JPWO2009001724A1 - Resin composition and film using the same - Google Patents

Abstract

The present invention provides 2-norbornene or 2-norbornene and a monomer mixture comprising a substituent-containing norbornene-based monomer, which is 80% or more of the carbon-carbon double bond of the ring-opening polymer obtained by ring-opening polymerization. The proportion of the repeating unit (A) derived from 2-norbornene obtained by hydrogenating 90 to 100% by weight of all repeating units (A) derived from a substituent and containing all repeating units (B) derived from a substituent-containing norbornene monomer A norbornene monomer ring-opening polymer hydride having an abundance ratio with respect to the repeating unit of 0 to 10% by weight and a melting point in the range of 110 to 145 ° C., and a polyolefin, Resin composition containing 10/90 to 80/20 by weight ratio of combined hydride) / (polyolefin), and a film using the resin compositionADVANTAGE OF THE INVENTION According to this invention, the film which is excellent in mechanical characteristics, such as water vapor | steam barrier property in a high temperature, high humidity environment, and tensile elongation at break, is provided.

Description

  The present invention relates to a resin composition and a film formed by molding the resin composition, and more specifically, a resin composition having excellent mechanical properties and water vapor barrier properties, and a film formed by molding the resin composition. About.

  Conventionally, films made of thermoplastic resins such as polyethylene, polypropylene, polybutene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, amorphous cyclic olefin polymer, food packaging bags such as candy and snacks, infusion solutions Widely used in medical packaging such as bags and press-through packages. However, films made of these thermoplastic resins may be inferior in water vapor barrier properties and mechanical properties, and further improvements have been desired.

  In order to solve these problems, Patent Document 1 discloses a norbornene ring-opening polymer having a melting point or a melting point obtained by hydrogenating a carbon-carbon double bond in the ring-opening polymer. A film formed by molding a norbornene-based ring-opening polymer hydride is disclosed. However, although the film described in Patent Document 1 is excellent in water vapor barrier properties and heat resistance, it sometimes has poor mechanical properties such as tensile elongation at break.

  In Patent Document 2, a composition containing a cyclic olefin copolymer having a glass transition temperature (Tg) of less than 30 ° C., a blocking agent and / or a lubricant, and an α-olefin polymer is used. It has been proposed to obtain a film having a high rate, excellent transparency, and usable in the packaging field, the medical field, and the agricultural field. However, the film described in this document is inferior in water vapor barrier property because a film having a crystallinity as small as 40% or less is suitably used as the cyclic olefin copolymer.

  In Patent Document 3, a sheet obtained from a resin composition containing an amorphous olefin having a heat distortion temperature of 100 ° C. or less, high-density polyethylene, a fatty acid ester lubricant, and a fatty acid lubricant is excellent in transparency, It is described that it is moisture-proof. However, since the sheet described in this document uses an amorphous olefin having a heat deformation temperature of 100 ° C. or less, the sheet may have poor water vapor barrier properties under high temperature conditions.

Japanese Patent Laid-Open No. 2002-194067 JP-A-5-51501 JP 7-33962 A

  The present invention has been made in view of such a state of the art, and an object thereof is to provide a film having excellent mechanical properties such as water vapor barrier properties and tensile elongation at break.

  As a result of intensive studies to solve the above problems, the present inventors have found that from 2-norbornene (bicyclo [2.2.1] hept-2-ene), or 2-norbornene and a substituent-containing norbornene-based monomer. The abundance ratio of the repeating unit (A) derived from 2-norbornene and the repeating unit (B) derived from a substituent-containing norbornene monomer obtained by subjecting the monomer mixture to ring-opening polymerization and hydrogenation is specific. When a resin composition containing a hydrogenated norbornene monomer ring-opening polymer having a melting point within a specific temperature range and a polyolefin is used, the water vapor barrier property is maintained even in a high temperature / high humidity environment. And the present invention was completed.

Thus, according to the present invention,
(1) More than 80% of the carbon-carbon double bonds of the ring-opening polymer obtained by ring-opening polymerization of a monomer mixture comprising 2-norbornene or 2-norbornene and a substituent-containing norbornene-based monomer The proportion of the repeating unit (A) derived from 2-norbornene obtained by hydrogenation is 90 to 100% by weight with respect to all repeating units, and all repeating units (B) derived from a substituent-containing norbornene monomer. A norbornene monomer ring-opening polymer hydride having an abundance ratio of 0 to 10% by weight and a melting point in the range of 110 to 145 ° C. and a polyolefin (norbornene monomer ring-opening polymer) A resin composition containing a hydride) / (polyolefin) in a weight ratio of 10/90 to 80/20.
(2) The average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC) of the norbornene monomer ring-opening polymer hydride is 50,000 to 200,000, And molecular weight distribution (Mw / Mn) is 1.5-7.0, The resin composition as described in (1) characterized by the above-mentioned,
(3) A film comprising the resin composition according to (1) or (2) is provided.

  The resin composition of the present invention is a carbon-carbon double bond of a ring-opening polymer obtained by ring-opening polymerization of a monomer mixture comprising 2-norbornene or 2-norbornene and a substituent-containing norbornene monomer. 90% to 100% by weight of the repeating unit (A) derived from 2-norbornene obtained by hydrogenating 80% or more of the repeating unit (A), and a repeating unit derived from a substituent-containing norbornene monomer ( (B) a norbornene monomer ring-opening polymer hydride having an abundance ratio with respect to all repeating units of 0 to 10% by weight and a melting point of 110 to 145 ° C., and a polyolefin It is contained at a ratio of 10/90 to 80/20 by weight ratio of the body ring-opening polymer hydride) / (polyolefin).

  The norbornene monomer ring-opening polymer hydride used in the present invention is a ring-opening polymer obtained by ring-opening polymerization of a monomer mixture comprising 2-norbornene or 2-norbornene and a substituent-containing norbornene monomer. This is obtained by hydrogenating 80% or more of the carbon-carbon double bond.

  2-norbornene or 2-norbornene and a monomer mixture composed of a substituent-containing norbornene-based monomer are subjected to ring-opening polymerization in the presence of a metathesis polymerization catalyst, whereby 2-norbornene homo-ring-opening polymer or 2-norbornene and A ring-opening copolymer of a substituent-containing norbornene monomer can be obtained.

  2-Norbornene is a known compound and can be obtained, for example, by reacting cyclopentadiene with ethylene.

The substituent-containing norbornene-based monomer is a compound having a norbornene skeleton in the molecule (excluding 2-norbornene). 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] F To-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) 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] To-2-ene, 2-methylpropionate 5-hydroxy-bicyclo [2.2.1] hept-2-ene, 2-methyloctanoate 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] And norbornenes having a polar group containing a nitrogen atom such as hept-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).

(In the formula, R ¹ and R ² each independently include a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a silicon atom, an oxygen atom, or a nitrogen atom. And may be bonded to each other to form a ring, 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-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-8,9-dicarboxylic anhydride Tetracyclododecenes having substituents containing oxygen atoms such as tetracyclododecenes having substituents containing nitrogen atoms such as 8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboxylic imides Decenes; tetracyclododecenes having a substituent containing a halogen atom such as 8-chlorotetracyclododecene; tetracyclododecenes having a substituent containing a silicon atom such as 8-trimethoxysilyltetracyclododecene Etc.

  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 and 12-cyclopentenylhexacycloheptadecene; having an aromatic ring such as 12-phenylhexacycloheptadecene Hexacycloheptadecenes; 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene Hexacycloheptadecenes having a substituent containing an oxygen atom such as 12,13-dicarboxylic acid and hexacycloheptadecene 12,13-dicarboxylic anhydride; 12-cyanohexacycloheptadecene, hexacycloheptadecene 12,13 -Hexacycloheptadecenes having a substituent containing a nitrogen atom such as dicarboxylic imide; hexacycloheptadecenes having a substituent containing a halogen atom such as 12-chlorohexacycloheptadecene; Such as hexamethylene cycloheptanone decene compound having a substituent containing a silicon atom such as trimethoxysilyl hexamethylene cycloheptanone decene 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 And cyclic dienes such as dienes and derivatives thereof.

  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 It is 0 to 10% by weight, preferably 1 to 5% by weight, more preferably 1 to 4% by weight.

  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 (Japanese Patent Application Laid-Open No. 7-179575, Schrock et al., J. Am. Chem. Soc., 1990, Vol. 112, page 3875-) and Grubbs type polymerization catalyst (Fu et al. , J. Am. Chem. Soc., 1993, 115, 9856-; Nguyen et al., J. Am. . M.Soc, 1992 years, 114th volume, 3974 pp ~;., And the like; Grubbs et al, such as WO98 / 21214 pamphlet) living ring-opening metathesis catalyst such as.

  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. Examples thereof include a complexed product of a complexing agent such as P (C ₆ H ₅ ) ₅ .

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 preferred from the viewpoint of polymerization activity, and these halides, oxyhalides, or alkoxy halides are particularly preferred.

  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, 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; Organoboron 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 polymer hydride are dissolved or dispersed under predetermined conditions and do not affect the polymerization and the hydrogenation reaction. 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; Diethyl ether and tetrahydrofuran What d - can be used solvents such as ethers. 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.

  It does not specifically limit as a molecular weight regulator to be used, A conventionally well-known thing 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 Halogen-containing vinyl compounds of the following: oxygen-containing vinyl compounds such as glycidyl methacrylate; nitrogen-containing vinyl compounds 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- Butadiene, 1,3-pentadiene, 1,3-hexa Such as a conjugated diene such as circles can be mentioned. 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 1 minute to 100 hours and is not particularly limited.
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 supplied to the next hydrogenation reaction step.
Further, as will be described later, it is also possible to continuously perform the hydrogenation reaction without adding a hydrogenation catalyst to the reaction solution subjected to the 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 norbornene monomer ring-opening polymer is hydrogenated to a carbon-carbon double bond existing in the main chain and / or side chain of the norbornene monomer ring-opening polymer. 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, any one of a homogeneous catalyst and a heterogeneous catalyst can be used as long as it is generally used for hydrogenation of an olefin compound. Considering the removal of residual metals in the resulting polymer, a heterogeneous catalyst is preferred.
Examples of the homogeneous catalyst include a combination of cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, and the like. 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 catalysts such as dichloride; and the like.
Examples of the heterogeneous catalyst 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, titanium oxide or the like can be mentioned.
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 for 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 temperature range of 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 hydrogenation rate is slow, and if it is too high, a high pressure reactor is required, which is not preferable.

Norbornene monomer ring-opened polymer hydride (hereinafter sometimes simply referred to as “ring-opened polymer hydride”) has a hydrogenation rate of carbon-carbon double bonds in the polymer of 80% or more, preferably It is 90% or more, more preferably 95% or more, further 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 ring-opened polymer hydride 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 from the reaction solution, and the target ring-opening polymer hydride is obtained by removing volatile components such as a solvent from the polymer solution after the filtration. Can do.
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, or a high viscosity reactor device. The degree of vacuum and temperature are appropriately selected depending on the device and are not limited.

  The proportion of the norbornene monomer ring-opening polymer hydride obtained as described above is 90 to 100% by weight, preferably 95 to 99% by weight, based on the total repeating units of the repeating unit (A) derived from 2-norbornene. , More preferably 97 to 99% by weight, and the proportion of the repeating unit (B) derived from the substituent-containing norbornene-based monomer with respect to all repeating units is 0 to 10% by weight, preferably 1 to 5% by weight, More preferably, it is 1 to 4% by weight.

  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. When the proportion of the repeating unit (B) is within the above range, the water vapor barrier property is excellent, and the mechanical properties of the molded article are excellent and suitable. Moreover, when there are too few repeating units (B), there exists a possibility that mechanical characteristics may fall.

The resulting norbornene monomer ring-opened polymer hydride has a weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC) using 1,2,4-trichlorobenzene as an eluent. And preferably 50,000 to 200,000, more preferably 70,000 to 180,000, still more preferably 80,000 to 150,000.
When Mw is in this range, it is preferable because molding is easy and the obtained molded article has sufficient mechanical properties and excellent oil resistance. On the other hand, when Mw is too high, it is difficult to mold, and when a film or a sheet is used, film thickness unevenness is likely to occur. On the other hand, if Mw is too low, the mechanical properties of the molded article may be lowered and the oil resistance may be poor.

The resulting norbornene monomer ring-opened polymer hydride 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 2. It is 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 the molded product is deteriorated and thickness unevenness may occur. Further, if Mw / Mn is too wide, the mechanical properties of the molded product may be deteriorated. Incidentally, Mn is a number average molecular weight measured as standard polystyrene conversion by gel permeation chromatography (GPC) using 1,2,4-trichlorobenzene as an eluent.

The melting point of the resulting norbornene ring-opening polymer hydride is 110 to 145 ° C, preferably 120 to 145 ° C, more preferably 130 ° C to 145 ° C.
It is preferable for the melting point to be in the above range since the heat resistance of the molded product is excellent. In particular, a melting point in the range of 130 to 145 ° C. is preferable because it can withstand steam sterilization performed in a medical molded product.
The melting point of the norbornene ring-opening polymer hydride can be controlled by the molecular weight, molecular weight distribution, isomerization rate, composition ratio, etc. of the norbornene ring-opening polymer hydride.

  The hydride of norbornene monomer ring-opening polymer is a polymer having a melting point, that is, a polymer forming a crystal structure. Therefore, when this is used as a molded body, a crystal part is formed inside the molded body, and this and the amorphous part combine to improve the mechanical properties of the molded body. Nevertheless, since the crystals are not large, the molded article is excellent in transparency.

The isomerization rate of the resulting norbornene monomer ring-opening polymer hydride is usually 40% or less, preferably 20% or less, more preferably 10% or less, and even more 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. 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.

  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.

  The resin composition of the present invention comprises the above norbornene monomer ring-opening polymer hydride and polyolefin in a weight ratio of (norbornene monomer ring-opening polymer hydride) / (polyolefin) of 10/90 to 80 /. 20, preferably 20/80 to 80/20, more preferably 30/70 to 75/25. By containing the norbornene monomer ring-opening polymer hydride and polyolefin in such a ratio, a film having excellent mechanical properties such as water vapor barrier properties and tensile elongation at break can be obtained.

  The polyolefin used in the present invention is obtained by polymerizing a chain olefin which may have a substituent. Examples of the substituent include a linear, branched or cyclic alkyl group.

  Specifically, polyethylene-based resins such as linear or branched ethylene-α-olefin copolymers, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultrahigh molecular weight polyethylene; homopolypropylene Polypropylene resins such as ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene-propylene-1-butene copolymer; and ethylene-propylene copolymer, polymethylpentene, polybutene, polymethyl And polyolefin-based crystalline resins represented by the group consisting of butene, polymethylhexene and the like.

  In the present invention, among the above polyolefins, polyethylene resins and polypropylene resins are preferable, and polyethylene resins are more preferable.

  Further, among polyethylene resins, branched ethylene-α-olefin copolymers, high-density polyethylene, low-density polyethylene, linear low-density polyethylene are more preferable, and branched ethylene-α-olefin copolymers. Linear low density polyethylene is particularly preferable, and linear low density polyethylene is particularly preferable.

The melting point of the polyolefin is not particularly limited, but is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, from the viewpoint of heat resistance.
Density of the polyolefin resin is not particularly limited, from the viewpoint of transparency, is preferably from 0.850~0.970g / cm ^3, more preferably in the range of 0.900~0.960g / cm ³ .

  The melt mass flow rate (MFR) at 190 ° C. measured according to JIS K 7210 of polyolefin is preferably 0.1 to 30 g / 10 minutes, more preferably 0.5 to 25 g / 10 minutes, and particularly preferably 1 ~ 20 g / 10 min. If the MFR is below the lower limit, the fluidity of the resin becomes too low to be molded, whereas if the upper limit is exceeded, the fluidity becomes too high and the strength of the molded product tends to decrease.

  A compounding agent can be added to the above-described norbornene monomer ring-opening polymer hydride, polyolefin, and a resin composition containing both as required.

  The compounding agents used include antioxidants, rubbery polymers, other resins, UV absorbers, weathering stabilizers, antistatic agents, slip agents, antifogging agents, dyes, pigments, colorants, natural oils, and synthetic oils. , Plasticizers, organic or inorganic fillers, antibacterial agents, deodorants, deodorizers and the like.

  As the antioxidant, those having a molecular weight of 700 or more are preferable. If the molecular weight of the antioxidant is too low, the antioxidant may be eluted from the molded product.

Specific examples of the antioxidant include octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl- 4'-hydroxyphenyl) propionate] methane, pentaerythrityl-
Phenolic antioxidants such as tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]; triphenyl phosphite, tris (cyclohexylphenyl) phosphite, 9,10-dihydro-9 -Phosphorous antioxidants such as oxa-10-phosphaphenanthrene; dimyristyl 3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropioate And sulfur-based antioxidants such as pentaerythritol-tetrakis (β-lauryl-thiopropionate).
These antioxidants can be used alone or in combination of two or more. Among these, a phenolic antioxidant is preferable.

  The blending amount of the antioxidant is 100 parts by weight of norbornene monomer ring-opening polymer hydride or polyolefin (in the case of a resin composition, 100 parts by weight of norbornene monomer ring-opening polymer hydride in the composition). On the other hand, it is usually 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight. If the amount of antioxidant added is too small, the molded product may be burned. On the other hand, when there is too much addition amount, there exists a possibility that a molded article may become cloudy or an antioxidant may elute from a molded article.

The rubbery polymer is a polymer having a glass transition temperature of 40 ° C. or lower. Rubbery polymers include rubber and thermoplastic elastomers. When there are two or more glass transition temperatures as in the block copolymer, the glass transition temperature can be used as a rubbery polymer if the lowest glass transition temperature is 40 ° C. or lower. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the rubbery polymer is appropriately selected according to the purpose of use, but is usually 5 to 300.

  Examples of rubber polymers include ethylene-α-olefin rubbers; ethylene-α-olefin-polyene copolymer rubbers; copolymers of ethylene and unsaturated carboxylic acid esters such as ethylene-methyl methacrylate and ethylene-butyl acrylate. Polymer; Copolymer of ethylene and fatty acid vinyl such as ethylene-vinyl acetate copolymer; alkyl acrylate such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, etc. Polymer: Polybutadiene, polyisoprene, random copolymer of styrene and butadiene or isoprene, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene- (meth) acrylic acid alkyl ester copolymer, butadiene- ( Diene rubber such as meth) acrylic acid alkyl ester-acrylonitrile copolymer, butadiene- (meth) acrylic acid alkyl ester-acrylonitrile-styrene copolymer; butylene-isoprene copolymer; styrene-butadiene block copolymer, hydrogen Aromatic vinyl-conjugated diene block copolymers such as hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-butadiene random copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer; Examples thereof include low crystalline polybutadiene resins; elastomers such as ethylene-propylene elastomers, styrene-grafted ethylene-propylene elastomers, and thermoplastic polyester elastomers; ethylene ionomer resins.

  The blending amount of the rubbery polymer is appropriately selected according to the purpose of use. When impact resistance and flexibility are required, the amount of the rubber polymer is 100 parts by weight of a norbornene monomer ring-opening polymer hydride or polyolefin (in the case of a resin composition, the norbornene unit in the composition). The amount is usually 0.01 to 100 parts by weight, preferably 0.1 to 70 parts by weight, and more preferably 1 to 50 parts by weight with respect to 100 parts by weight of the hydrated ring-opening polymer.

  Other resins include, for example, amorphous norbornene monomer ring-opening polymer, amorphous norbornene monomer ring-opening polymer hydride, crystalline norbornene-based addition polymer, amorphous norbornene-based addition type Polymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, polypropylene, polystyrene, hydrogenated polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyphenylene sulfide, polyphenylene ether, polyamide, polyester, polycarbonate , Cellulose triacetate, polyetherimide, polyimide, polyarylate, polysulfone, polyethersulfone and the like. These other resins can be used alone or in combination of two or more, and the blending ratio thereof can be appropriately selected within a range not impairing the object of the present invention.

  Examples of the ultraviolet absorber and the weathering stabilizer include 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, and bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 4- [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -1- {2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl} -2, Hindered amine compounds such as 2,6,6-tetramethylpiperidine; 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3-t-butyl-2-hydroxy-5-methylphenyl); Nyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxy Benzotriazole compounds such as phenyl) benzotriazole; 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4 -Bezoate compounds such as hydroxybenzoate. These ultraviolet absorbers and weathering stabilizers can be used alone or in combination of two or more. The amount of UV absorber and weathering stabilizer is 100 parts by weight of norbornene monomer ring-opening polymer hydride or polyolefin (in the case of a resin composition, 100 parts by weight of norbornene monomer ring-opening polymer hydride in the composition). Part) is usually in the range of 0.001 to 5 parts by weight, preferably 0.01 to 2 parts by weight.

Antistatic agents include: long-chain alkyl alcohols such as stearyl alcohol and behenyl alcohol; sodium alkyl sulfonates and / or phosphonium alkyl sulfonates; fatty acid esters such as glycerol esters of stearic acid; hydroxyamine compounds; amorphous carbon; Examples thereof include tin oxide powder and antimony-containing tin oxide powder. The amount of antistatic agent is 100 parts by weight of norbornene monomer ring-opening polymer hydride or polyolefin (in the case of a resin composition, 100 parts by weight of norbornene monomer ring-opening polymer hydride in the composition). In general, the range is 0.001 to 5 parts by weight.
These compounding agents are preferably blended with a norbornene monomer ring-opening polymer hydride or polyolefin to obtain a resin composition.

  Although there is no limitation in the manufacturing method of the resin composition of this invention, the method of knead | mixing each component mentioned above in a molten state is mentioned as a suitable method. As the melt-kneading apparatus, known devices such as an open type mixing roll, a non-open type Banbury mixer, an extruder, a kneader, and a continuous mixer can be used.

  The resin composition of the present invention can be formed into a film, a sheet, and various molded products by a known method. For example, single screw extruder, vent type extruder, twin screw extruder, conical twin screw extruder, conyder, plasticizer, mixed ruder, twin screw conical screw extruder, planetary screw extruder, gear type extruder Extrusion molding, injection molding, compression molding, blow molding, rotational molding, etc. are performed using a screwless extruder. Moreover, a film or a sheet can be obtained by T-die molding, inflation molding or the like. Moreover, you may shape | mold directly at the time of resin composition manufacture.

The film of the present invention is obtained by molding the resin composition of the present invention.
The film of the present invention contains the resin composition of the present invention usually at 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more.

  There is no restriction | limiting in the method of shape | molding the film of this invention, Well-known shaping | molding methods, such as extrusion molding, inflation molding, calendar molding, compression molding, and cast molding, are employable.

  The thickness of the film of the present invention 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.

  The film of the present invention may be a laminate having a layer containing the resin composition of the present invention and a layer containing a known polymer generally used in home appliances, food fields, medical fields and the like. .

  The number of layers to be laminated is usually two or three, but it can be a multilayer laminate. The arrangement order of the layers depending on the polymer species in three or more layers can be determined according to the purpose and application.

  The film of the present invention is excellent in water vapor barrier properties. The film of the present invention has excellent water vapor barrier properties, for example, based on JIS K 7129 (Method A) under the conditions of a temperature of 50 ° C. and a humidity of 90% RH (manufactured by LYSSY: L80-5000). It can be evaluated by measuring the water vapor transmission rate using a mold).

The water vapor permeability of the 250 μm thick film of the present invention is usually 0.5 (g / (m ² · 24 h)) or less, preferably 0.45 (g / (m ² · 24 h)) or less, more preferably It is 0.40 (g / (m ² · 24h)) or less, more preferably 0.35 (g / (m ² · 24 h)) or less.

The film of the present invention is excellent in mechanical properties. The fact that the film of the present invention is excellent in mechanical properties is, for example, that the autograph ( It can be evaluated by measuring the tensile elongation at break with AGS-5kNH (manufactured by Shimadzu Corporation).
The tensile elongation at break of the film of the present invention is usually 50% or more, preferably 60% or more, more preferably 70% or more.

  The film of the present invention can be used in various applications such as the food field, medical field, display field, energy field, optical field, electrical and electronic field, communication field, automobile field, consumer field, and civil engineering field. Above all, it is suitable for applications 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. The present invention is not limited only to these examples. In the following examples and comparative examples, parts and% are 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 were measured as standard polystyrene conversion values by gel permeation chromatography (GPC) using toluene as an eluent.
As a measuring device, GPC-8020 series (DP8020, SD8022, AS8020, CO8020, RI8020) manufactured by Tosoh Corporation was used. As the standard polystyrene, eight standard polystyrenes manufactured by Tosoh Corporation, Mw = 500, 2630, 10200, 37900, 96400, 427000, 1090000, and 5480000 were used.
The sample was prepared by dissolving the measurement sample in toluene so that the sample concentration would be 1 mg / ml, and then filtering through a cartridge filter (porous polytetrafluoroethylene filter having a pore diameter of 0.5 μm).
The measurement was performed under the conditions of using TSKgel GMHHR · H manufactured by Tosoh Corporation connected in series as a column, with 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 number average molecular weight (Mn) of the ring-opening polymer hydride of norbornene monomer are determined by gel permeation chromatography (GPC) using 1,2,4-trichlorobenzene as an eluent. It measured at 140 degreeC as a standard polystyrene conversion value. As a measuring device, HLC811GPC / HT manufactured by Tosoh Corporation was used.
As standard polystyrene, Tosoh Corporation standard polystyrene, Mw = 988, 2580, 5910, 9010, 18000, 37700, 95900, 186000, 351000, 889000, 1050,000, 2770000, 5110000, 7790,000 and 20000000 were used.
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.
The measurement was carried out under the conditions of using TSKgel GMHHR · H (20) HT manufactured by Tosoh Corporation as a column in series, using 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 norbornene monomer ring-opening polymer hydride was measured by ¹ H-NMR using deuterated chloroform as a solvent.

(4) The isomerization rate of the norbornene monomer ring-opening polymer hydride was calculated using the formula [(33.3) from the peak values of 31.8 ppm and 33.0 ppm measured by ¹³ C-NMR using deuterated chloroform as a solvent. 0 ppm peak integrated value) / (31.8 ppm peak integrated value + 33.0 ppm peak integrated value)] × 100.
The 31.8 ppm peak is derived from the cis isomer of a repeating unit derived from 2-norbornene in the ring-opened polymer hydride, and the 33.0 ppm peak is derived from 2-norbornene of the ring-opened polymer hydride. It is derived from the trans isomer of the repeating unit.

(5) The melting point (Tm) is determined by using a differential scanning calorimeter (DSC 6220SII, manufactured by Nanotechnology) based on JIS K 7121. After heating the sample to 30 ° C. or higher from the melting point, cooling rate −10 ° C. / The temperature was measured in the process of cooling to room temperature in minutes and then increasing the temperature at a rate of temperature increase of 10 ° C./min.
(6) The glass transition temperature (Tg) was measured based on JIS K 6911 using a differential scanning calorimeter (DSC 6220SII, manufactured by Nanotechnology).
(7) The melt mass flow rate was measured at 190 ° C. under a 2.16 kg load in accordance with JIS K 7210.

(8) The water vapor barrier property evaluation test is a water vapor permeability tester (L80-5000 type, manufactured by LYSSY) based on JIS K 7129 (Method A) under conditions of a temperature of 40 ° C. and a humidity of 90% RH. Measured with As water vapor transmission rate ^{(g / (m 2 · 24h} )) is small, indicating that the water vapor barrier property is good.
(9) The tensile breaking elongation was measured by performing a tensile test in the MD direction at a pulling rate of 200 mm / min using a JIS type 1B test piece in accordance with JIS K 7162.

[Production Example 1]
(Ring-opening copolymerization)
In a nitrogen atmosphere, 500 parts of dehydrated cyclohexane were 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. While maintaining the temperature at 55 ° C., 250 parts of 2-norbornene (2-NB) and 6 parts of a tungsten hexachloride 1.0% toluene solution were continuously added over 2 hours for polymerization. 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.

(Hydrogenation reaction)
The polymerization reaction solution containing the ring-opening polymer (A) obtained above was transferred to a pressure-resistant hydrogenation reactor, and 0.5 part of a diatomaceous earth-supported nickel catalyst (manufactured by Zude Chemie Catalysts; T8400, nickel support rate 58%) was added. In addition, the reaction was performed at 160 ° C. and a hydrogen pressure of 4.5 MPa for 6 hours. This solution was filtered with a filter equipped with a stainless steel wire mesh using diatomaceous earth as a filter aid to remove the catalyst.
The obtained reaction solution was poured into 3000 parts of isopropyl alcohol with stirring to precipitate a hydride, which was collected by filtration. Furthermore, after washing with 500 parts of acetone, it was dried in a vacuum drier set at 0.13 × 10 ³ Pa or less and 100 ° C. for 48 hours to obtain 190 parts of ring-opened polymer hydride (A).

(Polymer physical properties)
The hydrogenation rate of the obtained ring-opened polymer hydride (A) was 99.9%, the weight average molecular weight (Mw) was 82,200, the molecular weight distribution (Mw / Mn) was 2.9, and the isomerization rate was It was 5% and the melting point was 140 ° C.

(Preparation of pellets)
100 parts of the ring-opened polymer hydride (A) with an antioxidant (manufactured by Ciba Specialty Chemicals; Irganox 1010, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′- Hydroxyphenyl) propionate] methane) 0.1 part,
The pellets (A) were kneaded with a biaxial kneader (TEM-35B, manufactured by Toshiba Machine Co., Ltd.) to give pellets (A).

[Production Example 2]
(Ring-opening copolymerization)
In Production Example 1, the monomer was 240 parts 2-norbornene (2-NB), 10 parts dicyclopentadiene (DCP), 0.55 parts 1-hexene, 0.40 parts diisopropyl ether, 0.27 triisobutylaluminum. Polymerization was carried out in the same manner as in Production Example 1 except that 0.10 parts of isobutyl alcohol and 20 parts of tungsten hexachloride 1.0% toluene solution were used. The resulting ring-opening polymer (B) had a weight average molecular weight (Mw) of 83,000 and a molecular weight distribution (Mw / Mn) of 2.7. The conversion rate was almost 100%. Then, it carried out similarly to manufacture example 1, and hydrogenation reaction was performed, and 190 parts of ring-opening copolymer hydrides (B) were obtained.

(Polymer physical properties)
The hydrogenation rate of the obtained ring-opening copolymer hydride (B) was 99.9%, the weight average molecular weight (Mw) was 81,300, the molecular weight distribution (Mw / Mn) was 3.8, the isomerization rate Was 9% and the melting point was 134 ° C.

(Preparation of pellets)
Pellets were obtained by pelletizing in the same manner as in Production Example 1 except that the ring-opening copolymer hydride (B) was used.

[Production Example 3]
(Ring-opening copolymerization and hydrogenation reaction)
In Production Example 1, the monomers were 245 parts of 2-norbornene (2-NB) and 5 parts of 5-methyl-2-norbornene (hereinafter sometimes abbreviated as “MNB”), and 0.40 part of 1-hexene. Ring opening copolymerization in the same manner as in Production Example 1 except that 0.31 part of diisopropyl ether, 0.20 part of triisobutylaluminum, 0.08 part of isobutyl alcohol, and 15 parts of a tungsten hexachloride 1.0% toluene solution were used. Went. The polymerization conversion rate was almost 100%. The obtained ring-opening copolymer (C) had a weight average molecular weight Mw of 103,000 and a molecular weight distribution (Mw / Mn) of 1.9. Then, it carried out similarly to manufacture example 1, and hydrogenation reaction was performed, and 190 parts of ring-opening copolymer hydrides (C) were obtained.

(Polymer physical properties)
The resulting hydrogenated ring-opening copolymer (C) had a hydrogenation rate of 99.9%, a weight average molecular weight Mw of 100,000, a molecular weight distribution Mw / Mn of 2.9, an isomerization rate of 8%, and a melting point. Was 136 ° C.

(Preparation of pellets)
Pellets were obtained by pelletizing in the same manner as in Production Example 1 except that the ring-opening copolymer hydride (C) was used.

[Production Example 4]
(Ring-opening copolymerization and hydrogenation reaction)
In Production Example 1, instead of 250 parts by weight of 2-norbornene (2-NB), 50 parts by weight of 2-norbornene (2-NB) and 200 parts by weight of dicyclopentadiene (DCP) were used, and 0.58 of 1-hexene was used. Polymerization was carried out in the same manner as in Production Example 1 except that the amount was changed to parts by weight. The resulting ring-opening polymer (D) had a weight average molecular weight (Mw) of 40,000 and a molecular weight distribution (Mw / Mn) of 3.4. Thereafter, a hydrogenation reaction was carried out in the same manner as in Production Example 1 except that the diatomaceous earth-supported nickel catalyst was changed to 3 parts by weight to obtain a ring-opened polymer hydride (D).

(Polymer physical properties)
The hydrogenation rate of the obtained ring-opening polymer hydride (D) was 99.9%, the weight average molecular weight (Mw) was 45,000, the molecular weight distribution (Mw / Mn) was 4.2, and the isomerization rate was The glass transition temperature was 0% and the melting point was not observed.

(Preparation of pellets)
A pelletized pellet (D) was obtained in the same manner as in Production Example 1 except that the ring-opened polymer hydride (D) was used.

[Production Example 5]
In a nitrogen atmosphere, in an autoclave equipped with a stirrer, 33.4 parts of 70% 2-norbornene (2-NB) in toluene, 2.86 parts dicyclopentadiene (DCP), 0.020 parts 1-hexene, 49. cyclohensan. 3 parts were added 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 (E) had a weight average molecular weight (Mw) 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. Furthermore, after washing | cleaning with acetone, it dried for 48 hours in the vacuum dryer set to 0.13 * 10 < ³ > Pa or less and 100 degreeC, and the ring-opening copolymer hydride (E) was obtained.

(Polymer physical properties)
The hydrogenation rate of the obtained ring-opening copolymer hydride (E) was 99.9%, the weight average molecular weight (Mw) was 85,000, the molecular weight distribution (Mw / Mn) was 3.9, and the melting point was 101. ° C.

(Preparation of pellets)
Pellets were obtained by pelletizing in the same manner as in Production Example 1 except that the ring-opening copolymer hydride (E) was used.

[Production Example 6]
(Ring-opening polymerization)
Under a nitrogen atmosphere, 1.1 parts of tungsten (phenylimide) tetrachloride / diethyl ether and 18.5 parts of cyclohexane were added to an autoclave equipped with a stirrer. Further, a solution prepared by dissolving 0.87 parts of diethylaluminum ethoxide in 9.26 parts of hexane was added and stirred at room temperature for 30 minutes. To the obtained mixture, 139 parts of dicyclopentadiene (DCP) and 0.33 part of 1-hexane were added, and a polymerization reaction was carried out at 50 ° C. for 3 hours. The obtained ring-opening polymer (F) had a weight average molecular weight (Mw) of 78,000 and a molecular weight distribution (Mw / Mn) of 3.5.

(Hydrogenation reaction)
A hydrogenation catalyst solution prepared by dissolving 0.87 parts of bis (tricyclohexylphosphine) benzilidineruthenium (IV) dichloride and 20.4 parts of ethyl vinyl ether in 650 parts of cyclohexane was added to the polymerization solution obtained above, and the hydrogen pressure was 1 The hydrogenation reaction was performed at 0.0 MPa and 160 ° C. for 20 hours. The reaction solution was poured into a large amount of isopropanol to completely precipitate the polymer, which was collected by filtration. Furthermore, after washing with 500 parts of acetone, it was dried in a vacuum dryer set at 0.13 × 10 ³ Pa or less and 100 ° C. for 48 hours to obtain 130 parts of a ring-opened polymer hydride (F).
The obtained ring-opened polymer hydride (F) was not dissolved in the GPC solvent, and the molecular weight could not be measured. The melting point was 273 ° C.

(Preparation of pellets)
Pellets were obtained by pelletizing in the same manner as in Production Example 1 except that the ring-opened polymer hydride (F) was used.

  The physical properties of the norbornene monomer ring-opening polymer hydride are summarized in Table 1 below.

[Example 1]
70 parts of the pellet (A) obtained in Production Example 1 and 30 parts of linear low density polyethylene (LL) having a melting point of 123 ° C., a density of 0.931 g / cm ³ , and an MFR of 4.0 g / 10 min were mixed with a blender. did. Subsequently, it knead | mixed with the following kneading | mixing conditions with the twin-screw kneader (TEM-35B, Toshiba Machine Co., Ltd.), extruded, and pelletized, and the resin composition (A) was obtained.

Kneading conditions: screw diameter 37 mm, L / D = 32
Screw rotation speed 250rpm
Resin temperature 200 ℃
Feed rate 15kg / hour

  The resulting resin composition (A) pellets are hanger-manufactured type T-die film melt extrusion molding having a resin melt kneader equipped with a screw having a screw diameter of 50 mmφ, a compression ratio of 2.5, and L / D = 30. Using a machine, T-die molding was performed under the following molding conditions to obtain a single layer film (A) (layer thickness: 100 μm).

Molding conditions: Die lip 0.8mm
Molten resin temperature: 210 ° C
T die width 300mm
Cast roll temperature 40 ℃
Cooling roll temperature 30 ° C

  The appearance of the obtained single layer film (A) was good and there were no holes or breaks. The monolayer film (A) was evaluated for water vapor barrier properties and tensile elongation at break.

[Example 2]
A resin composition (B) and a single layer film (B) (layer thickness 100 μm) were obtained in the same manner as in Example 1 except that the pellet (B) obtained in Production Example 2 was used instead of the pellet (A). Obtained.
The appearance of the obtained single layer film (B) was good and there were no holes or breaks. The monolayer film (B) was evaluated for water vapor barrier properties and tensile elongation at break.

[Example 3]
A resin composition (C) and a single layer film (C) (layer thickness 100 μm) were obtained in the same manner as in Example 1 except that the pellet (C) obtained in Production Example 3 was used instead of the pellet (A). Obtained.
The appearance of the obtained single layer film (C) was good and there were no holes or breaks. The monolayer film (C) was evaluated for water vapor barrier properties and tensile elongation at break.

[Example 4]
Instead of linear low density polyethylene having a melting point of 123 ° C., a density of 0.931 g / cm ³ , and an MFR of 4.0 g / 10 min, a melting point of 134 ° C., a density of 0.963 g / cm ³ , and a high density of MFR of 7.0 g / 10 min. Except having used polyethylene (HD), it carried out similarly to Example 2, and obtained the resin composition (D) and the single layer film (D) (layer thickness of 100 micrometers).
The appearance of the obtained single layer film (D) was good and there were no holes or breaks. The monolayer film (D) was evaluated for water vapor barrier properties and tensile elongation at break.

[Example 5]
Mp 123 ° C., a density 0.931 g ^/ cm 3, instead of the MFR4.0g / 10 min linear low density polyethylene, melting point 125 ° C., a density 0.900g ^/ cm 3, MFR1.5g ^/ 10 min Polypropylene ( A resin composition (E) and a single layer film (E) (layer thickness 100 μm) were obtained in the same manner as in Example 2 except that PP) was used.
The appearance of the obtained single layer film (E) was good and there were no holes or breaks. The monolayer film (E) was evaluated for water vapor barrier properties and tensile elongation at break.

[Example 6]
Example 2 was repeated except that 50 parts of the pellet (B), a melting point of 123 ° C., a density of 0.931 g / cm ³ , and a linear low density polyethylene (LL) of MFR 4.0 g / 10 minutes were changed to 50 parts. Thus, a resin composition (F) and a single layer film (F) (layer thickness: 100 μm) were obtained.
The appearance of the obtained single-layer film (F) was good and there were no holes or breaks. The monolayer film (F) was evaluated for water vapor barrier properties and tensile elongation at break.

[Example 7]
Example 2 except that 20 parts of the pellet (B), melting point 123 ° C., density 0.931 g / cm ³ , MFR 4.0 g / 10 min linear low density polyethylene (LL) was changed to 80 parts. Thus, a resin composition (G) and a single layer film (G) (layer thickness: 100 μm) were obtained.
The appearance of the obtained single-layer film (G) was good and there were no holes or breaks. The monolayer film (G) was evaluated for water vapor barrier properties and tensile elongation at break.

[Comparative Example 1]
Resin composition (H), single resin was obtained in the same manner as in Example 1 except that the pellet (D) obtained in Production Example 4 was used in place of the pellet (A), and the kneading conditions and molding conditions were changed to conditions other than those. A layer film (H) (layer thickness: 100 μm) was obtained.
The appearance of the obtained single-layer film (H) was good and there were no holes or breaks. The monolayer film (H) was evaluated for water vapor barrier properties and tensile elongation at break.

Kneading conditions: screw diameter 37 mm, L / D = 32
Screw rotation speed 250rpm
Resin temperature 230 ° C
Feed rate 15kg / hour

Molding conditions: Die lip 0.8mm
Molten resin temperature: 240 ° C
T die width 300mm
Cast roll temperature 70 ℃
Cooling roll temperature 60 ° C

[Comparative Example 2]
Instead of the pellet (B), the pellet (D) obtained in Production Example 4 was used, except that the kneading conditions and the molding conditions were changed to the following conditions in the same manner as in Example 4, the resin composition (I), Single layer film (I) (layer thickness 100 micrometers) was obtained.
The appearance of the obtained monolayer film (I) was good and there were no holes or breaks. The monolayer film (I) was evaluated for water vapor barrier properties and tensile elongation at break.

Kneading conditions: screw diameter 37 mm, L / D = 32
Screw rotation speed 250rpm
Resin temperature 230 ° C
Feed rate 15kg / hour

Molding conditions: Die lip 0.8mm
Molten resin temperature: 230 ° C
T die width 300mm
Cast roll temperature 60 ℃
Cooling roll temperature 50 ° C

[Comparative Example 3]
A resin composition (J) and a single layer film (J) (layer thickness 100 μm) were obtained in the same manner as in Example 1 except that the pellet (E) obtained in Production Example 5 was used instead of the pellet (A). Obtained.
The appearance of the obtained single layer film (J) was good and there were no holes or breaks. The monolayer film (J) was evaluated for water vapor barrier properties and tensile elongation at break.

[Comparative Example 4]
The resin composition (K) was obtained in the same manner as in Example 1 except that the pellet (F) obtained in Production Example 6 was used in place of the pellet (A) and the kneading conditions and molding conditions were changed to the following conditions. It was. Next, molding was attempted using this, but since the viscosity difference between the pellet (F) and the linear low-density polyethylene (LL) became large and poor dispersion occurred, good quality pellets (K) that can withstand molding. Was not obtained.

Kneading conditions: screw diameter 37 mm, L / D = 32
Screw rotation speed 250rpm
Resin temperature 310 ° C
Feed rate 10kg / hour

[Comparative Example 5]
Example 2 except that the pellet (B) was changed to 90 parts by weight, a linear low density polyethylene having a melting point of 123 ° C., a density of 0.931 g / cm ³ , and an MFR of 4.0 g / 10 minutes was changed to 10 parts by weight. Resin composition (L) and single layer film (L) (layer thickness 100 μm) were obtained.
The appearance of the obtained single layer film (L) was good and there were no holes or breaks. The monolayer film (L) was evaluated for water vapor barrier properties and tensile elongation at break.

[Comparative Example 6]
Single layer film (M) (layer thickness) as in Example 1 except that only linear low density polyethylene (LL) having a melting point of 123 ° C., a density of 0.931 g / cm ³ , and MFR of 4.0 g / 10 min was used. 100 μm) was obtained.
The appearance of the obtained single layer film (M) was good and there were no holes or breaks. The monolayer film (M) was evaluated for water vapor barrier properties and tensile elongation at break.

  The evaluation results in Examples and Comparative Examples are shown in Table 2. In Table 2, “x” indicates that molding could not be performed.

The resin composition of the present invention is a carbon-carbon double bond of a ring-opening polymer obtained by ring-opening polymerization of a monomer mixture composed of 2-norbornene or 2-norbornene and a substituent-containing norbornene monomer. A hydrogenation product of a norbornene monomer ring-opening polymer obtained by hydrogenating 80% or more of the above, wherein the abundance ratio of 2-norbornene-derived repeating units (A) with respect to all repeating units is 90 to 100% by weight, The norbornene monomer ring-opening weight in which the proportion of the repeating unit (B) derived from the substituent-containing norbornene monomer is 0 to 10% by weight and the melting point is in the range of 110 to 145 ° C. It is a resin composition containing a combined hydride and polyolefin in a ratio of 10/90 to 80/20 (weight ratio).
Films obtained using the resin composition of the present invention have good water vapor barrier properties and excellent mechanical strength such as tensile elongation at break (Examples 1 to 7). In particular, when linear low density polyethylene is used as the polyolefin, it can be seen that the tensile elongation at break is particularly good (Examples 1 to 3, Examples 6 and 7).
On the other hand, when a norbornene monomer ring-opening polymer hydride having no melting point is used, the water vapor barrier property and the tensile elongation at break are inferior (Comparative Examples 1 and 2).
10-90 to 80/20 (weight) of 2-norbornene ring-opening polymer hydride having a ratio of the repeating unit (A) derived from 2-norbornene not exceeding 90 to 100% by weight with respect to all repeating units and polyolefin. When the resin composition contained in the ratio is used, the water vapor barrier property is inferior (Comparative Example 3).
When a resin composition containing 2-norbornene ring-opened polymer hydride having a melting point not in the range of 110 to 145 ° C. and polyolefin in a ratio of 10/90 to 80/20 (weight ratio) is used. Kneading was poor (Comparative Example 4).
Furthermore, when the resin composition in which the ratio of the 2-norbornene ring-opening polymer hydride and the polyolefin is not in the range of 10/90 to 80/20 (weight ratio) is used, the tensile elongation at break is inferior.

Claims (3)

Hydrogenate 80% or more of carbon-carbon double bonds in a ring-opening polymer obtained by ring-opening polymerization of a monomer mixture comprising 2-norbornene or 2-norbornene and a substituent-containing norbornene monomer. The existence ratio of the repeating unit (A) derived from 2-norbornene to all repeating units is 90 to 100% by weight, and the existence of the repeating unit (B) derived from a substituent-containing norbornene monomer to all repeating units. A norbornene monomer ring-opening polymer hydride having a proportion of 0 to 10% by weight and a melting point of 110 to 145 ° C;
Polyolefin and
A resin composition containing a weight ratio of (norbornene monomer ring-opening polymer hydride) / (polyolefin) in a ratio of 10/90 to 80/20.   The norbornene monomer ring-opened polymer hydride has a weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC) of 50,000 to 200,000, and a molecular weight. The resin composition according to claim 1, wherein the distribution (Mw / Mn) is 1.5 to 7.0.   The film formed using the resin composition of Claim 1 or 2.