JP2020066683A - Norbornene-based ring-opened polymer hydride, resin composition and molding - Google Patents

Abstract

To provide a norbornene-based ring-opened polymer hydride that has both of a moderate Abbe number and excellent heat coloring resistance.SOLUTION: A norbornene-based ring-opened polymer hydride is obtained by hydrogenating a norbornene-based ring-opened polymer that contains a norbornene compound-derived structural unit having an aromatic ring at a rate of 40 mass% or more and 100 mass% or less, with a hydrogenateion rate of a carbon-carbon unsaturated bond of the aromatic ring being 0% or more and 1.5% or less. The norbornene-based ring-opened polymer hydride preferably has a glass transition temperature of 100°C or higher.SELECTED DRAWING: None

Description

  The present invention relates to a norbornene-based ring-opening polymer hydride, a resin composition containing the norbornene-based ring-opening polymer hydride, and a molded article formed using the resin composition.

  A hydride of a ring-opening polymer of a norbornene (hereinafter, also referred to as "a hydride of a norbornene-based ring-opening polymer") is a kind of so-called cycloolefin polymer, and has transparency, low birefringence and molding process. Due to its excellent properties, it is used as a material that can be applied to various applications including optical applications.

  Specifically, for example, in Patent Document 1, as a norbornene-based ring-opening polymer hydride that has excellent performance and can be advantageously used as a material for various molded articles, a structural unit derived from tetracyclododecene, Ring-opening copolymer hydrogenated product obtained by hydrogenating a ring-opening copolymer containing a structural unit derived from dicyclopentadiene and a structural unit derived from 1,4-methano-1,4,4a, 9a-tetrahydrofluorene Is disclosed.

JP, 10-139865, A

  Here, from the viewpoint of increasing the degree of freedom in optical design in recent years, a norbornene-based material having an appropriate Abbe number (for example, about 35 to 50) is used as an optical material used for molding an optical element such as a lens. There is a need to develop ring polymer hydrides.

  Further, the norbornene-based ring-opening polymer hydride used as a material for various molded products such as optical elements is required not to be colored even when heated during kneading or molding (that is, excellent in heat resistant coloring). There is.

  However, the conventional norbornene-based ring-opening polymer hydride described in Patent Document 1 does not have both an appropriately large Abbe number and excellent heat resistance coloring.

Therefore, an object of the present invention is to provide a norbornene-based ring-opening polymer hydride that has both an appropriate Abbe number and excellent heat-resistant coloring.
Another object of the present invention is to provide a resin composition that can be advantageously used as a material for various molded products such as optical elements, and a molded product formed using the resin composition.

  The present inventor has conducted earnest studies for the purpose of solving the above problems. The present inventor, the norbornene-based ring-opening polymer containing a structural unit derived from a norbornene compound having an aromatic ring in a predetermined ratio, the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring is below a predetermined value. It was newly found that the hydrogenated norbornene ring-opening polymer hydride obtained by hydrogenating the above can achieve both an appropriate Abbe number and excellent heat-resistant colorability, and completed the present invention.

That is, the present invention has an object to advantageously solve the above problems, and the hydride of the norbornene-based ring-opening polymer of the present invention has a structural unit derived from a norbornene compound having an aromatic ring of 40% by mass or more. It is characterized by hydrogenating a norbornene-based ring-opening polymer contained at a ratio of 100% by mass or less, and the hydrogenation rate of carbon-carbon unsaturated bond of an aromatic ring is 0% or more and 1.5% or less. Thus, by hydrogenating a norbornene ring-opening polymer containing structural units derived from a norbornene compound having an aromatic ring in the above proportions, a norbornene type ring polymer having an appropriate Abbe number (for example, about 35 to 50) can be obtained. A ring-opening polymer hydride is obtained. When the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring is not more than the above upper limit value, the heat-resistant coloring property of the obtained norbornene-based ring-opening polymer hydride can be sufficiently enhanced.
In the present invention, "the content of the structural unit" ^can be measured using nuclear magnetic resonance (NMR) method such as 1 H-NMR and ¹³ C-NMR. In the present invention, the “hydrogenation rate of carbon-carbon unsaturated bond of aromatic ring” can be measured according to the method described in Examples of the present specification.

Here, the norbornene-based ring-opening polymer hydride of the present invention preferably has a glass transition temperature of 100 ° C. or higher. When the glass transition temperature is 100 ° C. or higher, the stress optical coefficient of the hydrogenated norbornene ring-opening polymer can be increased.
In addition, in this invention, "glass transition temperature" can be measured according to the method described in the Example of this specification.

The hydrogenation product of the norbornene-based ring-opening polymer of the present invention preferably has a hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond of 95% or more. When the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond is at least the above lower limit value, the Abbe number of the norbornene-based ring-opening polymer hydride can be appropriately increased.
In the present invention, the “hydrogenation rate of non-aromatic carbon-carbon unsaturated bond” can be measured according to the method described in Examples of the present specification.

  Moreover, this invention aims at solving the said subject advantageously, The resin composition of this invention is characterized by including any of the above-mentioned hydrogenated norbornene ring-opening polymer. . The resin composition containing the hydrogenated norbornene ring-opening polymer described above can be advantageously used as a material for various molded articles such as optical elements.

  Further, the present invention has an object to advantageously solve the above-mentioned problems, and the molded product of the present invention is characterized by being formed using the above-mentioned resin composition. A molded article formed by using the resin composition described above can exhibit excellent performance.

  The molded product of the present invention is preferably an optical film. A resin composition containing a hydride of a norbornene-based ring-opening polymer having an appropriate Abbe number and excellent heat-resistant coloring can be suitably used for forming an optical element such as an optical film.

According to the present invention, it is possible to provide a hydrogenated norbornene-based ring-opening polymer having both an appropriate Abbe number and excellent heat-resistant coloring.
Further, according to the present invention, it is possible to provide a resin composition that can be advantageously used as a material for various molded products such as optical elements, and a molded product formed using the resin composition.

Hereinafter, embodiments of the present invention will be described in detail.
Here, the hydride of the norbornene-based ring-opening polymer of the present invention has an appropriate Abbe number and excellent heat resistance coloring, and is suitable as a material for various molded articles such as optical elements. Can be used.

(Norbornene ring-opening polymer hydride)
The norbornene-based ring-opening polymer hydride is, for example, a ring-opening polymerization of a monomer composition containing a norbornene compound in the presence of a polymerization catalyst, and the carbon-carbon-free carbon atom present in the obtained norbornene-based ring-opening polymer. Obtained by hydrogenating a saturated bond. The norbornene-based ring-opening polymer hydride of the present invention contains a norbornene compound having an aromatic ring in a proportion of 40% by mass or more and 100% by mass or less, and optionally further contains other structural units. It is formed by hydrogenating a ring-opening polymer. The hydrogenated norbornene-based ring-opening polymer of the present invention has a hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring contained in the norbornene-based ring-opening polymer of 0% or more and 1.5% or less. Is.

<Norbornene ring-opening polymer>
The norbornene ring-opening polymer has a structural unit derived from a norbornene compound having an aromatic ring, and optionally a structural unit derived from a norbornene compound having no aromatic ring and a structure derived from a non-norbornene compound having no norbornene ring. It further comprises at least one of the units.

[Structural unit derived from norbornene compound having aromatic ring]
Examples of the norbornene compound capable of forming the structural unit derived from the norbornene compound having an aromatic ring include compounds having an aromatic ring and a norbornene ring in the molecule.
In addition, the aromatic ring and the norbornene ring may exist separately as a single ring, or may form a condensed ring. Among them, from the viewpoint of increasing the stress optical coefficient of the hydrogenated norbornene ring-opening polymer obtained by hydrogenating the norbornene ring-opening polymer, it is preferable that the aromatic ring and the norbornene ring form a condensed ring.

  Here, the aromatic ring is not particularly limited, and examples thereof include an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring and an anthracene ring, and an aromatic heterocycle such as a thiophene ring, a pyrrole ring and a pyridine ring. .

The compound having an aromatic ring and a norbornene ring in the molecule (norbornene compound having an aromatic ring) is not particularly limited, and examples thereof include phenylnorbornene such as 5-phenyl-2-norbornene and 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 [ie 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, 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, 11-phenyl-hexacyclo [6.6.1.1 ^3,6 . 1 ^{10, 13} . 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-diphenyl-bicyclo [2.2.1] -hept-2-ene, 9- (2-norbornen-5-yl) -carbazole, 1,4-methano-1,4,4a, 4b, 5,8 , 8a, 9a-octahydrofluorene, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-8-methyl-1,4,4a, 9a-tetrahydrofluorene, 1,4 -Methano-8-chloro-1,4,4a, 9a-tetra Drofluorene, 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, cyclopentadiene-acenaphthylene adduct further added with cyclopentadiene, 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.
Among them, from the viewpoint of exhibiting high refractive index at the time of molding, phenyl norbornene and tetracyclo ^{[6.5.1 2,5.} 0 ^1,6 . 0 ^8,13] trideca -3,8,10,12- tetraene (1,4-methano -1,4,4a, 9a- tetrahydrofluorene) are preferred, 1,4-methano -1,4,4a, 9a -Tetrahydrofluorene is more preferred.
The above norbornene compounds having an aromatic ring may be used alone or in combination of two or more.

  And, the ratio of the structural unit derived from the norbornene compound having an aromatic ring in all the structural units (100% by mass) of the norbornene ring-opening polymer needs to be 40% by mass or more and 100% by mass or less, Especially, 50 mass% or more is preferable and 80 mass% or less is preferable. When the proportion of the structural unit derived from the norbornene compound having an aromatic ring is within the above range, norbornene having an appropriate Abbe number (for example, about 35 to 50) when hydrogenating the norbornene ring-opening polymer is obtained. A hydrogenated ring-opening polymer can be obtained.

[Structural unit derived from norbornene compound having no aromatic ring]
The norbornene compound (norbornene compound having no aromatic ring) capable of forming a structural unit derived from a norbornene compound having no aromatic ring is not particularly limited, and examples thereof include norbornene; 5-methylnorbornene, and 5-ethyl. Norbornenes having an alkyl group such as norbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5-cyclohexylnorbornene, 5-cyclopentylnorbornene; 5-ethylidenenorbornene, 5-vinylnorbornene, 5-propenylnorbornene, Norbornenes having an alkenyl group such as 5-cyclohexenyl norbornene and 5-cyclopentenyl norbornene; 5-methoxycarbonyl norbornene, 5-ethoxycarbonyl norbornene, 5-methyl-5 Methoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-methylpropionate, norbornenyl-2-methyloctaneate, norbornene-5,6-dicarboxylic acid anhydride, 5-hydroxymethylnorbornene, 5, Oxygen atom such as 6-di (hydroxymethyl) norbornene, 5,5-di (hydroxymethyl) norbornene, 5-hydroxy-i-propylnorbornene, 5,6-dicarboxynorbornene, 5-methoxycarbonyl-6-carboxynorbornene norbornenes having polar group containing 5-cyano-norbornene, a nitrogen atom, such as norbornene-5,6-dicarboximide; norbornenes having polar group comprising dicyclopentadiene, tricyclo [4.3.0.1 ^{2 ，} ] Dec-3-ene, tricyclo ^{[4.4.1 2,5.} 0] und 3-dicyclopentadiene such as ene; tetracyclododecene (tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} - dodeca-3-ene); 8-methyl tetracyclododecene Tetracyclododecenes having an alkyl group such as dodecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, 8-cyclopentyltetracyclododecene; 8-methylidene tetracyclododecene, 8-ethylidene Tetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, 8-cyclopentenyltetracyclododecene, etc. Dodecenes; 8-methoxycarbonyltetracyclododecene, 8-methyl-8-meth Xycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-8,9-dicarboxylic acid anhydride, etc. Tetracyclododecenes having a substituent containing an oxygen atom; tetracyanododecenes having a substituent containing a nitrogen atom, such as 8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboxylic acid imide Tetracyclododecenes having a substituent containing a halogen atom such as 8-chlorotetracyclododecene; tetracyclododecenes having a substituent containing a silicon atom such as 8-trimethoxysilyltetracyclododecene; hexa Cycloheptadecene; 12-methylhexacycloheptadecene, 12-ethyl Hexacycloheptadecenes having an alkyl group such as sacycloheptadecene, 12-cyclohexylhexacycloheptadecene, 12-cyclopentylhexacycloheptadecene; 12-methylidene hexacycloheptadecene, 12-ethylidene hexacycloheptadecene, 12 -Hexacycloheptadecenes having a double bond outside the ring such as vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexacycloheptadecene, 12-cyclopentenylhexacycloheptadecene; 12- Methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacyclo Hexacycloheptadecenes having a substituent containing an oxygen atom, such as butadecene, hexacycloheptadecene 12,13-dicarboxylic acid, and hexacycloheptadecene 12,13-dicarboxylic anhydride; 12-cyanohexacycloheptadecene, hexa Hexacycloheptadecenes having a substituent containing a nitrogen atom such as cycloheptadecene 12,13-dicarboxylic acid imide; hexacycloheptadecenes having a substituent containing a halogen atom such as 12-chlorohexacycloheptadecene; 12 -Hexacycloheptadecenes having a substituent containing a silicon atom such as trimethoxysilylhexacycloheptadecene; and the like.
Among them, tricyclo [4.3.0.1 ^2,5 ] deca-3-ene and tetracyclododecene (tetracyclo [4.4.0.1 ^2,5 ] are preferable from the viewpoint of exhibiting a high refractive index during molding. .1 ^7,10 ] -dodeca-3-ene) is preferred.
The above-mentioned norbornene compounds having no aromatic ring may be used alone or in combination of two or more.

  The proportion of the structural unit derived from the norbornene compound having no aromatic ring in all the structural units (100% by mass) of the norbornene ring-opening polymer is usually 0% by mass or more and 60% by mass or less. When the ratio of the structural unit derived from the norbornene compound having no aromatic ring is within the above range, the Abbe number of an appropriate size (for example, about 35 to 50) is obtained when the norbornene ring-opening polymer is hydrogenated. It is possible to obtain a hydrogenated norbornene-based ring-opening polymer.

[Structural units derived from non-norbornene compounds]
The non-norbornene compound capable of forming a structural unit derived from the non-norbornene compound which the norbornene ring-opening polymer may optionally contain is not particularly limited, and examples thereof include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and 1 And monocyclic cycloalkenes such as 4-cyclooctadiene and cyclodecene.
The above-mentioned non-norbornene compounds may be used alone or in combination of two or more.

  The proportion of the structural units derived from the non-norbornene compound in all the structural units (100% by mass) of the norbornene ring-opening polymer is usually 0% by mass or more and 60% by mass or less.

[Method for producing norbornene ring-opening polymer]
The norbornene-based ring-opening polymer containing 40% by mass or more of the structural unit derived from the norbornene compound having an aromatic ring can be prepared by a known ring-opening polymerization method such as ring-opening polymerization using a metathesis polymerization catalyst. .

  Here, the metathesis polymerization catalyst is not particularly limited and a known catalyst can be used. Specifically, for example, a catalyst system consisting of a halide, nitrate or acetylacetone compound of a metal selected from ruthenium, rhodium, palladium, osmium, iridium and platinum and a reducing agent; titanium, vanadium, zirconium, tungsten and molybdenum. A catalyst system comprising a metal halide or an acetylacetone compound selected from the group consisting of the following and an organoaluminum compound as a cocatalyst; or JP-A-7-179575, J. Am. Chem. Soc. , 1986, 108, 733, J. Am. Chem. Soc. , 1993, 115, 9858, and J. Am. Chem. Soc. , 1996, 118, 100 and the like, known shrock type and Grubbs type living ring-opening metathesis catalysts can be used. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used may be appropriately selected depending on the polymerization conditions and the like.

  A polar compound may be further added to the above catalyst system to enhance the polymerization activity and the selectivity of ring-opening polymerization. Examples of polar compounds include molecular oxygen, alcohols, ethers, peroxides, carboxylic acids, acid anhydrides, acid chlorides, esters, ketones, nitrogen-containing compounds, sulfur-containing compounds, halogen-containing compounds, molecular iodine, and others. Lewis acid and the like. The nitrogen-containing compound is preferably an aliphatic or aromatic tertiary amine, and specific examples thereof include triethylamine, dimethylaniline, tri-n-butylamine, pyridine and α-picoline. These polar compounds may be used alone or in combination of two or more. The amount used is appropriately selected, but is usually 1 to 100,000, preferably 5 to 10,000 in terms of the ratio with the metal in the catalyst, that is, the ratio (molar ratio) of polar compound / metal. Is the range.

  The polymerization reaction may be performed by bulk polymerization without using a solvent, or may be performed in a solvent such as an organic solvent. The solvent is not particularly limited as long as it is inert to the polymerization reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, hexane and heptane. Alicyclic hydrocarbons such as cyclohexane; halogenated hydrocarbons such as styrene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene; nitromethane, nitrobenzene, acetonitrile, benzonitrile, etc. Nitrogen-containing hydrocarbons; and the like.

  Then, the polymerization conditions such as the polymerization temperature, the polymerization pressure and the polymerization time can be appropriately adjusted.

<Hydrogenation of norbornene ring-opening polymer>
Hydrogenation of the obtained norbornene ring-opening polymer can be carried out using hydrogen and a hydrogenation catalyst.

Here, the hydrogenation of the norbornene ring-opening polymer is carried out by setting the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring present in the norbornene ring-opening polymer to 0% or more and 1.5% or less. If possible, it can be carried out using any hydrogenation catalyst and hydrogenation conditions.
Among them, the hydrogenation of the norbornene ring-opening polymer is performed so that the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring present in the norbornene ring-opening polymer is 1.0% or less. Preferably, it is more preferably 0.8% or less. If the hydrogenation rate of the aromatic ring is at most the above upper limit, even if the norbornene ring-opening polymer in which the proportion of the structural unit derived from the norbornene compound having an aromatic ring is 40% by mass or more is hydrogenated, It is possible to sufficiently enhance the heat resistant coloration property while making the Abbe number moderate.

  Further, the hydrogenation of the norbornene ring-opening polymer results in the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond existing in the norbornene ring-opening polymer being 95% or more and 100% or less. It is preferable to carry out so as to be 99% or more, more preferably to be 99.5% or more. If the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond such as the olefinic double bond present in the main chain and / or side chain of the norbornene ring-opening polymer is at least the above lower limit, it is favorable. It is possible to improve the Abbe number while imparting heat resistant coloration.

  The hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring and the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond are adjusted by changing the type of the hydrogenation catalyst and / or the hydrogenation conditions. can do.

  Then, as the hydrogenation catalyst, for example, a hydrogenation catalyst composed of dicyclopentadienyl titanium halide, nickel organic carboxylate, cobalt organic carboxylate and the like and an organometallic compound of Group 1 to 3 of the periodic table; carbon, Nickel, platinum, palladium, ruthenium, rhenium, rhodium metal catalysts, metal catalysts such as cobalt, nickel, rhodium, ruthenium complexes supported on silica, diatomaceous earth, etc .; hydrogenated compounds such as lithium aluminum hydride, p-toluenesulfonyl hydrazide And the like can be used. Among these, a ruthenium compound is preferable as the hydrogenation catalyst from the viewpoint that the desired product can be obtained in good yield without isomerization.

The ruthenium compound, for _{example, RuHCl (CO) (PPh 3} ) 3, RuHCl (CO) [P (p-Me-Ph) 3] 3, RuHCl (CO) (PCy 3) 2, RuHCl (CO) [P _{(n-Bu) 3] 3} , RuHCl (CO) [P (i-Pr) 3] 2, RuH 2 (CO) (PPh 3) 3, RuH 2 (CO) [P (p-Me-Ph) 3 _{] 3, RuH 2 (CO)} (PCy 3) 3, RuH 2 (CO) [P (n-Bu) 3] 3, RuH (OCOCH 3) (CO) (PPh 3) 2, RuH (OCOPh) (CO _{) (PPh 3) 2, RuH} (OCOPh-CH 3) (CO) (PPh 3) 2, RuH (OCOPh-OCH 3) (CO) (PPh 3) 2, RuH (OCOPh) (CO) (PCy 3) ₂ Hitoshigakyo It is.

  The hydrogenation reaction of the norbornene ring-opening polymer can be usually performed 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 decahydronaphthalene; tetrahydrofuran, Ether solvents such as ethylene glycol dimethyl ether; and the like.

Then, the reaction temperature when hydrogenating the norbornene-based ring-opening polymer by adding hydrogen to the system in which the norbornene-based ring-opening polymer and the hydrogenation catalyst are present is different depending on the hydrogenation catalyst to be used. , -20 ° C to 250 ° C, preferably -10 ° C to 220 ° C, more preferably 0 ° C to 200 ° C. If the reaction temperature is too low, the hydrogenation rate may be too slow, and if it is too high, side reactions may occur.
The pressure of hydrogen is usually 0.01 to 20 MPa, preferably 0.05 to 15 MPa, and more preferably 0.1 to 10 MPa. If the hydrogen pressure is too low, the hydrogenation rate may be too slow, and if it is too high, there is a restriction on the equipment in that a high pressure resistant reactor is required.
Further, the reaction time is usually 0.1 to 10 hours, though it depends on the reaction scale.

  After the hydrogenation reaction, the obtained hydride of the norbornene-based ring-opening polymer may be recovered by a conventional method, and the catalyst residue can be removed by a method such as filtration when recovering the hydride.

<Norbornene ring-opening polymer hydride>
The norbornene-based ring-opening polymer hydride obtained by hydrogenating the norbornene-based ring-opening polymer described above usually has a structural unit derived from a norbornene compound having an aromatic ring, and optionally a norbornene having no aromatic ring. At least one of a structural unit derived from a compound and a structural unit derived from a non-norbornene compound having no norbornene ring, and a structural unit obtained by hydrogenating a carbon-carbon unsaturated bond contained in the aforementioned structural unit. have.
The hydride of the norbornene ring-opening polymer preferably has the following physical properties. The physical properties of the norbornene-based ring-opening polymer hydride include, for example, the types and proportions of the structural units contained in the norbornene-based ring-opening polymer hydride used for the preparation of the norbornene-based ring-opening polymer hydride, and hydrogenation. It can be adjusted by adjusting the rate.

[Glass-transition temperature]
Here, the hydride of the norbornene ring-opening polymer has a glass transition temperature of preferably 100 ° C. or higher, more preferably 120 ° C. or higher. When the glass transition temperature is at least the above lower limit, the stress optical coefficient of the hydrogenated norbornene ring-opening polymer can be increased. The glass transition temperature of the hydrogenated norbornene ring-opening polymer is usually 200 ° C or lower.

[Abbe number]
The norbornene-based ring-opening polymer hydride preferably has an Abbe number (νd) of 35 or more and 50 or less, and more preferably 35 or more and 49 or less. If the Abbe number is within the above range, a high performance lens module can be designed.
The Abbe number can be measured according to the method described in the examples of the present specification.

[Stress optical coefficient]
The stress-optical coefficient (CR) of the hydrogenated norbornene ring-opening polymer is preferably 3000 or more, more preferably 3500 or more, preferably 8000 or less, and 6500 or less. More preferable. When the stress optical coefficient is within the above range, a film having a large retardation can be obtained.
The stress optical coefficient can be measured according to the method described in the examples of the present specification.

(Resin composition)
The resin composition of the present invention contains the norbornene-based ring-opening polymer hydride of the present invention described above, and optionally further contains a polymer material other than the norbornene-based ring-opening polymer hydride of the present invention, and various additives. Contains.
Then, the resin composition of the present invention contains the norbornene-based ring-opening polymer hydride of the present invention, which has both an appropriate Abbe number and excellent heat-resistant coloring, It can be used particularly advantageously as a material for various molded products such as optical elements.

  Here, the polymer material and the additive that the resin composition may contain are not particularly limited, and examples thereof include the polymer material and the additive described in Patent Document 1 (JP-A-10-139865). To be

  Among them, the resin composition preferably contains an antioxidant such as a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant.

  The polymer material and the additive are not particularly limited as long as they can be sufficiently dispersed in the hydride of the norbornene ring-opening polymer, and the hydrogen of the norbornene ring-opening polymer can be obtained by any method. It can be mixed with a compound. Specifically, the polymer material and the additive may be added in any step during the preparation of the norbornene-based ring-opening polymer hydride, or the norbornene-based ring-opening polymer hydride may be added using a kneader. It may be kneaded or may be mixed with a hydrogenated norbornene ring-opening polymer in a molding apparatus.

(Molded body)
The molded article of the present invention is formed by using the resin composition of the present invention and contains the hydride of the norbornene ring-opening polymer of the present invention, and therefore can exhibit excellent performance.

  Here, as the molding method, for example, injection molding method, extrusion blow molding method, injection blow molding method, two-stage blow molding method, multilayer blow molding method, connection blow molding method, stretch blow molding method, rotational molding method, A vacuum molding method, an extrusion molding method, a calendar molding method, a solution casting method, a hot press molding method, an inflation method and the like can be used.

Among them, the molded product of the present invention is preferably a film, and more preferably an optical film.
The film is not particularly limited, and for example, the resin composition of the present invention is uniformly heated and melted to form a preformed body, and then the preformed body is heated and stretched, and then heat-fixed if necessary. Can be obtained.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In addition, the measurement and evaluation in each example were performed by the following methods. Further, in the following description, “part” and “%” representing the amount are based on mass unless otherwise specified.

（７）耐熱着色性
得られたノルボルネン系開環重合体水素化物を温度２８０℃で５分混練した時の着色の有無を目視評価した。 (1) Weight average molecular weight and molecular weight distribution of norbornene-based ring-opening polymer hydride A gel containing cyclohexane as an eluent for the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the norbornene-based ring-opening polymer hydride. It was measured by permeation chromatography (GPC) and determined as a standard polyisoprene conversion value. Then, the molecular weight distribution (Mw / Mn) was calculated.
When the norbornene-based ring-opening polymer hydride is insoluble in cyclohexane, the weight average molecular weight (Mw) and number average molecular weight (Mn) are determined by gel permeation chromatography (tetrahydrofuran at a temperature of 40 ° C.) using tetrahydrofuran as an eluent. It was measured by GPC) and calculated as a converted value with standard polystyrene. Then, the molecular weight distribution (Mw / Mn) was calculated.
Here, the measurement was performed under the conditions of three columns (TSKgel G5000HXL, TSKgel G4000HXL and TSKgel G2000HXL) manufactured by Tosoh Corp. connected in series, a flow rate of 1.0 mL / min, a sample injection amount of 100 μL, and a column temperature of 40 ° C. .
(2) Hydrogenation rate The hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring and the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond were measured by ¹ H-NMR.
(3) Glass transition temperature The glass transition temperature (Tg) of the hydride of the norbornene-based ring-opening polymer is increased according to JIS K6911 using a differential scanning calorimeter (Nanotechnology, product name: DSC6220SII). The measurement was performed under the condition of a speed of 10 ° C./min.
(4) Stress optical coefficient (CR)
The obtained hydrogenated norbornene ring-opening polymer was formed into a film having a size of 35 mm × 10 mm × 1 mm. After fixing both ends of the obtained film with clips, a weight was fixed to one of the clips. Next, the sheet was suspended for 60 minutes in an oven at a temperature higher than the glass transition temperature of the norbornene ring-opening polymer hydride by 15 ° C. (= Tg + 15 ° C.), starting from the clip with the weight not fixed. A stretching process was performed and this was used as a measurement sample. A plurality of measurement samples were prepared with different weights.
With respect to the obtained measurement sample, the retardation value of the central portion of the measurement sample was measured using a birefringence meter (manufactured by Photonic Lattice, product name: WPA-100) at a wavelength of 650 nm (this measurement value is referred to as a Yes.). In addition, the thickness of the central portion of the measurement sample was measured (this measurement value is referred to as b (mm)). Then, the birefringence amount (δn) per unit thickness was obtained using the formula: δn = a × (1 / b).
Here, the closer the value of δn is to 0, the smaller the birefringence. Further, those having birefringence in the stretching direction show positive values, and those having birefringence in the direction orthogonal to the stretching direction show negative values.
Then, δn was plotted on the Y axis, and the stress applied to the cross section of the measurement sample by the weight was plotted on the X axis, an approximate straight line passing through the origin was created, and the inclination of the obtained approximate curve was defined as the stress optical coefficient (CR).
(5) Refractive index The obtained norbornene-based ring-opening polymer hydride was formed into a sheet having a thickness of 5 mm, and the temperature was 15 ° C lower than the glass transition temperature of the norbornene-based ring-opening polymer hydride (= Tg- The sample left for 20 hours in an atmosphere of 15 ° C.) was used as a measurement sample.
The refractive index (nd) at 25 ° C. of the obtained measurement sample was measured using a precision refractometer (manufactured by Shimadzu Corporation, product name: KPR-200, light source = He lamp (wavelength 587.6 nm)).
(6) Abbe number (νd)
When measuring the refractive index (nd) in “(5) Refractive index”, the refractive index (nC) at a wavelength of 656.3 nm and the refractive index (nF) at a wavelength of 486.1 nm were also measured at the same time.
Then, using the refractive index (nd, nC, nF) at a temperature of 25 ° C., the Abbe number (νd) was calculated according to the following formula (1).

(7) Heat resistant coloration The presence or absence of coloration when the obtained hydrogenated norbornene ring-opening polymer was kneaded at a temperature of 280 ° C for 5 minutes was visually evaluated.

(Example 1)
In a glass reaction vessel whose interior was replaced with nitrogen, (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride as a polymerization catalyst 0.05 part, toluene as a solvent 500 parts, 100 parts of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene (hereinafter sometimes abbreviated as "MTF") as a norbornene compound having an aromatic ring, and 1-hexene as a chain transfer agent 0.75 parts was added, and the whole volume was stirred at 60 ° C. for 2 hours to carry out ring-opening polymerization. The conversion rate of the monomer to the polymer was 100%.
Next, 300 parts of the obtained polymerization reaction solution was transferred to an autoclave equipped with a stirrer, and 0.01 part of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (hereinafter abbreviated as "ruthenium catalyst") as a hydrogenation catalyst. After the addition, hydrogenation reaction was carried out at a hydrogen pressure of 4.5 MPa and a temperature of 160 ° C. for 6 hours.
After completion of the hydrogenation reaction, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals, product name “IRGA” as an antioxidant (Knox (registered trademark) 1010 "), and then put in an aluminum pad and dried in a vacuum dryer (180 ° C, 1 Torr) for 10 hours to obtain a resin composition containing a hydrogenated norbornene ring-opening polymer. I got a thing.
Then, various measurements and evaluations were performed. The results are shown in Table 1.

(Example 2)
In a glass reaction vessel whose interior was replaced with nitrogen, (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride as a polymerization catalyst 0.05 part, toluene as a solvent 500 parts, as norbornene compound having an aromatic ring 1,4-methano -1,4,4a, 9a- tetrahydrofluorene (MTF) 50 parts, tricyclo as norbornene compound having no aromatic ring [4.3.0.1 ^{2 , 5} ] Deca-3-ene (hereinafter sometimes abbreviated as “DCP”) and 0.75 part of 1-hexene as a chain transfer agent are added, and the whole volume is stirred at 60 ° C. for 2 hours, Ring-opening polymerization was performed. The conversion rate of the monomer to the polymer was 100%.
Then, 300 parts of the obtained polymerization reaction solution was transferred to an autoclave equipped with a stirrer, 0.01 part of a ruthenium catalyst as a hydrogenation catalyst was added, and a hydrogenation reaction was carried out at a hydrogen pressure of 4.5 MPa and 160 ° C. for 6 hours. .
After completion of the hydrogenation reaction, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals, product name “IRGA” as an antioxidant (Knox (registered trademark) 1010 "), and then put in an aluminum pad and dried in a vacuum dryer (180 ° C, 1 Torr) for 10 hours to obtain a resin composition containing a hydrogenated norbornene ring-opening polymer. I got a thing.
Then, various measurements and evaluations were performed. The results are shown in Table 1.

(Example 3)
In a glass reaction vessel whose interior was replaced with nitrogen, (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride as a polymerization catalyst 0.05 part, toluene as a solvent 500 parts, as norbornene compound having an aromatic ring 1,4-methano -1,4,4a, 9a- tetrahydrofluorene (MTF) 40 parts, tetracyclic as norbornene compound having no aromatic ring [4.4.0.1 ^{2 , 5} . 30 parts of 1 ^7,10 ] dodec-3-ene (hereinafter sometimes abbreviated as “TCD”) and 30 parts of tricyclo [4.3.0.1 ^2,5 ] deca-3-ene (DCP), and Then, 0.75 part of 1-hexene as a chain transfer agent was added, and the whole volume was stirred at 60 ° C. for 2 hours to perform ring-opening polymerization. The conversion rate of the monomer to the polymer was 100%.
Then, 300 parts of the obtained polymerization reaction solution was transferred to an autoclave equipped with a stirrer, 0.01 part of a ruthenium catalyst as a hydrogenation catalyst was added, and a hydrogenation reaction was carried out at a hydrogen pressure of 4.5 MPa and 160 ° C. for 6 hours. .
After completion of the hydrogenation reaction, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals, product name “IRGA” as an antioxidant (Knox (registered trademark) 1010 "), and then put in an aluminum pad and dried in a vacuum dryer (180 ° C, 1 Torr) for 10 hours to obtain a resin composition containing a hydrogenated norbornene ring-opening polymer. I got a thing.
Then, various measurements and evaluations were performed. The results are shown in Table 1.

(Example 4)
In a glass reaction vessel whose interior was replaced with nitrogen, (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride as a polymerization catalyst 0.05 part, toluene as a solvent 500 parts, 100 parts of phenyl norbornene (hereinafter sometimes abbreviated as "Ph-NB") as a norbornene compound having an aromatic ring, and 0.75 part of 1-hexene as a chain transfer agent were added, and the total volume was 2 at 60 ° C. After stirring for an hour, ring-opening polymerization was performed. The conversion rate of the monomer to the polymer was 100%.
Then, 300 parts of the obtained polymerization reaction solution was transferred to an autoclave equipped with a stirrer, 0.01 part of a ruthenium catalyst as a hydrogenation catalyst was added, and a hydrogenation reaction was carried out at a hydrogen pressure of 4.5 MPa and 160 ° C. for 6 hours. .
After completion of the hydrogenation reaction, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals, product name “IRGA” as an antioxidant (Knox (registered trademark) 1010 "), and then put in an aluminum pad and dried in a vacuum dryer (180 ° C, 1 Torr) for 10 hours to obtain a resin composition containing a hydrogenated norbornene ring-opening polymer. I got a thing.
Then, various measurements and evaluations were performed. The results are shown in Table 1.

(Comparative Example 1)
In a glass reaction vessel whose interior was replaced with nitrogen, (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride as a polymerization catalyst 0.05 part, toluene as a solvent 500 parts, as norbornene compound having an aromatic ring 1,4-methano -1,4,4a, 9a- tetrahydrofluorene (MTF) 50 parts, tetracyclic as norbornene compound having no aromatic ring [4.4.0.1 ^{2 , 5} . 30 parts of 1 ^7,10 ] dodec-3-ene (TCD) and 20 parts of tricyclo [4.3.0.1 ^2,5 ] dec-3-ene (DCP), and 1-hexene as a chain transfer agent. 0.75 parts was added, and the whole volume was stirred at 60 ° C. for 2 hours to carry out ring-opening polymerization. The conversion rate of the monomer to the polymer was 100%.
Next, 300 parts of the obtained polymerization reaction solution was transferred to an autoclave equipped with a stirrer, 5.0 parts of 5% Pd carbon powder as a hydrogenation catalyst was added, and hydrogenation reaction was carried out at 150 ° C. for 6 hours under hydrogen pressure of 4.5 MPa. Was done.
After completion of the hydrogenation reaction, the reaction solution was filtered to remove 5% Pd carbon powder, and pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) was used as an antioxidant. Propionate] (manufactured by Ciba Specialty Chemicals, product name "Irganox (registered trademark) 1010") is added in an amount of 0.1 part, and the mixture is placed in an aluminum pad for 10 hours in a vacuum dryer (180 ° C, 1 Torr). A resin composition containing a hydrogenated norbornene ring-opening polymer was obtained by drying.
Then, various measurements and evaluations were performed. The results are shown in Table 1.

(Comparative example 2)
In a glass reaction vessel whose interior was replaced with nitrogen, (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride as a polymerization catalyst 0.05 part, toluene as a solvent 500 parts, as norbornene compound having an aromatic ring 1,4-methano -1,4,4a, 9a- tetrahydrofluorene (MTF) 40 parts, tetracyclic as norbornene compound having no aromatic ring [4.4.0.1 ^{2 , 5} . 40 parts of 1 ^7,10 ] dodec-3-ene (TCD) and 20 parts of tricyclo [4.3.0.1 ^2,5 ] dec-3-ene (DCP), and 1-hexene as a chain transfer agent. 0.75 parts was added, and the whole volume was stirred at 60 ° C. for 2 hours to carry out ring-opening polymerization. The conversion rate of the monomer to the polymer was 100%.
Next, 300 parts of the obtained polymerization reaction solution was transferred to an autoclave equipped with a stirrer, 5.0 parts of 5% Pd carbon powder as a hydrogenation catalyst was added, and hydrogenation reaction was performed at a hydrogen pressure of 4.5 MPa and 130 ° C. for 6 hours. Was done.
After completion of the hydrogenation reaction, the reaction solution was filtered to remove 5% Pd carbon powder, and pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) was used as an antioxidant. Propionate] (manufactured by Ciba Specialty Chemicals, product name "Irganox (registered trademark) 1010") is added in an amount of 0.1 part, and the mixture is placed in an aluminum pad for 10 hours in a vacuum dryer (180 ° C, 1 Torr). A resin composition containing a hydrogenated norbornene ring-opening polymer was obtained by drying.
Then, various measurements and evaluations were performed. The results are shown in Table 1.

(Comparative example 3)
In a glass reaction vessel whose interior was replaced with nitrogen, (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride as a polymerization catalyst 0.05 part, toluene as a solvent 500 parts, as norbornene compound having an aromatic ring 1,4-methano -1,4,4a, 9a- tetrahydrofluorene (MTF) 20 parts, tetracyclic as norbornene compound having no aromatic ring [4.4.0.1 ^{2 , 5} . 30 parts of 1 ^7,10 ] dodec-3-ene (TCD) and 50 parts of tricyclo [4.3.0.1 ^2,5 ] dec-3-ene (DCP), and 1-hexene as a chain transfer agent. 0.75 parts was added, and the whole volume was stirred at 60 ° C. for 2 hours to carry out ring-opening polymerization. The conversion rate of the monomer to the polymer was 100%.
Then, 300 parts of the obtained polymerization reaction solution was transferred to an autoclave equipped with a stirrer, 0.01 part of a ruthenium catalyst as a hydrogenation catalyst was added, and a hydrogenation reaction was carried out at a hydrogen pressure of 4.5 MPa and 160 ° C. for 6 hours. .
After completion of the hydrogenation reaction, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals, product name “IRGA” as an antioxidant (Knox (registered trademark) 1010 "), and then put in an aluminum pad and dried in a vacuum dryer (180 ° C, 1 Torr) for 10 hours to obtain a resin composition containing a hydrogenated norbornene ring-opening polymer. I got a thing.
Then, various measurements and evaluations were performed. The results are shown in Table 1.

(Comparative example 4)
In a glass reaction vessel whose interior was replaced with nitrogen, (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride as a polymerization catalyst 0.05 part, toluene as a solvent 500 parts, as norbornene compound having an aromatic ring 1,4-methano -1,4,4a, 9a- tetrahydrofluorene (MTF) 10 parts, tetracyclic as norbornene compound having no aromatic ring [4.4.0.1 ^{2 , 5} . 40 parts of 1 ^7,10 ] dodec-3-ene (TCD) and 50 parts of tricyclo [4.3.0.1 ^2,5 ] dec-3-ene (DCP), and 1-hexene as a chain transfer agent. 0.75 parts was added, and the whole volume was stirred at 60 ° C. for 2 hours to carry out ring-opening polymerization. The conversion rate of the monomer to the polymer was 100%.
Then, 300 parts of the obtained polymerization reaction solution was transferred to an autoclave equipped with a stirrer, 0.01 part of a ruthenium catalyst as a hydrogenation catalyst was added, and a hydrogenation reaction was carried out at a hydrogen pressure of 4.5 MPa and 160 ° C. for 6 hours. .
After completion of the hydrogenation reaction, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals, product name “IRGA” as an antioxidant (Knox (registered trademark) 1010 "), and then put in an aluminum pad and dried in a vacuum dryer (180 ° C, 1 Torr) for 10 hours to obtain a resin composition containing a hydrogenated norbornene ring-opening polymer. I got a thing.
Then, various measurements and evaluations were performed. The results are shown in Table 1.

(Comparative example 5)
In a reactor whose inside was replaced with nitrogen, tricyclo [4.3.0.1 ^2,5 ] dec-3-ene (DCP) and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene and (TCD), 1,4-methano -1,4,4a, 9a- mixture of tetrahydrofluorene (MTF) (DCP / TCD / MTF = 50/40/10 ( (Mass ratio)) 7 parts, and 1600 parts of cyclohexane as a solvent were added. Furthermore, in the reactor, 0.55 parts of tri-i-butylaluminum, 0.21 part of isobutyl alcohol, 0.84 part of diisopropyl ether as a reaction modifier, and 3.24 parts of 1-hexene as a molecular weight modifier. Was added. To this was added 24.1 parts of a tungsten hexachloride solution having a concentration of 0.65% dissolved in cyclohexane, and the mixture was stirred at 55 ° C for 10 minutes. Then, while maintaining the reaction system at 55 ° C., a mixture of DCP, TCD, and MTF (DCP / TCD / MTF = 50/40/10 (mass ratio)) was dissolved in 693 parts and cyclohexane as a solvent. Then, 48.9 parts of the tungsten hexachloride solution having a concentration of 0.65% was continuously dropped into the system over 150 minutes. Then, the reaction was continued for 30 minutes to complete the polymerization. As a result, a ring-opening polymerization reaction liquid containing a norbornene-based ring-opening polymer in cyclohexane was obtained. After the polymerization was completed, the polymerization conversion rate of the monomer measured by gas chromatography was 100% at the completion of the polymerization.
The obtained ring-opening polymerization reaction solution was transferred to a pressure-resistant hydrogenation reactor, and a diatomaceous earth-supported nickel catalyst as a hydrogenation catalyst (manufactured by JGC Chemical Co., Ltd., product name "T8400RL", nickel-supporting rate 57%) was used. 4 parts and 167 parts of cyclohexane were added, and the mixture was reacted at 180 ° C. and hydrogen pressure of 4.6 MPa for 6 hours. By this hydrogenation reaction, a reaction solution containing a hydrogenated norbornene ring-opening polymer was obtained. This reaction solution was pressure filtered at a pressure of 0.25 MPa using a pressure filter (manufactured by Ishikawajima Harima Heavy Industries Co., Ltd., product name “Funda Filter”) using Radiolite # 500 as a filter bed to obtain a hydrogenation catalyst. Removal gave a colorless transparent solution.
Next, 0.5 part of antioxidant (pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] per 100 parts of norbornene-based ring-opening polymer hydride, Ciba Specialty. -Chemicals, Inc., product name "Irganox 1010") was added and dissolved in the obtained solution. Then, it is filtered through a Zeta Plus filter 30H (manufactured by Kyuno Filter Co., Ltd., pore size 0.5 μm to 1 μm) sequentially, and further filtered by another metal fiber filter (manufactured by Nichidai Co., pore size 0.4 μm) to give a minute amount. Solids were removed.
Then, the solution obtained by the above filtration is treated at a temperature of 270 ° C. and a pressure of 1 kPa or less using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.) to remove cyclohexane and other solvents from the solution. Volatiles were removed. Then, the solid component contained in the solution was extruded into a strand form in a molten state from a die directly connected to the concentrator, and cooled to obtain pellets of hydride of norbornene ring-opening polymer.
Then, various measurements and evaluations were performed. The results are shown in Table 1.

(Comparative example 6)
In a reactor whose inside was replaced with nitrogen, tricyclo [4.3.0.1 ^2,5 ] dec-3-ene (DCP) and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene and (TCD), 1,4-methano -1,4,4a, 9a- mixture of tetrahydrofluorene (MTF) (DCP / TCD / MTF = 40/35/25 ( (Mass ratio)) 7 parts, and 1600 parts of cyclohexane as a solvent were added. Further, 0.55 parts of tri-i-butylaluminum, 0.21 parts of isobutyl alcohol, 0.84 parts of diisopropyl ether as a reaction modifier, and 3.24 parts of 1-hexene as a molecular weight modifier were added to the reactor. did. To this was added 24.1 parts of a tungsten hexachloride solution having a concentration of 0.65% dissolved in cyclohexane, and the mixture was stirred at 55 ° C for 10 minutes. Next, while maintaining the reaction system at 55 ° C., 693 parts of a mixture of DCP, TCD, and MTF (DCP / TCD / MTF = 40/35/25 (mass ratio)) was dissolved in cyclohexane as a solvent. And 48.9 parts of a tungsten hexachloride solution having a concentration of 0.65% were continuously dropped into the system over 150 minutes. Then, the reaction was continued for 30 minutes to complete the polymerization. As a result, a ring-opening polymerization reaction liquid containing a norbornene-based ring-opening polymer in cyclohexane was obtained. After the polymerization was completed, the polymerization conversion rate of the monomer measured by gas chromatography was 100% at the completion of the polymerization.
The obtained ring-opening polymerization reaction solution was transferred to a pressure-resistant hydrogenation reactor, and a diatomaceous earth-supported nickel catalyst as a hydrogenation catalyst (manufactured by JGC Chemical Co., Ltd., product name "T8400RL", nickel-supporting rate 57%) was used. 4 parts and 167 parts of cyclohexane were added, and the mixture was reacted at 180 ° C. and hydrogen pressure of 4.6 MPa for 6 hours. By this hydrogenation reaction, a reaction solution containing a hydrogenated norbornene ring-opening polymer was obtained. This reaction solution was pressure filtered at a pressure of 0.25 MPa using a pressure filter (manufactured by Ishikawajima Harima Heavy Industries Co., Ltd., product name “Funda Filter”) using Radiolite # 500 as a filter bed to obtain a hydrogenation catalyst. Removal gave a colorless transparent solution.
Next, 0.5 part of antioxidant (pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] per 100 parts of norbornene-based ring-opening polymer hydride, Ciba Specialty. -Chemicals, Inc., product name "Irganox 1010") was added and dissolved in the obtained solution. Then, it is filtered through a Zeta Plus filter 30H (manufactured by Kyuno Filter Co., Ltd., pore size 0.5 μm to 1 μm) sequentially, and further filtered by another metal fiber filter (manufactured by Nichidai Co., pore size 0.4 μm) to give a minute amount. Solids were removed.
Then, the solution obtained by the above filtration is treated at a temperature of 270 ° C. and a pressure of 1 kPa or less using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.) to remove cyclohexane and other solvents from the solution. Volatiles were removed. Then, the solid component contained in the solution was extruded into a strand form in a molten state from a die directly connected to the concentrator, and cooled to obtain pellets of hydride of norbornene ring-opening polymer.
Then, various measurements and evaluations were performed. The results are shown in Table 1.

From Table 1, it is understood that the hydrogenated norbornene ring-opening polymers of Examples 1 to 4 have both an appropriate Abbe number and excellent heat resistance coloring.
On the other hand, it can be seen from Table 1 that the norbornene-based ring-opening polymer hydrides of Comparative Examples 1 and 2 in which the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring is large, have low heat resistance. Moreover, from Table 1, the norbornene-based ring-opening polymer hydrides of Comparative Examples 3 to 6 obtained by hydrogenating a norbornene-based ring-opening polymer having a small proportion of structural units derived from a norbornene compound having an aromatic ring have Abbe numbers of It turns out that it becomes excessively large.

According to the present invention, it is possible to provide a hydrogenated norbornene-based ring-opening polymer having both an appropriate Abbe number and excellent heat-resistant coloring.
Further, according to the present invention, it is possible to provide a resin composition that can be advantageously used as a material for various molded products such as optical elements, and a molded product formed using the resin composition.

Claims (6)

A norbornene ring-opening polymer containing a structural unit derived from a norbornene compound having an aromatic ring in a proportion of 40% by mass or more and 100% by mass or less is hydrogenated,
A hydrogenated norbornene ring-opening polymer having a hydrogenation rate of carbon-carbon unsaturated bonds of an aromatic ring of 0% or more and 1.5% or less.   The norbornene-based ring-opening polymer hydride according to claim 1, which has a glass transition temperature of 100 ° C. or higher.   The hydrogenated norbornene ring-opening polymer according to claim 1 or 2, wherein the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond is 95% or more.   A resin composition comprising the norbornene-based ring-opening polymer hydride according to claim 1.   A molded body formed by using the resin composition according to claim 4.   The molded product according to claim 5, which is an optical film.