JP5041233B2 - Plastic molded product - Google Patents

Description

  The present invention is excellent in water vapor barrier properties, heat resistance, oil resistance, chemical resistance, mechanical properties, transparency, processability, etc., which are required in recent information fields, food fields, medical fields, civil engineering fields, etc. The present invention relates to a plastic molded product such as a resin film or sheet obtained by molding a hydrogenated norbornene monomer ring-opening polymer.

Since the norbornene monomer ring-opening polymer hydrogenated product is excellent in transparency and has low birefringence, use as a resin material for optical lenses, optical disk substrates, and optical sheets has been proposed (Patent Document 1). 2). In addition, it has excellent fluidity when melted, and also has excellent dissolution properties and chemical resistance, so it is useful as various resin materials other than optical applications, including packaging films and medical containers. Has also been proposed (Patent Documents 3 and 4).
However, since many of the hydrogenated norbornene monomer ring-opening polymers are amorphous, depending on the application, water vapor barrier properties, sebum resistance, solvent resistance, etc. are insufficient, and physical properties are further increased. Improvement was desired.

On the other hand, Patent Document 5 discloses heat resistance, solvent resistance, mechanical strength, etc. by irradiating an active energy ray to a molded product formed of a hydrogenated norbornene monomer ring-opening polymer. Improved plastic moldings have been proposed.
However, the norbornene monomer ring-opening polymer hydrogenated product described here is a so-called amorphous polymer having a glass transition point, and a plastic molded product obtained using this polymer has a room temperature. Although the solvent resistance is improved, the solvent does not dissolve but may swell under a temperature environment (40 ° C.) exceeding room temperature. In some cases, the solvent resistance is not always sufficient depending on the application used. There were problems such as.

By the way, the norbornene monomer ring-opening polymer hydrogenated product having crystallinity (that is, having a melting point) is a repeating unit of a norbornene monomer having three or more rings described in Patent Documents 6 to 8. A crystalline norbornene monomer ring-opening polymer hydrogenated product containing is known. Plastic molded products such as resin films and sheets obtained from hydrogenated norbornene monomer ring-opening polymers described in these documents are excellent in transparency, heat resistance and chemical resistance, and also in mechanical strength. It is.
However, these crystalline norbornene monomer ring-opening polymer hydrogenated products have poor solubility in solvents, and after hydrogenation of the ring-opening polymer, they are precipitated from the solvent and polymer purification such as removal of catalyst residues. May not be sufficient. Further, the water vapor barrier property of the film formed using the norbornene monomer ring-opening polymer hydrogenated product does not sufficiently satisfy the requirements.

JP 60-26024 A JP-A-9-263627 JP 2000-313090 A JP 2003-183361 A JP-A-4-23838 JP 2000-201826 A JP 2000-393316 A JP 2006-52333 A

  The present invention has been made in view of such a state of the art, and in recent information fields, food fields, medical fields, civil engineering fields, etc., water vapor barrier properties, heat resistance, oil resistance, solvent resistance, It is an object of the present invention to provide a plastic molded product such as a resin film or sheet obtained by molding a resin material that satisfies the requirements for better performance such as mechanical properties, transparency, and workability.

  As a result of intensive studies to obtain a molded product that does not swell with an organic solvent even under temperature conditions exceeding room temperature while ensuring low moisture permeability, the present inventor has obtained a certain crystalline norbornene monomer. If the ring-opening polymer hydrogenated product is first molded into a desired shape and then crosslinked by irradiation with active energy rays, a molded product excellent in solvent resistance, mechanical strength, water vapor barrier properties, etc. can be obtained. I found out.

  Here, by utilizing the unsaturated bond remaining in the hydrogenated norbornene monomer ring-opening polymer or by adding a crosslinking aid, the crosslinking reaction easily proceeds by irradiation with active energy rays. The addition of the crosslinking aid can be carried out by a method of blending in the norbornene monomer ring-opening polymer hydrogenated product or infiltrating the surface of the primary molded product.

  According to this method, a molded product having excellent physical properties can be obtained, and the present invention has been completed based on these findings.

  Thus, according to the present invention, ring-opening polymerization of a polymerizable monomer containing 90 to 100% by weight of 2-norbornene and 10 to 0% by weight of a substituent-containing norbornene is carried out and hydrogenated. The hydrogenation rate is 80% or more, the melting point is 110 to 145 ° C., the weight average molecular weight measured by gel permeation chromatography is 50,000 to 200,000, and the weight average molecular weight / number average molecular weight is 1. A primary molded article formed of a crystalline norbornene monomer ring-opening polymer hydrogenated product having an irradiation dose of 100 to 500 kGy in the presence or absence of a crosslinking aid is 5 to 10.0. There is provided a plastic molded product obtained by irradiating a line and being crosslinked.

  According to the present invention, water vapor barrier properties, heat resistance, oil resistance, solvent resistance, mechanical properties, transparency, workability, etc., in recent information fields, food fields, medical fields, civil engineering fields, etc. Plastic molded products such as resin films and sheets that satisfy performance requirements are provided.

Hereinafter, the present invention will be described in detail.
(Norbornene monomer ring-opening polymer hydrogenated product)
A melting point of 110 to 145 obtained by ring-opening polymerization of a polymerizable monomer containing 90 to 100% by weight of 2-norbornene and 10 to 0% by weight of a substituent-containing norbornene and hydrogenation. Norbornene monomer ring-opening polymer having a weight average molecular weight of 50,000 to 200,000 and a weight average molecular weight / number average molecular weight of 1.5 to 10.0 as measured by gel permeation chromatography It is a hydrogenated product.

  The crystalline norbornene monomer ring-opening polymer used in the present invention is 90 to 100% by weight of 2-norbornene (bicyclo [2.2.1] hept-2-ene) and 10 to 0 substituent-containing norbornenes. A polymerizable monomer comprising, by weight, ring-opening polymerization and hydrogenation, the melting point is 110 to 145 ° C., and the weight average molecular weight measured by gel permeation chromatography is 50, The weight average molecular weight / number average molecular weight is 1.5 to 10.0. Particularly preferred are those obtained by hydrogenating 80% or more of the carbon-carbon double bonds of the ring-opened polymer by hydrogenation after the ring-opening polymerization.

2-norbornene or a monomer mixture composed of 2-norbornene and a substituent-containing norbornene-based monomer is subjected to ring-opening polymerization in the presence of a metathesis polymerization catalyst to give 2-norbornene homo-ring-opening polymer or 2-norbornene Crystalline norbornene monomer ring-opening polymer by hydrogenating ring-opening copolymer with substituent-containing norbornene monomer (hereinafter collectively referred to as “norbornene monomer ring-opening polymer”) A hydrogenated product can be obtained.
2-Norbornene is a known compound and can be obtained, for example, by reacting cyclopentadiene with ethylene.

The substituent-containing norbornene monomer is a compound having a norbornene skeleton in the molecule and having a substituent. The “substituent-containing norbornene monomer” used in the present invention includes a norbornene compound having a condensed ring in addition to a 2-norbornene derivative having a substituent.
Examples of the substituent-containing norbornene monomer include a norbornene monomer that does not have a ring condensed with a norbornene ring in the molecule, and a polycyclic norbornene monomer having three or more rings.

  Specific examples of the norbornene monomer having no ring condensed with the norbornene ring in the molecule include 5-methyl-bicyclo [2.2.1] hept-2-ene (5-methyl-2-norbornene). 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-hexyl-bicyclo [2.2.1] hept 2-ene, 5-decyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclopentyl-bicyclo [2.2 .1] Norbornenes having an alkyl group such as hept-2-ene; 5-ethylidene-bicyclo [2.2.1] hept-2-ene (5-ethylidene-2-norbornene), 5-vinyl-bicyclo [ 2.2.1] Hep 2-ene, 5-propenyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexenyl-bicyclo [2.2.1] hept-2-ene, 5-cyclopentenyl-bicyclo [2] 2.1] norbornenes having an alkenyl group such as hept-2-ene; aromatic rings such as 5-phenyl-bicyclo [2.2.1] hept-2-ene (5-phenyl-2-norbornene) Norbornenes: 5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene (5-methoxycarbonyl-2-norbornene), 5-ethoxycarbonyl-bicyclo [2.2.1] hept-2- Ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-ethoxycarbonyl-5-methyl-bicyclo [2.2.1] hept- -Ene, 2-hydroxypropionic acid 5-hydroxy-bicyclo [2.2.1] hept-2-ene, 2-methyloctanoic acid 5-hydroxy-bicyclo [2.2.1] hept-2-ene, 5 -Hydroxymethyl-bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) -bicyclo [2.2.1] hept-2-ene, 5,5-di (hydroxymethyl) ) -Bicyclo [2.2.1] hept-2-ene, 5-hydroxyisopropyl-bicyclo [2.2.1] hept-2-ene, 5,6-dicarboxy-bicyclo [2.2.1] Norbornenes having a polar group containing an oxygen atom such as hept-2-ene, 6-carboxy-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene; 5-cyano-bicyclo [2.2 .1] Hept- And norbornenes having a polar group containing a nitrogen atom such as 2-ene and 6-carboxy-5-cyano-bicyclo [2.2.1] hept-2-ene;

  The polycyclic norbornene monomer having three or more rings is a norbornene monomer having a norbornene ring and one or more rings condensed with the norbornene ring in the molecule. Specific examples thereof include monomers represented by the following formula (1) or formula (2).

(Wherein R ¹ and R ² are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

(Wherein R ^{4 to} R ⁷ are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ⁴ and R ⁶ may be bonded to each other to form a ring, and m is 1 or 2.)

Specific examples of the monomer represented by the formula (1) include bicyclo [2.2.1] hept-2-ene (common name: 2-norbornene), tricyclo [4.3.0.1 ^{2 , 5} ] Deca-3,7-diene (common name: dicyclopentadiene), methyldicyclopentadiene, dimethyldicyclopentadiene, and the like. In addition, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), tetracyclo [10.2.1.0 ^{2 , 11} . Norbornene derivatives having an aromatic ring such as 0 ^4,9 ] pentadeca-4,6,8,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene) Can be mentioned.

Examples of the monomer represented by the formula (2) include tetracyclododecenes in which m is 1 and hexacycloheptadecenes in which m is 2.
Specific examples of tetracyclododecenes include tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and 8-cyclopentyltetracyclododecene. Tetracyclododecenes having a substituted or alkyl group; 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetra Tetracyclododecenes having a double bond outside the ring such as cyclododecene and 8-cyclopentenyltetracyclododecene; tetracyclododecenes having an aromatic ring such as 8-phenyltetracyclododecene; 8-methoxy Carbonyltetracyclododecene, 8-methyl-8- Toxicarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-8,9-dicarboxylic anhydride, etc. Tetracyclododecenes having substituents containing oxygen atoms; tetracyclododecenes having substituents containing nitrogen atoms such as 8-cyanotetracyclododecene, tetracyclododecene-8,9-dicarboxylic imide A tetracyclododecene having a substituent containing a halogen atom such as 8-chlorotetracyclododecene; a tetracyclododecene having a substituent containing a silicon atom such as 8-trimethoxysilyltetracyclododecene; Can be mentioned.

  Specific examples of hexacycloheptadecenes include hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, and 12-cyclopentylhexacycloheptadecene. Hexacycloheptadecenes having a substituted or alkyl group; 12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexa Hexacycloheptadecenes having a double bond outside the ring such as cycloheptadecene, 12-cyclopentenylhexacycloheptadecene, etc .; Heterocyclic rings such as 12-phenylhexacycloheptadecene Sacycloheptadecenes; 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene 12 , 13-dicarboxylic acid, hexacycloheptadecene 12,13-dicarboxylic anhydride, etc., hexacycloheptadecenes having a substituent containing an oxygen atom; 12-cyanohexacycloheptadecene, hexacycloheptadecene 12,13- Hexacycloheptadecenes having a substituent containing a nitrogen atom such as dicarboxylic acid imide; Hexacycloheptadecenes having a substituent containing a halogen atom such as 12-chlorohexacycloheptadecene; Hexa cycloheptanone decene and the like having a substituent containing a Le hexa cycloheptanone de silicon atoms Sen and the like. These norbornene monomers can be used alone or in combination of two or more.

  In the present invention, the above-mentioned 2-norbornene and substituent-containing norbornene monomers can be used in combination with other monomers capable of ring-opening copolymerization.

  Examples of other monomers capable of ring-opening copolymerization with 2-norbornene and substituent-containing norbornene monomers include, for example, monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and their derivatives; cyclohexadiene, cyclohepta Cyclic dienes such as dienes and derivatives thereof; and the like.

  The composition of the monomer is such that 2-norbornene is usually 90 to 100% by weight, preferably 95 to 99% by weight, more preferably 97 to 99% by weight, and the substituent-containing norbornene monomer is usually 0%. -10 wt%, preferably 1-5 wt%, more preferably 1-4 wt%.

  Examples of the metathesis polymerization catalyst include, for example, Japanese Patent Publication No. Sho 41-20111, Japanese Patent Publication No. Sho 46-14910, Japanese Patent Publication No. Sho 57-17883, Japanese Patent Publication No. Sho 57-61044, Japanese Patent Publication No. Sho 54-86600, A general metathesis polymerization catalyst consisting essentially of (a) a transition metal compound catalyst component and (b) a metal compound co-catalyst component as described in JP-A-58-127728 and JP-A-1-240517; Schrock type polymerization catalyst (JP-A-7-179575, Schrock et al., J. Am. Chem. Soc., 1990, Vol. 112, page 3875-) and Grubbs type polymerization catalyst (Fu et al. Nguyen et al., J. Am. Chem., 1993, 115, 9856 et seq., J. Am. . Soc, 1992 years, 114th volume, 3974 pp ~;., And the like; Grubbs et al, living ring-opening metathesis catalyst brochures etc.) and No. WO98 / 21214.

  Among these, a metathesis polymerization catalyst comprising (a) a transition metal compound catalyst component and (b) a metal compound promoter component is preferable in order to adjust the molecular weight distribution of the obtained polymer to a suitable range.

The (a) transition metal compound catalyst component is a compound of a transition metal of Groups 3 to 11 of the periodic table. For example, halides, oxyhalides, alkoxyhalides, alkoxides, carboxylates, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes, derivatives of these, or derivatives of these transition metals. A complexed product of a complexing agent such as P (C ₆ H ₅ ) ₅ may be mentioned.

Specific examples include TiCl ₄ , TiBr ₄ , VOCl ₃ , WBr ₃ , WCl ₆ , WOCl ₄ , MoCl ₅ , MoOCl ₄ , WO ₂ and H ₂ WO ₄ . Of these, W, Mo, Ti, or V is preferable from the viewpoint of polymerization activity and the like, and these halides, oxyhalides, and alkoxy halides are particularly preferable.

  The (b) metal compound promoter component is a metal compound of Groups 1 to 2 and Groups 12 to 14 of the periodic table, and has at least one metal element-carbon bond or metal element-hydrogen bond. is there. Examples thereof include organic compounds such as Al, Sn, Li, Na, Mg, Zn, Cd, and B.

  Specific examples include organoaluminum compounds such as trimethylaluminum, triisobutylaluminum, diethylaluminum monochloride, methylaluminum sesquichloride, and ethylaluminum dichloride; organotin compounds such as tetramethyltin, diethyldimethyltin, tetrabutyltin, and tetraphenyltin. Organic lithium compounds such as n-butyl lithium; organic sodium compounds such as n-pentyl sodium; organic magnesium compounds such as methyl magnesium iodide; organic zinc compounds such as diethyl zinc; organic cadmium compounds such as diethyl cadmium; Organic boron compounds; and the like. Of these, Group 13 metal compounds are preferred, and Al organic compounds are particularly preferred.

In addition to the components (a) and (b), a metathesis polymerization activity can be increased by adding a third component. As the third component to be used, aliphatic tertiary amine, aromatic tertiary amine, molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound , Halogen-containing compounds, and other Lewis acids.
The compounding ratio of these components is the molar ratio of the (a) component: (b) component to the metal element, and is usually in the range of 1: 1 to 1: 100, preferably 1: 2 to 1:10. Moreover, (a) component: 3rd component is the range of 1: 0.005-1: 50 normally by molar ratio, Preferably it is the range of 1: 1-1: 10.

  The polymerization catalyst is used in a molar ratio of (transition metal in the polymerization catalyst) :( total monomer), usually 1: 100 to 1: 2,000,000, preferably 1: 1,000 to 1: 20,000, more preferably 1: 5,000 to 1: 8,000. If the amount of catalyst is too large, it may be difficult to remove the catalyst after the polymerization reaction, and the molecular weight distribution may be widened. On the other hand, if the amount is too small, sufficient polymerization activity cannot be obtained.

  The ring-opening polymerization can be carried out without a solvent, but is preferably carried out in a suitable solvent. The organic solvent to be used is not particularly limited as long as the polymer and the hydrogenated polymer are dissolved or dispersed under predetermined conditions and do not affect the polymerization and the hydrogenation reaction, but are widely used industrially. A solvent is preferred.

Examples of such organic solvents include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, Cycloaliphatic hydrocarbons such as cyclodecane, hexahydroindenecyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; chlorobenzene, Halogen-based aromatic hydrocarbons such as dichlorobenzene; Nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, and acetonitrile; Ethers such as diethyl ether and tetrahydrofuran The solvent etc. can be used. These organic solvents can be used alone or in combination of two or more.
Among these, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and ethers that are widely used in industry are preferable.

  When the polymerization is performed in an organic solvent, the monomer concentration is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and particularly preferably 3 to 40% by weight. If the concentration of the monomer mixture is less than 1% by weight, the productivity may be lowered, and if it is more than 50% by weight, the solution viscosity after polymerization may be too high, and the subsequent hydrogenation reaction may be difficult.

In the ring-opening polymerization, a molecular weight regulator can be added to the reaction system. The molecular weight of the resulting ring-opening polymer can be adjusted by adding a molecular weight regulator.
The molecular weight regulator to be used is not particularly limited, and conventionally known ones can be used. For example, α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; allyl chloride and the like A halogen-containing vinyl compound such as glycidyl methacrylate; a nitrogen-containing vinyl compound such as acrylamide; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl- Non-conjugated dienes such as 1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene, or 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3- Conjugates such as butadiene, 1,3-pentadiene, 1,3-hexadiene Mention may be made of the ene or the like. Among these, α-olefins are preferable because of easy molecular weight adjustment.

  The addition amount of the molecular weight regulator may be an amount sufficient to obtain a polymer having a desired molecular weight, and is usually 1:50 to 1: 1 in a molar ratio of (molecular weight regulator) :( total monomer). 1,000,000, preferably 1: 100 to 1: 5,000, more preferably 1: 300 to 1: 3,000.

Ring-opening polymerization is initiated by mixing the monomer and the polymerization catalyst.
Although the temperature which performs ring-opening polymerization is not specifically limited, Usually, it superposes | polymerizes at -20- + 100 degreeC, Preferably it is 10-80 degreeC. If the temperature is too low, the reaction rate decreases, and if it is too high, the molecular weight distribution may be widened due to side reactions.
The polymerization time is not particularly limited, and is usually 1 minute to 100 hours.
Although the pressure conditions at the time of superposition | polymerization are not specifically limited, When superposing | polymerizing on pressurization conditions, the pressure to apply is 1 MPa or less normally.
After completion of the reaction, the desired norbornene monomer ring-opening polymer can be isolated by ordinary post-treatment operations.

The obtained norbornene monomer ring-opening polymer is subjected to the next hydrogenation reaction step.
Further, as will be described later, the hydrogenation catalyst can be continuously carried out without adding a hydrogenation catalyst to the reaction solution subjected to ring-opening polymerization and isolating the norbornene monomer ring-opening polymer.

  The hydrogenation reaction of the norbornene monomer ring-opening polymer is a reaction in which the carbon-carbon double bond existing in the main chain and / or side chain of the norbornene monomer ring-opening polymer is hydrogenated. This hydrogenation reaction is performed by adding a hydrogenation catalyst to an inert solvent solution of a norbornene monomer ring-opening polymer and supplying hydrogen into the reaction system.

As the hydrogenation catalyst, either a homogeneous catalyst or a heterogeneous catalyst can be used as long as it is generally used for hydrogenation of olefin compounds. Considering the removal of residual metals in the resulting polymer, a heterogeneous catalyst is preferable.
Examples of homogeneous catalysts include combinations of cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, etc. Catalyst system comprising a combination of a transition metal compound and an alkali metal compound; dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium, bis (tricyclohexylphosphine) benzilidineruthenium (IV) noble metal complex catalyst such as dichloride; and the like.
Examples of heterogeneous catalysts include nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina, nickel, palladium, platinum, rhodium, ruthenium, Alternatively, a solid catalyst system in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina, or titanium oxide can be used.
The usage-amount of a catalyst is 0.05-10 weight part normally with respect to 100 weight part of norbornene monomer ring-opening polymers.

  As the inert organic solvent used in the hydrogenation reaction, the same aliphatic hydrocarbons as those exemplified as the organic solvent that can be used in the ring-opening polymerization of 2-norbornene and a substituent-containing norbornene monomer described above. , Alicyclic hydrocarbons, aromatic hydrocarbons, halogenated aromatic hydrocarbons, nitrogen-containing hydrocarbons, ethers and the like.

The suitable temperature range for the hydrogenation reaction varies depending on the hydrogenation catalyst used, but the hydrogenation temperature is usually −20 ° C. to + 300 ° C., preferably 0 ° C. to + 250 ° C. If the hydrogenation temperature is too low, the reaction rate may be slow, and if it is too high, side reactions may occur.
The hydrogen pressure is usually 0.01 to 20 MPa, preferably 0.1 to 10 MPa, more preferably 1 to 5 MPa. If the hydrogen pressure is too low, the hydrogen addition rate is slow, and if it is too high, a high pressure reactor is required, which is not preferable.

The crystalline norbornene monomer ring-opening polymer hydrogenated product has a hydrogenation rate of carbon-carbon double bonds in the norbornene monomer ring-opening polymer of usually 80% or more, preferably 90% or more, more preferably It is 95% or more, more preferably 99% or more, and particularly preferably 99.9% or more. When it is in the above range, it is preferable because coloring due to resin burning of the molded product is suppressed.
The hydrogenation rate of the crystalline norbornene monomer ring-opening polymer hydrogenated product can be determined by measuring by ¹ H-NMR using deuterated chloroform as a solvent.

After completion of the hydrogenation reaction, the hydrogenation catalyst and the like are filtered off from the reaction solution, and volatile components such as a solvent are removed from the polymer solution after the filtration, so that the desired crystalline norbornene monomer ring-opening weight is obtained. A combined hydrogenated product can be obtained.
As a method for removing volatile components such as a solvent, a known method such as a coagulation method or a direct drying method can be employed.

The coagulation method is a method in which a polymer is precipitated by mixing a polymer solution with a poor solvent for the polymer. Examples of the poor solvent to be used include polar solvents such as alcohols such as ethyl alcohol, n-propyl alcohol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and butyl acetate;
The particulate component obtained by solidification is dried by heating, for example, in vacuum, nitrogen or air, or is extruded into a pellet from a melt extruder as necessary. be able to.

  The direct drying method is a method in which the polymer solution is heated under reduced pressure to remove the solvent. This method can be carried out using a known apparatus such as a centrifugal thin film continuous evaporation dryer, a scratched heat exchange type continuous reactor type dryer, a high viscosity reactor device or the like. The degree of vacuum and temperature are appropriately selected depending on the device and are not limited.

  The proportion of the crystalline norbornene monomer ring-opening polymer hydrogenated product obtained as described above in the presence of the repeating unit (A) derived from 2-norbornene is usually 90 to 100% by weight, preferably 95%. -99% by weight, more preferably 97-99% by weight, and the proportion of the repeating unit (B) derived from the substituent-containing norbornene-based monomer is 0 to 10% by weight, preferably 1 to 10% by weight. 5% by weight, more preferably 1 to 4% by weight.

  When the ratio of the repeating unit (A) and the repeating unit (B) is within such a range, the crystalline norbornene monomer ring-opening polymer hydrogenated product has good solubility in the solvent, so that the production of the polymer. And the polymer is easily purified, and the mechanical properties, transparency, heat resistance and water vapor barrier properties of the molded article are good. When there are too many repeating units (B), there exists a possibility that the heat resistance and water vapor | steam barrier property of a molded object may deteriorate. If the proportion of the repeating unit (B) is too small, the solubility of the polymer hydrogenated product in the solvent may deteriorate, the polymer productivity may deteriorate, and the polymer purification may become difficult. The mechanical properties of the body may be reduced.

  The resulting crystalline norbornene monomer ring-opening polymer hydrogenated product has a weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) using 1,2,4-trichlorobenzene as an eluent. It is preferably 50,000 to 200,000, more preferably 70,000 to 180,000, still more preferably 80,000 to 150,000 in terms of standard polystyrene.

  If the Mw of the crystalline norbornene monomer ring-opening polymer hydrogenated product is in this range, the polymer is excellent in solubility in a solvent, so that the productivity of the polymer is excellent and the purification of the polymer is easy. Moreover, molding is easy, and the mechanical properties and heat resistance of the molded body are improved. That is, if the Mw is too high, the solution viscosity becomes too high and the filterability is lowered, so that the productivity may be deteriorated. Also, when the resin is formed into a film, the film thickness accuracy is increased. Therefore, it is necessary to increase the resin temperature, and there is a possibility that a die line resulting from resin burning may occur. On the other hand, if Mw is too low, the mechanical properties and heat resistance of the molded product may be lowered, and the polymer hydrogenated product is crystalline, so that it is difficult to dissolve in the solution, and the polymer productivity is deteriorated. It may be difficult to purify the polymer.

The resulting crystalline norbornene monomer ring-opening polymer hydrogenated product has a molecular weight distribution (Mw / Mn) of preferably 1.5 to 7.0, more preferably 2.0 to 6.5, and even more preferably. Is 2.5 to 6.0, particularly preferably 2.5 to 5.5.
If Mw / Mn is too narrow, the melt viscosity with respect to the temperature of the polymer tends to change sensitively, so that the workability of molded products such as films and sheets may be deteriorated. Further, if Mw / Mn is too wide, the mechanical properties of the molded product may be deteriorated.

  The melting point of the crystalline norbornene monomer ring-opening polymer hydrogenated product is usually 110 to 145 ° C, preferably 120 to 145 ° C, more preferably 130 ° C to 145 ° C. It is preferable for it to be in the above range since the film has excellent heat resistance.

  Since the crystalline norbornene monomer ring-opening polymer hydrogenated product is a polymer having a melting point, that is, a polymer that forms a crystal structure, a crystalline part is formed inside the molded body, and this is combined with an amorphous part. In combination, the mechanical properties of the molded product are improved. Nevertheless, since the crystal is not large, it also provides good transparency.

The isomerization rate of the obtained crystalline norbornene monomer ring-opening polymer hydrogenated product is usually 40% or less, preferably 20% or less, more preferably 10% or less, and further preferably 5% or less. If the isomerization rate is too high, the heat resistance of the polymer may be lowered. The isomerization rate can be calculated from 33.0 ppm peak integrated value / (31.8 ppm peak integrated value + 33.0 ppm peak integrated value) × 100 measured by ¹³ C-NMR using deuterated chloroform as a solvent. ^{In the 13} C-NMR spectrum, the 31.8 ppm peak is derived from a cis isomer of a repeating unit derived from 2-norbornene in the polymer, and the 33.0 ppm peak is a repeating unit derived from 2-norbornene in the polymer. It is derived from the trans form.

  In order to make the isomerization ratio within the above range, in the hydrogenation reaction of the norbornene monomer ring-opening polymer, the reaction temperature is preferably 100 to 200 ° C, more preferably 120 to 170 ° C, and particularly preferably 130 to 160. And the amount of the hydrogenation catalyst used is preferably 0.2 to 5 parts by weight, more preferably 0.2 to 1 part by weight with respect to 100 parts by weight of the norbornene monomer ring-opening polymer. To do. Within such a range, the balance between the hydrogenation reaction rate and the heat resistance of the resulting polymer is excellent and suitable.

  In the present invention, it is preferable to synthesize a ring-opened polymer that is substantially a cis-form by ring-opening polymerization and hydrogenate it to obtain a hydrogenated ring-opened polymer. In the hydrogenation reaction, isomerization to the trans isomer usually occurs, but it is preferable to suppress this isomerization and to keep the content of the trans isomer low.

  If the isomerization rate of the crystalline norbornene monomer ring-opening polymer hydrogenated product is too high, the heat resistance may be lowered. On the other hand, when the isomerization rate is too low, the solubility of the ring-opened polymer hydrogenated product in an organic solvent is lowered and may be precipitated. Therefore, the isomerization rate of the ring-opening polymer hydrogenated product may be 0%, but preferably exhibits a certain degree of isomerization within a range of 10% or less.

  In order to make the isomerization ratio within the above range, in the hydrogenation reaction of the ring-opening polymer, the reaction temperature is preferably 120 to 170 ° C., more preferably 130 to 160 ° C., and the use of the hydrogenation catalyst to be used The amount is preferably 0.2 to 5 parts by weight, more preferably 0.2 to 1 part by weight with respect to 100 parts by weight of the crystalline norbornene monomer ring-opening polymer hydrogenated product. When the reaction temperature of the hydrogenation reaction and the amount of the hydrogenation catalyst used are in such ranges, the balance between the hydrogenation reaction rate and the heat resistance of the resulting polymer is excellent, which is preferable.

  It is preferable that the crystalline norbornene monomer ring-opening polymer hydrogenated product has few foreign matters. Metal residues, foreign matters, and the like of plastic molded products such as films may cause deterioration of electrical characteristics when applied to electronic components. After the polymerization reaction or after the hydrogenation reaction, metal residues and foreign matters can be precisely removed by filtering the polymer solution with a filter having a pore size of 0.2 μm or less.

  Since the crystalline norbornene monomer ring-opening polymer hydrogenated product used in the present invention is a polymer having a melting point, that is, a polymer forming a crystal structure, a crystal part is formed (crystallized) inside the molded body. In combination with this, the amorphous part improves the mechanical properties such as tensile elongation at break of the molded product.

(Crosslinking aid)
In the present invention, a crosslinking aid can be added to the above-described crystalline norbornene monomer ring-opening polymer. The crosslinking aid to be used is not particularly limited, and may be one known in JP-A No. 62-34924, etc., and oxime / nitroso-based crosslinking aids such as quinonedioxime, benzoquinonedioxime, p-nitrosophenol; N , Nm-phenylene bismaleimide and other maleimide crosslinking auxiliaries; diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and other allylic crosslinking aids; ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and other methacrylates Examples of crosslinking aids include vinyl-based crosslinking aids such as vinyltoluene, ethylvinylbenzene, divinylbenzene, and the like. Among these, acrylic crosslinking assistants and methacrylate crosslinking assistants are preferable because they can be easily dispersed uniformly.

  The addition amount of the crosslinking aid is 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0 to 100 parts by weight of the crystalline norbornene monomer ring-opening polymer hydrogenated product. 0.1 to 3 parts by weight. If the addition amount of the crosslinking aid is too small, crosslinking is difficult to occur, and if the addition amount of the crosslinking aid is too large, the moisture resistance, water vapor barrier property and the like of the crosslinked resin molded product are lowered.

(Crosslinking aid added)
Examples of the method for adding the crosslinking aid to the crystalline norbornene monomer ring-opening polymer hydrogenated product include a dry blend method in which the material is pre-molded and a method in which it is put in the system during the synthesis. However, when molding is performed by heating and melting at a high temperature, such as an injection molding method or an extrusion molding method, a crosslinking assistant with a high boiling point or decomposition temperature is used so that the crosslinking aid does not decompose or volatilize during molding. It is preferable to use an agent. When the heating time is relatively short as in press molding, or when the ring-opening polymer hydrogenated product and the crosslinking aid are dissolved together in a solvent and cast and spun to form, the crosslinking agent from the surface of the molded product, When the crosslinking aid is soaked, it is not necessary that the crosslinking aid has a particularly high boiling point or decomposition temperature.

  Crystalline norbornene monomer ring-opening polymer hydrogenated products include, in addition to crosslinking aids, antioxidants (stabilizers), nucleating agents, foaming agents, flame retardants, thermoplastic resins and soft heavy materials as necessary. Other polymers such as coalescents, compounding agents such as lubricants, and other compounding agents usually used in the resin industry such as dyes, antistatic agents, ultraviolet absorbers, light stabilizers, waxes, etc. Good.

  A resin composition is prepared by mixing a crystalline norbornene monomer ring-opening polymer hydrogenated product with a nucleating agent and a compounding agent used as required. There are no particular restrictions on the method for preparing the resin composition, but the ring-opening polymer hydrogenated product, nucleating agent and compounding agent are melted by a kneader such as a single screw extruder, twin screw extruder, roll or Banbury mixer. A mixing method is preferable from the viewpoint of productivity.

  The crystalline norbornene monomer ring-opening polymer hydrogenated product when mixed with the compounding agent is isolated from the reaction solution containing the crystalline norbornene monomer ring-opened polymer hydrogenated product, It may be a solution obtained by filtering insoluble matter from a liquid or a reaction solution before filtration. The compounding agents may be those dissolved in an appropriate solvent. The crystalline norbornene monomer ring-opening polymer hydrogenated solution and / or the compounding agent solution may be heated and used as necessary.

  The crystalline norbornene monomer ring-opening polymer hydrogenated product obtained as described above is usually processed into a primary molded body after being processed into a size of about rice grains called pellets for easy handling.

(Primary molded product and molding method)
The primary molded product and the molding method are not particularly limited as long as they are obtained using the above-described crystalline norbornene monomer ring-opening polymer hydrogenated product to which a crosslinking agent or the like is added as necessary. For example, what is obtained by injection molding like an optical disk or a lens, what is melt-extruded into a tube or rod shape, a sheet or film wound up by a melt-extrusion roll, what is formed into a sheet shape by hot press, Examples thereof include a film obtained by dissolving in an appropriate solvent and casting the solution, and a film or sheet stretched.

  The ratio of the crystalline norbornene monomer ring-opening polymer hydrogenated product to the whole polymer constituting the primary molded product is usually 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight. % Or more.

(Crosslinking method)
Various known methods can be used to crosslink the primary molded article, but a method of crosslinking by irradiating active energy rays such as an electron beam or radiation is suitable.

  When the crystalline norbornene monomer ring-opening polymer hydrogenated product is irradiated with an electron beam or radiation, various active species are generated and a crosslinking reaction occurs. This crosslinking reaction proceeds if the irradiation energy is sufficiently high without using a crosslinking aid. In particular, in the case of a ring-opened polymer hydrogenated product in which the hydrogenation rate is 80 to 99.5% and an unsaturated bond remains, the crosslinking reaction occurs efficiently. If various crosslinking assistants are added, a crosslinking reaction can be efficiently carried out even with a hydrogenated ring-opening polymer having a high hydrogenation rate.

  On the other hand, although heat crosslinking is possible, the primary molded product is exposed to a high temperature for a long time of about 30 minutes at 160 ° C., for example, and may be thermally deformed. There are drawbacks that require time and energy consumption. Cross-linking with an electron beam or radiation has the advantages of low energy consumption, high processing speed, and low temperature rise of the molded product.

  Curing technology used in the paint field, such as the EBC method, can be applied to crosslinking by electron beam or radiation.

(Active energy rays)
Examples of active energy rays include α rays, β rays, and γ rays from radioisotopes; or electrons from various accelerators such as a Van de Graaf type electron beam accelerator, Cockcroft, Walton type electron beam accelerator, linear electron beam accelerator, etc. And ultraviolet rays from ultraviolet lamps, microwaves, and the like. X-rays can also be used.
The irradiation amount of the active energy ray is 100 to 500 kGy, preferably 100 to 300 kGy. The acceleration voltage is usually about 10 to 750 kV. If the irradiation amount of the active energy ray is too small, crosslinking is difficult to occur, and if it is too much, it leads to thermal deformation and a decrease in molecular weight.

Below, the case where a film is manufactured as a plastic molded product of this invention is explained in full detail.
There is no restriction | limiting in particular in the method of manufacturing a film, Both a heat-melt-molding method and a solution casting method can be used.
The hot melt molding method is a method in which the above pellets are heated to a temperature equal to or higher than the melting point (Tm) of the polymer and lower than the thermal decomposition temperature to form a fluidized film.
Examples of the heat-melt molding method include an extrusion molding method, a calendar molding method, a compression molding method, an inflation molding method, an injection molding method, a blow molding method, and a stretch molding method.
Further, after forming a film by an extrusion molding method, a calendar molding method, an inflation molding method, or the like, a stretch molding method may be performed.

The heating and pressurizing conditions in the hot melt molding method may be appropriately selected depending on the characteristics of the molding machine, the crystalline norbornene monomer ring-opening polymer hydrogenated product used, and the temperature is usually Tm to (Tm + 100 ° C.). It is preferably (Tm + 20 ° C.) to (Tm + 50 ° C.).
The pressure at the time of molding is usually 0.5 to 100 MPa, preferably 1 to 50 MPa. The pressurizing time is usually about several seconds to several tens of minutes.

The crystalline norbornene monomer ring-opening polymer hydrogenated product used in the present invention has a relatively high Tm and high heat resistance, but has a characteristic that the viscosity becomes extremely low between 200 to 400 ° C. and becomes fluid. Have.
The reason for this is not clear, but it is considered that since it has crystallinity, it becomes a liquid crystal state and the viscosity rapidly decreases. Therefore, although the crystalline norbornene monomer ring-opening polymer hydrogenated product has a high melting temperature, it flows well and can be formed into a film in a short time.

  On the other hand, in the solution casting method, a crystalline norbornene monomer ring-opening polymer hydrogenated product or a compounding agent blended as necessary is dissolved in an organic solvent, and this is cast on a flat surface or a roll. The solvent is removed by heating to form a film and a sheet.

  As the solvent to be used, the same aliphatic hydrocarbon and alicyclic as those exemplified as the solvent for the ring-opening polymerization reaction of 2-norbornene and a substituent-containing norbornene-based monomer and the hydrogenation reaction of the ring-opening polymer Examples thereof include hydrocarbons, aromatic hydrocarbons, halogenated aromatic hydrocarbons, nitrogen-containing hydrocarbons, ethers and the like.

  In the solution casting method, the temperature at which the solvent is volatilized becomes the molding temperature, and the temperature is appropriately set depending on the type of solvent used.

  Further, the molded body may be annealed after the molding in order to reveal the crystallinity of the molded product more strongly.

  The thickness of the film is not particularly limited, but is usually 1 μm to 20 mm, preferably 5 μm to 5 mm, more preferably 10 μm to 2 mm. There is no special rule for the distinction between film and sheet, and there are cases where they are differentiated by thickness, but the actual situation is that the name changes depending on the usage and customs in the industry.

  In order to increase the mechanical strength and water vapor barrier property of the film, the film may be stretched to increase the crystallinity. Stretching means that the formed film is subsequently stretched by about 1.1 to 10 times to give plastic deformation. This plastic deformation has an effect of stretching and aligning not only the crystal chain but also the amorphous chain by internal friction.

  The film may be a laminate having a layer containing a crystalline norbornene monomer ring-opening polymer hydrogenated product and a layer containing another polymer.

  Examples of other polymers include rubbery polymers or other resins, and specific examples thereof are all described above as those that can be used by blending with crystalline norbornene monomer ring-opening polymer hydrogenated products. It is the same as that.

  The number of layers to be laminated is usually two or three, but it may be a multi-layer laminate. The arrangement order of the layers depending on the polymer species in three or more layers can be appropriately set depending on the purpose and application.

  In addition, a polymer layer of the same kind may be disposed with a separation of another polymer layer. For example, polystyrene may be interposed between two layers containing a crystalline norbornene monomer ring-opening polymer hydrogenated product. A three-layer laminate sandwiching the layers to be included, a four-layer laminate in which a layer containing a hydrogenated styrene-isoprene block copolymer is further laminated on one outer side, and the like are possible.

As a lamination method, a method of applying an adhesive between layers and bonding the layers, a method of fusing a single layer or a plurality of layers of films or sheets by heating to a melting point or higher by heat or high frequency, a crystalline norbornene unit An organic solvent in which other polymer or crystalline norbornene monomer ring-opening polymer hydrogenated product is dissolved is applied to the surface of a polymer ring-opened polymer hydrogenated product or other polymer film or sheet. There are methods such as drying.
Moreover, a crystalline norbornene monomer ring-opening polymer hydrogenated product and other polymers can be coextruded with an extruder to produce a laminate.

A film, which is one of the molded articles of the present invention, is excellent in water vapor barrier properties, heat resistance, transparency, oil resistance, and excellent mechanical properties such as tensile elongation at break. Further, since the pyrolysis temperature is high, there is an advantage that the processing temperature range is wide. Moreover, this film is excellent in water vapor | steam barrier property. The moisture permeability measured based on JIS K 7129 (Method A) of a resin film or sheet having a thickness of 100 μm of the present invention is usually 0.50 g / (m ² · 24 h) or less, preferably 0.40 g / (m ² · 24h) or less.

  Films having these characteristics can be used in various applications such as food, medical, display, energy, optical, electrical and electronic, communications, automobile, consumer, and civil engineering. .

Especially, it is suitable for uses in the food field, medical field, energy field, display field and the like.
In the food field, processed foods such as ham, sausage, retort food, frozen food, dried food, specified insurance food, cooked rice, confectionery, meat, wrap film, shrink film, and other food packaging bags, blister packaging films, etc. Can be used.
In the medical field, it can be used in medicine plugs, infusion bags, infusion bags, press-through package (PTP) films, blister package films, and the like.
In the energy field, it can be used as a solar power generation system peripheral member, a fuel cell peripheral member, an alcohol-containing fuel system member, and a packaging film thereof.
In the display field, it can be used as a barrier film, a retardation film, a polarizing film, a light diffusion sheet, a light collecting sheet, and the like.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited only to these examples. In the following examples and comparative examples, “part” or “%” is based on weight unless otherwise specified.

In the following Examples and Comparative Examples, various physical properties are measured as follows.
(1) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the norbornene monomer ring-opening polymer are measured as standard polystyrene conversion values by gel permeation chromatography (GPC) using toluene as an eluent. did.

GPC-8020 series (DP8020, SD8022, AS8020, CO8020, RI8020, manufactured by Tosoh Corporation) was used as a measuring apparatus.
As the standard polystyrene, standard polystyrene (Mw of 500, 2630, 10200, 37900, 96400, 427000, 909000, 5480000, a total of 8 points, manufactured by Tosoh Corporation) was used.

  The sample was prepared by dissolving the measurement sample in toluene so as to have a sample concentration of 1 mg / ml, and then filtering with a cartridge filter (polytetrafluoroethylene, pore size 0.5 μm).

  The measurement was performed using two TSKgel GMHHR · H (manufactured by Tosoh Corporation) connected in series to the column under the conditions of a flow rate of 1.0 ml / min, a sample injection amount of 100 μml, and a column temperature of 40 ° C.

(2) The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the crystalline norbornene monomer ring-opening polymer hydrogenated product are gel permeation using 1,2,4-trichlorobenzene as an eluent. It measured as a standard polystyrene conversion value by chromatography (GPC).

The sample was prepared by heating and dissolving the measurement sample in 1,2,4-trichlorobenzene at 140 ° C. so that the sample concentration was 1 mg / ml.
As standard polystyrene, standard polystyrene (Mw is 988, 2580, 5910, 9010, 18000, 37700, 95900, 186000, 351000, 889000, 1050,000, 2770000, 5110000, 7790,000, 20000000 total, 16 points, manufactured by Tosoh Corporation). Using.

As a measuring device, HLC8121GPC / HT (manufactured by Tosoh Corporation) was used.
The measurement was performed using three TSKgel GMHHR · H (20) HT (manufactured by Tosoh Corporation) connected in series to the column under the conditions of a flow rate of 1.0 ml / min, a sample injection amount of 300 μml, and a column temperature of 140 ° C.

(3) The hydrogenation rate of the crystalline norbornene monomer ring-opening polymer hydrogenated product was measured by ¹ H-NMR using deuterated chloroform as a solvent.

(4) The isomerization rate was 33.0 ppm peak integrated value / (31.8 ppm peak integrated value + 33.0 ppm peak integrated value) measured by ¹³ C-NMR using deuterated chloroform as a solvent.
Calculated from x100.
By the way, the 31.8 ppm peak is derived from the cis isomer of 2-norbornene repeating units in the polymer, and the 33.0 ppm peak is derived from the trans isomer of 2-norbornene repeating units in the polymer. is there.

(5) The melting point is determined by using a differential scanning calorimeter (product name “DSC6220SII”, manufactured by Nanotechnology Co., Ltd.) based on JIS K7121, after heating the sample to 30 ° C. or higher from the melting point, and then cooling rate −10 ° C. / It cooled to room temperature by min, and measured it with the temperature increase rate of 10 degrees C / min after that.

(6) The glass transition temperature was measured based on JIS K6911 using a differential scanning calorimeter (product name “DSC6220SII”, manufactured by Nanotechnology Inc.).

(7) The solvent resistance was obtained by immersing the molded body in a 40 ° C. toluene solution and visually observing the state of swelling and dissolution of the molded body after 24 hours.

[Production Example 1]
(Ring-opening polymerization)
Under nitrogen atmosphere, 500 parts of dehydrated cyclohexane was mixed with 0.55 part of 1-hexene, 0.30 part of diisopropyl ether, 0.20 part of triisobutylaluminum, and 0.075 part of isobutyl alcohol at room temperature. . Thereto, 250 parts of bicyclo [2.2.1] hept-2-ene (hereinafter sometimes referred to as “2-NB”) and 15 parts of a tungsten hexachloride 1.0% toluene solution were kept at 55 ° C. However, the polymerization was continued by adding continuously over 2 hours.
The resulting ring-opening polymer (A) had a weight average molecular weight (Mw) of 83,000 and a molecular weight distribution (Mw / Mn) of 1.8. The polymerization conversion rate was almost 100%.
(Hydrogenation reaction)
The polymerization reaction liquid obtained above was transferred to a pressure-resistant hydrogenation reactor, and 0.6 parts of diatomaceous earth-supported nickel catalyst (product name “T8400”; nickel support rate 58%, manufactured by Zudehemy Catalysts) was added thereto. The reaction was carried out at 200 ° C. and a hydrogen pressure of 4.5 MPa for 6 hours. This solution was filtered under pressure at a pressure of 0.25 MPa using a radiofilter # 500 (manufactured by Showa Chemical Co., Ltd.) and a pressure filter (product name “Funda filter”, manufactured by Ishikawajima-Harima Heavy Industries). Thus, a colorless and transparent solution of the ring-opening polymer hydrogenated product (A) was obtained.
(Polymer physical properties)
The resulting hydrogenated ring-opened polymer (A) had a hydrogenation rate of 95%, a weight average molecular weight (Mw) of 82,200, a molecular weight distribution (Mw / Mn) of 2.9, and an isomerization rate of 5 %, Melting point was 140 ° C.
(Preparation of resin composition)
To the obtained solution, an antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane per 100 parts of polymer solids; product name “ Irganox 1010 ", manufactured by Ciba Geigy Co., Ltd. (hereinafter abbreviated as" Antioxidant (A) ") 0.1 part, and crystal nucleating agent (manufactured by Nippon Talc Co., Ltd .; MS, food talc; major axis 15 μm) 0.5 weight Part was added and dissolved.
(Dry)
After filtering this solution through a metal fiber filter (pore size 0.5 μm, manufactured by Nichidai), the filtrate was filtered through “Zeta Plus Filter 30S” (pore size 0.5-1 μm, manufactured by Cuno), Foreign matter was removed by filtering with a metal fiber filter (pore size 0.2 μm, manufactured by Nichidai). The obtained filtrate was heated to 200 ° C. with a preheating device and continuously supplied to a thin film dryer (manufactured by Hitachi, Ltd.) at a pressure of 3 MPa. The operating conditions of the thin film dryer were a pressure of 13.4 kPa and a temperature of the polymer solution concentrated inside was 240 ° C. (first stage drying).
Next, the concentrated solution was continuously led out from the thin film dryer, and further supplied to the same type of thin film dryer at a pressure of 1.5 MPa while maintaining the temperature at 240 ° C. The operating conditions were a pressure of 0.7 kPa and a temperature of 240 ° C. (second stage drying).
(Pelletized)
The polymer in a molten state is continuously derived from a thin film dryer, extruded from a die in a class 100 clean room, water-cooled, and then cut by a pelletizer (product name “OSP-2”, manufactured by Nagata Seisakusho) to form a resin. A pellet of composition (A) was obtained.

[Production Example 2]
In Production Example 1, except that the amount of catalyst during the hydrogenation reaction was changed to 1.0 part, a hydrogenation reaction was performed in the same manner as in Production Example 1 to obtain 190 parts of a ring-opened polymer hydrogenated product (B). It was.
(Polymer physical properties)
The resulting hydrogenated ring-opened polymer (B) has a hydrogenation rate of 99.9%, a weight average molecular weight of 83,200, a molecular weight distribution (Mw / Mn) of 3.0, an isomerization rate of 5%, The melting point was 140 ° C.
(Preparation of resin)
A pelletized resin (B) was obtained in the same manner as in Production Example 1 except that the ring-opening polymer hydrogenated product (B) was used.

[Production Example 3]
(Ring-opening polymerization and hydrogenation reaction)
In Production Example 1, 240 parts of 2-NB and 10 parts of tricyclo [4.3.12,5] dec-3-ene (hereinafter referred to as “DCP”) are used as polymerizable monomers, and 1-hexene is used. 0.55 parts, diisopropyl ether quantity 0.40 parts, triisobutylaluminum quantity 0.27 parts, isobutyl alcohol quantity 0.10 parts, tungsten hexachloride 1.0% toluene solution quantity The polymerization was carried out in the same manner as in Production Example 1 except that the amount was changed to 20 parts. The resulting ring-opening polymer (B) had a weight average molecular weight of 83,000 and a molecular weight distribution (Mw / Mn) of 2.7. The polymerization addition rate was almost 100%. Thereafter, a hydrogenation reaction was performed in the same manner as in Production Example 2 to obtain 190 parts of a ring-opened polymer hydrogenated product (C).
(Polymer physical properties)
The hydrogenation rate of the obtained ring-opening polymer hydrogenated product (C) was 99.9%, the weight average molecular weight was 81,300, the molecular weight distribution (Mw / Mn) was 3.8, the isomerization rate was 9%, The melting point was 134 ° C.
(Preparation of resin)
A pelletized resin (C) was obtained in the same manner as in Production Example 1 except that the ring-opening polymer hydrogenated product (C) was used.

[Production Example 4]
(Ring-opening polymerization)
Under a nitrogen atmosphere, 33.4 parts of a 70% 2-NB toluene solution, 2.86 parts of DCP, 0.020 part of 1-hexene, and 49.3 parts of cyclohensan were added to an autoclave equipped with a stirrer and stirred. Subsequently, a solution prepared by dissolving 0.023 parts of bis (tricyclohexylphosphine) benzilidineruthenium (IV) dichloride in 8.6 parts of toluene was added and reacted at 60 ° C. for 30 minutes. The polymerization conversion rate was almost 100%. The resulting ring-opening polymer (D) had a weight average molecular weight of 81,000 and a molecular weight distribution (Mw / Mn) of 3.6.
(Hydrogenation reaction)
After 0.020 part of ethyl vinyl ether was added to the polymerization solution obtained above and stirred, a hydrogenation reaction was performed at a hydrogen pressure of 1.0 MPa and 150 ° C. for 20 hours. Thereafter, the mixture was cooled to room temperature, a solution in which 0.5 part of activated carbon powder was suspended in 10 parts of cyclohexane was added, and the mixture was reacted at a hydrogen pressure of 1.0 MPa and 150 ° C. for 2 hours. Next, the reaction solution was filtered through a filter having a pore size of 0.2 μm to remove the activated carbon powder. The reaction solution was poured into a large amount of isopropanol to completely precipitate the polymer, which was collected by filtration. Further, after washing with acetone, it was dried for 48 hours in a vacuum dryer set at 0.13 × 10 3 Pa or less and 100 ° C. to obtain a ring-opening polymer hydrogenated product (D).
(Polymer physical properties)
The resulting hydrogenated ring-opened polymer (D) had a hydrogenation rate of 99.9%, a weight average molecular weight of 85,000, a molecular weight distribution (Mw / Mn) of 3.9, and a melting point of 101 ° C. .
(Preparation of resin)
A pelletized resin (D) was obtained in the same manner as in Production Example 1 except that the ring-opening polymer hydrogenated product (D) was used.

[Production Example 5]
(Ring-opening polymerization and hydrogenation reaction)
35.7 parts of a 70% norbornene / toluene solution, 0.048 part of 1-hexene, and 49.3 parts of cyclohexane were added to 6-methyl-1,4: 5,8-dimethano-1,4,4a. 5,6,7,8,8a-Octahydronaphthalene (hereinafter referred to as “MTD”) 25.0 parts, 1-hexene 0.17 parts, cyclohexane 65.0 parts Then, polymerization was carried out. The resulting ring-opening polymer (E) had a weight average molecular weight of 14,600 and a molecular weight distribution (Mw / Mn) of 2.1. The polymerization addition rate was almost 100%. Thereafter, a hydrogenation reaction was carried out in the same manner as in Production Example 2 to obtain a ring-opening polymer hydrogenated product (E).
(Polymer physical properties)
The hydrogenation rate of the obtained ring-opening polymer hydrogenated product (E) was 99.9%, the weight average molecular weight was 28,000, the molecular weight distribution (Mw / Mn) was 1.9, and the glass transition temperature was 142 ° C. There was no melting point observed.
(Preparation of resin)
A pelletized resin (E) was obtained in the same manner as in Production Example 1 except that the ring-opening polymer hydrogenated product (E) was used and the crystal nucleating agent was not added.

[Example 1]
When 20 parts of the resin (A) obtained in Production Example 1 was dispersed in 80 parts of toluene, a solution (A) free from precipitation or the like was obtained.
The solution (A) obtained above was applied on a mirror-finished SUS plate to a thickness of 500 μm using a coating machine. It was left to dry at 60 ° C. for 20 minutes and further at 120 ° C. for 10 minutes. Thereafter, the formed sheet was peeled from the SUS plate and irradiated with 120 rGy of γ rays. The thickness of the obtained single layer film (A) was 101 μm.
The moisture permeability of the obtained single layer film (A) was 0.32 g / m ² · day. When the film (A) was immersed in toluene at 40 ° C. and left for 24 hours, swelling and dissolution were not observed.

[Example 2]
When 20 parts of the resin (B) obtained in Production Example 2 and 0.5 part of triallyl cyanurate were dispersed in 80 parts of toluene, a solution (B) free from precipitation or the like was obtained.
Using the solution (B) obtained above, γ rays were irradiated in the same manner as in Example 1 except that the irradiation amount of γ rays was changed to 150 rGy. The thickness of the obtained single layer film (B) was 101 μm.
The moisture permeability of the obtained single layer film (B) was 0.32 g / m ² · day. When the film (B) was immersed in toluene at 40 ° C. and left for 24 hours, swelling and dissolution were not observed.

[Example 3]
When 20 parts of the resin (C) obtained in Production Example 3 and 0.5 part of triallyl cyanurate were dispersed in 80 parts of toluene, a solution (C) in which no precipitation occurred was obtained.
Gamma rays were irradiated in the same manner as in Example 2 except that the solution (C) obtained above was used. The thickness of the obtained single layer film (C) was 102 μm.
The moisture permeability of the obtained single layer film (C) was 0.30 g / m ² · day. Further, when the film (C) was immersed in toluene at 40 ° C. and left for 24 hours, swelling and dissolution were not observed.

[Comparative Example 1]
When 20 parts of the resin (D) obtained in Production Example 4 and 0.5 part of triallyl cyanurate were dispersed in 80 parts of toluene, a solution (D) free from precipitation or the like was obtained.
Except for using the solution (D) obtained above, γ rays were irradiated in the same manner as in Example 2. The thickness of the obtained single layer film (D) was 101 μm.
The moisture permeability of the obtained single layer film (D) was 0.68 g / m ² · day. Further, when the film (D) was immersed in toluene at 40 ° C. and left for 24 hours, swelling was observed.

[Comparative Example 2]
When 20 parts of the resin (E) obtained in Production Example 5 and 0.5 part of triallyl cyanurate were dispersed in 80 parts of toluene, a solution (E) free from precipitation or the like was obtained.
Gamma rays were irradiated in the same manner as in Example 2 except that the solution (E) obtained above was used. The thickness of the obtained single layer film (E) was 102 μm.
The moisture permeability of the obtained single layer film (E) was 1.05 g / m ² · day. When the film (E) was immersed in toluene at 40 ° C. and left for 24 hours, swelling was observed.

[Comparative Example 3]
Gamma rays were irradiated in the same manner as in Example 1 except that the irradiation amount of γ rays was changed to 550 rGy. The thickness of the obtained single layer film (F) was 103 μm.
The obtained single layer film (F) was remarkably discolored and had a poor appearance. When the film (F) was immersed in toluene at 40 ° C. and left for 24 hours, swelling and dissolution were not observed.

[Comparative Example 4]
Gamma rays were irradiated in the same manner as in Example 2 except that the irradiation amount of γ rays was changed to 80 rGy. The thickness of the obtained single layer film (G) was 103 μm.
The moisture permeability of the obtained single layer film (G) was 0.62 g / m ² · day. When the film (G) was immersed in toluene at 40 ° C. and left for 24 hours, swelling was observed.

<Discussion>
Crystalline norbornene monomer ring-opening polymer hydrogenated film The obtained film is excellent in solvent resistance and water vapor barrier properties (Examples 1 to 3).
On the other hand, in the case of 2-norbornene ring-opening polymer hydrogenated product having a low melting point, the proportion of 2-norbornene-derived repeating units is not in the range of 90 to 100% by weight with respect to all repeating units, and there are many amorphous parts. Therefore, it is inferior to water vapor | steam barrier property and solvent resistance (Comparative Examples 1 and 2).
When the amount of active energy ray irradiation is large, the color changes and the appearance is poor (Comparative Example 3). When the active energy ray irradiation amount is small, crosslinking is difficult to occur and the solvent resistance is poor (Comparative Example 4).

Claims (1)

A hydrogenation rate of 80% or more obtained by ring-opening polymerization of a polymerizable monomer containing 90 to 100% by weight of 2-norbornene and 10 to 0% by weight of a substituent-containing norbornene and hydrogenating the polymerizable monomer. The melting point is 110 to 145 ° C., the weight average molecular weight measured by gel permeation chromatography is 50,000 to 200,000, and the weight average molecular weight / number average molecular weight is 1.5 to 10.0. A plastic molded article obtained by crosslinking a primary molded article formed of a crystalline norbornene monomer ring-opening polymer hydrogenated product by irradiating an active energy ray with an irradiation dose of 100 to 500 kGy.