevenness of the film is also generally within ± 5%, preferably ± 3%, more preferably ± 2% of the average thickness over the entire surface, but the distortion of the image and the variation of the retardation are small, It is suitable as a protective layer of a polarizing film for a display. Further, the light transmittance of the film is usually 8
0% or more, preferably 85% or more, more preferably 90% or more.
% Or more.

[0052]

The present invention will be specifically described below with reference to Synthesis Examples, Examples and Comparative Examples. The measuring method of the physical properties is as follows. (1) Glass transition temperature The glass transition temperature (Tg) is measured by a differential scanning calorimeter (DSC).
It was measured by the method. (2) Molecular Weight The molecular weight was measured as a value in terms of polystyrene by gel permeation chromatography (GPC) using toluene as a solvent, unless otherwise specified. (3) Hydrogenation rate The hydrogenation rates of the polymer main chain and side chains were measured by ¹ H-NMR. (4) Retardation Retardation was measured with a Beccle Concentrator having a wavelength of 550 nm. (5) Film Thickness The film thickness was measured with a dial-type thickness gauge. (6) Light transmittance The light transmittance was measured at a wavelength of 400 to 700 n using a spectrophotometer.
For the range of m, measure while continuously changing the wavelength,
The minimum transmittance was defined as the light transmittance. (7) Amount of residual solvent The amount of residual solvent in the film was measured by gas chromatography. (8) Water vapor transmission rate (water vapor transmission rate) The water vapor transmission rate of the film is 25 ° C. and 90% RH (relative humidity).
Under the environment of, measured in accordance with JISZ0208,
It is shown in terms of a thickness of m. (9) Endurance Test of Laminated Plate The endurance test of the laminated plate was visually performed after repeating a heat cycle test at 80 ° C., 90% RH and 1 hour for 200 cycles, and evaluated according to the following criteria. ：: When there is no abnormality in both the degree of polarization and visual observation. ×: There is a decrease in degree of polarization and / or bubbles (tunnel) are generated between the adhesive layer and the protective layer. (10) Tensile test Tensile strength and tensile elongation were measured according to JIS K7127.

[Synthesis Example 1] To a 1-liter flask purged with nitrogen, 5 g of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene (hereinafter abbreviated as MTF) and 120 g of toluene were added, and a polymerization catalyst was added. 0.287 mmol of triisobutylaluminum and 0.287 mmol of isobutyl alcohol, and 2.30 mmol of 1-hexene as a molecular weight regulator were added. Here, 0.057 mmol of tungsten hexachloride was added, and the mixture was stirred at 40 ° C. for 5 minutes. Thereafter, 45 g of MTF and 0.086 mmol of tungsten hexachloride were continuously dropped into the system in about 30 minutes, and after the completion of dropping, the mixture was stirred for 30 minutes to complete the polymerization. The polymerization reaction solution was transferred to a 1-liter autoclave, 160 g of toluene was added, and 0.5 g of nickel acetylacetonate and 3 g of triisobutylaluminum were added.
A mixture of 5.15 g of a 0% by weight toluene solution was added, the inside of the reactor was replaced with hydrogen, and the temperature was raised to 80 ° C. while stirring. When the temperature is stable, increase the hydrogen pressure to 30 kg
/ Cm ² and reacted for 3 hours while replenishing hydrogen consumed in the reaction process. Then 4.2 g of water and activated alumina (surface area 320 cm ² / g, pore volume 0.8 cm ³
/ G, average particle size 15 μm, Neobead D powder, manufactured by Mizusawa Chemical Co., Ltd.), and after stirring at 80 ° C. for 1 hour, the solid content was removed by filtration. The mixture was poured into alcohol to precipitate, collected by filtration. The recovered resin was dried at 100 ° C. and 1 Torr or less for 48 hours. The synthesis results are shown in Table 1. This polymer is designated as A.

[Synthesis Example 2] MTF was added to 70% by weight of MTF.
A white powder was obtained in the same manner as in Synthesis Example 1 except that the mixed monomer was changed to a mixed monomer of 30% by weight of dicyclopentadiene (hereinafter abbreviated as DCP). The synthesis results are shown in Table 1.
This polymer is designated as B.

[Synthesis Example 3] MTF was prepared by adding 50% by weight of MTF.
A white powder was obtained in the same manner as in Synthesis Example 1 except that the mixture was replaced with a mixed monomer of DCP and 50% by weight of DCP. The synthesis results are shown in Table 1. This polymer is designated as C.

[Synthesis Example 4] MTF was converted to 5-phenyl-2
A white powder was obtained in the same manner as in Synthesis Example 1 except that -norbornene (hereinafter abbreviated as PNB) was used. The synthesis results are shown in Table 1. This polymer is designated as D.

[Synthesis Example 5] MTF was added to PNB at 70% by weight.
A white powder was obtained in the same manner as in Synthesis Example 1, except that the mixture was changed to a mixed monomer of 30% by weight of tetracyclododecene (hereinafter abbreviated as TCD). The synthesis results are shown in Table 1.
This polymer is designated as E.

[Synthesis Example 6] MTF was added to PNB at 50% by weight.
A white powder was obtained in the same manner as in Synthesis Example 1 except that the mixture was replaced with a mixed monomer of 50% by weight of TCD. The synthesis results are shown in Table 1. This polymer is designated as F.

[Synthesis Example 7] In a 1-liter polymerization vessel purged with nitrogen, a cyclohexane solution of MTF was prepared.
O (OC ₂ H ₅ ) Cl ₂ in cyclohexane and ethyl aluminum sesquichloride [Al (C ₂ H ₅ ) _1.5
Cl _1.5 ] of cyclohexane solution in a polymerization vessel having a concentration of 60 g / l, 0.5 mmol / l, respectively.
The solution was supplied so as to have a concentration of 4.0 mmol / liter, and ethylene was supplied thereto at a rate of 15 liter / Hr, and hydrogen was supplied at a rate of 0.5 liter / Hr. On the other hand, the polymerization solution in the flask was continuously extracted from the upper portion of the polymerization vessel so that the total amount of the polymerization solution was 1 liter and the average residence time was 0.5 hour. The polymerization was terminated by adding a small amount of isopropyl alcohol to the withdrawn polymerization solution, and then mixing the aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid with respect to 1 liter of water and the polymerization solution in a ratio of 1: 1 under strong stirring using a homogenizer. Contact was made and the catalyst residue was transferred to the aqueous phase. The mixture was allowed to stand, and after removing the aqueous phase, the mixture was further washed twice with distilled water to purify and separate the polymerization solution. This polymerization solution was poured into 3 liters of acetone to precipitate, and was collected by filtration. The recovered resin was dried at 100 ° C. and 1 Torr or less for 48 hours to obtain a white powder. The synthesis results are shown in Table 1. This polymer is designated G.

[0060]

[Table 1] (* 1): molar ratio

[Examples 1 to 7] 15 g of each polymer obtained in Synthesis Examples 1 to 7 was dissolved in 85 g of methylene chloride, and 500 ppm of a leveling agent (Fluorard FC-430; manufactured by Sumitomo 3M Limited) and an ultraviolet light stabilizer were added. (Vioso
rb 80; manufactured by Kyodo Pharmaceutical Co.)
A liquid composition was obtained. This was put on a glass plate whose surface was polished, and was 300 mm wide and 500 mm long by a bar coater.
An appropriate amount was cast in mm. This is the first stage of drying,
25 ° C to 60 ° C together with the glass plate in an air circulation type oven
The temperature was raised to 15 ° C. over 15 minutes and dried. Next, as a second stage of drying, the resin film was peeled from the glass plate,
After drying in an oven at ℃ and cooling to room temperature, the surrounding area was cut off by 10 mm to obtain a film having an average thickness of 80 μm. When the physical properties of each film were measured, all of the films were found to have good residual solvent concentration, heat resistance, thickness unevenness, light transmittance, retardation value, water vapor permeability, tensile strength, and tensile elongation. The results are shown in Table 2. A styrene-butadiene rubber-based adhesive (Scotch) is provided on both sides of a PVA polarizing film (thickness: about 100 μm) stretched by adsorbing iodine.
Each of the films having a thickness of 80 μm was laminated as a protective layer using a 3M adhesive for each application (Plastic, Sumitomo 3M Limited). In addition, a thickness of 8 on one side
It was laminated on a 1.2 mm-thick glass substrate via a μm adhesive (Diabond DA 753 manufactured by Nogawa Chemical). Table 2 shows the durability test results of this laminate.

[0062]

[Table 2]

Comparative Example 1 As a polymer, a hydrogenated ring-opening polymer (ZEONEX480 manufactured by Zeon Corporation; number average molecular weight (Mn): 28,500; weight average molecular weight (M
w) is 57,800, the hydrogenation rate of the main chain is 99% or more,
^No absorption peak of the aromatic ring is confirmed by ¹ H-NMR. )
Was tried to be dissolved in methylene chloride in the same manner as in the example, but was not dissolved at all.

Comparative Example 2 As a polymer, a cyclic olefin-based addition polymer (APEL50 manufactured by Mitsui Petrochemical Co., Ltd.)
15; the number average molecular weight (Mn) is 47,200, the weight average molecular weight (Mw) is 83,100, and no absorption peak of aromatic ring is confirmed by ¹ H-NMR. ) Was attempted to be dissolved in methylene chloride in the same manner as in the example, but was not dissolved at all.

[0065]

According to the present invention, water resistance, moisture resistance, physical strength, heat resistance, and optical transparency are obtained by dissolving or dispersing an aromatic ring-containing norbornene polymer in a halogenated hydrocarbon solvent. The present invention can provide a liquid composition that can easily produce a cast film having excellent properties such as properties with a simple production facility. Further, according to the present invention, there is provided a cast film excellent in various physical properties formed by forming a film of such a liquid composition by a solution casting method.
The cast film of the present invention is useful, for example, as a protective layer of a polarizer.

Claims (2)

[Claims] 1. A liquid composition obtained by dissolving or dispersing an aromatic ring-containing norbornene polymer in a halogenated hydrocarbon solvent. 2. A cast film obtained by casting a liquid composition obtained by dissolving or dispersing an aromatic ring-containing norbornene polymer in a halogenated hydrocarbon solvent on a carrier and removing the solvent by drying.