Cyclic olefin ring-opening polymer hydride, resin composition, and film

Abstract

The purpose of the present invention is to provide a cyclic olefin ring-opening polymer hydride having excellent surface hardness and film-forming properties. This cyclic olefin ring-opened polymer hydride is characterized by containing two or more structural units (A) derived from a polycyclic norbornene monomer having a tetracyclic or higher polycyclic structure and a structural unit (B) derived from a polycyclic norbornene monomer having a bicyclic or tricyclic polycyclic structure, when the content ratio of all repeating units contained in the cyclic olefin ring-opening polymer hydride is taken as 100 mass%, the content ratio of the structural unit (A) is 80 mass% or more, and the content ratio of the structural unit (B) is 5-20 mass%. The weight average molecular weight of the cyclic olefin ring-opening polymer hydride is from 27,000 to 50,000 (inclusive).

Description

Technical Field

[0001] The present invention relates to a cyclic olefin ring-opening polymer hydride, a resin composition containing the cyclic olefin ring-opening polymer hydride, and a film. Background Art

[0002] Due to the excellent optical properties such as transparency, heat resistance, and low birefringence, moldability, and chemical resistance of cyclic olefin ring-opening polymer hydrides, they have attracted attention as molding materials applicable to various uses including optical uses. Therefore, in recent years, various proposals have been made to improve the physical properties of cyclic olefin ring-opening polymer hydrides.

[0003] Specifically, for example, Patent Document 1 discloses the following: In a cyclic olefin ring-opening polymer hydride composed of repeating units derived from tetracyclododecene and repeating units derived from other norbornene-based monomers, by controlling the respective content ratios of the repeating units derived from tetracyclododecene and the repeating units derived from other norbornene-based monomers, the ratio of syndiotactic dyad groups of the repeating units derived from tetracyclododecene, and the weight-average molecular weight of the cyclic olefin ring-opening polymer hydride, the heat-resistant yellowing property, dimensional stability at high temperature, and moldability of the cyclic olefin ring-opening polymer hydride are improved.

[0004] In addition, Patent Document 2 discloses the following: In a tetracyclododecene-containing ring-opening polymer hydride as a cyclic olefin ring-opening polymer hydride containing repeating units (A) derived from tetracyclododecene and repeating units (B) derived from methano-tetrahydrofluorene, by controlling the content ratio of repeating unit (A) and repeating unit (B), and the ratio of syndiotactic dyad groups to isotactic dyad groups of repeating unit (A), the solubility, fluidity, transparency, and low birefringence of the tetracyclododecene-containing ring-opening polymer hydride are improved.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: International Publication No. 2016 / 052302;

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 2008-013604. Summary of the Invention

[0009] Problems to be Solved by the Invention

[0010] Here, in recent years, as an optical material used for molding an optical film as a surface member in display devices such as liquid crystal displays, organic EL displays, and μLED displays, a cyclic olefin ring-opening polymer hydride having excellent surface hardness is required to be developed.

[0011] In addition, for a cyclic olefin ring-opening polymer hydride used as a material for films such as optical films, it is also required that when it is formed into a film and wound into a roll, it does not break or crack (that is, it has excellent film-forming properties).

[0012] However, the surface hardness and film-forming properties of the cyclic olefin ring-opening polymer hydrides of the above-mentioned prior art are not necessarily sufficient.

[0013] Means for Solving the Problems

[0014] Therefore, an object of the present invention is to provide a cyclic olefin ring-opening polymer hydride having excellent surface hardness and film-forming properties, a resin composition containing the cyclic olefin ring-opening polymer hydride, and a film.

[0015] The inventors of the present invention conducted in-depth research to solve the above problems. Then, the inventors found that a cyclic olefin ring-opening polymer hydride containing structural units (A) of two or more polycyclic norbornene monomers having a polycyclic structure of four or more rings and structural units (B) of a polycyclic norbornene monomer having a bicyclic or tricyclic polycyclic structure in a specified ratio and having a weight average molecular weight in a specified range has excellent surface hardness and film-forming properties, and thus completed the present invention.

[0016] That is, an object of the present invention is to advantageously solve the above problems, and the present invention is [1] A cyclic olefin ring-opening polymer hydride, which contains two or more structural units (A) from polycyclic norbornene monomers having a polycyclic structure of four or more rings and structural units (B) from polycyclic norbornene monomers having a bicyclic or tricyclic polycyclic structure. When the content ratio of all the repeating units contained in the cyclic olefin ring-opening polymer hydride is 100% by mass, the content ratio of the structural unit (A) is 80% by mass or more, and the content ratio of the structural unit (B) is 5% by mass or more and 20% by mass or less. The weight average molecular weight of the cyclic olefin ring-opening polymer hydride is 27,000 or more and 50,000 or less. If, in this way, in a cyclic olefin ring-opening polymer hydride containing two or more structural units (A) from polycyclic norbornene monomers having a polycyclic structure of four or more rings and structural units (B) from polycyclic norbornene monomers having a bicyclic or tricyclic polycyclic structure, the content ratios of the structural unit (A) and the structural unit (B) are respectively controlled within the above-specified ranges, and the weight average molecular weight of the cyclic olefin ring-opening polymer hydride is controlled within the above-specified range, a cyclic olefin ring-opening polymer hydride having excellent surface hardness and film-forming properties can be obtained.

[0017] In addition, in the present invention, the weight average molecular weight of the ring-opening polymer hydride of cyclic olefin can be measured by the method described in the examples. Further, in the present invention, the content ratio of the structural unit can be measured by 1 1H-NMR, 13 13C-NMR and other nuclear magnetic resonance (NMR) methods.

[0018] [2] The ring-opening polymer hydride of cyclic olefin in the above [1] preferably contains a structural unit derived from tetracyclododecene and a structural unit derived from methylene tetrahydrofluorene. If it contains a structural unit derived from tetracyclododecene and a structural unit derived from methylene tetrahydrofluorene in this way, the surface hardness and film-forming property of the ring-opening polymer hydride of cyclic olefin can be further improved.

[0019] [3] The ring-opening polymer hydride of cyclic olefin in the above [1] or [2] preferably contains a structural unit derived from dicyclopentadiene. If it contains a structural unit derived from dicyclopentadiene in this way, the surface hardness of the ring-opening polymer hydride of cyclic olefin can be further improved.

[0020] [4] Regarding the ring-opening polymer hydride of cyclic olefin in any one of the above [1] to [3], when it is formed into a film, the value of the scratch hardness measured based on JIS K5600 is preferably B or more. In this way, the surface hardness of the ring-opening polymer hydride of cyclic olefin with a scratch hardness value of B or more measured based on JIS K5600 when formed into a film is excellent.

[0021] In addition, in the present invention, the scratch hardness is obtained based on the pencil method and can be measured by the method described in the examples.

[0022] [5] Regarding the ring-opening polymer hydride of cyclic olefin in any one of the above [1] to [4], when it is formed into a film, a yield point is preferably confirmed in the stress-strain curve of the tensile test based on JIS K7127. In this way, the film-forming property of the ring-opening polymer hydride of cyclic olefin with a yield point confirmed in the stress-strain curve of the specified tensile test when formed into a film is excellent.

[0023] In addition, in the present invention, the tensile test and the confirmation of the yield point in the stress-strain curve can be measured by the method described in the examples.

[0024] Furthermore, an object of the present invention is to advantageously solve the above problems, and the present invention is [6] a resin composition containing the ring-opening polymer hydride of cyclic olefin in any one of the above [1] to [5]. If a resin composition containing the ring-opening polymer hydride of cyclic olefin of any one of the above is used in this way, a film with excellent surface hardness and capable of suppressing breakage and cracks when wound into a roll can be manufactured.

[0025] In addition, an object of the present invention is to advantageously solve the above problems. The present invention is [7] a film formed by molding the above-mentioned [6] resin composition. In this way, the film formed by molding the above-mentioned resin composition has excellent surface hardness and can suppress breakage and cracks when wound into a roll.

[0026] Advantages of the Invention

[0027] According to the present invention, it is possible to provide a cyclic olefin ring-opening polymer hydride excellent in surface hardness and film-forming property, a resin composition containing the cyclic olefin ring-opening polymer hydride, and a film. Detailed Embodiments

[0028] Hereinafter, embodiments of the present invention will be described in detail.

[0029] Here, since the cyclic olefin ring-opening polymer hydride of the present invention has excellent surface hardness and film-forming property, it can be preferably used as a material for molding films such as optical films. The resin composition of the present invention can be preferably used as a material for manufacturing the film of the present invention, for example. In addition, the film of the present invention can be preferably used as an optical film for display devices and the like.

[0030] (Cyclic Olefin Ring-Opening Polymer Hydride)

[0031] The cyclic olefin ring-opening polymer hydride is obtained by, for example, ring-opening polymerizing a monomer composition containing a norbornene compound in the presence of a polymerization catalyst, and then hydrogenating the carbon-carbon unsaturated bonds present in the obtained cyclic olefin ring-opening polymer.

[0032] The cyclic olefin ring-opening polymer hydride of the present invention contains, respectively, structural units (A) derived from two or more polycyclic norbornene-based monomers having a polycyclic structure of four or more rings and structural units (B) derived from polycyclic norbornene-based monomers having a polycyclic structure of two or three rings in proportions of 80% by mass or more and 5% by mass or more and 20% by mass or less, and may further optionally contain other structural units.

[0033] The weight-average molecular weight of the cyclic olefin ring-opening polymer hydride of the present invention needs to be 27,000 or more and 50,000 or less. If the weight-average molecular weight is 27,000 or more, film-forming properties can be ensured. On the other hand, if the weight-average molecular weight is 50,000 or less, deterioration of the solubility of the cyclic olefin ring-opening polymer and the cyclic olefin ring-opening polymer hydride in the solvent can be suppressed in the ring-opening polymerization step or the hydrogenation step, productivity can be ensured, and surface hardness can be ensured. From the viewpoint of further improving surface hardness and film-forming properties, the weight-average molecular weight of the cyclic olefin ring-opening polymer hydride is preferably 30,000 or more, more preferably 33,000 or more, preferably 45,000 or less, and more preferably 42,000 or less.

[0034] The weight-average molecular weight of the cyclic olefin ring-opening polymer hydride can be adjusted, for example, by changing the type and / or the blending amount of a molecular weight regulator (chain transfer agent) used when preparing the cyclic olefin ring-opening polymer which is a precursor of the cyclic olefin ring-opening polymer hydride.

[0035] <Structural unit (A) derived from a polycyclic norbornene monomer having a polycyclic structure of four or more rings>

[0036] Examples of the polycyclic norbornene monomer having a polycyclic structure of four or more rings that can form the structural unit (A) (hereinafter also simply referred to as "structural unit (A)") derived from a polycyclic norbornene monomer having a polycyclic structure of four or more rings include compounds having one or more norbornene rings and two or more ring structures (other than norbornene rings) in the molecule.

[0037] Here, the ring structure and the norbornene ring may each exist alone as a monocyclic ring or may form a fused ring. Among them, from the viewpoint of improving the surface hardness and film-forming properties of the cyclic olefin ring-opening polymer hydride, it is preferable that at least one ring structure forms a fused ring with the norbornene ring, and more preferably all ring structures form a fused ring with the norbornene ring.

[0038] In addition, the ring structure and / or the norbornene ring may have one or more substituents. There is no particular limitation on this substituent, and examples thereof include: halogen atoms such as chlorine, fluorine, and bromine; linear alkyl groups such as methyl, ethyl, and butyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl and tolyl; alkenyl groups such as vinyl and propenyl; alkoxy groups such as methoxy and ethoxy; hydroxyalkyl groups such as hydroxymethyl; alkoxycarbonyl groups such as methoxycarbonyl; propionic acid alkyl ester groups such as methyl propionate; amino; imide; cyano; carboxyl; silyl; hydroxy; cyclic anhydride groups such as dicarboxylic anhydride.

[0039] As for the above ring structure, there is no particular limitation, and examples thereof include an aliphatic ring and an aromatic ring. In addition, the above ring structure may be a monocyclic structure or a polycyclic structure formed by condensing at least one ring selected from aliphatic rings and aromatic rings.

[0040] As for the aliphatic ring, there is no particular limitation, and examples thereof include an aliphatic hydrocarbon ring and an aliphatic heterocyclic ring.

[0041] Examples of the aliphatic hydrocarbon ring include cycloalkyl rings such as a cyclopentane ring and a cyclohexane ring; cycloalkenyl rings such as a cyclopentene ring and a cyclohexene ring; and saturated crosslinked hydrocarbon rings such as a bicycloheptane ring (norbornane ring) and a bicyclooctane ring.

[0042] Examples of the aliphatic heterocyclic ring include nitrogen-containing heterocyclic rings such as a piperidine ring, a piperazine ring, and a hexamethyleneimine ring.

[0043] From the viewpoint of improving the surface hardness and film-forming property of the hydrogenated product of the cyclic olefin ring-opening polymer, it is particularly preferable that the above aliphatic ring is an aliphatic hydrocarbon ring.

[0044] As for the aromatic ring, there is no particular limitation, and examples thereof include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring; and aromatic heterocyclic rings such as a thiophene ring, a pyrrole ring, and a pyridine ring. From the viewpoint of improving the surface hardness and film-forming property of the hydrogenated product of the cyclic olefin ring-opening polymer, it is particularly preferable that the above aromatic ring is an aromatic hydrocarbon ring.

[0045] Specific examples of the compound having one or more norbornene rings and two or more ring structures in the molecule (a polycyclic norbornene-based monomer having a polycyclic structure of four or more rings) include: tetracyclododecene (tetracyclo[4.4.0.1 2,5 .1 7,10-dodec-3-ene); tetracyclododecenes with alkyl groups such as 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, 8-cyclopentyltetracyclododecene; tetracyclododecenes with double bonds outside the ring such as 8-methylene tetracyclododecene, 8-ethylene tetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, 8-cyclopentenyltetracyclododecene; tetracyclododecenes with substituents containing oxygen atoms such as 8-methoxycarbonyltetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-8,9-dicarboxylic anhydride; tetracyclododecenes with substituents containing nitrogen atoms such as 8-cyanotetracyclododecene, tetracyclododecene-8,9-dicarboximide; tetracyclododecenes with substituents containing halogen atoms such as 8-chlorotetracyclododecene; tetracyclododecenes with substituents containing silicon atoms such as 8-trimethoxysilyltetracyclododecene; hexacycloheptadecene; hexacycloheptadecenes with alkyl groups such as 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, 12-cyclopentylhexacycloheptadecene; hexacycloheptadecenes with double bonds outside the ring such as 12-methylenehexacycloheptadecene, 12-ethylenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexacycloheptadecene, 12-cyclopentenylhexacycloheptadecene; hexacycloheptadecenes with substituents containing oxygen atoms such as 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene-12,13-dicarboxylic acid, hexacycloheptadecene-12,13-dicarboxylic anhydride; hexacycloheptadecenes with substituents containing nitrogen atoms such as 12-cyanohexacycloheptadecene, hexacycloheptadecene-12,13-dicarboximide; hexacycloheptadecenes with substituents containing halogen atoms such as 12-chlorohexacycloheptadecene; hexacycloheptadecenes with substituents containing silicon atoms such as 12-trimethoxysilylhexacycloheptadecene; 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-(anthryl)-tetracyclo[4.4.0.1 2,5 .1 7,10 -3-Dodecene, 11-phenyl-hexacyclo[6.6.1.1 3,6 .1 10,13 .0 2,7 .0 9,14 -4-Heptadecene, 6-(α-naphthyl)-bicyclo[2.2.1]-hept-2-ene, 5-(anthryl)-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-diphenyl-bicyclo[2.2.1]-hept-2-ene, 9-(2-norbornene-5-yl)-carbazole, 1,4-methano-1,4,4a,4b,5,8,8a,9a-octahydrofluorene, 1,4-methano-1,4,4a,9a-tetrahydrofluorene (common name: methano-tetrahydrofluorene), 1,4-methano-8-methyl-1,4,4a,9a-tetrahydrofluorene, 1,4-methano-8-chloro-1,4,4a,9a-tetrahydrofluorene, 1,4-methano-8-bromo-1,4,4a,9a-tetrahydrofluorene, 1,4-methano-1,4,4a,9a-tetrahydrodibenzofuran, 1,4-methano-1,4,4a,9a-tetrahydrocarbazole, 1,4-methano-9-phenyl-1,4,4a,9a-tetrahydrocarbazole, 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene, 7,10-methano-6b,7,10,10a-tetrahydrofluoranthene, cyclopentadiene-acenaphthylene adduct, a compound obtained by further adding cyclopentadiene to the cyclopentadiene-acenaphthylene adduct, 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, 14,15-benzo-heptacyclo[8.7.0.1 2,9 .1 4,7 .1 11,17 .0 3,8 .0 12,16 -5-eicosene and the like.

[0046] Two or more of the polycyclic norbornene-based monomers having a polycyclic structure with four or more rings are required. That is, the hydrogenated ring-opening polymer of cyclic olefin needs to contain two or more structural units (A). If two or more are used, the surface hardness and film-forming property of the hydrogenated ring-opening polymer of cyclic olefin can be ensured. From the viewpoint of further improving the surface hardness and film-forming property of the hydrogenated ring-opening polymer of cyclic olefin, it is preferable to use two or more polycyclic norbornene-based monomers having a polycyclic structure with four rings.

[0047] In addition, from the viewpoint of further improving the surface hardness and film-forming property of the hydrogenated ring-opening polymer of cyclic olefin, in the combination of two or more polycyclic norbornene-based monomers having a polycyclic structure with four or more rings, it is preferable to include tetracyclo[4.4.0.1 2,5 .1 7,10 -dodec-3-ene (tetracyclododecene) and 1,4-methano-1,4,4a,9a-tetrahydrofluorene (methanotetrahydrofluorene). The polycyclic norbornene-based monomer having a polycyclic structure with four or more rings is more preferably a combination of tetracyclododecene and methanotetrahydrofluorene. That is, the hydrogenated ring-opening polymer of cyclic olefin preferably contains a structural unit derived from tetracyclododecene and a structural unit derived from methanotetrahydrofluorene.

[0048] Here, from the viewpoint of further improving the surface hardness and film-forming property of the hydrogenated ring-opening polymer of cyclic olefin, the mass ratio of the structural unit derived from tetracyclododecene to the structural unit derived from methanotetrahydrofluorene in the hydrogenated ring-opening polymer of cyclic olefin (structural unit derived from tetracyclododecene / structural unit derived from methanotetrahydrofluorene) is preferably 40 / 60 or more and 80 / 20 or less.

[0049] In addition, from the viewpoint of further improving the surface hardness and film-forming property of the hydrogenated ring-opening polymer of cyclic olefin, when the content ratio of all the repeating units contained in the hydrogenated ring-opening polymer of cyclic olefin is 100% by mass, the content ratio of the structural unit derived from tetracyclododecene is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more.

[0050] Furthermore, from the viewpoint of further improving the surface hardness and film-forming property of the cyclic olefin ring-opening polymer hydride, when the content ratio of all the repeating units contained in the cyclic olefin ring-opening polymer hydride is 100% by mass, the content ratio of the structural unit derived from methylene tetrahydrofluorene is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more.

[0051] Moreover, in all the structural units (100% by mass) of the cyclic olefin ring-opening polymer hydride, the proportion of the structural unit (A) (the total proportion of two or more structural units (A)) needs to be 80% by mass or more. If the proportion of the structural unit (A) is less than 80% by mass, the surface hardness cannot be ensured. From the viewpoint of obtaining a cyclic olefin ring-opening polymer hydride with more excellent surface hardness, the proportion of the structural unit (A) is preferably 85% by mass or more.

[0052] <Structural unit (B) derived from a polycyclic norbornene monomer having a bicyclic or tricyclic polycyclic structure>

[0053] As the polycyclic norbornene monomer having a bicyclic or tricyclic polycyclic structure that can form the structural unit (B) (hereinafter also simply referred to as "structural unit (B)") derived from a polycyclic norbornene monomer having a bicyclic or tricyclic polycyclic structure, compounds having only one norbornene ring as a ring structure in the molecule (polycyclic norbornene monomers having a bicyclic polycyclic structure) and compounds having one norbornene ring and one monocyclic structure in the molecule (polycyclic norbornene monomers having a tricyclic polycyclic structure) can be cited.

[0054] In addition, from the viewpoint of further improving the surface hardness of the cyclic olefin ring-opening polymer hydride, it is preferable to use a polycyclic norbornene monomer having a tricyclic polycyclic structure.

[0055] [Compounds having only one norbornene ring as a ring structure in the molecule]

[0056] As the compound having only one norbornene ring as a ring structure in the molecule (polycyclic norbornene monomer having a bicyclic polycyclic structure), there is no particular limitation as long as it has one norbornene ring and does not have a ring structure other than the norbornene ring, and compounds having one norbornene ring in the molecule can be cited, and the above norbornene ring may have one or more substituents.

[0057] As this substituent, as long as it does not have a ring structure, there is no particular limitation, and examples thereof include: halogen atoms such as chlorine, fluorine, and bromine; chain-like alkyl groups such as methyl, ethyl, and butyl; chain-like alkenyl groups such as vinyl and propenyl; chain-like alkoxy groups such as methoxy and ethoxy; chain-like hydroxyalkyl groups such as hydroxymethyl; chain-like alkoxycarbonyl groups such as methoxycarbonyl; alkyl propionate groups such as methyl propionate; amino group; amide group; imide group; cyano group; carboxyl group; silyl group; hydroxy group, etc.

[0058] As specific examples of the compound having only one norbornene ring as a ring structure in the molecule (a polycyclic norbornene-based monomer having a bicyclic polycyclic structure), examples include: bicyclo[2.2.1]hept-2-ene (common name: norbornene); norbornene having a chain-like alkyl group such as 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene; norbornene having a chain-like alkenyl group such as 5-ethylidene norbornene, 5-vinylnorbornene, 5-propenylnorbornene; norbornene having a polar group containing an oxygen atom such as 5-methoxycarbonyl norbornene, 5-ethoxycarbonyl norbornene, 5-methyl-5-methoxycarbonyl norbornene, 5-methyl-5-ethoxycarbonyl norbornene, norbornenyl-2-methyl propionate, norbornenyl-2-methyl octanoate, 5-hydroxymethyl norbornene, 5,6-bis(hydroxymethyl) norbornene, 5,5-bis(hydroxymethyl) norbornene, 5-hydroxy-isopropyl norbornene, 5,6-dicarboxy norbornene, 5-methoxycarbonyl-6-carboxy norbornene; norbornene having a polar group containing a nitrogen atom such as 5-cyano norbornene. Norbornene is particularly preferred.

[0059] These polycyclic norbornene-based monomers having a bicyclic polycyclic structure can be used alone or in combination of two or more.

[0060] [Compound having one norbornene ring and one monocyclic structure in the molecule]

[0061] As a compound having one norbornene ring and one monocyclic structure in the molecule (a polycyclic norbornene-based monomer having a tricyclic polycyclic structure), examples include compounds having one monocyclic structure and one norbornene ring in the molecule. The above monocyclic structure may have one or more substituents, and the above norbornene ring may have one or more substituents. As this substituent, as long as it does not have a cyclic structure, there is no particular limitation, and examples thereof include the substituents described in the item of "compound having only one norbornene ring as a ring structure in the molecule" above.

[0062] Here, the monocyclic structure and the norbornene ring can each exist alone as a monocyclic ring or can form a fused ring. From the viewpoint of improving the surface hardness and film-forming properties of the cyclic olefin ring-opening polymer hydride, it is particularly preferred that the monocyclic structure and the norbornene ring form a fused ring.

[0063] The monocyclic structure is not particularly limited, and examples thereof include aliphatic monocyclic rings and aromatic monocyclic rings. Examples of the aliphatic monocyclic ring include saturated or unsaturated aliphatic hydrocarbon rings such as cycloalkyl rings and cycloalkenyl rings; and nitrogen-containing aliphatic heterocyclic rings such as piperidine rings, piperazine rings, and hexamethyleneimine rings. From the viewpoint of improving the surface hardness and film-forming properties of the cyclic olefin ring-opening polymer hydride, aliphatic hydrocarbon rings are particularly preferred.

[0064] Examples of the cycloalkyl ring include a cyclopentane ring and a cyclohexane ring. In addition, examples of the cycloalkene ring include a cyclopentene ring and a cyclohexene ring.

[0065] Examples of the aromatic monocyclic ring include aromatic hydrocarbon rings such as a benzene ring; and aromatic heterocyclic rings such as a thiophene ring, a pyrrole ring, and a pyridine ring. From the viewpoint of improving the surface hardness and film-forming properties of the cyclic olefin ring-opening polymer hydride, aromatic hydrocarbon rings are particularly preferred.

[0066] Specific examples of the compound having one monocyclic structure and one norbornene ring in the molecule (a polycyclic norbornene-based monomer having a polycyclic structure with three rings) include: dicyclopentadiene, tricyclo[4.3.0.1 2,5 dec-3-ene, tricyclo[4.4.1 2,5 .0]undec-3-ene and other dicyclopentadiene-based compounds; norbornenes having one cyclic alkyl group such as 5-cyclohexylnorbornene and 5-cyclopentylnorbornene; norbornenes having one cyclic alkenyl group such as 5-cyclohexenylnorbornene and 5-cyclopentenylnorbornene; phenylnorbornenes having one phenyl group such as 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 [i.e., 5-(4-methylphenyl)-2-norbornene]; 5-(ethylphenyl)-bicyclo[2.2.1]hept-2-ene; 5-(isopropylphenyl)-bicyclo[2.2.1]hept-2-ene; 5-methyl-5-carboxybenzylbicyclo[2.2.1]hept-2-ene and the like.

[0067] These polycyclic norbornene-based monomers having a polycyclic structure with three rings can be used alone or in combination of two or more. From the viewpoint of further improving the surface hardness of the cyclic olefin ring-opening polymer hydride, dicyclopentadiene is particularly preferably used. That is, the cyclic olefin ring-opening polymer hydride preferably contains a structural unit derived from dicyclopentadiene.

[0068] Moreover, in all the structural units (100% by mass) of the ring-opening polymer hydride of cyclic olefin, the proportion of the structural unit (B) (total proportion of the structural unit (B)) needs to be 5% by mass or more and 20% by mass or less. If the proportion of the structural unit (B) is 5% by mass or more, film formability can be ensured. In addition, if the proportion of the structural unit (B) is 20% by mass or less, surface hardness can be ensured. From the viewpoint of obtaining a ring-opening polymer hydride of cyclic olefin with further excellent surface hardness and film formability, the proportion of the structural unit (B) is preferably 10% by mass or more and preferably 15% by mass or less.

[0069] <Other structural units>

[0070] As other structural units that the ring-opening polymer hydride of cyclic olefin can optionally contain, there is no particular limitation as long as they are structural units other than the above structural unit (A) and structural unit (B), and examples thereof include structural units derived from non-norbornene compounds.

[0071] The non-norbornene compound capable of forming a structural unit derived from a non-norbornene compound is not particularly limited, and examples thereof include monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, 1,4-cyclooctadiene, and cyclodecene. The above non-norbornene compounds can be used alone or in combination of two or more.

[0072] Moreover, in all the structural units (100% by mass) of the ring-opening polymer hydride of cyclic olefin, the proportion of other structural units (total proportion of other structural units) is usually 0% by mass or more and 15% by mass or less.

[0073] <Method for producing ring-opening polymer hydride of cyclic olefin>

[0074] [Preparation of ring-opening polymer of cyclic olefin]

[0075] As the ring-opening polymer of cyclic olefin, which is a precursor of the ring-opening polymer hydride of cyclic olefin containing 80% by mass or more of the structural unit (A) and 5% by mass or more and 20% by mass or less of the structural unit (B), it can be obtained by ring-opening polymerization of a monomer composition (mixture) containing the monomers described in the item of the above "ring-opening polymer hydride of cyclic olefin". Specifically, for example, the ring-opening polymer of cyclic olefin can be prepared by ring-opening polymerization of the above monomer composition using a known ring-opening polymerization method such as ring-opening polymerization using a metathesis polymerization catalyst.

[0076] In addition, by carrying out ring-opening polymerization, the number of rings of each of the above monomers is reduced by at least one.

[0077] Here, as the metathesis polymerization catalyst, there is no particular limitation, and known metathesis polymerization catalysts can be used. Specifically, the following catalysts can be used: a catalyst system composed of a metal halide, nitrate or acetylacetone compound selected from ruthenium, rhodium, palladium, osmium, iridium, platinum, etc., and a reducing agent; a catalyst system composed of a metal halide or acetylacetone compound selected from titanium, vanadium, zirconium, tungsten, and molybdenum, and an organoaluminum compound as a cocatalyst; or known Schrock-type and Grubbs-type living ring-opening metathesis catalysts disclosed in Japanese Patent Laid-Open No. 7-179575, J. Am. Chem. Soc., 1986, 108, 733, J. Am. Chem. Soc., 1993, 115, 9858, and J. Am. Chem. Soc., 1996, 118, 100, etc. These catalysts can be used alone or in combination of two or more. The amount of the catalyst used can be appropriately selected according to the polymerization conditions, etc.

[0078] In addition, by further adding a polar compound to the above catalyst system, the polymerization activity and the selectivity of ring-opening polymerization can be improved. Examples of the polar compound include molecular oxygen, alcohols, ethers, peroxides, carboxylic acids, acid anhydrides, acyl chlorides, esters, ketones, nitrogen-containing compounds, sulfur-containing compounds, halogen-containing compounds, molecular iodine, and other Lewis acids. As the nitrogen-containing compound, aliphatic or aromatic tertiary amines are preferred, and specific examples include triethylamine, dimethylaniline, tri-n-butylamine, pyridine, α-methylpyridine, etc. These polar compounds can be used alone or in combination of two or more. Moreover, the amount used is appropriately selected, but in terms of the ratio to the metal in the above catalyst, that is, the ratio of the polar compound / metal (molar ratio), it is usually in the range of 1 to 100,000, preferably 5 to 10,000.

[0079] The polymerization reaction can be carried out by bulk polymerization without using a solvent, or in a solvent such as an organic solvent. As the solvent, there is no particular limitation as long as it is a solvent that is non-reactive to the polymerization reaction, and examples include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, hexane, and heptane; cycloaliphatic hydrocarbons such as cyclohexane; halogenated hydrocarbons such as styrene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, dichlorobenzene, and trichlorobenzene; and nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, acetonitrile, and benzonitrile.

[0080] Polymerization conditions such as polymerization temperature, polymerization pressure, and polymerization time can be appropriately adjusted.

[0081] [Hydrogenation of the Ring-Opening Polymer of Cyclic Olefin]

[0082] Hydrogenation of the resulting ring-opening polymer of cyclic olefin can be carried out using hydrogen and a hydrogenation catalyst. The hydrogenation of the ring-opening polymer of cyclic olefin can be carried out using any hydrogenation catalyst and hydrogenation conditions as long as it can hydrogenate non-aromatic carbon-carbon unsaturated bonds such as olefinic double bonds present in the ring-opening polymer of cyclic olefin.

[0083] Generally, it is preferred to hydrogenate the ring-opening polymer of cyclic olefin in such a way that the hydrogenation rate of non-aromatic carbon-carbon unsaturated bonds such as olefinic double bonds present in the ring-opening polymer of cyclic olefin (the ratio of the non-aromatic carbon-carbon unsaturated bonds after hydrogenation to the non-aromatic carbon-carbon unsaturated bonds of the ring-opening polymer of cyclic olefin) is 90% or more. It is preferred to hydrogenate the ring-opening polymer of cyclic olefin in such a way that the hydrogenation rate of non-aromatic carbon-carbon unsaturated bonds such as olefinic double bonds present in the ring-opening polymer of cyclic olefin is 95% or more. More preferably, it is to hydrogenate the ring-opening polymer of cyclic olefin in such a way that the hydrogenation rate of non-aromatic carbon-carbon unsaturated bonds such as olefinic double bonds present in the ring-opening polymer of cyclic olefin is 99% or more. Here, when an aromatic ring is present in the ring-opening polymer of cyclic olefin, as long as the effects of the present invention are not impaired, the carbon-carbon unsaturated bonds (aromatic carbon-carbon unsaturated bonds) of the aromatic ring may or may not be hydrogenated. If the hydrogenation rate of non-aromatic carbon-carbon unsaturated bonds such as olefinic double bonds contained in the ring-opening polymer of cyclic olefin is above the above lower limit value, good surface hardness and film-forming properties can be imparted to the hydrogenated product of the ring-opening polymer of cyclic olefin.

[0084] In addition, in the present invention, the hydrogenation rates of non-aromatic carbon-carbon unsaturated bonds and aromatic carbon-carbon unsaturated bonds can be measured by the methods described in the examples.

[0085] Furthermore, the hydrogenation rates of non-aromatic carbon-carbon unsaturated bonds and aromatic carbon-carbon unsaturated bonds can be adjusted by, for example, changing the type of hydrogenation catalyst and / or the conditions of the hydrogenation reaction.

[0086] As the hydrogenation catalyst, for example, a hydrogenation catalyst composed of dicyclopentadienyl titanium halide, nickel organic carboxylate, cobalt organic carboxylate, etc. and organometallic compounds of Groups 1 to 3 of the periodic table; nickel, platinum, palladium, ruthenium, rhenium, rhodium metal catalysts supported by carbon, silica, diatomaceous earth, etc., metal catalysts such as cobalt, nickel, rhodium, ruthenium complexes; hydrogenation compounds such as lithium aluminum hydride and p-toluenesulfonyl hydrazide, etc. Among these, as the hydrogenation catalyst, from the viewpoint of obtaining the target product without isomerization and with good yield, ruthenium compounds are preferred.

[0087] Examples of ruthenium compounds include RuHCl(CO)(PPh3)3, RuHCl(CO)[P(p-Me-Ph)3]3, RuHCl(CO)(PCy3)2, RuHCl(CO)[P(n-Bu)3]3, RuHCl(CO)[P(i-Pr)3]2, RuH2(CO)(PPh3)3, RuH2(CO)[P(p-Me-Ph)3]3, RuH2(CO)(PCy3)3, RuH2(CO)[P(n-Bu)3]3, RuH(OCOCH3)(CO)(PPh3)2, RuH(OCOPh)(CO)(PPh3)2, RuH(OCOPh-CH3)(CO)(PPh3)2, RuH(OCOPh-OCH3)(CO)(PPh3)2, RuH(OCOPh)(CO)(PCy3)2, etc.

[0088] In addition, the hydrogenation reaction of the ring-opening polymer of cyclic olefins can generally be carried out in an inert organic solvent. Examples of the inert organic solvent include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as pentane and hexane; alicyclic hydrocarbon solvents such as cyclohexane and decalin; ether solvents such as tetrahydrofuran and ethylene glycol dimethyl ether, etc.

[0089] Moreover, when hydrogenating the ring-opening polymer of cyclic olefins by adding hydrogen in a system containing the ring-opening polymer of cyclic olefins and a hydrogenation catalyst, the reaction temperature varies depending on the hydrogenation catalyst used, and is generally -20°C to 250°C, preferably -10°C to 220°C, more preferably 0°C to 200°C. When the reaction temperature is too low, the hydrogenation rate may become too slow, and when the reaction temperature is too high, side reactions may occur.

[0090] In addition, the hydrogen pressure is generally 0.01 to 20 MPa, preferably 0.05 to 15 MPa, more preferably 0.1 to 10 MPa. When the hydrogen pressure is too low, the hydrogenation rate may become too slow, and when the hydrogen pressure is too high, there are equipment limitations in terms of the need for a high-pressure-resistant reaction device.

[0091] Furthermore, the reaction time also depends on the reaction scale and is generally 0.1 to 10 hours.

[0092] In addition, after the hydrogenation reaction, the hydrogenated product of the ring-opening polymer of cyclic olefins obtained by recovery according to a conventional method is sufficient. When recovering the hydrogenated product, catalyst residues can be removed by methods such as filtration.

[0093] [Hydrogenated product of ring-opening polymer of cyclic olefins]

[0094] The cyclic olefin ring-opening polymer hydride obtained by hydrogenating a cyclic olefin ring-opening polymer usually has two or more structural units (A) derived from polycyclic norbornene monomers having a polycyclic structure with four or more rings, and structural units (B) derived from polycyclic norbornene monomers having a polycyclic structure with two or three rings, and may optionally further have other structural units.

[0095] Herein, among the structural units (A) derived from polycyclic norbornene monomers having a polycyclic structure with four or more rings in the cyclic olefin ring-opening polymer hydride, it includes the structural units obtained by ring-opening polymerization of polycyclic norbornene monomers having a polycyclic structure with four or more rings and the structural units obtained by hydrogenating the said structural units. Similarly, among the structural units (B) derived from polycyclic norbornene monomers having a polycyclic structure with two or three rings in the cyclic olefin ring-opening polymer hydride, it includes the structural units obtained by ring-opening polymerization of polycyclic norbornene monomers having a polycyclic structure with two or three rings and the structural units obtained by hydrogenating the said structural units.

[0096] In addition, the "structural units obtained by ring-opening polymerization of polycyclic norbornene monomers having a polycyclic structure with four or more rings" and the "structural units obtained by ring-opening polymerization of polycyclic norbornene monomers having a polycyclic structure with two or three rings" in the cyclic olefin ring-opening polymer hydride are unhydrogenated structural units (repeating units) that are not hydrogenated during the hydrogenation of the cyclic olefin ring-opening polymer.

[0097] Moreover, the cyclic olefin ring-opening polymer hydride preferably has the following properties.

[0098] -Scratch hardness-

[0099] For the cyclic olefin ring-opening polymer hydride, when formed into a film, the value of the scratch hardness measured based on JIS K5600 is preferably B or more, more preferably HB or more. The surface hardness of the cyclic olefin ring-opening polymer hydride with the value of the scratch hardness being B or more is excellent, and the surface hardness of the cyclic olefin ring-opening polymer hydride with the value of the scratch hardness being HB or more is further excellent.

[0100] -Yield point-

[0101] In addition, for the cyclic olefin ring-opening polymer hydride, when formed into a film, it is preferably confirmed to have a yield point in the stress-strain curve of the tensile test conducted based on JIS K7127. The film-forming property of the cyclic olefin ring-opening polymer hydride in which a yield point is confirmed in the stress-strain curve of the said tensile test is excellent.

[0102] (Resin composition)

[0103] The resin composition of the present invention contains the cyclic olefin ring-opening polymer hydride of the present invention as described above, and optionally further contains a polymer material and / or various additives other than the cyclic olefin ring-opening polymer hydride of the present invention.

[0104] There is no particular limitation on the polymer materials and additives that can be contained in the resin composition, and examples thereof include the polymer materials and additives described in Japanese Patent Laid-Open No. 10-139865.

[0105] The resin composition particularly preferably contains antioxidants such as phenolic antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

[0106] There is no particular limitation on the polymer materials and additives as long as they can be sufficiently dispersed in the cyclic olefin ring-opening polymer hydride, and any method can be used to mix them with the cyclic olefin ring-opening polymer hydride. Specifically, the polymer materials and additives can be added in any process during the preparation of the cyclic olefin ring-opening polymer hydride, or can be kneaded with the cyclic olefin ring-opening polymer hydride using a kneader, or can be mixed with the cyclic olefin ring-opening polymer hydride in a molding device.

[0107] There is no particular limitation on the compounding amount of the polymer materials and additives as long as the effects of the present invention are not impaired. For example, it can be 0.01 parts by mass or more and 2.0 parts by mass or less relative to 100 parts by mass of the cyclic olefin ring-opening polymer hydride.

[0108] (Film)

[0109] The film of the present invention is formed by molding the above-described resin composition of the present invention into a film shape. Since the film of the present invention contains the cyclic olefin ring-opening polymer hydride of the present invention as described above, it has excellent surface hardness and can suppress breakage and cracks when wound into a roll.

[0110] The film of the present invention is not particularly limited and is preferably an optical film. This is because the film of the present invention has excellent surface hardness, and therefore, it can preferably be used as a surface member in display devices such as liquid crystal displays, organic EL displays, and μLED displays.

[0111] Here, as the molding method, there is no particular limitation as long as the resin composition can be molded into a film shape, and molding methods such as an extrusion molding method, a casting molding method, a blow molding method, and a blown film molding method can be used. An extrusion method is particularly preferred, and a melt extrusion method is more preferred.

[0112] The film of the present invention can be obtained, for example, by heating and melting the particles of the resin composition, then melt-extruding the obtained molten resin to obtain a film, and then winding the film into a roll.

[0113] In addition, the film of the present invention can also be configured as a multilayer structure in which an arbitrary intermediate layer is sandwiched between multiple films of the present invention.

[0114] Moreover, the film of the present invention obtained in this way preferably has the following properties.

[0115] <Scratch hardness>

[0116] For the film of the present invention, for at least one surface, the value of the scratch hardness measured based on JIS K5600 is preferably B or more, more preferably HB or more. If the value of the above scratch hardness is B or more, the surface hardness is excellent, and if the value of the above scratch hardness is HB or more, the surface hardness is further excellent. For the film of the present invention, for both surfaces, the value of the above scratch hardness is preferably B or more, more preferably HB or more.

[0117] <Yield point>

[0118] For the film of the present invention, it is preferable to confirm the yield point in the stress-strain curve of the tensile test conducted based on JIS K7127. A film in which the yield point is confirmed in the stress-strain curve of the above tensile test can suppress breakage and cracks from occurring when wound into a roll.

[0119] <Thickness>

[0120] The film of the present invention preferably has a thickness of 20 μm or more. If the thickness is at the above lower limit value or more, breakage and cracks generated when wound into a roll can be further suppressed.

[0121] In addition, the film of the present invention can have a hard coat on the surface. The surface hardness of the film of the present invention is excellent, and the strength after providing the hard coat can be further improved.

[0122] The hard coat can be provided on only one surface of the film or on both surfaces.

[0123] Examples

[0124] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0125] In addition, the measurements and evaluations in each example were carried out by the following methods. In addition, unless otherwise specified, "parts" and "%" indicating amounts in the following description are based on mass.

[0126] (1) Weight-average molecular weight of the cyclic olefin ring-opening polymer hydride

[0127] The weight-average molecular weight (Mw) of the cyclic olefin ring-opening polymer hydride was measured by gel permeation chromatography (GPC) using cyclohexane as the eluent and obtained as a standard polyisoprene conversion value.

[0128] As the standard polyisoprene, standard polyisoprene manufactured by Tosoh Corporation (Mw = 602, 1390, 3920, 8050, 13800, 22700, 58800, 71300, 109000, 280000) was used.

[0129] The measurement was carried out using three chromatographic columns (manufactured by Tosoh Corporation, TSKgel G5000HXL, TSKgel G4000HXL, and TSKgel G2000HXL) connected in series, at a flow rate of 1.0 mL / minute, a sample injection volume of 100 μL, and a column temperature of 40 °C.

[0130] (2) Hydrogenation rate

[0131] The hydrogenation rate of non-aromatic carbon-carbon unsaturated bonds was measured by 1 1H-NMR.

[0132] (3) Scratch hardness (pencil method)

[0133] Using the films produced in the examples and comparative examples as test pieces, a friction and wear testing machine (manufactured by Shinto Kagaku Co., Ltd., Type-38) was used, and in accordance with JIS-K5600, under the conditions of a load of 750 g and a test speed of 1 mm / s, the pencil concentration was determined by visual inspection. The higher the scratch hardness (pencil hardness), the better the surface hardness.

[0134] (4) Film-forming property

[0135] The films produced in the examples and comparative examples were continuously wound at a speed of 15 m / minute for 20 minutes to form a roll, and the film-forming property was evaluated according to the following criteria.

[0136] Good: The film did not show breakage or cracks.

[0137] Poor: The film showed breakage or cracks more than once.

[0138] (5) Tensile test

[0139] The films produced in the examples and comparative examples were punched in the shape of test piece type 1B of JIS K7127:1999 standard along the MD direction (MD: Machine Direction) to produce tensile test samples. For the obtained samples, a universal material testing machine (manufactured by Instron Corporation, model 5582) was used, and a tensile test was carried out under the condition of a tensile speed of 50 mm / minute, and the presence or absence of a yield point in the obtained stress-strain curve was evaluated according to the following criteria.

[0140] Yes: More than 3 yield points could be confirmed among 5 test points.

[0141] None: Only less than 2 yield points can be confirmed among 5 test points

[0142] (Example 1)

[0143] Into a polymerization reactor that has been dried inside and purged with nitrogen, 2.0 parts of a monomer mixture (1% relative to the total amount of monomers used for polymerization) composed of 55% by mass of tetracyclo[4.4.0.1 2,5 .1 7,10 -dodecene-3-ene (hereinafter sometimes simply referred to as "TCD"), 30% by mass of 1,4-methano-1,4,4a,9a-tetrahydrofluorene (hereinafter sometimes simply referred to as "MTF"), and 15% by mass of dicyclopentadiene (hereinafter sometimes simply referred to as "DCPD") as a polycyclic norbornene monomer having a bicyclic or tricyclic polycyclic structure, 583 parts of dehydrated cyclohexane, 0.87 part of 1-hexene as a molecular weight regulator (chain transfer agent), 1.10 parts of a hexane solution of ethoxydiethylaluminum (concentration: 19%) as a polymerization catalyst, and 13.0 parts of a toluene solution of (phenylimide)tungsten tetrachloride·tetrahydrofuran (concentration: 2.0%) as a polymerization catalyst were added, and all the contents were stirred at 50°C for 10 minutes.

[0144] Next, while maintaining all the contents at 50°C and stirring, 198.0 parts of the same monomer mixture as described above were continuously added dropwise to the above polymerization reactor over 150 minutes. After the addition was completed, stirring was continued for 30 minutes, and then 4 parts of isopropyl alcohol were added to terminate the polymerization reaction. The polymerization reaction solution was measured by gas chromatography, and as a result, the conversion rate of the monomer to the polymer was 100%.

[0145] Next, 300 parts of the obtained polymerization reaction solution were transferred to an autoclave equipped with a stirrer, and 75 parts of cyclohexane as a solvent and 8.0 parts of a nickel-on-diatomite catalyst (manufactured by Nippon Kayaku Co., Ltd., "T8400RL", nickel loading rate: 58%) as a hydrogenation catalyst were added. After purging the inside of the autoclave with hydrogen, a hydrogenation reaction was carried out at 190°C and a hydrogen pressure of 4.5 MPa for 6 hours.

[0146] After the hydrogenation reaction was completed, using diatomaceous earth ("RADIOLITE (registered trademark) #500") as a filter bed and a pressure filter (manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd., "FUNDA Filter"), pressure filtration was carried out at a pressure of 0.25 MPa to obtain a colorless and transparent solution containing a hydrogenated product of a cyclic olefin ring-opening polymer.

[0147] In the resulting solution, 0.5 part of pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by Ciba Specialty Chemicals Corporation, product name “Irganox (registered trademark) 1010”) as an antioxidant was added to 100 parts of the cyclic olefin ring-opening polymer hydride and dissolved therein. Subsequently, foreign matters were removed by filtration using a filter (manufactured by CUNO Filter Corporation, “Zeta plus (registered trademark) 30H”, pore diameter 0.5 to 1 μm) and a filter made of metal fiber (manufactured by NICHIDAI Co., Ltd., pore diameter 0.4 μm).

[0148] Next, the filtrate obtained above was added to a cylindrical concentration dryer (manufactured by Hitachi, Ltd.) and treated under the conditions of a temperature of 290 °C and a pressure of 1 kPa or less, whereby cyclohexane as a solvent and other volatile components were removed from the solution. Then, the solid components contained in the solution were extruded in a molten state into strands from a die directly connected to the concentrator, and after water cooling, they were cut using a granulator (manufactured by Nagata Seisakusho, “OSP-2”). According to the above steps, particles of a resin composition containing a cyclic olefin ring-opening polymer hydride were obtained. In addition, the hydrogenation rate of the carbon-carbon double bonds (non-aromatic carbon-carbon unsaturated bonds) present in the cyclic olefin ring-opening polymer hydride was 99% or more.

[0149] The above particles were put into a film extruder (manufactured by Optical Control Systems, MeasuringExtruder Type Me-20 / 2800V3) and melt-extruded under the conditions of a resin temperature of 280 °C and a screw rotation speed of 50 rpm to obtain a film having a thickness of 30 μm and a width of 120 mm.

[0150] Then, various evaluations were carried out. The results are shown in Table 1.

[0151] (Example 2)

[0152] In Example 1, a monomer mixture composed of 60% by mass of TCD, 30% by mass of MTF, and 10% by mass of norbornene (hereinafter sometimes simply referred to as “NB”) as a polycyclic norbornene-based monomer having a bicyclic or tricyclic polycyclic structure was used, and the amount of 1-hexene as a molecular weight regulator was changed to 1.05 parts. Except for this, various operations and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0153] (Example 3)

[0154] In Example 1, a monomer mixture composed of 75% by mass of TCD, 20% by mass of MTF, and 5% by mass of NB was used, and other than this, various operations and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0155] (Example 4)

[0156] In Example 1, a monomer mixture composed of 50% by mass of TCD, 40% by mass of MTF, and 10% by mass of DCPD was used, and further, the amount of 1 - hexene as a molecular weight regulator was changed to 0.67 parts. Other than this, various operations and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0157] (Comparative Example 1)

[0158] In Example 1, a monomer mixture composed of 80% by mass of TCD, 10% by mass of MTF, and 10% by mass of DCPD was used, and further, the amount of 1 - hexene as a molecular weight regulator was changed to 1.35 parts. Other than this, various operations and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0159] (Comparative Example 2)

[0160] In Example 1, a monomer mixture composed of 75% by mass of TCD and 25% by mass of MTF was used, and further, the amount of 1 - hexene as a molecular weight regulator was changed to 1.05 parts. Other than this, various operations and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0161] (Comparative Example 3)

[0162] In Example 1, a monomer mixture composed of 40% by mass of TCD, 20% by mass of MTF, and 40% by mass of DCPD was used, and further, the amount of 1 - hexene as a molecular weight regulator was changed to 0.56 parts. Other than this, various operations and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0163] (Comparative Example 4)

[0164] In Example 1, a monomer mixture composed of 75% by mass of TCD, 15% by mass of NB, and 10% by mass of DCPD was used, and other than this, various operations and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0165] [Table 1]

[0166]

[0167] In Table 1,

[0168] "TCD" represents tetracyclododecene,

[0169] "MTF" represents methylene tetrahydrofluorene,

[0170] "NB" represents norbornene,

[0171] "DCPD" represents dicyclopentadiene.

[0172] As can be seen from Table 1, the cyclic olefin ring-opening polymer hydrides of Examples 1 to 4, which contain structural units (A) from polycyclic norbornene monomers having a polycyclic structure with four or more rings and structural units (B) from polycyclic norbornene monomers having a polycyclic structure with two or three rings, with the content ratio of the above structural units (A) being 80% by mass or more, the content ratio of the above structural units (B) being 5% by mass or more and 20% by mass or less, and the weight-average molecular weight being 27,000 or more and 50,000 or less, have excellent surface hardness and film-forming properties.

[0173] Industrial applicability

[0174] According to the present invention, it is possible to provide a cyclic olefin ring-opening polymer hydride having excellent surface hardness and film-forming properties, and a resin composition and a film containing the cyclic olefin ring-opening polymer hydride.

Claims

1. A cyclic olefin ring-opening polymer hydride, which contains two or more structural units (A) derived from polycyclic norbornene monomers having a polycyclic structure with four or more rings, and structural units (B) derived from polycyclic norbornene monomers having a polycyclic structure with two or three rings. When the content ratio of all the repeating units contained in the cyclic olefin ring-opening polymer hydride is 100% by mass, the content ratio of the structural unit (A) is 80% by mass or more, and the content ratio of the structural unit (B) is 5% by mass or more and 20% by mass or less. The cyclic olefin ring-opening polymer hydride has a weight-average molecular weight of 27,000 or more and 50,000 or less.

2. The cyclic olefin ring-opening polymer hydride according to claim 1, wherein, The cyclic olefin ring-opening polymer hydride contains structural units derived from cyclododecene and structural units derived from methano-tetrahydrofluorene.

3. The cyclic olefin ring-opening polymer hydride according to claim 1, wherein, The cyclic olefin ring-opening polymer hydride contains structural units derived from dicyclopentadiene.

4. The cyclic olefin ring-opening polymer hydride according to claim 1, wherein, When formed into a film, the value of the scratch hardness measured based on JIS K5600 is B or more.

5. The cyclic olefin ring-opening polymer hydride according to claim 1, wherein, When formed into a film, a yield point is confirmed in the stress-strain curve of the tensile test conducted based on JIS K7127.

6. A resin composition, which contains the cyclic olefin ring-opening polymer hydride according to any one of claims 1 to 5.

7. A film, which is formed by molding the resin composition according to claim 6.

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