JP5895738B2 - POLYMER COMPOSITION AND SHEET COMPRISING THE SAME - Google Patents

Description

  This invention relates to the sheet | seat for blister packs which made low moisture permeability and favorable blister moldability compatible.

Patent Document 1 discloses a polymer composition in which an amorphous polyvinylcyclohexane-based resin, which is a kind of an amorphous alicyclic structure-containing polymer, is blended with crystalline polyolefin. It is described that this polymer composition can achieve excellent heat resistance, rigidity, hardness, and small molding shrinkage while maintaining the characteristics of the crystalline polyolefin resin.
In Patent Document 2, 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 has excellent transparency and high moisture resistance. It is described that. However, the compatibility between the amorphous olefin and the high-density polyethylene is not sufficient, and the transparency tends to be inferior.
Patent Document 3 discloses that a composition in which a crystalline cyclic olefin-based polymer is blended with an amorphous alicyclic structure-containing polymer is made transparent by a molding method such as injection molding, compression molding, or extrusion molding. It is disclosed that a molded article having improved solvent crack resistance can be obtained.
Furthermore, Patent Document 4 discloses a crystalline norbornene-based ring-opening polymer obtained by ring-opening polymerization of a polymerizable monomer mainly composed of 2-norbornene and hydrogenating, and non-condensation of 2-norbornene and dicyclopentadiene. It is disclosed that a polymer composition comprising a crystalline alicyclic structure-containing polymer is useful as a film having low water vapor permeability and low haze (high transparency).

JP-A-5-271482 JP 7-33962 A JP 2007-016102 A JP 2009-179650 A

As a result of the study by the present inventors, it was confirmed that the moisture-proof property was lowered when the film described in Patent Document 4 was used for the production of blister packs. As a result of further studies, it has been found that the cause is that cracks that cannot be confirmed with the naked eye occur in the stretching stage, which is the secondary processing stage.
The present inventor has 10 to 90% by weight of a tetracyclododecene compound having a linear aliphatic hydrocarbon group having 2 to 10 carbon atoms, and 10 to 90% by weight of a dicyclopentadiene compound. A ring-opening polymerization of a polymerizable monomer having a total amount of a tetracyclododecene compound having a straight chain aliphatic hydrocarbon group having 2 to 10 carbon atoms and a dicyclopentadiene compound of 80% by weight to 100% by weight The amorphous alicyclic structure-containing polymer having a glass transition temperature of 50 ° C. or higher and having no melting point obtained by hydrogenation is excellent in compatibility with the above-described crystalline norbornene-based ring-opening polymer. I found out. And if it was the resin composition which combined these, it discovered that an internal crack did not arise in the extending | stretching step of blister molding, and came to complete this invention.

Thus, according to the present invention, a polymerizable monomer containing 90 to 100% by weight of 2-norbornene and 10 to 0% by weight of substituent-containing norbornene is obtained by ring-opening polymerization and hydrogenation. A crystal having a melting point of 110 to 145 ° C., a weight average molecular weight measured by gel permeation chromatography of 50,000 to 200,000, and a weight average molecular weight / number average molecular weight of 1.5 to 10.0. -Based norbornene-based ring-opening polymer (1), 10 to 90% by weight of a tetracyclododecene compound having a straight chain aliphatic hydrocarbon group having 2 to 10 carbon atoms, and 10% by weight of a dicyclopentadiene compound The total amount of the tetracyclododecene compound having a linear aliphatic hydrocarbon group having 2 to 10 carbon atoms and the dicyclopentadiene compound is 80% by weight or more. An amorphous alicyclic structure-containing polymer (2) obtained by ring-opening polymerization of 00% by weight of a polymerizable monomer and hydrogenation, having a glass transition temperature of 50 ° C. or higher and having no melting point; , 90/10 to 50/50 (weight ratio).
Moreover, according to this invention, the sheet | seat for blister packs which consists of a polymer composition which consists of the said polymer composition is provided.

  The polymer composition of the present invention comprises a crystalline norbornene-based ring-opening polymer (1) and an amorphous alicyclic structure-containing polymer (2), preferably 90/10 to 50/50 (weight ratio), preferably It is contained at a ratio of 90/10 to 55/45 (weight ratio), more preferably 90/10 to 60/40 (weight ratio). If the proportion of the crystalline norbornene-based ring-opening polymer is too large, blister moldability tends to deteriorate, and if the proportion of the amorphous alicyclic structure-containing polymer is too large, the water permeability tends to increase.

  The crystalline norbornene-based 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% by weight of substituent-containing norbornenes. Is obtained by ring-opening polymerization of a polymerizable monomer containing a hydrogen atom, and hydrogenated. The melting point is 110 to 145 ° C., and the weight average molecular weight measured by gel permeation chromatography is 50,000 to 200,000, 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 A crystalline norbornene-based ring-opening polymer is obtained by hydrogenating a ring-opening copolymer with a substituent-containing norbornene-based monomer (hereinafter collectively referred to as “norbornene monomer ring-opening polymer”). be able to.
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.
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 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.

In the crystalline norbornene-based ring-opening polymer, the hydrogenation rate of the carbon-carbon double bond in the norbornene monomer ring-opening polymer is usually 80% or more, preferably 90% or more, more preferably 95% or more, Preferably it is 99% or more, Most preferably, it is 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-based ring-opening polymer 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 the target crystalline norbornene-based ring-opening polymer is removed by removing volatile components such as a solvent from the polymer solution after the filtration. 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 ratio of the crystalline norbornene-based ring-opening polymer obtained as described above to the repeating units (A) derived from 2-norbornene is usually 90 to 100% by weight, preferably 95 to 99% by weight, More preferably, it is 97 to 99% by weight, and the proportion of the repeating unit (B) derived from the substituent-containing norbornene monomer is 0 to 10% by weight, preferably 1 to 5% by weight, based on all repeating units. Preferably it is 1-4 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 obtained crystalline norbornene-based ring-opening polymer 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, Preferably it is 50,000-200,000, More preferably, it is 70,000-180,000, More preferably, it is 80,000-150,000.
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 it is made into a sheet, 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 crystalline norbornene-based ring-opening polymer 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 2.5 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 obtained crystalline norbornene-based ring-opening polymer is usually 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 of 130 to 145 ° C. is preferable because deformation and warpage do not occur even in a high temperature environment such as in a container during transportation.
The melting point of the crystalline norbornene-based ring-opening polymer can be controlled by the molecular weight, molecular weight distribution, isomerization rate, composition ratio, etc. of the crystalline norbornene-based ring-opening polymer.

  Since the crystalline norbornene-based ring-opening polymer is a polymer having a melting point, that is, a polymer forming a crystal structure, a crystalline part is formed inside the molded body, and this and the amorphous part are combined. The mechanical properties of the molded product are improved.

The isomerization rate of the obtained crystalline norbornene-based ring-opening polymer 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. Incidentally, 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 derived from a trans isomer of a repeating unit derived from 2-norbornene in the polymer. Is.

  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 amorphous alicyclic structure-containing polymer used in the present invention is composed of 10% to 90% by weight of a tetracyclododecene compound having a linear aliphatic hydrocarbon group having 2 to 10 carbon atoms, and a dicyclopentadiene compound. Polymerization in which the total amount of tetracyclododecene compound and dicyclopentadiene compound having a linear aliphatic hydrocarbon group having 2 to 10 carbon atoms is 80 wt% or more and 100 wt%, which is 10 wt% to 90 wt% The glass transition temperature obtained by ring-opening polymerization of the functional monomer and hydrogenation does not have a melting point of 50 ° C. or higher. The amorphous alicyclic structure-containing polymer is a ring-opening polymer hydrogen produced by hydrogenating a ring-opening polymer obtained by ring-opening polymerization of a polymerizable monomer by a known method. It is an additive.
The tetracyclododecene compound having a straight-chain aliphatic hydrocarbon group having 2 to 10 carbon atoms is 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-butyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-hexyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like. Among these, a tetracyclododecene compound having a linear aliphatic hydrocarbon group having 2 to 4 carbon atoms is preferable because the Tg of the obtained resin is increased and the heat resistance is increased.
Dicyclopentadiene compound is tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene), methyldicyclopentadiene, dimethyldicyclopentadiene, ethyldicyclopentadiene , Vinyl dicyclopentadiene, propenyl dicyclopentadiene and the like.
Tetracyclododecene compounds include tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.
As a polymerizable monomer used for obtaining an amorphous alicyclic structure-containing polymer, other than tetracyclododecene compounds and dicyclopentadiene compounds having a linear aliphatic hydrocarbon group having 2 to 10 carbon atoms Examples thereof include polymerizable monomers copolymerizable with these. Examples of such a polymerizable monomer include 2-norbornene and a substituent-containing norbornene monomer, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene. Among these, 2-norbornene is particularly preferable because it is widely used industrially and can be easily obtained.

  The glass transition temperature (Tg) of the amorphous alicyclic structure-containing polymer is usually 50 ° C. or higher, preferably 55 ° C. or higher, more preferably 60 ° C. or higher. If Tg is low, the water vapor permeability tends to be high, which is not preferable.

  A compounding agent can be added to the polymer composition of this invention as needed. Compounding agents include antioxidants, rubbery polymers, UV absorbers, weathering stabilizers, antistatic agents, nucleating agents, slip agents, antifogging agents, dyes, pigments, colorants, natural oils, synthetic oils, Examples include plasticizers, organic or inorganic fillers, antibacterial agents, deodorants, and deodorizers.

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-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and other phenolic antioxidants; triphenyl phosphite, tris (Cyclohexylphenyl) phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene and other phosphorus antioxidants; dimyristyl 3,3′-thiodipropionate, distearyl-3,3′-thiodipro Pionate, lauryl stearyl-3,3'-thiodipropionate, pentaerythritol-teto Kiss - sulfur-based antioxidants such as (beta-laurylthiopropionate); and the like. 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 usually 0.01 to 1 part by weight, preferably 0.05 with respect to 100 parts by weight of the total of the crystalline norbornene-based ring-opening polymer and the amorphous alicyclic structure-containing polymer. -0.5 parts 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 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- ( Meta) Diene rubbers such as alkyl acrylate-acrylonitrile copolymer and butadiene- (meth) acrylic acid alkyl ester-acrylonitrile-styrene copolymer; butylene-isoprene copolymer; styrene-butadiene block copolymer, hydrogenated styrene -Aromatic vinyl-conjugated diene block copolymers such as butadiene block copolymer, hydrogenated styrene-butadiene random copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, low crystal And polybutadiene resins, ethylene-propylene elastomers, styrene-grafted ethylene-propylene elastomers, thermoplastic polyester elastomers, and 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 rubbery polymer is usually based on 100 parts by weight of the total of the crystalline norbornene-based ring-opening polymer and the amorphous alicyclic structure-containing polymer. It is 0.01-100 weight part, Preferably, it is 0.1-70 weight part, More preferably, it is the range of 1-50 weight part.

  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-methylphenol); ) -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 the ultraviolet absorber and the weathering stabilizer is usually 0.001 to 5 parts by weight, preferably 100 parts by weight based on the total of the crystalline norbornene ring-opening polymer and the amorphous alicyclic structure-containing polymer, The range is 0.01 to 2 parts by weight.

  Antistatic agents include: long-chain alkyl alcohols such as stearyl alcohol and behenyl alcohol; alkylsulfonic acid sodium salts and / or alkylsulfonic acid phosphonium salts; fatty acid esters such as glycerin ester of stearic acid; hydroxyamine compounds; amorphous carbon; Examples thereof include tin oxide powder and antimony-containing tin oxide powder. The amount of the antistatic agent is usually in the range of 0.001 to 5 parts by weight with respect to a total of 100 parts by weight of the crystalline norbornene-based ring-opening polymer and the amorphous alicyclic structure-containing polymer.

  Examples of the nucleating agent include dibenzylidene sorbitol derivatives, phosphate metal salts, benzoic acid metal salts, metal salts of carboxylic acids, etc., rosin acid metal salts, high density polyethylene, 3,3-dimethylbutene-1, etc. Examples thereof include 5 or more 3-position branched olefins, polymers of vinyl cycloalkanes, metal salts of sebacic acid, silica, titanium oxide, carbon black, talc, alum, calcium carbonate, and other inorganic compounds, butyl benzoates, and pigments. These nucleating agents may be used alone or in combination of at least two kinds. The amount of the nucleating agent is usually 0.005 to 10 parts by weight, preferably 0.05 to 100 parts by weight in total of the crystalline norbornene-based ring-opening polymer and the amorphous alicyclic structure-containing polymer. The range is ˜5 parts by weight.

  Although there is no limitation in the manufacturing method of the polymer composition of this invention, The method of kneading | 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 polymer composition of the present invention can form a blister pack sheet by a known method.
The sheet for blister packs of the present invention contains the polymer composition of the present invention in an amount of usually 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 sheet | seat of this invention, Well-known shaping | molding methods, such as extrusion molding, inflation molding, calendar molding, compression molding, and cast molding, are employable.

  Although the thickness of the sheet | seat of this invention is not specifically limited, Usually, 10 micrometers-10 mm, Preferably they are 30 micrometers-3 mm, More preferably, they are 100 micrometers-1 mm. If it has this thickness, sufficient moisture resistance can be obtained even in a blister pack package particularly requiring moisture resistance.

The sheet of the present invention may be a laminate having a layer containing the polymer composition of the present invention and a layer containing a known polymer generally used in home appliances, food fields, medical fields, etc. Good.
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 method for forming the blister pack sheet of the present invention into a blister pack is not particularly limited, but (1) a lower mold having holes adapted to be supplied with high-pressure air after heating and softening the sheet; “Plate type pressure forming method” in which pockets are formed by supplying air to the upper mold having pocket-shaped recesses. (2) Heat-softening the sheet, and vacuuming the recesses of the drum having pocket-shaped recesses. “Drum vacuum forming method” for forming pockets, (3) “Plug forming method” for crimping a heat-softened sheet with a pocket-shaped concavo-convex mold, and (4) Examples thereof include a “plug assist pressure forming method” in which the plug is raised and lowered to assist the forming.
Among them, the sheet of the present invention does not cause molding defects not only by the vacuum forming method but also by the pressure forming method. Therefore, the sheet is formed by a pressure forming method such as “flat plate type pressure forming method” or “plug assist pressure forming method”. It is suitable as a sheet for blister packs.

  The shape, size, depth, number, arrangement, and the like of the pocket portion of the blister pack of the present invention can be appropriately selected depending on the shape and convenience of the stored item.

Such a sheet forms blisters having a shape matched to an article to be packaged by vacuum forming, pressure forming, or the like, and PTP packaging or blister pack packaging is performed. Vacuum forming and pressure forming for forming blisters are performed under the same conditions as those of conventional sheets. Usually, the sheet surface temperature is 30 to 300 ° C., preferably about 50 to 150 ° C., and the forming pressure is 0.2 to 20 kg / cm ² G. Preferably, it is performed at about 0.2 to 10 kg / cm ² G.

  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.

The measurement methods for various physical properties are shown below.
(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer before the hydrogenation reaction
It was measured as a standard polystyrene conversion value 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, a total of 8 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, a flow rate of 1.0 ml / min, a sample injection amount of 100 μl, and a column temperature of 40 ° C.

(2) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer after the hydrogenation reaction
It was measured at 140 ° C. as a standard polystyrene equivalent value by gel permeation chromatography (GPC) using 1,2,4-trichlorobenzene as an eluent. 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 performed using three TSKgel GMHHR.H (20) HTs manufactured by Tosoh Corporation connected in series as a column, under conditions of a flow rate of 1.0 ml / min, a sample injection amount of 300 μl, and a column temperature of 140 ° C.

(3) Hydrogenation rate It measured by < ¹ > H-NMR using deuterated chloroform as a solvent.

(4) Isomerization rate of crystalline norbornene-based ring-opening polymer Using deuterated chloroform as a solvent, from the peak values of 31.8 ppm and 33.0 ppm measured by ¹³ C-NMR, the formula [(33.0 ppm peak integral value ) / (31.8 ppm peak integrated value + 33.0 ppm peak integrated value)] × 100.
The peak at 31.8 ppm is derived from the cis isomer of the repeating unit derived from 2-norbornene in the ring-opening polymer hydrogenated product, and the peak at 33.0 ppm is from 2-norbornene of the ring-opened polymer hydrogenated product. It is derived from the trans isomer of the repeating unit derived from it.

(5) Melting point Tm
Using a differential scanning calorimeter (DSC6220SII, manufactured by Nanotechnology Co., Ltd.), based on JIS K 7121, the sample was heated to 30 ° C. or higher from the melting point, and then cooled to room temperature at a cooling rate of −10 ° C./min. It measured in the process of heating up with the temperature increase rate of 10 degree-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 Inc.).

(7) Moisture permeability A spherical silica gel (manufactured by Kanto Chemical Co., Inc.) having a particle size of 0.35 to 2.00 mm was used as the blister pack package, and the obtained prestar pack was 40 ° C., 90% humidity and 25 ° C. The sample was stored in a constant temperature and humidity chamber with a humidity of 90% for 10 days. Ten pre-star packs were tested, and the water permeation amount was calculated from the weight before and after the test according to the following formula to obtain an average value.
Moisture permeation (mg) = Weight after test-Weight before test

(8) Blister moldability The thickness of the pocket bottom part and the side part of the blister pack molded at each heating plate temperature was measured using a magnetic thickness meter Magna-Mike (registered trademark) 8500 (manufactured by Olympus). The heating plate temperature range from which a molded product with a small thickness deviation within a range of 70 to 130 μm is obtained is 10 ° C. or more, ○ 5 ° C. or more and less than 10 ° C. Δ, less than 5 ° C. Was marked with x. The wider the temperature range of the heating plate, the better the blister formability.

[Production Example 1]
(Ring-opening polymerization)
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 at 55 ° C., 250 parts of bicyclo [2.2.1] hept-2-ene (hereinafter referred to as “2-NB”) as a polymerizable monomer and 1.0% of tungsten hexachloride as a polymerization catalyst 15 parts of a toluene solution was continuously added over 2 hours for polymerization. The resulting ring-opening polymer (A) had a weight average molecular weight 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%) 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 hydrogenated product, 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 a ring-opening polymer hydrogenated product (A).
(Polymer physical properties)
The resulting hydrogenated ring-opened polymer (A) has a hydrogenation rate of 99.9%, a weight average molecular weight of 82,200, a molecular weight distribution (Mw / Mn) of 2.9, an isomerization rate of 5%, The melting point was 140 ° C.
(Preparation of resin)
100 parts of the ring-opened polymer hydrogenated product (A) was added with an antioxidant (Ciba Specialty Chemicals; Irganox (registered trademark) 1010, tetrakis [methylene-3- (3 ′, 5′-di-tert- Butyl-4′-hydroxyphenyl) propionate] methane) 0.1 part was added and kneaded with a twin-screw kneader (TEM-35B, manufactured by Toshiba Machine Co., Ltd.) to obtain a pelletized resin (A).

[Production Example 2]
(Ring-opening copolymerization and hydrogenation reaction)
In Production Example 1, the polymerizable monomer was mixed into 240 parts of 2-NB and 10 parts of tricyclo [4.3.0.1 ^2,5 ] dec-3-ene (hereinafter referred to as “DCP”). The amount of 1-hexene is 0.55 parts, the amount of diisopropyl ether is 0.40 parts, the amount of triisobutylaluminum is 0.27 parts, the amount of isobutyl alcohol is 0.10 parts, tungsten hexachloride 1 Polymerization was carried out in the same manner as in Production Example 1 except that the amount of the 0.0% toluene solution 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 1 to obtain 190 parts of a ring-opened polymer hydrogenated product (B).
(Polymer physical properties)
The resulting hydrogenated ring-opening copolymer (B) had a hydrogenation rate of 99.9%, a weight average molecular weight of 81,300, a molecular weight distribution (Mw / Mn) of 3.8, and an isomerization rate of 9%. The melting point was 134 ° C.

[Production Example 3]
(Ring-opening copolymerization and hydrogenation reaction)
In Production Example 1, 212.5 parts of DCP and 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (hereinafter referred to as “ETD”) 37.5 parts of mixed monomer, 1-hexene amount to 1.74 parts, diisopropyl ether amount to 0.40 parts, The same procedure as in Production Example 1 except that the amount of triisobutylaluminum was changed to 0.20 parts, the amount of isobutyl alcohol was changed to 0.08 parts, and the amount of 1.0% tungsten hexachloride toluene solution was changed to 20 parts. Polymerization was performed. The obtained ring-opening polymer (C) had a weight average molecular weight of 35,600 and a molecular weight distribution (Mw / Mn) of 2.2. The polymerization addition rate was almost 100%. Thereafter, 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 (C).
(Polymer physical properties)
The hydrogenation rate of the obtained ring-opening copolymer hydrogenated product (C) was 99.9%, the weight average molecular weight was 38,000, the molecular weight distribution (Mw / Mn) was 2.5, and the glass transition temperature was 102 ° C. Met.
(Preparation of resin)
A pelletized resin (C) was obtained in the same manner as in Production Example 1, except that the ring-opening copolymer hydrogenated product (C) was used.
(Preparation of resin)
A pelletized resin (C) was obtained in the same manner as in Production Example 1, except that the ring-opening copolymer hydrogenated product (C) was used.

[Production Example 4]
(Ring-opening copolymerization and hydrogenation reaction)
In Production Example 1, the polymerizable monomer was mixed with 25 parts of 2-NB and 225 parts of ETD, the amount of 1-hexene was 1.74 parts, the amount of diisopropyl ether was 0.40 parts, triisobutyl Except for changing the amount of aluminum to 0.20 parts, the amount of isobutyl alcohol to 0.08 parts, and the amount of tungsten hexachloride 1.0% toluene solution to 20 parts, the same as in Production Example 1, Polymerization was performed. The obtained ring-opening polymer (D) had a weight average molecular weight of 37,200 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 1 to obtain 190 parts of a ring-opened polymer hydrogenated product (D).
(Polymer physical properties)
The resulting hydrogenated ring-opening copolymer (D) had a hydrogenation rate of 99.9%, a weight average molecular weight of 39,500, a molecular weight distribution (Mw / Mn) of 2.9, and a glass transition temperature of 123 ° C. Met.
(Preparation of resin)
A pelletized resin (D) was obtained in the same manner as in Production Example 1 except that the ring-opening copolymer hydrogenated product (D) was used.
(Preparation of resin)
A pelletized resin (D) was obtained in the same manner as in Production Example 1 except that the ring-opening copolymer hydrogenated product (D) was used.

[Production Example 5]
(Ring-opening copolymerization and hydrogenation reaction)
In Production Example 1, 212.5 parts of TCD and 8-hexyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (hereinafter referred to as “HTD”) in 37.5 parts of mixed monomer, 1-hexene in an amount of 1.74 parts, diisopropyl ether in an amount of 0.40 parts, The same procedure as in Production Example 1 except that the amount of triisobutylaluminum was changed to 0.20 parts, the amount of isobutyl alcohol was changed to 0.08 parts, and the amount of 1.0% tungsten hexachloride toluene solution was changed to 20 parts. Polymerization was performed. The resulting ring-opening polymer (D) had a weight average molecular weight of 32,400 and a molecular weight distribution (Mw / Mn) of 2.6. The polymerization addition rate was almost 100%. Thereafter, a hydrogenation reaction was carried out in the same manner as in Production Example 1 to obtain 190 parts of a ring-opened polymer hydrogenated product (E).
(Polymer physical properties)
The hydrogenation rate of the obtained ring-opening copolymer hydrogenated product (E) was 99.9%, the weight average molecular weight was 34,000, the molecular weight distribution (Mw / Mn) was 2.8, and the glass transition temperature was 127 ° C. Met.
(Preparation of resin)
A pelletized resin (E) was obtained in the same manner as in Production Example 1 except that the ring-opening copolymer hydrogenated product (E) was used.
(Preparation of resin)
A pelletized resin (E) was obtained in the same manner as in Production Example 1 except that the ring-opening copolymer hydrogenated product (E) was used.

[Production Example 6]
(Ring-opening copolymerization and hydrogenation reaction)
In Production Example 1, the polymerizable monomer was 250 parts of DCP, the amount of 1-hexene was 1.52 parts, the amount of diisopropyl ether was 0.55 parts, and the amount of triisobutylaluminum was 0.25 parts. The polymerization was conducted in the same manner as in Production Example 1 except that the amount of isobutyl alcohol was changed to 0.10 parts, the amount of tungsten hexachloride 1.0% toluene solution was changed to 20 parts, and the reaction temperature was changed to 70 ° C. went. The resulting ring-opening polymer (F) had a weight average molecular weight of 23,800 and a molecular weight distribution (Mw / Mn) of 2.3. The polymerization addition rate was almost 100%. Thereafter, 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 (F).
(Polymer physical properties)
The hydrogenation rate of the obtained ring-opening copolymer hydrogenated product (F) was 99.9%, the weight average molecular weight was 25,900, the molecular weight distribution (Mw / Mn) was 2.6, and the glass transition temperature was 97 ° C. Met.
(Preparation of resin)
A pelletized resin (F) was obtained in the same manner as in Production Example 1 except that the ring-opening copolymer hydrogenated product (F) was used.

[Production Example 7]
(Ring-opening copolymerization and hydrogenation reaction)
In Production Example 1, the polymerizable monomer was a mixed monomer of 5 parts of 2-NB, 73 parts of DCP and 22 parts of TCD, the amount of 1-hexene was 1.74 parts, and the amount of diisopropyl ether was 0.3. Production Example 1 except that the amount of triisobutylaluminum was changed to 0.25 parts, the amount of isobutyl alcohol was changed to 0.10 parts, and the amount of tungsten hexachloride 1.0% toluene solution was changed to 20 parts. Polymerization was carried out in the same manner as described above. The resulting ring-opening polymer (G) had a weight average molecular weight of 20,200 and a molecular weight distribution (Mw / Mn) of 1.9. The polymerization addition rate was almost 100%. Thereafter, 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 (G).
(Polymer physical properties)
The hydrogenation rate of the obtained ring-opening copolymer hydrogenated product (G) was 99.9%, the weight average molecular weight was 21,300, the molecular weight distribution (Mw / Mn) was 2.1, and the glass transition temperature was 101 ° C. Met.
(Preparation of resin)
A pelletized resin (G) was obtained in the same manner as in Production Example 1 except that the ring-opening copolymer hydrogenated product (G) was used.

[Production Example 8]
(Ring-opening copolymerization and hydrogenation reaction)
In Production Example 1, 90 parts of DCP and 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (hereinafter referred to as “MTD”) in 10 parts of mixed monomer, 1-hexene in 1.74 parts, diisopropyl ether in 0.3 parts, triisobutyl Except for changing the amount of aluminum to 0.25 parts, the amount of isobutyl alcohol to 0.10 parts, and the amount of tungsten hexachloride 1.0% toluene solution to 20 parts, the same as in Production Example 1, Polymerization was performed. The resulting ring-opening polymer (H) had a weight average molecular weight of 52,200 and a molecular weight distribution (Mw / Mn) of 2.8. The polymerization addition rate was almost 100%. Thereafter, 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 (H).
(Polymer physical properties)
The hydrogenation rate of the obtained ring-opening copolymer hydrogenated product (H) was 99.9%, the weight average molecular weight was 52,800, the molecular weight distribution (Mw / Mn) was 3.0, and the glass transition temperature was 99 ° C. Met.
(Preparation of resin)
A pelletized resin (H) was obtained in the same manner as in Production Example 1 except that the ring-opening copolymer hydrogenated product (H) was used.

[Example 1]
80 parts of pellets of resin (A) obtained in Production Example 1 and 20 parts of pellets of resin (C) obtained in Production Example 3 were mixed with a blender. Subsequently, it knead | mixed with the following kneading | mixing conditions with the biaxial kneader (TEM-35B, Toshiba Machine Co., Ltd.), extruded, and pelletized, and the pellet of the polymer composition (1) was obtained.
Kneading conditions: screw diameter 37 mm, L / D = 32
Screw rotation speed 250rpm
Resin temperature 230 ° C
Feed rate 20 kg / hour A pellet of the obtained polymer composition (1) is a hanger-manufactured type T having a resin melt kneader equipped with a screw having a screw diameter of 30 mmφ, a compression ratio of 2.5, and L / D = 30. Using a die film melt extrusion molding machine, T-die molding was performed under the following molding conditions to obtain a sheet (1) having a thickness of 300 μm.
Molding conditions: Die lip: 0.8mm
Molten resin temperature: 220 ° C
T die width: 300mm
Cooling roll: 80 ° C
Cast roll: 80 ℃
Using the obtained sheet (1), using a plug-assisted pressure forming chemical packaging molding machine (manufactured by CKD, FBP-M1), the temperature of the heating plate is increased in increments of 2.5 ° C. from 70 to 90 ° C. Under the conditions of each temperature and the plug temperature of 65 ° C., the cylindrical portion (pocket: diameter 10 mm × height 5 mm) containing the sheet (1) and the tablet (8 mmφ × maximum thickness 4 mm) is compressed in an array with a center interval of 17 mm. Then, the surface of the pocket on the concave side (non-projecting side) and the maleic acid-modified polyolefin-coated surface of the hard aluminum foil (thickness 20 μm) coated with maleic acid-modified polyolefin are superposed and heat sealed at 210 ° C., After putting the slitter at 180 ° C, it is punched into a width 37mm, length 94mm, corner 5mmR and blister pack (1) (number of pockets: 5 vertical, 2 horizontal) To obtain a total of 10). Table 2 shows the results of the blister formability of the obtained blister (1) and the moisture permeation amount of the prestar having a heating plate temperature of 85 ° C. with the least uneven thickness.

[Example 2]
Kneading and sheeting in the same manner as in Example 1 except that 70 parts of the pellet of resin (A) obtained in Production Example 1 and 30 parts of pellet of resin (C) obtained in Production Example 4 were used as raw materials. Molding and blister molding were performed to obtain a polymer composition (2), a sheet (2), and a blister pack (2). Table 2 shows the results of the blister formability of the obtained blister pack (2) and the moisture permeation amount of the prestar having a heating plate temperature of 85 ° C. with the least uneven thickness.

[Example 3]
Kneading and sheeting as in Example 1 except that 75 parts of the resin (B) pellets obtained in Production Example 2 and 25 parts of the resin (E) pellets obtained in Production Example 5 were used as raw materials. Molding and blister molding were performed to obtain a polymer composition (3), a sheet (3), and a blister pack (3). Table 2 shows the results of the blister formability of the obtained prestar pack (3) and the moisture permeation amount of the prestar having a heating plate temperature of 82.5 ° C. with the least uneven thickness.
[Comparative Example 1]
Kneading and sheeting in the same manner as in Example 1 except that 80 parts of the pellet of the resin (A) obtained in Production Example 1 and 20 parts of the pellet of the resin (F) obtained in Production Example 6 were used as raw materials. Molding and blister molding were performed to obtain a polymer composition (4), a sheet (4) and a blister pack (4). Table 2 shows the results of the blister formability of the obtained blister pack (4) and the moisture permeation amount of the prestar having a heating plate temperature of 85 ° C. with the least uneven thickness.
[Comparative Example 2]
Kneading and sheeting in the same manner as in Example 1 except that 70 parts of the pellet of resin (A) obtained in Production Example 1 and 30 parts of pellet of resin (G) obtained in Production Example 7 were used as raw materials. Molding and blister molding were performed to obtain a polymer composition (5), a sheet (5), and a blister pack (5). Table 2 shows the results of the blister formability of the resulting blister pack (5) and the moisture permeation amount of the prestar having a heating plate temperature of 85 ° C. with the least uneven thickness.
[Comparative Example 3]
Kneading and sheeting as in Example 1 except that 95 parts of the resin (B) pellets obtained in Production Example 1 and 5 parts of the resin (D) pellets obtained in Production Example 4 were used as raw materials. Molding and blister molding were performed to obtain a polymer composition (6), a sheet (6), and a blister pack (6). Table 2 shows the results of the blister formability of the obtained blister pack (6) and the moisture permeation amount of the prestar having a heating plate temperature of 82.5 ° C. with the least uneven thickness.
[Comparative Example 4]
Kneading and sheeting as in Example 1 except that 75 parts of the resin (B) pellets obtained in Production Example 2 and 25 parts of the resin (H) pellets obtained in Production Example 8 were used as raw materials. Molding and blister molding were performed to obtain a polymer composition (7), a sheet (7), and a blister pack (7). Table 2 shows the results of the blister formability of the obtained blister pack (7) and the moisture permeation amount of the prestar having a heating plate temperature of 82.5 ° C. with the least uneven thickness.
[Comparative Example 5]
Kneading and sheeting in the same manner as in Example 1 except that 45 parts of the resin (B) pellets obtained in Production Example 2 and 65 parts of the resin (C) pellets obtained in Production Example 3 were used as raw materials. Molding and blister molding were performed to obtain a polymer composition (8), a sheet (8), and a blister pack (8). Table 2 shows the results of the blister formability of the obtained blister pack (8) and the moisture permeation amount of the prestar having a heating plate temperature of 82.5 ° C. with the least uneven thickness.

<Discussion>
It turns out that the sheet | seat for blister packs obtained using the polymer composition of this invention has low water permeability, and its blister moldability is favorable (Examples 1-3).
On the other hand, a polymer kneaded with an amorphous alicyclic structure-containing polymer produced from a monomer not containing a tetracyclododecene compound having a linear aliphatic hydrocarbon group having 2 to 10 carbon atoms It can be seen that the sheet obtained by using the composition has a high moisture permeation amount (Comparative Examples 1, 2, and 4). When the moisture permeation amount at 25 ° C. and 40 ° C. is compared, it is presumed that the temperature dependency is not so large that it is due to a defect in the blister pack.
In the case of a polymer composition in which the 2-norbornene ring-opening polymerization hydrogenated product and the amorphous alicyclic structure-containing polymer are not in the range of 90/10 to 50/50 (weight ratio), 2-norbornene ring-opening It can be seen that blister moldability deteriorates when the amount of the polymerized hydrogen additive is large (Comparative Example 3), and that the water vapor barrier property is poor when the amount of the amorphous alicyclic structure-containing polymer is large (Comparative Example 5).

Claims (2)

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. Crystalline norbornene-based 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 (1), a tetracyclododecene compound having a straight chain aliphatic hydrocarbon group having 2 to 10 carbon atoms is 10 wt% to 90 wt%, and a dicyclopentadiene compound is 10 wt% to 90 wt%, Polymerizability in which the total amount of the tetracyclododecene compound having a straight-chain aliphatic hydrocarbon group having 2 to 10 carbon atoms and the dicyclopentadiene compound is 80% by weight or more and 100% by weight 90/10 to 50/50 of an amorphous alicyclic structure-containing polymer (2) having a glass transition temperature of 50 ° C. or higher and having no melting point, obtained by ring-opening polymerization of a monomer and hydrogenation. A polymer composition contained at a ratio of (weight ratio). A blister pack sheet comprising the polymer composition according to claim 1.