JPH111548A - Norbornene-based polymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To offer a norbornene-based polymer and a method for producing it, suitable for obtaining a polarizing film-protecting film material excellent in light permeability, tensile strength, tensile elongation and resistance to steam permeability, and also in adhesiveness to a PVA film. SOLUTION: This norbornene-based polymer contains (A) 10-90 wt.% of bound norbornene-based monomer units each containing an aromatic ring and (B) 10-90 wt.% of bound norbornene-based monomer units each not containing any aromatic ring, and has the weight average molecular weight(Mw) of 1000-500000 and the ratio of the weight average molecular weight(Mw) to the number average molecular weight(Mn) of <=2.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a norbornene-based polymer which is excellent as a film material having excellent light transmittance, tensile strength, tensile elongation, and resistance to water vapor transmission, and also having excellent adhesion to a polarizing film. And its manufacturing method. Further, the present invention relates to a film useful as a protective film for a polarizing film having excellent light transmittance, tensile strength, tensile elongation, and resistance to water vapor transmission, and also having excellent adhesion to the polarizing film.

[0002]

2. Description of the Related Art Polarizing films make use of various functions such as removal of reflected light and light lock properties, for example, sunglasses, filters for cameras, sports goggles, lighting gloves, anti-glare coatings for automobile headlights, and prevention of indoor see-through. It is used in a wide range of fields, such as a light quantity adjusting filter, a fluorescent display contraster, a continuously changing transmittance plate, and a polarizing film for a microscope. Recently, it is used for a liquid crystal display (LCD), and its functionality has been highlighted. The polarizing film for an LCD has a function of transmitting and shielding light, and has a role of displaying an electric signal together with a liquid crystal that performs a light switching function. In exhibiting such functionality, optical properties, durability,
Other required quality is stricter.

A polarizing film is generally used as a polarizer.
A thin-film type polarizer (polarizing film) is used, and has a structure in which protective layers made of various polymer films are laminated on both surfaces thereof with an adhesive. As the polarizing film, a polarizing film having a structure in which a transparent polymer film is molecularly arranged in a certain direction and a dichroic substance is adsorbed in a gap between micelles is usually used. In such a polarizing film, a thin sheet (film) of polyvinyl alcohol (hereinafter abbreviated as PVA) is widely used as a polymer film serving as a substrate. More specifically, a polarizing film having a structure in which a polarizing element (iodine, dye, etc.) is adsorbed and dispersed on a polarizing substrate made of a PVA film is widely used. A specific example is P
There are PVA-based polarizing films such as VA / iodine-based, PVA / dye-based, and PVA / polyvinylene-based.

However, PVA-based polarizing films have low mechanical strength in the direction of the transmission axis, and are liable to shrink due to heat or moisture or to have a reduced polarizing function. Laminated with an adhesive, which ensures durability and mechanical strength.
This laminate is called a polarizing film or a polarizing plate. The protective layer has, for example, no birefringence, high light transmittance, good moisture resistance and heat resistance, high mechanical strength, a smooth surface, high resolution,
Performance such as good adhesion to the polarizing film and excellent appearance is required. Conventionally, as the protective layer, a solution cast film of cellulose triacetate (hereinafter abbreviated as TAC) having low birefringence and good appearance has been mainly used. However, the PV constituting the polarizing substrate
A film having a water vapor transmission rate of 25 μm
1000 ° C, 90% RH (relative humidity) environment
Whereas a 00g / m ² · 24hr approximately, TAC films of the protective layer, 700g / m ² · 24 under the same conditions
It has a water vapor permeability of about hr and insufficient moisture resistance. Therefore, a polarizing film having a TAC film as a protective layer has poor durability at high temperature and high humidity.
Under an environment of 80 ° C. and 90% RH, it deteriorates in 100 hours or less, and the polarization performance is rapidly lowered.

A TAC film has a tensile strength of 6 to
It is only about 11 kg / mm ² and its physical strength is insufficient. Therefore, a TAC film having a thickness of 50 μm or less has a low strength and durability, and is usually 80 μm or less.
Thicknesses of the order of magnitude are used. As a technique for solving these problems, a composite sheet of a polymer sheet made of a thermoplastic norbornene-based resin and a PVA-based sheet has been developed.
It has been reported that it has excellent properties in light transmittance, appearance, tensile strength, tensile elongation, and water vapor permeability (JP-A-4-339821, JP-A-5-2128).
No. 28). However, this method is inferior in durability because the adhesiveness between the thermoplastic norbornene-based resin sheet and the PVA sheet is not sufficient. In addition, there is an increasing demand for making the protective layer thinner, and it has been desired for the protective film of the polarizing film to have improved mechanical properties such as tensile strength and elongation.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polarizing film protective film which is excellent in light transmittance, tensile strength, tensile elongation, and water vapor transmission resistance, and also has excellent adhesion to a PVA film. An object of the present invention is to provide a norbornene-based polymer suitable as a material and a method for producing the same. Another object of the present invention is to provide a polarizing film protective film which is excellent in light transmittance, appearance, tensile strength, tensile elongation, and water vapor permeability, and which has sufficiently excellent adhesion to a polarizing film. It is to provide a film and a method for producing the film.

The inventors of the present invention have conducted intensive studies to overcome the above-mentioned problems of the prior art. By using a norbornene-based polymer having a unit bond amount, light transmittance,
The present inventors have found that a polymer film having excellent tensile strength, tensile elongation, and resistance to water vapor transmission and excellent adhesion to a PVA film can be obtained, and the present invention has been completed based on the findings.

[0008]

Thus, according to the present invention, the bond amount of the aromatic ring-containing norbornene monomer unit (A) is 10 to 90% by weight and the bond of the aromatic ring-containing norbornene monomer unit (B) is 10 to 90% by weight. And a weight average molecular weight (Mw) of 1,000 to 500,
000, the weight average molecular weight (Mw) and the number average molecular weight (M
A norbornene-based polymer having a ratio (Mw / Mn) to n) of 2.0 or less is provided.

Further, according to the present invention, a ring-opening polymerization of an aromatic ring-containing norbornene monomer (a) and an aromatic ring-containing norbornene monomer (b) in the presence of a metathesis catalyst system is carried out by a metathesis catalyst. The system includes at least one transition metal compound (i), an organoaluminum compound (ii), and an alcohol (iii) selected from the group consisting of W compounds, Mo compounds, and Re compounds, and an organic residue of an alcohol. Wherein the sum of the number of carbon atoms of the organic residue of the organic aluminum compound (ii) and the number of carbon atoms of the organic residue of the alcohol (iii) is 9 or more. A method for producing a norbornene-based polymer is provided.

According to the present invention, the bond amount of the aromatic ring-containing norbornene monomer unit (A) is 10 to 90% by weight and the bond amount of the aromatic ring-containing norbornene monomer unit (B) is 10 to 90% by weight. Weight average molecular weight (M
w) is 1,000 to 500,000, and the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn)
Which is 2.0 or less, comprising a norbornene-based polymer.

According to the present invention, the bond amount of the aromatic ring-containing norbornene monomer unit (A) is 10 to 90% by weight and the bond amount of the aromatic ring-containing norbornene monomer unit (B) is 10 to 90% by weight. Weight average molecular weight (M
w) is 1,000 to 500,000, and the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn)
A solution of a norbornene-based polymer having a value of 2.0 or less is provided.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Norbornene-based Polymer (1) Polymer The norbornene-based polymer of the present invention comprises an aromatic ring-containing norbornene-based monomer unit (A) and an aromatic ring-free norbornene-based monomer unit (B). It is a copolymer containing.
Here, the “monomer unit” means a bonding unit or a repeating unit in a polymer derived from each monomer. As the aromatic ring-containing norbornene-based monomer unit (A),
There is no particular limitation, and examples thereof include a repeating unit represented by the formula (A ₄ ).

[0013]

Embedded image In the formula (A ₄ ), 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. ... : represents a carbon-carbon single bond or a double bond. 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 polar groups 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 polar groups 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 (A ₄ ), 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 carbon atoms. It may be bonded via an alkylene group of the formulas 1 to 3. When j = k = 0, R ¹⁶ and R ¹³ or R
¹⁶ and R ²⁰ are bonded to each other to form a carbon-carbon unsaturated bond,
A monocyclic or polycyclic aromatic ring may be formed.

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, 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. Among the aromatic ring-containing norbornene-based monomer units (A), those represented by the formula (A ₄ ) include, for example, a compound represented by the formula (A _4-1 ) or the formula (A)
_4-2 ) is preferred.

[0016]

Embedded image In the formula (A _4-1 ), the meaning of each symbol is as follows. t: 0 or 1 R ^{21 to} R ²³ each independently represent a hydrogen atom, a carbon number of 1 to 4;
Is a lower alkyl group or a lower alkenyl group having 2 to 4 carbon atoms, and is preferably a hydrogen atom. ... : represents a carbon-carbon single bond or a double bond.

[0017]

Embedded image In the formula (A _4-2 ), the meaning of each symbol is as follows. u is 0 or 1. R ^{24 to} R ²⁷ each independently represent a hydrogen atom, a carbon number of 1 to 4;
Is a lower alkyl group or a lower alkenyl group having 2 to 4 carbon atoms, and is preferably a hydrogen atom. R ²⁴ and R ²⁵ may form a lower alkylidene group having 1 to 4 carbon atoms, and R ²⁴ and R ²⁶ may form a carbon-carbon unsaturated bond. ... : represents a carbon-carbon single bond or a double bond.

The amount of these aromatic ring-containing norbornene-based monomer units (A) in the norbornene-based polymer of the present invention is 10 to 90% by weight, preferably 30 to 85% by weight, more preferably 50 to 80% by weight. % Range. If the bond amount of the aromatic ring-containing norbornene-based monomer unit (A) in the norbornene-based polymer is excessively small, the adhesiveness of the resulting film to the polarizing film is not sufficient. Inferior in mechanical strength characteristics such as elongation, and both are not preferred. The norbornene-based monomer unit (B) having no aromatic ring is not particularly limited, and examples thereof include a repeating unit represented by the formula (B ₄ ).

[0019]

Embedded image In the formula (B ₄ ), the meaning of each symbol is as follows. n is 0 or 1. s: 0 or 1 p: 0, 1 or 2. q is 0 or 1. r: 0 or 1. ... : represents a carbon-carbon single bond or a double bond. 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, a halogen atom, a hydroxyl group, an ester group, an alkoxy group,
An atom or group selected from the group consisting of polar groups such as 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 (B ₄ ), R _{15 to} R ₁₈ may combine with each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring has a double bond. You may. 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, preferably 6 to 16, 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. Norbornene-based monomer unit having no aromatic ring (B), although these formulas (B ₄₎ Among them, for example, represented by the formula (B _4-1) or formula (B _4-2) Are preferred.

[0022]

Embedded image In the formula (B _4-1 ), the meaning of each symbol is as follows. x: 0 or 1. y is 0 or 1. z is 0 or 1. R _{21 to} R ₂₄ each independently represent a hydrogen atom, a carbon number of 1 to 4;
Is a lower alkyl group and a lower alkenyl group having 2 to 4 carbon atoms, and is preferably a hydrogen atom. R _{25 to} R ₂₈ each independently represent a hydrogen atom, a carbon number of 1 to 4;
Is a lower alkyl group or a lower alkenyl group having 2 to 4 carbon atoms. R ₂₅ and R ₂₆ or R ₂₇ and R ₂₈ may form a lower alkylidene group having 1 to 4 carbon atoms, and R ₂₅ and R ₂₇ may form a carbon-carbon unsaturated bond. Good. ... : represents a carbon-carbon single bond or a double bond.

[0023]

Embedded image In the formula (B _4-2 ), the meaning of each symbol is as follows. w: 0 or 1. R _{29 to} R ₃₂ each independently represent a hydrogen atom, a carbon number of 1 to 4;
Is a lower alkyl group or a lower alkenyl group having 2 to 4 carbon atoms. R ₂₅ and R ₂₆ or R ₂₇ and R ₂₈ may form a lower alkylidene group having 1 to 4 carbon atoms, and R ₂₅ and R ₂₇ may form a carbon-carbon unsaturated bond. Good. ... : represents a carbon-carbon single bond or a double bond.

In the norbornene-based polymer of the present invention,
Norbornene monomer units containing no aromatic ring
The bonding amount of (B) is the same as that of the aromatic ring-containing norbornene-based monomer.
Is the remainder of the bond amount of the mer unit (A), usually 10 to 90
% By weight, preferably 15-70% by weight, more preferably
It is in the range of 20 to 50% by weight. The above formula (A_Four), (A
_4-1), (A_4-2), (B_Four), (B_4-1) And (B_4-2)
At...Represents a carbon-carbon single bond (CC)
Or a double bond (C = C). Norbornene of the present invention
-Based polymer is an aromatic ring-containing norbornene-based monomer (a)
And a norbornene-based monomer (b) containing no aromatic ring
Is subjected to ring-opening copolymerization in the presence of a metathesis catalyst system, and
And then hydrogenation. This opening
The ring copolymer has a carbon-carbon double bond in the main chain.
When this ring-opening copolymer is hydrogenated, a double bond in the main chain is formed.
Hydrogenation forms a carbon-carbon single bond. in this case,
If the hydrogenation rate does not reach 100%, carbon-carbon
The single bond and the double bond of coexist....
Of unhydrogenated, hydrogenated, and partially hydrogenated
Represents everything.

The carbon-carbon double bond in the main chain may be hydrogenated at a hydrogenation rate of 95% or more. When a non-conjugated carbon-carbon double bond is present in the side chain, they are similarly hydrogenated at the time of hydrogenation of the double bond in the main chain. Partial hydrogenation is performed so as to fall within the range of the content of the contained norbornene-based monomer unit (A). The hydrogenation will be described later in detail. Further, the more specific contents of the symbols in the other formulas will be described in detail in the description of the method for producing a norbornene-based polymer.

The molecular weight of the norbornene-based polymer of the present invention is 1,000 to 1,000 in terms of polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) using toluene as a solvent.
500,000, preferably 2,000 to 200,00
0, more preferably in the range of 5,000 to 100,000. Weight average molecular weight of the norbornene polymer (M
If w) is too small, the mechanical strength properties are not sufficient. Conversely, if w) is too large, the moldability is poor, and neither is preferred. The molecular weight distribution of the norbornene-based polymer of the present invention is determined by polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (M) measured by GPC using toluene as a solvent.
The ratio (Mw / Mn) to n) is 2.00 or less, preferably 1.95 or less, more preferably 1.90 or less.
If the molecular weight distribution (Mw / Mn) of the norbornene-based polymer is too wide, the mechanical strength characteristics are not sufficient, which is not preferable.

(2) Norbornene-Based Monomer The norbornene-based polymer of the present invention is prepared, for example, by mixing an aromatic ring-containing norbornene-based monomer (a) and a norbornene-based monomer (b) having no aromatic ring in the presence of a metathesis catalyst system. And, if necessary, hydrogenation. As the aromatic ring-containing norbornene-based monomer (a), for example, a compound represented by the formula (A ₁ )

[0028]

Embedded image [Wherein the symbols have the same meanings as in the expression (A ₄ ). ] Can be mentioned.
Further, as a preferable norbornene-based monomer (a), for example, a monomer represented by the formula ( _A1-1 ) or ( _A1-2 ) can be exemplified.

[0029]

Embedded image [Wherein the symbols have the same meaning as in the expression (A _4-1 ). ]

[0030]

Embedded image [In the formula, the meaning of each code is the same as that in the formula (A _4-2 ). ]

An aromatic ring-containing norbornene monomer (a)
Are, for example, 5-phenyl-bicyclo [2.2.1] hept-2-ene (5-phenyl-2-ene)
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.
0.1 ^2,5 . 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, 1
1-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.
12 ⁹ . ^14,7 . 1 ^11,17 . 0 ^3,8 . 0 ^12,16 ] -5-eicosene, cyclopentadiene-acenaphthylene adduct, and the like.

The aromatic ring-containing norbornene-based monomer (a) includes, in addition to the compounds of the above specific examples, alkyl,
Alkylidene, alkenyl-substituted derivatives, and polar substituents of these substituted or unsubstituted compounds such as halogen, hydroxyl, ester (eg, alkyl ester), alkoxy, cyano, amide, imide, and silyl groups. You may. These aromatic ring-containing norbornene monomers (a) can be used alone or in combination of two or more. The amount of the aromatic ring-containing norbornene-based monomer (a) used is appropriately selected so as to be the amount of the aromatic ring-containing norbornene-based monomer unit (A) in the norbornene-based polymer. Examples of the norbornene-based monomer (b) having no aromatic ring include, for example, a compound represented by the formula (B ₁ )

[0033]

Embedded image [Wherein the meanings of the symbols are the same as those in the expression (B ₄ ). ] Can be mentioned.
Further, as preferred norbornene-based monomers (b) having no aromatic ring, for example, a compound represented by the formula ( _B1-1 ) or (B-1)
_Examples of the monomer represented by _1-2 ) can be given.

[0034]

Embedded image [Wherein the symbols have the same meanings as in the equation (B _4-1 ). ]

[0035]

Embedded image [Wherein the symbols have the same meanings as in the equation (B _4-2 ). ]

Examples of the norbornene monomer (b) containing no aromatic ring include, for example, JP-A-2-227424, JP-A-2-276842, and JP-A-8-27642.
Known monomers disclosed in, for example, Japanese Patent No. 72210 can be used. Specific examples of the norbornene-based monomer (b) containing no aromatic ring include, for example, norbornene, its alkyl, alkylidene, aromatic-substituted derivatives, and halogen, hydroxyl, ester, and alkoxy groups of these substituted or unsubstituted norbornenes. Examples of the substituent include polar groups 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, as other specific examples, a monomer obtained by adding one or more cyclopentadiene to norbornene, a derivative or a substituted 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. These norbornene-based monomers (b) not containing an aromatic ring can be used alone or in combination of two or more. The amount of the norbornene-based monomer (b) not containing an aromatic ring is appropriately selected so as to be the bonding amount of the norbornene-based monomer unit (B) not containing an aromatic ring in the norbornene-based polymer.

The norbornene-based polymer of the present invention may contain a copolymerizable vinyl compound binding unit as long as the object of the present invention is not impaired. As the vinyl compound, 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, 1-octadecene,
C2-C20 ethylene or α-olefin such as 1-eicosene; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-
Cyclohexene, cyclooctene, 3a, 5,6,7a
Cycloolefins such as -tetrahydro-4,7-methano-1H-indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene and 1,7-octadiene; Non-conjugated dienes;
Styrene, α-methylstyrene, o-methylstyrene,
aromatic vinyls such as p-methylstyrene, 1,3-dimethylstyrene, and vinylnaphthalene; and the like. These vinyl compounds can be used alone or in combination.
More than one species can be used in combination.

(3) Catalyst and Polymerization Method In the norbornene-based polymer of the present invention, for example, each of the above monomers may be prepared by converting at least one type of transition metal compound (i) selected from the group consisting of (1) compounds of W, Mo and Re. ), An organoaluminum compound (ii) and an alcohol (iii)
Wherein the carbon number of the alcohol (iii) is 2 or more, and the sum of the carbon number of the organic residue of the organoaluminum compound (ii) and the carbon number of the alcohol (iii) is 9 or more, preferably Is 10 to 30, more preferably 12
To 20 and can be obtained by ring-opening copolymerization using a catalyst system of ２０20. Further, the norbornene-based polymer of the present invention is characterized in that each of the above-mentioned monomers is (2) at least one transition metal compound (i) selected from the group consisting of compounds of W, Mo and Re, an organoaluminum compound (ii) and an alcohol. It can be obtained by ring-opening copolymerization using a catalyst system containing (iii) and an oxygen-containing organic compound (iv) other than an alcohol.

The transition metal compound (i) used in the methods (1) and (2) is, for example, WCl ₆ , WC
_{l 5, WCl 4, WCl 2} , WBr 6, WBr 4, WBr 2,
WF ₆ , WF ₄ , WI ₆ , WI ₄ , WOCl ₄ , WOBr ₄ ,
WOF ₄ , W (OC ₆ H ₅ ) ₆ , WCl ₂ (OC ₆ H ₅ ) ₄ , W
(CO) _3. (CH ₃ CN) ₃ , W (OC ₂ H ₅ ) ₂ Cl ₃ ,
W (CO) ₆ , (CO) ₅ WC (OCH ₃ ) (CH ₃ ),
_{(CO) 5 WC (OC 2} H 5) (CH 3), (CO) 5 WC
(OC ₂ H ₅ ) (C ₄ H ₅ ), W (CO) ₃ · (CH ₃ CN)
₃ , MoCl ₅ , MoCl ₄ , MoCl ₃ , MoBr ₄ ,
MoBr ₃ , MoBr ₂ , MoF ₄ , MoOCl ₃ , MoO
F ₃ , Mo (OC ₂ H ₅ ) ₂ Cl ₃ , Mo (OC ₂ H ₅ ) ₅ , M
oO ₂ (acac) ₂ , Mo (CO) ₆ , (CO) ₅ MoC
(OC ₂ H ₅ ) (CH ₃ ); ReCl ₃ , ReOCl ₃ , R
eOBr ₃ , Re ₂ (CO) ₁₆ , ReOBr ₃ · P (C ₆ H
₅ ) ₃ ; Among these, particularly preferred compounds are MoCl ₅ , Mo (OC ₂ H ₅ ) ₂ Cl ₃ ,
WCl ₆ , W (OC ₂ H ₅ ) ₂ Cl _{3 and the} like can be mentioned.

In the method (1), the alcohol (iii) used has two or more carbon atoms, and the organic aluminum (ii) and the alcohol (ii)
It is characterized in that i) is used in a combination such that the total amount of carbon atoms of the organic residue is 9 or more, preferably 10 to 30, and more preferably 12 to 20. Examples of the organoaluminum (ii) include, for example, a compound represented by the formula (1) R ³¹ R ³² R ³³ Al (1) (wherein R ³¹ , R ³² and R ³³ each independently represent
Shows organic residues. ).

The organic residues R ^{31 to} R ³³ include, for example,
Examples include hydrocarbon groups such as an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, and are preferably an alkyl group. The carbon number of R ^{31 to} R ³³ is not particularly limited,
Usually 2 or more, preferably 3 to 20, more preferably 4 to
The range is 10. Specifically, for example, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecanyl, dodecanyl, tridecanyl, tetradecanyl, pentadecanyl, octadecanyl, eicosyl, cyclopentyl, cyclohexyl And the like; an alkenyl group such as propenyl and pentenyl; an alkynyl group such as propargyl; an aryl group such as phenyl, benzyl and naphthyl; Among these, propyl, butyl, isobutyl, sec
-Butyl, pentyl, hexyl, heptyl, octyl,
Nonyl, decanyl and the like are preferred, and butyl, isobutyl, sec-butyl, pentyl, hexyl and the like are particularly preferred.

Preferred specific examples of the organoaluminum (ii) include triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum and the like. These organic aluminums (ii) can be used alone or in combination of two or more. The amount of the organoaluminum (ii) to be used is appropriately selected according to the reaction conditions.
The range is 1: 1000, preferably 1: 2 to 1: 100, more preferably 1: 5 to 1:50.

As the alcohol (iii), for example,
Formula (2) R ³⁴ OH (2) (In the formula, R ³⁴ represents an organic residue having 2 or more carbon atoms.)
It is represented by The number of carbon atoms in R ³⁴ is usually 2 to 20, preferably from 2 to 15, more preferably 3 to 10. R
Examples of the organic residue ³⁴ include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, preferably an alkyl group and an aryl group, and more preferably an alkyl group. Usually a hydrocarbon group, for example, ethyl, propyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecanyl, dodecanyl, tridecanyl, tetradecanyl, pentadecanyl, octadecanyl, eicosyl, cyclopentyl, cyclohexyl and the like An alkenyl group such as propenyl and pentenyl; an alkynyl group such as propargyl; an aryl group such as phenyl, benzyl and naphthyl; Among these, ethyl, propyl, butyl, isobutyl, sec
-Butyl, pentyl, hexyl, heptyl, octyl,
Nonyl, decanyl, phenyl, benzyl and the like are preferable, propyl, butyl, isobutyl, sec-butyl,
Pentyl, hexyl, phenyl and the like are particularly preferred.

Specific examples of preferred alcohols (iii) include, for example, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, pentanol, hexanol, octanol,
Decanol, cyclopentanol, cyclohexanol, phenol, benzyl alcohol and the like,
More preferred are propanol, isopropanol, butanol, pentanol, phenol and the like. These alcohols (iii) can be used alone or in combination of two or more. The amount of the alcohol (iii) to be used is appropriately selected according to the reaction conditions, and is usually 1: 1 in a molar ratio of (i) :( iii).
１ ： 1: 1000, preferably 1: 2 to 1: 100, more preferably 1: 5 to 1:50.

The feature of the production method (1) is that the component (i), the organoaluminum compound (ii) and the alcohol (iii) are used, the alcohol (iii) has 2 or more carbon atoms, and The organic aluminum compound (ii) and the alcohol (iii) are characterized in that the sum of the carbon atoms of the organic residues is 9 or more, preferably 10 to 30, more preferably 12 to 20.
That is, in the general formulas (1) and (2), R ³⁴ has 2 or more carbon atoms, and R ³¹ , R ³² , and R ³³
Organic residue and the sum of the number of carbon atoms of the organic residue R ³⁴ is 9 or more, preferably 10 to 30, more preferably 12 to 20
Range. R ³⁴ has a small number of carbon atoms, or
If the sum of the carbon atoms of R ^{31 to} R ³⁴ is too small, gelation occurs during the polymerization reaction, and the desired norbornene-based polymer cannot be obtained, which is not preferable.

In the production method (2), at least one transition metal compound (i) selected from the group consisting of compounds of W, Mo, and Re as a metathesis catalyst system, an organoaluminum compound (ii), and In addition to the use of the alcohol (iii), the composition contains an oxygen-containing organic compound (iv) other than the alcohol. The metathesis catalyst system comprises (i) component, (ii) component, and (iv)
If only the components are used, gelation is likely to occur during the polymerization reaction,
The desired norbornene-based polymer cannot be obtained, which is not preferable.

The number of carbon atoms of the organic aluminum (ii) and the alcohol (iii) used in the method (2) is not necessarily limited as in the method (1). Examples of the oxygen-containing organic compound (iv) other than the alcohol include, for example,
Ethers, ketones, esters, carboxylic acids and the like can be mentioned. Of these, ether is preferred. Examples of the ether include chain ethers such as dimethyl ether, methyl ethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, dihexyl ether, and anisole; cyclic ethers such as tetrahydrofuran, dioxane, and paraformaldehyde; And the like. These oxygen-containing organic compounds (iv) other than alcohols can be used alone or in combination of two or more. The amount of the component (iv) to be used is appropriately selected according to the reaction conditions.
0, more preferably in the range of 1: 5 to 1:50.

The solvent can be polymerized without using it.
It is preferred to work in an inert organic solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclohexane; styrene dichloride, dichloroethane, dichloroethylene, Halogenated hydrocarbons such as tetrachloroethane, chlorobenzene, dichlorobenzene, and trichlorobenzene; and the like.

The method of preparing these polymerization catalysts is not particularly limited, but in the method (1), after the organoaluminum compound (ii) and the alcohol (iii) are mixed, at least a part of the norbornene monomer is mixed. (1 of the whole monomer
~ 30% by weight, preferably 5-15% by weight)
At least a part of the transition metal compound (i) (usually 10 to 60% by weight, preferably 20 to 50% by weight of the whole catalyst) is added to initiate polymerization, and the remaining norbornene monomer and the transition metal compound (i) are added. And continue the polymerization. In the method (2), a catalyst system is prepared by sequentially mixing an organoaluminum compound (ii), an alcohol (iii), a part of a monomer, and a part of a transition metal compound (i) in that order, and then Then, the remaining monomer and the transition metal compound (i) are propped to carry out polymerization. The polymerization temperature is usually −50 ° C. to 100 ° C., preferably −30 ° C. to 80 ° C., more preferably −20 ° C. to 60 ° C., and the polymerization pressure is usually 0 to 50 kg / cm ² , preferably 0 to 50 kg / cm ² . 20kg /
cm ² .

The ring-opening copolymer of the aromatic ring-containing norbornene monomer (a) represented by the formula (A ₁ ) and the aromatic ring-free norbornene monomer (b) represented by the formula (B ₁ ) is And a polymer containing a repeating unit represented by the following formulas (A ₂ ) and (B ₂ ).

[0052]

Embedded image [Wherein the symbols have the same meaning as in the expression (A ₁ ). ]

[0053]

Embedded image [In the formula, the meaning of each symbol is the same as that in the formula (B ₁ ). ]

(4) Hydrogenation The norbornene-based polymer of the present invention is an unhydrogenated product containing the repeating units represented by the formulas (A ₂ ) and (B ₂ ), A carbon double bond may remain, but from the viewpoint of heat resistance and weather resistance, it is preferable that at least a carbon-carbon double bond in the main chain is hydrogenated. The hydrogenated product can be obtained by a method in which the ring-opened polymer is hydrogenated with hydrogen in the presence of a hydrogenation catalyst according to a conventional method. As the hydrogenation catalyst, a catalyst comprising a combination of a transition metal compound and an alkyl metal compound, for example, cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n
-Butyl lithium, zirconocene dichloride / sec-
Butyl lithium, a combination of tetrabutoxy titanate / dimethylmagnesium and the like.

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.

The norbornene-based polymer of the present invention preferably has high weather resistance and high light degradation resistance.
Preferably 98% or more, more preferably 99% or more is saturated. When a non-conjugated unsaturated bond such as an alkylidene group is present in the side chain, hydrogenation is performed simultaneously with hydrogenation of the unsaturated bond in the main chain. It is desirable that 20% or more, preferably 30% or more, preferably 40% or more, and most preferably 100%, of the aromatic ring in the side chain remains. Unsaturated bonds in the main chain structure and unsaturated bonds in the aromatic ring structure can be distinguished and recognized by ¹ H-NMR analysis. In order to mainly hydrogenate unsaturated bonds in the main chain structure, it is necessary to use -20 ° C to 120 ° C,
Preferably 0-100 ° C, more preferably 20-80 ° C
At a temperature of 0.1 to 50 kg / cm ² , preferably 0.1 kg / cm ² .
5 to 30 kg / cm ² , more preferably 1 to ²⁰ kg / cm ²
It is desirable to carry out the hydrogenation reaction at a hydrogen pressure of cm ² . In order to hydrogenate the aromatic ring, for example, the hydrogenation temperature is increased to about 150 to 250 ° C.

The hydrogenated product of the ring-opened polymer of the aromatic ring-containing norbornene-based monomer represented by the formula (A ₁ ) and the aromatic ring-containing norbornene-based monomer represented by the formula (B ₁ ) has a main chain Is a polymer containing a repeating unit represented by the following formulas (A ₃ ) and (B ₃ ) in which unsaturated bonds are hydrogenated.

[0058]

Embedded image [Wherein the symbols have the same meaning as in the expression (A ₁ ). ]

[0059]

Embedded image [In the formula, the meaning of each symbol is the same as that in the formula (B ₁ ). However, hydrogenated products of these ring-opened polymers having a small hydrogenation rate have the double bonds of the side chains represented by the formulas (A ₂ ) and (B ₂ ) remaining. . On the other hand, when part of the aromatic ring in the side chain is hydrogenated, in the repeating unit represented by the formula (A ₃ ), part of the aromatic ring is hydrogenated and saturated.

Film The film of the present invention can be obtained by forming a film from the norbornene-based polymer. (1) Optional Components In the present invention, a rubbery polymer or other thermoplastic resin, or various compounding agents generally used for norbornene-based resins may be added to the above-mentioned norbornene-based polymer, if necessary. Can be. The rubbery polymer is a polymer having a glass transition temperature of 0 ° C. or less, and includes ordinary rubbery polymers and thermoplastic elastomers. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the rubbery polymer is appropriately selected depending on the purpose of use, and is usually 5 to 200.

As the rubbery polymer, for example, ethylene-
α-olefin rubbery polymer; ethylene-α-olefin-polyene copolymer rubber; copolymer of ethylene and unsaturated carboxylic acid ester such as ethylene-methyl methacrylate and ethylene-butyl acrylate; ethylene-vinyl acetate Copolymer of ethylene and a fatty acid vinyl; a polymer of an alkyl acrylate such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, or lauryl acrylate;
Polybutadiene, polysoprene, styrene-butadiene or styrene-isoprene random copolymer, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene- (meth) acrylic acid alkyl ester copolymer, butadiene- (meth) acrylic Diene rubbers such as acid alkyl ester-acrylonitrile copolymer, butadiene- (meth) acrylic acid alkyl ester-acrylonitrile-styrene copolymer; and butylene-isoprene copolymer.

Examples of the thermoplastic elastomer include aromatic vinyl such as styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer and hydrogenated styrene-isoprene block copolymer. -Conjugated diene-based block copolymers, low-crystalline polybutadiene resins, ethylene-propylene elastomers, styrene-grafted ethylene-propylene elastomers, thermoplastic polyester elastomers, ethylene ionomer resins, and the like. Of these thermoplastic elastomers, preferably, hydrogenated styrene-butadiene block copolymer,
And hydrogenated styrene-isoprene block copolymers. Specific examples thereof include JP-A-2-133406, JP-A-2-305814, JP-A-3-72512, and JP-A-3-74409. Can be mentioned.

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.

Examples of various compounding agents generally used in the norbornene-based polymer include an antioxidant; an ultraviolet absorber; a leveling agent; a pigment; a dye; Lubricants such as natural oils, synthetic oils and waxes; flame retardants; antistatic agents; 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. Of these, phenol-based antioxidants are preferred, and alkyl-substituted phenol-based antioxidants are preferred. Agents are particularly preferred. As the phenolic antioxidant, conventionally known phenolic antioxidants 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-
JP-A-63-179953 and JP-A-Heisei 1-79, such as 2-hydroxyphenyl) ethyl) phenyl acrylate.
Acrylate compounds described in JP-B-168463; 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 [i.e., pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]], triethylene glycol bis (3- (3-tert-butyl-4-hydroxy-
Alkyl-substituted phenolic compounds such as 5-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-1,3,3
5-triazine, 2-octylthio-4,6-bis-
(3,5-di-t-butyl-4-oxyanilino)-
Triazine group-containing phenolic compounds such as 1,3,5-triazine; and the like.

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 (nonylphenylphosphite), 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 and 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 in the range of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the thermoplastic norbornene resin.

As the ultraviolet absorber, 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-t-butyl-4-hydroxyphenyl) propionyloxy ) -1- (2-
(3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl) -2,2,6,6
A hindered amine-based ultraviolet absorber such as tetramethylpiperidine; 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3-t-butyl-2-
(Hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole,
Benzotriazole ultraviolet absorbers such as 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole; 2,4-di-t-butylphenyl-3,5
Bezoate ultraviolet absorbers such as -di-t-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; Each of these UV absorbers, alone,
Alternatively, two or more kinds can be used in combination. The amount of the ultraviolet absorber is usually 10 to 10 based on the weight of the polymer.
100,000 ppm, preferably 100 to 10,000
The range is 0 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 amount of addition is usually 5 to 50,000 ppm based on the weight of the polymer,
Preferably it is 10 to 20,000 ppm. Examples of the antistatic agent include sodium alkylsulfonate and / or phosphonium alkylsulfonate, and fatty acid ester hydroxyamine compounds such as glycerin ester of stearic acid.
These antistatic agents can be used alone or in combination of two or more. The amount of the antistatic agent is usually in the range of 0 to 5 parts by weight based on 100 parts by weight of the thermoplastic norbornene resin.

(2) Film Forming The film forming method may be a conventional method and is not particularly limited. For example, a method such as a melt forming method or a solution casting method may be used. The solution casting method is preferable in that a film having excellent physical properties is easily obtained. The solution casting method can be performed according to a conventional method, for example,
A liquid composition in which each component is dissolved or finely dispersed in a solvent,
It can be carried out by casting on a suitable carrier (support) and then drying off the solvent. The carrier is not particularly limited, 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 PVC film, a fluororesin belt, a metal foil, etc. A flat plate, a belt or a roll can be used.

Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic hydrocarbons such as cyclohexane; esters such as butyl acetate; ethers such as tetrahydrofuran and dimethoxyethane; Alcohols such as ethanol and isopropanol; ketones such as methyl ethyl ketone; halogenated solvents such as methylene chloride, chloroform, carbon tetrachloride and ethylene dichloride; These solvents can be used alone or in combination of two or more.

The concentration of the norbornene-based polymer in the solvent is as follows:
It is appropriately selected according to the thickness of the polymer film to be produced,
Usually 0.1 to 60% 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 thermoplastic norbornene-based resin is in this range, the film thickness can be easily adjusted and the film-forming property is excellent, which is preferable. The method of casting the liquid composition on the carrier is not particularly limited, and includes, for example, a bar coater,
It can be performed using a T-die, a T-die with a bar, a doctor knife, a Meyer 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 method of removing the solvent by drying is not particularly limited and can be carried out according to a conventional method, but the residual solvent concentration is 5% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less.
In order to reduce the content to 0.5% by weight or less, drying is usually 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. After the first stage of drying, the sheet is peeled off from the flat plate or roll after the completion of the drying, and the second stage of drying is performed. , A second stage of drying may be performed. Drying of the solvent, if necessary,
It can be performed under reduced pressure.

When a sheet is produced by a melt molding method, T
Examples include a method using a die, a melt extrusion method such as an inflation method, a calendar method, a hot press method, and an injection molding method. Above all, a melt extrusion method using a T-die, which has a small thickness unevenness, is easy to be processed to a thickness of about 10 to 500 μm, and can reduce the absolute value of the retardation and its variation, is preferable. The conditions of the melt molding method are similar Tg
For example, in a melt extrusion method using a T-die, the resin temperature is about 240 to 300 ° C. and the temperature of the take-up roll is 10
It is preferable to select a relatively high temperature of about 0 to 150 ° C. and conditions under which the resin sheet can be gradually cooled. In order to reduce surface defects such as die lines, the die needs to have a structure in which the stagnation portion is minimized, and it is preferable to use a die or a lip with as little scratches as possible.

The thickness of the polymer film thus obtained is usually 0.5 μm to 5 mm, preferably 1 μm to 2 m
m, more preferably in the range of 5 μm to 0.5 mm. When the thickness of the polymer film is within this range, drying of the solvent is facilitated and the appearance of the film is also excellent and suitable. When the polymer film produced by the production method of the present invention is used as a protective film for a polarizing film, the film thickness is usually 5 to 500 μm, preferably 10 to 150 μm, more preferably 20 to 100 μm.
The range of μm is preferable because characteristics such as mechanical strength, transparency, and birefringence are highly balanced. In addition, the thickness unevenness of the film is generally ± 5% of the average thickness over the entire surface.
%, Preferably ± 3%, more preferably ± 2%
Those having a value within the range are suitable for a protective layer of a polarizing film for a liquid crystal display, because the distortion of the image and the dispersion of the retardation are small.

(3) Characteristics of Film The film composed of the norbornene-based polymer of the present invention is:
It has the following properties and is particularly useful as a protective film for a polarizing film. The light transmittance of the film of the present invention is at least 80%, preferably at least 85%, more preferably at least 90%. If the light transmittance is excessively small, the thickness of the protective film must be extremely thin, and the reinforcing effect cannot be sufficiently exhibited. The water vapor permeability of the film of the present invention is 100 g
/ M ² · 24 hr or less, preferably 50g / m ² · 24h
r or less, more preferably 20 g / m ² · 24 hr or less. If the water vapor permeability of the polymer film is excessively high, the durability such as adhesion at high temperature and high humidity is poor, which is not preferable.

The polarizing film (usually PVA) of the film of the present invention
Adhesive strength with the system polarizing film) is 5.5 kg / cm ² or more,
Preferably at least 6.0 kg / cm ² , more preferably at least 6.5 kg / cm ² , most preferably at least 7.0 kg / cm ^2.
cm ² or more. If the adhesive strength to the polarizing film is excessively small, the resulting polarizing film is not preferable because of poor durability. The tensile strength of the film of the present invention is usually 400 kg
/ Cm ² or more, preferably 450 kg / cm ² or more, more preferably 500 kg / cm ² or more, and most preferably 5 kg / cm ² or more.
30 kg / cm ² or more. If the tensile strength of the film is excessively small, the film becomes too thick to exert a reinforcing effect as a protective film, which is not preferable.

The elongation of the film of the present invention is usually at least 20%, preferably at least 50%, more preferably at least 100%. If the elongation of the film is too small, the reinforcing effect and the durability are poor, which is not preferable. The thickness of the polymer film of the present invention may be appropriately selected depending on the purpose of use,
R.I. which is usually in the range of 1 to 200 µm, preferably 5 to 100 µm, more preferably 10 to 50 µm. When the polymer film is in this range, the mechanical strength and the light transmittance are highly balanced, which is preferable.

(4) Polarizing Film The polymer film of the present invention is useful as a protective film to be laminated on a polarizing film. The polarizing film is formed by laminating the polymer film on one side or both sides of the polarizing film. It is preferable to laminate a protective polymer film on both sides, but it is also possible to laminate the polymer film of the present invention on only one side and laminate a polymer film of another material on multiple sides. The bonding method may be in accordance with a conventional method, and usually an adhesive is used. The adhesive is not particularly limited, but an acrylic pressure-sensitive adhesive is preferably used. As the acrylic pressure-sensitive adhesive, a solution in which one or more (co) polymers of an acrylate ester is dissolved in an organic solvent such as toluene or ethyl acetate, or an aqueous emulsion of these (co) polymers can be used.

An acrylic pressure-sensitive adhesive is generally used as a main constituent monomer in the glass transition temperature (T.sub.T) of its homopolymer.
g) having a temperature of -50 ° C or lower (low Tg monomer) is used, and an appropriate comonomer is selected for adjusting the Tg and the adhesive property of the copolymer. Specifically, it is mainly composed of a low Tg monomer that imparts tackiness such as butyl acrylate or 2-ethylhexyl acrylate, and these monomers are
Copolymers such as vinyl acetate, methyl methacrylate, styrene, unsaturated carboxylic acid, and acrylonitrile with a high Tg monomer that imparts adhesiveness and cohesion can be given. The acrylic pressure-sensitive adhesive may be used in combination with a cross-linking agent such as isocyanate or butylated melamine. In this case, the acrylic pressure-sensitive adhesive is used by being mixed with the cross-linking agent before application. These adhesives can be used alone or in combination of two or more.

The application of the adhesive to the polarizing film and / or the polymer film is performed by a method such as brush coating, a method using a gun spray, a method using a spin coater, a method using a bar coater, or the like. These coating methods are not limited to these, but it is preferable to use a bar coater for easy and uniform coating. The coating thickness of the adhesive is usually 1 to 100 μm, preferably 10 to 50 μm.
μm, more preferably in the range of 15 to 30 μm. In order to reduce optical refraction unevenness and the like, it is preferable to reduce unevenness in the applied thickness of the adhesive. Similarly, the release film used in the transfer method preferably has excellent surface smoothness.

In the present invention, a more preferable polarizing film is obtained by laminating a norbornene-based polymer film on at least one surface of a polarizing film via an adhesive layer, and then applying heat and pressure to bond (thermocompression bonding). Can be manufactured. Usually in the range of 50 to 120 ° C, preferably 80 to 100 ° C,
The adhesive is held for 1 to 10 minutes, preferably 1.5 to 5 minutes, and then pressed under a pressure of 1 to 10 kg / cm ² , preferably 4 to 7 kg / cm ² . The polarizing film obtained by the present invention has excellent light transmittance, interlayer adhesive strength, and durability, and low birefringence, moisture resistance, heat resistance, and physical strength inherent to thermoplastic norbornene-based resin films. Because of these properties, it is useful as a polarizing film in various fields.

[0083]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Reference Examples, Examples, and Comparative Examples, but the present invention is not limited to only these Examples. Parts and percentages are by weight unless otherwise specified.
The measuring methods of various physical properties are as follows. (1) The molecular weight was measured in terms of polystyrene by a GPC method using toluene as a solvent. (2) The hydrogenation rate was measured by ¹ H-NMR. (3) The retardation is Belek wavelength 550 nm.
It was measured by a conventioner. (4) The thickness of the sheet and the film was measured by a dial thickness gauge. (5) The light transmittance is determined by a spectrophotometer at a wavelength of 400 to
Measurement was performed by continuously changing the wavelength in the range of 700 nm, and the minimum transmittance was defined as the light transmittance. (6) The water vapor permeability was measured in an environment of 25 ° C. and 90% RH in accordance with JIS K7129 and converted to a thickness of 25 μm. (7) Tensile strength and elongation were measured using a No. 3 test piece obtained by punching a sheet having a thickness of 80 μm, and a tensile speed of 100 mm / mi.
n according to JIS K7127. (8) The adhesive strength was measured by a T-peel peel test (JIS Z02).
37). (9) The durability test of the polarizing film is performed at 80 ° C. and 90% R
H, a heat cycle test at -40 ° C. for 1 hour and at 1 hour were repeated 200 times, and the test was visually observed and evaluated according to the following criteria. ：: When there is no abnormality in both the decrease in the degree of polarization and the visual observation, ×: There is a decrease in the degree of polarization / or bubbles (tunnel) are generated between the adhesive layer and the protective layer.

Reference Synthesis Example 1 In a 1-liter flask purged with nitrogen, 1,4-methano-1,4,4a, 9a
-Tetrahydrofluorene (hereinafter abbreviated as MTF) 5
g of toluene and 120 g of toluene, 0.287 mmol of triisobutylaluminum and 0.287 mmol of isobutyl alcohol as a polymerization catalyst, and 1 as a molecular weight regulator.
-Hexene 2.30 mmol was added. To this, 0.057 mmol of tungsten hexachloride was added and 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 dropping was completed, 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, a mixture of 0.5 g of nickel acetylacetonate and 5.15 g of a 30% by weight toluene solution of triisobutylaluminum was added, and the inside of the reactor was purged with hydrogen. 80 ° C with stirring
The temperature rose. When the temperature is stable, increase the hydrogen pressure to 30k
The reaction was performed for 3 hours while increasing the pressure to g / cm ² and replenishing the 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 [mu] m, manufactured by Mizusawa Chemical Co., Neobido D powder) of 2.5g was added and after stirring for 1 hour at 80 ° C., the hydrogenation reaction solution was filtered to remove solids, 3
It was precipitated by pouring into 1 liter of isopropyl alcohol, and collected by filtration. 100 ℃, 1T
It was dried at orr or lower for 48 hours. The synthesis results are shown in Table 1. This polymer is designated as A.

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

<Reference Synthesis Example 3> A white powder was obtained in the same manner as in Reference Synthesis Example 1 except that MTF was changed to dicyclopentadiene (hereinafter abbreviated as DCP). Table 1 shows the synthesis results.
It was shown to. This polymer is designated as C.

<Reference Synthesis Example 4> A cyclohexane solution of MTF, a cyclohexane solution of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst, and ethyl aluminum sesquichloride [Al (C
₂ H _{5) 1.5} concentration in the polymerization vessel a cyclohexane solution of Cl _1.5], respectively 60 g / l, 0.5 mmol /
Liter, 4.0 mmol / l, ethylene was supplied at 15 liter / hr, and hydrogen was added at 0.1 liter.
The solution was supplied at a rate of 5 L / Hr, and the inside of the system was controlled at 10 ° C. 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 stopped by adding a small amount of isopropyl alcohol to the withdrawn polymerization solution, and then
An aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water was brought into contact with the polymerization solution at a ratio of 1 to 1 using a homogenizer under vigorous stirring to transfer the catalyst residue 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, and the polymerization liquid was purified and separated. 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 as D.

<Example 1> MTF was added to 70% by weight of MTF.
A white powder was obtained in the same manner as in Reference Synthesis Example 1 except that the mixed monomer was changed to 30% by weight of DCP. The synthesis results are shown in Table 1. This polymer is designated as E.

<Example 2> MTF was added to 50% by weight of MTF.
A white powder was obtained in the same manner as in Reference Synthesis Example 1 except that the mixed monomer was replaced with DCP and 50% by weight of DCP. The synthesis results are shown in Table 1. This polymer is designated as F.

Example 3 MTF was added to PNB at 70% by weight.
A white powder was obtained in the same manner as in Reference Synthesis Example 1, except that a mixed monomer of 30% by weight and tetracyclododecene (hereinafter abbreviated as TCD) was used. The synthesis results are shown in Table 1. This polymer is designated G.

Example 4 MTF was added to PNB at 50% by weight.
A white powder was obtained in the same manner as in Reference 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 H.

[0092]

[Table 1] (* 1): mol ratio

[Examples 5 to 8, Reference Examples 1 to 4, Comparative Example 1]
~ 3] 15 g of each of the polymers obtained in Reference Synthesis Examples 1 to 4 and Examples 1 to 4 or a commercially available norbornene-based resin containing no aromatic ring (described in Table 2) was dissolved in 85 g of xylene, Add a leveling agent (Florald F
C-430; Sumitomo 3M) 500 ppm (based on the amount of polymer) and UV stabilizer (Viosorb 80; Kyodo Pharmaceutical) 300 ppm (based on the amount of polymer) were added to obtain a resin solution. This solution was spread on a surface-polished glass plate, and an appropriate amount was cast to a width of 300 mm and a length of 500 mm using a bar coater. This was the first stage of drying, and the glass plate was heated by heating from 25 ° C. to 60 ° C. for 15 minutes together with the glass plate and dried. Next, as a second stage of drying, the resin film was peeled off from the glass plate, dried in an oven at 90 ° C. for 30 minutes, and cooled to room temperature.
A sheet having an average thickness of 30 μm was obtained by cutting off the surrounding 10 mm. When the properties of each sheet were measured, all of the sheets 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. An acrylic pressure-sensitive adhesive (DD-624, manufactured by Nogawa Chemical Co., Ltd.) was applied to a surface of a release film (manufactured by Fujimori Kogyo Co., Ltd., DD-624) using a bar coater to a thickness of 20 μm and dried at 80 ° C. for 2 minutes. Was transferred to a sheet. Next, a PVA polarizing film (thickness of about 100 μm) uniaxially stretched by adsorbing iodine.
m), attached to the transfer sheet via an acrylic pressure-sensitive adhesive layer on both sides, kept at 90 ° C. for 2 hours, and kept at 5 kg / cm ²
Pressure was applied for bonding. Table 2 shows the adhesive strength immediately after the bonding and after the heat cycle test and the visual results.

[0094]

[Table 2]

(Footnotes) (1) ZNX; ZEONEX450 manufactured by Zeon Corporation; number-average molecular weight (Mn) is 37,500, weight-average molecular weight (Mw) is 81,400, and hydrogenation rate of the main chain is 99% or more; ^No absorption peak of the aromatic ring is confirmed by ¹ H-NMR. (2) APEL; Mitsui Petrochemical's APEL5015;
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. (3) ARTON; APEL501 manufactured by Nippon Synthetic Rubber Co., Ltd.
5; the number average molecular weight (Mn) is 17,600, the weight average molecular weight (Mw) is 57,700, and no absorption peak of aromatic ring is confirmed by ¹ H-NMR.

[0096]

According to the present invention, a norbornene-based polymer which can provide a film which is excellent in light transmittance, tensile strength, tensile elongation, and water vapor permeability and excellent in adhesion to a polarizing film. , And a method of manufacturing the same. Further, according to the present invention, there is provided a film having excellent characteristics as described above and a method for producing the film.

Claims (5)

[Claims] 1. A bonding amount of an aromatic ring-containing norbornene monomer unit (A) of 10 to 90% by weight and a bonding amount of an aromatic ring-containing norbornene monomer unit (B) of 10 to 90% by weight.
% By weight and a weight average molecular weight (Mw) of 1,000
A norbornene-based polymer having a weight-average molecular weight (Mw) and a number-average molecular weight (Mn) of 2.0 to 500,000; 2. A ring-opening polymerization of an aromatic ring-containing norbornene-based monomer (a) and an aromatic ring-containing norbornene-based monomer (b) in the presence of a metathesis catalyst system. At least one transition metal compound (i), an organoaluminum compound (ii), and an alcohol (iii) selected from the group consisting of Mo compounds and Re compounds, and the organic residue of the alcohol has two carbon atoms The production of a norbornene-based polymer characterized in that the sum of the carbon number of the organic residue of the organoaluminum compound (ii) and the carbon number of the organic residue of the alcohol (iii) is 9 or more. Method. 3. The method for producing a norbornene-based polymer according to claim 2, wherein after the ring-opening polymerization, carbon-carbon unsaturated bonds in the polymer are hydrogenated while leaving at least a part of the aromatic ring. 4. A bond amount of the aromatic ring-containing norbornene monomer unit (A) of 10 to 90% by weight and a bond amount of the aromatic ring-containing norbornene monomer unit (B) of 10 to 90%.
% By weight and a weight average molecular weight (Mw) of 1,000
A film made of a norbornene-based polymer having a weight-average molecular weight (Mw) and a number-average molecular weight (Mn) of 2.0 to 500,000 or less (Mw / Mn). 5. The bonding amount of the aromatic ring-containing norbornene monomer unit (A) is 10 to 90% by weight, and the bonding amount of the aromatic ring-containing norbornene monomer unit (B) is 10 to 90%.
% By weight and a weight average molecular weight (Mw) of 1,000
A solution-casting of a norbornene-based polymer having a weight-average molecular weight (Mw) to number-average molecular weight (Mn) ratio (Mw / Mn) of 2.0 or less at a concentration of up to 500,000. Production method.