JP5206946B2 - Norbornene monomer ring-opening polymer Multilayer film and package comprising a resin composition layer containing a hydrogenated product and a polypropylene resin composition layer - Google Patents

Description

  The present invention relates to a multilayer film and a package comprising a resin composition layer containing a hydrogenated norbornene monomer ring-opening polymer and a polypropylene resin composition layer, and more specifically, a crystalline norbornene monomer ring-opening. Excellent interlayer adhesion, comprising a resin composition layer containing a hydrogenated polymer and a polypropylene resin composition layer containing a specific aromatic vinyl-conjugated diene copolymer hydride and polypropylene. The present invention relates to a multilayer film and a package.

Conventionally, polyolefin-based multilayer films have been used as various packaging materials. The use of cyclic olefin-based resins as packaging materials has also been examined in terms of excellent moisture resistance and transparency. However, amorphous cyclic olefin-based resins have been pointed out to have problems such as a narrow margin for molding conditions because they suddenly soften near the glass transition temperature and change their physical properties. In order to improve this, it has been studied to laminate an amorphous cyclic olefin resin layer and a polypropylene layer which is a crystalline resin, but there is a problem with the adhesion between the amorphous cyclic olefin resin and polypropylene. was there.
Therefore, for example, Patent Document 1 proposes to use a material in which high density polyethylene is blended with polypropylene in order to solve this problem.
Patent Document 2 proposes blending this polypropylene with an ethylene / α-olefin copolymer.

By the way, the cyclic olefin resin is generally amorphous, but a cyclic olefin resin having crystallinity (that is, having a melting point) also exists in the world.
Specifically, crystalline norbornene monomer ring-opening polymer hydrogenated products containing repeating units of triborn or higher norbornene monomers described in Patent Documents 3 to 5 are known. The resin film or sheet obtained from the norbornene monomer ring-opening polymer hydrogenated product described in these documents is excellent in transparency, heat resistance and chemical resistance, and excellent in mechanical properties.

  However, these crystalline norbornene monomer ring-opening polymer hydrogenated products are poorly soluble in the solvent, and after hydrogenation of the ring-opening copolymer, they are precipitated from the solvent to remove the catalyst residue, etc. In some cases, purification could not be performed sufficiently. Further, the moisture permeability of the film formed using the norbornene monomer ring-opening copolymer hydrogenated product did not sufficiently satisfy the requirements.

Non-patent documents 1 and 2 disclose hydrogenated ring-opening copolymers of norbornene monomers having a certain crystallinity.
However, these documents do not describe the specific physical properties of the polymer. Further, among the polymers disclosed specifically, polymers having a large molecular weight and a narrow molecular weight distribution have a high shear viscosity at a high shear rate when forming a film, so that melt fracture is likely to occur and the surface is smooth. It was difficult to obtain a good film. Further, a polymer having a small molecular weight has a small tensile elongation at break of the molded film, and has a problem in mechanical properties when formed into a film. Furthermore, since the hydrogenation rate is not always sufficient, there is a problem that the molded product obtained by molding this polymer is easily burnt.

JP-A-6-226934 JP-A-11-165387 JP 2000-201826 A JP 2000-393316 A JP 2006-52333 A Polymer International, 1994, 34, 49-57. Macromolecules, 2000, 37, 7278-7284.

The laminated films described in the above Patent Documents 1 and 2 were obtained by coextrusion molding. As a result of investigations by the present inventors, however, the amorphous properties specifically described in Patent Documents 1 and 2 were obtained. It was found that when a laminated film was obtained by coextrusion molding using a cyclic olefin resin, the interlayer adhesive strength was insufficient, and it was difficult to use as a practical packaging film.
As a result of intensive studies on a compounding agent for polypropylene in order to solve the above-mentioned problems, the present inventors have used a certain crystalline cyclic olefin resin as the cyclic olefin resin, and also used an aromatic vinyl-conjugated diene as the propylene resin. It has been found that when a polymer hydride is blended, a laminated film can be obtained with high interlayer adhesion strength, and the present invention has been completed.
Accordingly, an object of the present invention is to provide a resin composition layer comprising a crystalline norbornene monomer ring-opening polymer hydrogenated product, which has a high interlayer adhesive strength and can be used as a film for packaging, and a polypropylene resin. It is to provide a multilayer film with a composition layer.

Thus, according to the present invention,
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 monomer ring opening 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 at 0 ° C. A layer composed of a resin composition (A) containing a polymer hydrogenated product, and a layer composed of a polypropylene resin composition (B) comprising a hydrogenated aromatic vinyl-conjugated diene copolymer and polypropylene. A multilayer film having at least one set of directly laminated layers is provided.
Moreover, in the polypropylene resin composition (B) comprising an aromatic vinyl-conjugated diene copolymer hydride and polypropylene,
(1) The aromatic vinyl-conjugated diene copolymer is a random copolymer,
(2) The weight ratio of (polypropylene) / (hydride of aromatic vinyl-conjugated diene random copolymer) in the polypropylene resin composition (B) is in the range of 95/5 to 60/40,
(3) The proportion of structural units derived from 1,2- and 3,4-addition polymerization in the structural units derived from the conjugated diene compound of the aromatic vinyl-conjugated diene random copolymer is 60% by weight or more.
Alternatively, in a polypropylene resin composition (B) comprising an aromatic vinyl-conjugated diene copolymer hydride and polypropylene,
(1) The aromatic vinyl-conjugated diene copolymer is
(1-1) consisting of an aromatic vinyl block (I) and a conjugated diene block (II),
(1-2) The proportion of the structural unit derived from 1,2- and 3,4-addition polymerization in the structural unit derived from the conjugated diene compound of the conjugated diene block (II) is 40% by weight or more.
(1-3) The ratio of the aromatic vinyl block (I) in the aromatic vinyl-conjugated diene block copolymer is in the range of 15 to 55% by weight,
(2) The weight ratio of (polypropylene) / (aromatic vinyl-conjugated diene block copolymer hydride) in the polypropylene resin composition (B) is preferably in the range of 85/15 to 60/40, More preferably, the multilayer film is formed by co-extrusion of a resin composition (A) containing a crystalline norbornene monomer ring-opening polymer hydrogenated product and a polypropylene resin composition (B).
Furthermore, the package which consists of this multilayer film is provided.

  The multilayer film of the present invention has an interlayer adhesion strength between a layer composed of a resin composition (A) containing a crystalline norbornene monomer ring-opening polymer hydrogenated product and a layer composed of a polypropylene resin composition (B). Is expensive.

  The multilayer film of the present invention comprises a layer comprising a resin composition (A) containing a crystalline norbornene monomer ring-opening polymer hydrogenated product, an aromatic vinyl-conjugated diene block copolymer hydride, The layer made of the polypropylene resin composition (B) containing polypropylene has at least one layer formed by direct lamination.

  In the present invention, the film refers to a flat-shaped molded body (generally referred to as “film”) having a thickness of 250 μm or less, and a flat-shaped molded body (generally “sheet”) having a thickness of 3 mm to 250 μm. Called).

(Resin Composition (A) Containing Crystalline Norbornene Monomer Ring-Opening Polymer Hydrogenated Product)
The crystalline norbornene monomer ring-opening polymer hydrogenated product used in the present invention has 90 to 100% by weight of 2-norbornene (bicyclo [2.2.1] hept-2-ene) and a substituent-containing norbornene. A weight-average molecular weight obtained by ring-opening polymerization of a polymerizable monomer containing 10 to 0% by weight and hydrogenated, and having a melting point of 110 to 145 ° C. and measured by gel permeation chromatography Is 50,000 to 200,000, and the weight average molecular weight / number average molecular weight is 1.5 to 10.0. Particularly preferred are those obtained by hydrogenating 80% or more of the carbon-carbon double bonds of the ring-opening polymer by hydrogenation after ring-opening polymerization.

  2-norbornene or a monomer mixture comprising 2-norbornene and a substituent-containing norbornene monomer is subjected to ring-opening polymerization in the presence of a metathesis polymerization catalyst to replace 2-norbornene homo-ring-opening polymer or 2-norbornene. Hydrogenation of crystalline norbornene monomer ring-opening polymer by hydrogenating ring-opening copolymer with group-containing norbornene monomer (hereinafter collectively referred to as “norbornene monomer ring-opening polymer”) You can get things.

  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 has 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 having no 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] Hept 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; having an aromatic ring 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-2 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] hept Norbornenes having a polar group containing an oxygen atom such as 2-ene, 6-carboxy-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene; 5-cyano-bicyclo [2.2. 1] Hept-2 And norbornenes having a polar group containing a nitrogen atom such as -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 in its molecule a norbornene ring and one or more rings condensed with the norbornene ring. 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 aforementioned 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 derivatives thereof; cyclohexadiene, cycloheptadiene Cyclic diene 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 to 100% by weight. It is 10% by weight, preferably 1 to 5% by weight, more preferably 1 to 3% 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 (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 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; 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 for the hydrogenation reaction, aliphatic hydrocarbons similar to 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, Examples thereof include 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 monomer ring-opening polymer, the hydrogenation rate of the carbon-carbon double bond in the polymer is usually 80% or more, preferably 90% or more, more preferably 95% or more, and further preferably 99%. Thus, the content is particularly preferably 99.9% or more. When it is in the above range, it is preferable because coloring due to resin burning of the molded product is suppressed.
The hydrogenation rate of the crystalline norbornene monomer ring-opening polymer can be determined by measuring by ¹ H-NMR using deuterated chloroform as a solvent.

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

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

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

  The proportion of the crystalline norbornene monomer ring-opening polymer hydrogenated product obtained as described above in the presence of the repeating unit (A) derived from 2-norbornene is usually 90 to 100% by weight, preferably 95%. -99% by weight, more preferably 97-99% by weight, and the ratio of the repeating unit (B) derived from the substituent-containing norbornene monomer to the entire repeating unit is 0-10% by weight, preferably 1-5% % By weight, more preferably 1 to 3% 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 crystalline norbornene monomer ring-opening polymer hydrogenated product has a weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) using 1,2,4-trichlorobenzene as an eluent. It is preferably 50,000 to 200,000, more preferably 60,000 to 180,000, still more preferably 70,000 to 150,000 in terms of standard polystyrene.
When Mw is in this range, molding is easy, and the obtained molded body is preferable because it has sufficient mechanical properties. On the other hand, when Mw is too high, molding is difficult, and when a film or sheet is used, film thickness unevenness is likely to occur. Moreover, when Mw is too low, there exists a possibility that the mechanical characteristic of a molded object may fall.

The resulting crystalline norbornene monomer ring-opening polymer hydrogenated product has a molecular weight distribution (Mw / Mn) of preferably 1.5 to 7.0, more preferably 2.0 to 6.5, and even more preferably. Is 2.5 to 6.0, particularly preferably 2.5 to 5.5.
If Mw / Mn is too narrow, the melt viscosity with respect to the temperature of the polymer tends to change sensitively, so that the workability of 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 melt mass flow rate (MFR) of the crystalline norbornene monomer ring-opening polymer hydrogenated product used in the present invention may be appropriately selected according to the purpose of use of the multilayer film, but is 2 to 40 g / 10 min. It is preferable that it is in the range, more preferably in the range of 3 to 30 g / 10 min, and particularly preferably in the range of 5 to 25 g / 10 min. When the MFR is in this range, the resulting resin composition is excellent in moldability.
In the present invention, melt mass flow rate (MFR) is a value measured according to JIS K 6719 under the conditions of a temperature of 230 ° C. and a load of 21.18 N.

The melting point of the crystalline norbornene monomer ring-opening polymer hydrogenated product is usually 110 to 145 ° C, preferably 120 to 145 ° C, more preferably 130 ° C to 145 ° C.
It is preferable for 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 crystalline norbornene monomer ring-opening polymer hydrogenated product can be controlled by the molecular weight, molecular weight distribution, isomerization rate, composition ratio, etc. of the crystalline norbornene monomer ring-opening polymer hydrogenated product.

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

The isomerization rate of the obtained crystalline norbornene monomer ring-opening polymer hydrogenated product is usually 40% or less, preferably 20% or less, more preferably 10% or less, and further preferably 5% or less. If the isomerization rate is too high, the heat resistance of the polymer may be lowered. The isomerization rate can be calculated from deuterated chloroform as a solvent and 33.0 ppm peak integrated value / (31.8 ppm peak integrated value + 33.0 ppm peak integrated value) × 100 measured by 13 C-NMR.
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.

  In the resin composition (A) used for this invention, the other well-known additive may be contained in the range by which the effect of invention is not impaired as needed. Other known additives include anti-blocking agents, lubricants and dispersion aids, lubricants, antioxidants, thermal stabilizers, light stabilizers, UV absorbers, antistatic agents, dispersants, chlorine scavengers, Examples include flame retardants, crystallization nucleating agents, antifogging agents, pigments, organic fillers, neutralizing agents, decomposing agents, metal deactivators, antifouling agents, antibacterial agents and other resins, and thermoplastic elastomers.

  Examples of the anti-blocking agent include silica, silica alumina, natural zeolite, synthetic zeolite, kaolin, talc, silicone resin, silicone rubber, fused silica, melamine resin, acrylic resin, hydrotalcite-based fine particles, and the like.

Lubricants include fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid; fatty acid metal salts composed of fatty acids and metals such as lithium, sodium, magnesium, calcium, and zinc; olein Examples thereof include fatty acid amides such as acid amide, stearic acid amide, erucic acid amide, behenic acid amide, stearyl ercamide and oleyl palmitoamide. Of these, fatty acid metal salts are preferable, and calcium stearate is particularly preferable.
Examples of the dispersion aid include silane-based or titanium-based coupling agents.

  As the lubricant, polyolefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, and low molecular weight polybutylene; plant-based natural waxes such as candelilla, carnauba, rice, wood wax, jojoba; petroleum-based oils such as paraffin, microcrystalline, and petrolactam And synthetic waxes such as Fischer-Tropsch wax; polyfunctional ester compounds such as pentaerythritol tetrapalmitate, pentaerythritol tetramyristate, dipentaerythritol hexamyristate and dipentaerythritol hexapalmitate; .

Antioxidants include phenolic antioxidants, organic phosphite antioxidants, sulfur antioxidants, and the like.
Examples of light stabilizers include hindered amine stabilizers.
Examples of ultraviolet absorbers include benzophenone ultraviolet absorbers and benzotriazole ultraviolet absorbers.

Examples of the antistatic agent include nonionic antistatic agents, cationic antistatic agents, and anionic antistatic agents.
Examples of the dispersant include a bisamide dispersant, a wax dispersant, and an organic metal salt dispersant.
Examples of the flame retardant include phosphoric acid flame retardant, antimony trioxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, red phosphorus, and the like.

  Other resins include, for example, an amorphous norbornene monomer ring-opening polymer, a crystalline norbornene addition polymer, an amorphous norbornene addition polymer, a dicyclopentadiene-based petroleum resin, an aromatic petroleum resin, Terpene resins, coumarone-indene resins, aromatic vinyl-conjugated diene block copolymers, and their hydrides, amorphous polyvinyl chloride, low density polyethylene, high density polyethylene, linear low density polyethylene, ultra Low density polyethylene, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, polypropylene, polystyrene, hydrogenated polystyrene, polymethyl methacrylate, polymethyl methacrylate-styrene copolymer, polyacrylonitrile, polyacrylonitrile-styrene copolymer Combined, high impact poly Tylene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride, polyvinylidene chloride, polyphenylene sulfide, polyphenylene ether, polyamide, polyester, polycarbonate, cellulose triacetate, polyetherimide, polyimide, polyarylate, Examples thereof include polysulfone and polyethersulfone. These other resins can be used alone or in combination of two or more.

  Examples of the thermoplastic elastomer include olefin-based thermoplastic elastomers and styrene-based thermoplastic elastomers. Styrenic thermoplastic elastomers include styrene / butadiene / styrene block copolymer (SBS), styrene / ethylene / butadiene / styrene block copolymer (SEBS), styrene / isoprene / styrene block copolymer (SIS), and styrene. -Ethylene / propylene / styrene block copolymer (SEPS), and hydrides thereof.

The method for preparing the resin composition (A) containing the crystalline norbornene monomer ring-opening polymer hydrogenated product used in the present invention is not particularly limited.
For example, a method of mixing the crystalline norbornene monomer ring-opening polymer hydrogenated product and a compounding agent used as necessary using a mixer such as a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, or a conical blender. Or, after this mixing, a method of melt-kneading with a single screw extruder, twin screw extruder, kneader or the like; a compounding agent used as necessary in the solution of the crystalline norbornene monomer ring-opening polymer hydrogenated product; A method in which a dissolved solution is added and dispersed, and then the solvent is removed by a coagulation method, a casting method, or a direct drying method; a compound used as necessary in the stage of ring-opening (co) polymerization reaction or hydrogenation reaction And the like.

(Polypropylene resin composition (B))
The polypropylene resin composition (B) used in the present invention comprises a hydride of an aromatic vinyl-conjugated diene random copolymer or a hydride of an aromatic vinyl-conjugated diene block copolymer, and polypropylene. .

(Hydride of aromatic vinyl-conjugated diene random copolymer)
The hydride of an aromatic vinyl-conjugated diene random copolymer used in the present invention is a copolymer of a conjugated diene compound and an aromatic vinyl compound, and the random copolymer portion in the copolymer is 50. This is a hydrogenated carbon-carbon double bond in a structural unit derived from a conjugated diene of a copolymer of at least wt%.
In the present invention, the structural unit derived from a conjugated diene of an aromatic vinyl-conjugated diene random copolymer is a structural unit derived from a conjugated diene compound used for polymerization.

  Examples of the conjugated diene compound used here include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3- Examples include hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, and chloroprene. Among these, 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, 1,3-butadiene and isoprene are more preferable, and 1,3-butadiene is particularly preferable.

  Examples of the aromatic vinyl compound used here include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, divinylbenzene, N, N-dimethyl-p-aminoethylstyrene, and N, N-diethyl. -P-aminoethylstyrene, vinylpyridine, etc. are mentioned. Among these, styrene and α-methylstyrene are preferable, and styrene is more preferable.

The proportion of the random copolymer moiety in the aromatic vinyl-conjugated diene random copolymer is not particularly limited as long as it is 50% by weight or more, but is preferably 60% by weight or more, and more preferably 80% by weight or more. 90 to 98% by weight is particularly preferable.
When the proportion of the random copolymerized portion is within this range, the flexibility of the resulting multilayer film is excellent.

The hydrogenation rate of the carbon-carbon double bond in the structural unit derived from the conjugated diene is not particularly limited, but is preferably 80% or more, and more preferably 90% or more.
The hydrogenation rate of the aromatic ring derived from aromatic vinyl is usually less than 50%, preferably less than 30%, more preferably less than 10%, and most preferably less than 5%.
When the hydrogenation rate is within this range, the resulting multilayer film is excellent in transparency, mechanical strength, heat resistance, and weather resistance.

In the structural unit derived from the conjugated diene of the aromatic vinyl-conjugated diene random copolymer used in the present invention, the ratio of the structural unit derived from 1,2- and 3,4-addition polymerization is 60% by weight or more. And preferably 80% by weight or more, more preferably 90% by weight or more.
When the proportion of the structural units derived from 1,2- and 3,4-addition polymerization in the structural units derived from the conjugated diene is within this range, the flexibility of the resulting multilayer film is excellent.
In the present invention, the structural unit derived from 1,2-addition polymerization in the structural unit derived from conjugated diene is, for example, a formula obtained by 1,2-addition polymerization when isoprene is used as the conjugated diene compound. It is a structural unit represented by ( 3 ).

In the present invention, the structural unit derived from 3,4-addition polymerization in the structural unit derived from conjugated diene is, for example, a formula obtained by 3,4-addition polymerization when isoprene is used as the conjugated diene compound. It is a structural unit represented by ( 4 ).

In the present invention, the structural unit derived from 1,4-addition polymerization in the structural unit derived from conjugated diene is, for example, a formula obtained by 1,4-addition polymerization when isoprene is used as the conjugated diene compound. It is a structural unit represented by ( 5 ) or Formula ( 6 ).

  The proportion of structural units derived from 1,2- and 3,4-addition polymerization in the structural units derived from conjugated dienes can be calculated by the Morello method using infrared analysis.

Although the ratio (weight ratio) of the structural unit derived from the conjugated diene compound and the structural unit derived from the aromatic vinyl compound in the aromatic vinyl-conjugated diene random copolymer is not particularly limited, (structural unit derived from the conjugated diene compound) / (Structural unit derived from an aromatic vinyl compound), preferably in the range of 95/5 to 40/60, and more preferably in the range of 93/7 to 50/50.
The ratio of the structural unit derived from the conjugated diene compound and the structural unit derived from the aromatic vinyl compound can be determined by preparing a calibration curve for absorption based on a phenyl group of 679 cm ⁻¹ by infrared analysis.

  The aromatic vinyl-conjugated diene random copolymer may be a polymer in which a polymer molecular chain is extended or branched through a coupling agent residue by using a coupling agent. Examples of the coupling agent used at this time include diethyl adipate, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2- Examples include dibromoethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate, and the like.

  Although the hydride of the aromatic vinyl-conjugated diene random copolymer used in the present invention is not limited depending on the production method thereof, for example, an aromatic vinyl compound and a conjugated diene compound are mixed in an organic solvent with an organic alkali metal compound. There is a method in which living anion polymerization is carried out using as an initiator, and the resulting polymer is hydrogenated using a hydrogenation catalyst.

The proportion of structural units derived from 1,2- and 3,4-addition polymerization in the structural units derived from conjugated dienes in the aromatic vinyl-conjugated diene random copolymer used in the present invention is It can be prepared by using a base together.
Examples of the Lewis base include ethers such as diethyl ether, tetrahydrofuran, and ethylene glycol dibutyl ether; amines such as tetramethylethylenediamine, pyridine, and tributylamine.

The number average molecular weight of the hydride of the aromatic vinyl-conjugated diene random copolymer is not particularly limited, but is preferably in the range of 50,000 to 700,000, more preferably in the range of 50,000 to 600,000. 50,000 to 400,000 is particularly preferable.
When the number average molecular weight is within this range, the processability of the hydride of the aromatic vinyl-conjugated diene random copolymer is excellent, and when the hydride is pelletized, it is difficult to block, and when blended with polypropylene In addition, the mechanical strength, the molding appearance, and the molding processability of the resulting film are excellent.

The melt mass flow rate (MFR) of the hydride of the aromatic vinyl-conjugated diene random copolymer is not particularly limited, but is preferably 0.1 to 20 g / 10 minutes, more preferably 0.5 to 20 g / 10 minutes, particularly Preferably it is 0.5-10g / 10min, Most preferably, it is 1-5g / 10min.
When the MFR is in this range, the extrudability and layer forming property of the resulting polypropylene resin composition (B) are excellent.
In the present invention, the MFR of the hydride of an aromatic vinyl-conjugated diene random copolymer is a value measured according to JIS K 6758 (230 ° C., load 21.18 N).

(Hydride of aromatic vinyl-conjugated diene block copolymer)
The hydrogenated aromatic vinyl-conjugated diene block copolymer used in the present invention is a hydrogenated aromatic vinyl-conjugated diene block copolymer.
The aromatic vinyl-conjugated diene block copolymer is a block copolymer of a conjugated diene compound and an aromatic vinyl compound comprising an aromatic vinyl block (I) and a conjugated diene block (II).

  Examples of the aromatic vinyl compound used here include styrene, α-methylstyrene, 1-vinylnaphthalene, p-methylstyrene, 4-propylstyrene, t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2- Examples include ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, divinylbenzene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine, and the like. Among these, styrene and α-methylstyrene are preferable, and styrene is more preferable.

These aromatic vinyl compounds may be used alone or in combination of two or more.
When two or more aromatic vinyl compounds are used in combination, the conjugated diene block (II) may be a random copolymer or a block copolymer of two or more aromatic vinyl compounds. Tapered copolymer may be used.

  Examples of the conjugated diene compound used here include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1, Examples include 3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, and chloroprene. Among these, 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, 1,3-butadiene and isoprene are more preferable, and isoprene is particularly preferable.

These conjugated diene compounds are used alone or in combination of two or more.
When two or more conjugated diene compounds are used in combination, the conjugated diene block (II) may be a random copolymer or a block copolymer of two or more conjugated diene compounds. It may be copolymerized.

The combination of the conjugated diene compound is not particularly limited, but a combination of isoprene and 1,3-butadiene is preferable.
When the combination of the conjugated diene compound is isoprene and 1,3-butadiene, the proportion of the structural unit derived from isoprene in all the structural units of the conjugated diene block (II) is preferably 60% or more. When the proportion of structural units derived from isoprene is within this range, the resulting multilayer film is excellent in transparency.

  The aromatic vinyl-conjugated diene block copolymer used in the present invention is not limited by its production method. For example, (1) an aromatic vinyl compound is polymerized using an organolithium compound as an initiator, and then a conjugated diene compound. (2) An aromatic vinyl compound is polymerized using an organolithium compound as an initiator to obtain an aromatic vinyl polymer, and a conjugated diene compound is polymerized using an organolithium compound as an initiator. And then coupling these polymers with a coupling agent; and the like.

Examples of the organic lithium compound include monolithium compounds such as methyllithium, ethyllithium, pentyllithium, and butyllithium; dilithium compounds such as naphthalenedilithium and dithiohexylbenzene.
The proportion of the organolithium compound used is not particularly limited, but is usually 0.005 to 0.2 parts by weight with respect to 100 parts by weight of the monomer.

Coupling agents include dichloromethane, trichloromethane, tetrachloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, diethyl adipate, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyltrichlorosilicon, tetrachlorotin, butyltrichloro Examples thereof include tin, dimethylchlorosilicon, tetrachlorogermanium, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate, and the like.
Although the usage-amount of a coupling agent is not specifically limited, Usually, it is 0.04-0.8 weight part with respect to 100 weight part of monomers.

The polymerization reaction is preferably performed in a solvent.
The solvent is not particularly limited as long as it is an organic solvent inert to the polymerization initiator, and examples thereof include hexane, heptane, cyclohexane, methylcyclohexane, and benzene.

  Although the reaction temperature of a polymerization reaction is not specifically limited, Usually, it is 0-80 degreeC. Moreover, although the reaction time of a polymerization reaction is not specifically limited, Usually, it is 0.5 to 50 hours.

The mode of the block of the aromatic vinyl-conjugated diene block copolymer is not particularly limited, and examples thereof include a diblock, a triblock, and more multiblocks.
For example, the aromatic vinyl block (I) and the conjugated diene block (II) are ((I)-(II)) n, (II)-((I)-(II)) n, ((I)-( II)) An aromatic vinyl-conjugated diene block copolymer which is a block embodiment represented by n- (I). Here, n is an integer of 1 or more.
Among these, an aromatic vinyl-conjugated diene block copolymer having a block form represented by (I)-(II)-(I) is preferable.

  The ratio of the aromatic vinyl block (I) in the aromatic vinyl-conjugated diene block copolymer used in the present invention is in the range of 15 to 55% by weight. Among them, the ratio of the aromatic vinyl block (I) is preferably in the range of 20 to 50% by weight, preferably in the range of 25 to 45% by weight, and the ratio of the aromatic vinyl block (I) is in this range. When it exists, it is excellent in the ease of adjustment of a polypropylene resin composition, and the interlayer adhesive strength of the multilayer film obtained.

  The number average molecular weight of the aromatic vinyl block (I) in the aromatic vinyl-conjugated diene block copolymer is not particularly limited, but is preferably in the range of 2,500 to 40,000. When the number average molecular weight of the aromatic vinyl block (I) is within this range, the hydride of the resulting aromatic vinyl-conjugated diene block copolymer and polypropylene can be easily mixed. The number average molecular weight of the aromatic vinyl block (I) can be adjusted by the molar ratio of the aromatic vinyl compound to be used and the initiator.

The number average molecular weight of the conjugated diene block (II) in the aromatic vinyl-conjugated diene block copolymer is not particularly limited, but is preferably in the range of 10,000 to 200,000. When the number average molecular weight of the conjugated diene block (II) is within this range, it is easy to mix the hydride of the resulting aromatic vinyl-conjugated diene block copolymer with polypropylene.
The number average molecular weight of the conjugated diene block (II) can be adjusted by the molar ratio of the conjugated diene compound to be used and the initiator.

  The number average molecular weight of the aromatic vinyl-conjugated diene block copolymer is not particularly limited, but is preferably in the range of 30,000 to 300,000. When the number average molecular weight of the aromatic vinyl-conjugated diene block copolymer is within this range, the resulting multilayer film is excellent in strength and moldability.

  The conjugated diene block (II) in the aromatic vinyl-conjugated diene block copolymer used in the present invention is a structural unit derived from 1,2- and 3,4-addition polymerization in a structural unit derived from a conjugated diene compound. The ratio is 40% by weight or more. Among them, the proportion of structural units derived from 1,2- and 3,4-addition polymerization is preferably in the range of 45 to 90% by weight, and more preferably in the range of 50 to 80% by weight. When the proportion of structural units derived from 1,2- and 3,4-addition polymerization is in this range, the resulting multilayer film is excellent in transparency.

The structural unit in the conjugated diene block (II) is a structural unit derived from 1,2-addition polymerization, a structural unit derived from 3,4-addition polymerization, depending on the reaction site of the conjugated diene compound in the polymerization reaction of the conjugated diene compound, and It is classified into any one of structural units derived from 1,4-addition polymerization.
In the present invention, the structural unit derived from 1,2-addition polymerization of the conjugated diene block (II) is a structural unit obtained by 1,2-addition polymerization of a conjugated diene compound. -A structural unit represented by (1-methyl-1-vinyl) ethylene obtained by 1,2-polymerization when methyl-1,3-pentadiene is used.
The structural unit derived from 3,4-addition polymerization of the conjugated diene block (II) is a structural unit obtained by 3,4-addition polymerization of a conjugated diene compound. For example, 2-methyl-1 is used as the conjugated diene compound. , 3-pentadiene is a structural unit represented by 1- (1-methyl-1-vinyl) ethylene obtained by 3,4-polymerization.
The structural unit derived from 1,4-addition polymerization of the conjugated diene block (II) is a structural unit obtained by 1,4-addition polymerization of a conjugated diene compound. For example, 2-methyl-1 as a conjugated diene compound , 3-pentadiene is a structural unit represented by 2-methyl-2-butenylene obtained by 1,4-polymerization.
The proportion of structural units derived from 1,2- and 3,4-addition polymerization in the structural units derived from the conjugated diene compound in the conjugated diene block (II) can be calculated by the Morero method using infrared analysis. it can.

The proportion of structural units derived from 1,2- and 3,4-addition polymerization in the structural units derived from the conjugated diene compound in the conjugated diene block (II) is determined by co-catalyzing the Lewis base during the polymerization of the conjugated diene compound. It can adjust by using as.
Examples of Lewis bases include ethers such as dimethyl ether, diethyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and ethylene glycol dibutyl ether; triethylamine, N, N, N ′, N′-tetramethylethylenediamine (TMEDA) , Amine compounds such as pyridine, tributylamine, N-methylmorpholine; and the like.
The amount of these Lewis bases used is usually in the range of 0.1 to 1000 mol with respect to 1 mol of lithium as a polymerization initiator.

The aromatic vinyl-conjugated diene block copolymer hydride used in the present invention is obtained by hydrogenating the above aromatic vinyl-conjugated diene block copolymer in the presence of a hydrogenation catalyst.
Examples of hydrogenation catalysts include Raney nickel or heterogeneous catalysts such as those in which a metal such as Pt, Pd, Ru, Rh, Ni is supported on a carrier such as carbon, alumina, diatomaceous earth, or transition metals and alkylaluminum compounds, alkyls. Examples include Ziegler type catalysts composed of combinations of lithium compounds.
The hydrogenation reaction is usually carried out in a solvent, the hydrogen pressure is from atmospheric pressure to 20 MPa, the reaction temperature is from room temperature to 250 ° C., and the reaction time is from 0.1 to 100 hours.

The hydrogenation rate of the carbon-carbon double bond in the conjugated diene block (II) is usually 60% or more, preferably 70% or more, more preferably 80% or more.
The hydrogenation rate of the aromatic ring in the aromatic vinyl block (I) is usually less than 40%, preferably less than 30%, more preferably less than 10%, and most preferably less than 5%.
When the hydrogenation rate of the carbon-carbon double bond in the conjugated diene block (II) and the hydrogenation rate of the aromatic ring in the aromatic vinyl block (I) are in this range, the transparency of the resulting multilayer film, Excellent mechanical strength, heat resistance, and weather resistance.

The melt mass flow rate (MFR) of the hydride of the aromatic vinyl-conjugated diene block copolymer is not particularly limited, but is preferably 0.1 to 20 g / 10 minutes, more preferably 0.5 to 20 g / 10 minutes, particularly Preferably it is 0.5-10g / 10min, Most preferably, it is 1-5g / 10min.
When the MFR is in this range, the polypropylene resin composition (B) to be obtained is excellent in extrudability and layer forming property.
In the present invention, the MFR of the hydride of an aromatic vinyl-conjugated diene random copolymer is a value measured under conditions of 230 ° C. and a load of 21.18 N in accordance with JIS K 6719.

(polypropylene)
The polypropylene used in the present invention may be a homopolymer of propylene or a copolymer such as a random or block copolymer of propylene and ethylene or / and an α-olefin having 4 or more carbon atoms. .
Examples of the block copolymer include diblock, triblock, or more multiblock and gradient block copolymers, and are not particularly limited.
Examples of the α-olefin having 4 or more carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4, 4 -Dimethylpentene-1 etc. can be mentioned. The proportion of propylene-derived structural units (propylene units) in the random copolymer is preferably 80% by weight or more, particularly preferably 85% by weight or more.
The proportion of propylene units in the block copolymer is preferably 55% by weight or more, more preferably 60% by weight or more.
The method for producing polypropylene is not particularly limited.

The melting temperature of polypropylene is usually 130 ° C. or higher, but is not particularly limited.
The melt mass flow rate (MFR) of polypropylene is not particularly limited, but is preferably 0.1 to 20 g / 10 minutes, more preferably 0.5 to 20 g / 10 minutes, particularly preferably 0.5 to 10 g / 10 minutes, most preferably Preferably it is 1-5 g / 10min.
When the MFR is in this range, the polypropylene resin composition (B) to be obtained is excellent in extrudability and layer forming property.
In the present invention, the MFR of polypropylene is a value measured under conditions of 230 ° C. and a load of 21.18 N in accordance with JIS K 6719.

The ratio (weight ratio) of the hydride of aromatic vinyl-conjugated diene block copolymer and polypropylene in the polypropylene resin composition (B) is (polypropylene) / (aromatic vinyl-conjugated diene block copolymer). Hydride) in the range of 85/15 to 60/40.
Among them, the ratio (weight ratio) of the hydride of aromatic vinyl-conjugated diene block copolymer and polypropylene is preferably in the range of 80/20 to 60/40, and in the range of 75/25 to 65/35. More preferably.
When the ratio (weight ratio) of the hydride of aromatic vinyl-conjugated diene block copolymer and polypropylene is in this range, the moldability of the resin composition, the transparency of the resulting multilayer film and the interlayer adhesion strength are excellent.

The method for preparing the polypropylene resin composition (B) used in the present invention is not particularly limited.
For example, the hydride of aromatic vinyl-conjugated diene block copolymer, polypropylene, and the compounding agent used as necessary are mixed using a mixer such as a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, or a conical blender. The method of doing is mentioned.
As the compounding agent, among the compounding agents exemplified as those that can be used for the resin composition (A) containing a crystalline norbornene monomer ring-opening polymer hydrogenated product, polypropylene and aromatic vinyl-conjugated The compounding agent except the hydride of a diene block copolymer is mentioned.

  These compounding agents can be used alone or in combination of two or more. The compounding amount of the compounding agent is appropriately selected, but is usually less than 100 parts by weight, preferably less than 60 parts by weight, more preferably less than 30 parts by weight with respect to 100 parts by weight of polypropylene. When the blending amount is within this range, the transparency of the resulting multilayer film and the moldability at the time of molding are highly balanced.

(Multilayer film)
The multilayer film of the present invention comprises a layer comprising a resin composition (A) containing a crystalline norbornene monomer ring-opening polymer hydrogenated product, a hydrogenated aromatic vinyl-conjugated diene copolymer and polypropylene. The layer made of the polypropylene resin composition (B) containing the above has at least one layer formed by direct lamination.

  The layer comprising the resin composition (A) containing the crystalline norbornene monomer ring-opening polymer hydrogenated product is a resin composition containing the crystalline norbornene monomer ring-opening polymer hydrogenated product. A layer formed of the polypropylene resin composition (B) formed by molding (A) and containing a hydride of aromatic vinyl-conjugated diene copolymer and polypropylene is used as the polypropylene resin composition (B ).

  The molding method is not particularly limited, and can be obtained by a known method such as a T-die method, an inflation method, or a press molding method.

The lamination method is not particularly limited,
(1) A co-extrusion T die that simultaneously performs molding and lamination using a resin composition (A) containing a crystalline norbornene monomer ring-opening polymer hydrogenated product and a polypropylene resin composition (B) (2) Crystalline norbornene monomer ring-opening polymer hydrogen; co-extrusion method (multi-manifold type, feedback type), co-extrusion inflation method (in-die adhesion method, outside-die adhesion method), co-extrusion lamination method, etc. A layer composed of a resin composition (A) containing an additive (hereinafter sometimes abbreviated as layer (FA)), a hydride of a conjugated diene portion of an aromatic vinyl-conjugated diene copolymer, and polypropylene. A hot press for hot pressing the layer (FA) and the layer (FB) after forming a layer (hereinafter sometimes abbreviated as layer (FB)) made of a polypropylene resin composition (B) containing ; (3) the vacuum lamination method; (4) heat lamination method; and the like.
In the coextrusion method and the hot press method, the hot press method is superior in terms of the interlayer adhesive strength, but the multilayer film of the present invention has a sufficiently high interlayer adhesive strength even in the coextrusion method. It is preferable to laminate by a highly coextruding method.

The lamination mode of the multilayer film of the present invention is not particularly limited as long as it has at least one layer in which the layer (FA) and the layer (FB) are directly laminated. Further, the layer (FA), the layer (FB), A layer made of another resin (hereinafter sometimes abbreviated as layer (FC)) can be laminated.
As the lamination mode, layer (FA) / layer (FB), layer (FB) / layer (FA) / layer (FB), layer (FA) / layer (FB) / layer (FA), layer (FA) / Examples thereof include layer (FB) / layer (FC), layer (FC) / layer (FA) / layer (FB), and the like.
Examples of other resins include polyethylene resins, polyester resins, polyamide resins, and fluorine resins.

Although the thickness of the multilayer film of this invention is not specifically limited, It is preferable that it is the range of 10 micrometers-1 mm. When the thickness of the multilayer film is within this range, the transparency and mechanical strength of the multilayer film are excellent.
The thicknesses of the layer (FA) and the layer (FB) are not particularly limited, but both the layer (FA) and the layer (FB) are preferably in the range of 5 to 500 μm, and more preferably in the range of 10 to 300 μm. preferable. When the thickness is within this range, the transparency and mechanical strength of the multilayer film are excellent.
The ratio of the thicknesses of the layer (FA) and the layer (FB) is not particularly limited. For example, the layer (FA) / layer (FB) is preferably 1/100 to 100/1.

The multilayer film of the present invention can be stretched as necessary.
The method of extending | stretching is not specifically limited, For example, it can carry out by any system of a roll system, a tenter system, and a tube system.
The stretching temperature is preferably 0 to 60 ° C., preferably 10 to 40 ° C. higher than the melting point of the crystalline norbornene monomer ring-opening polymer hydrogenated product constituting the unstretched film.
In the present invention, either uniaxial stretching or biaxial stretching may be used, but it is preferable to stretch in uniaxial stretching (lateral direction; TD direction). Although the draw ratio is not particularly limited, it is preferably in the range of 1.2 to 10.0 times in the TD direction, and more preferably in the range of 2.0 to 6.0 times.
Even in uniaxial stretching, a stretching process can be performed at a low stretching ratio (for example, 1.5 times or less) in the length direction (longitudinal direction; MD direction) as necessary. Thus, the multilayer film of the present invention includes a uniaxially stretched film stretched only in one direction and a biaxially stretched film stretched mainly in one direction and slightly stretched in a direction perpendicular to the direction.

The multilayer film of the present invention can be subjected to printing.
The printing method is not particularly limited, and a known method may be used. Examples thereof include relief printing, intaglio printing, and flat printing. The type of printing ink applied to printing may be appropriately selected and used depending on the printing method. For example, letterpress ink, flexographic ink, dry offset ink, gravure ink, gravure offset ink, offset Ink and screen ink are listed.
Further, for the purpose of improving the adhesion of the ink, it is preferable to perform a surface treatment on the layer to be printed before using the printing ink. Examples of the surface treatment include corona discharge treatment, plasma discharge treatment, flame treatment, embossing treatment, sand matte treatment, and satin finish treatment.

  The multilayer film of the present invention has an interlayer adhesion between a layer composed of a resin composition (A) containing a crystalline norbornene monomer ring-opening polymer hydrogenated product and a layer composed of a polypropylene resin composition (B). Is expensive.

(Packaging body)
Since the multilayer film of the present invention has high interlayer adhesion and is excellent in transparency, moisture resistance, and gas barrier properties, it can be used as a package and a material for the package.
Examples of the items to be packaged include electronic materials, drugs, infusions, medical instruments, dental tools, medical containers, foods, daily necessities, and miscellaneous goods.
Since the package of the present invention is particularly excellent in interlayer adhesion, transparency, moisture resistance, and gas barrier properties, tablets, capsules, powders, solid or liquid drugs; rice cakes, snacks, cookies, etc. It is suitable as a packaged body having a package of food, specified insurance food, tobacco, tea bag, and the like.
Packaging forms include bags, packs, press-through packages, blister packs, hand twists, wrapping, shrink labels, easy peel films, etc .; containers assembled with films such as tetra packs, milk packs, laminate tubes, etc. It is done.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited only to these examples. Unless otherwise specified, parts and% are based on weight, and pressure is gauge pressure. The measuring method of the physical property in an Example and a comparative example is as follows.
(1) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the norbornene monomer ring-opening polymer
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, 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) Weight average molecular weight (Mw) and number average molecular weight (Mn) of hydrogenated norbornene monomer ring-opening polymer
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 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 hydrogenated product was measured by ¹ H-NMR using deuterated chloroform as a solvent.

(4) Isomerization rate of norbornene monomer ring-opening polymer hydrogenated product From the peak values of 31.8 ppm and 33.0 ppm measured by ¹³ C-NMR using deuterated chloroform as a solvent, the formula [(33.0 ppm Peak integrated 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 (product name “DSC6220SII”, manufactured by Nanotechnology Co., Ltd.), the sample was heated from the melting point to 30 ° C. or higher based on JIS K 7121, and then cooled to room temperature at a cooling rate of −10 ° C./min. Then, it measured in the process of heating up at a heating rate of 10 ° C./min.
(6) Proportion of structural units derived from 1,2- and 3,4-addition polymerization in all structural units derived from a conjugated diene compound Calculated by the Morello method using an infrared analysis method.
(7) Melt mass flow rate (MFR)
Measurement was performed in accordance with JIS K 6719 under conditions of a temperature of 230 ° C. and a load of 21.18 N.
(8) Interlaminar adhesive strength A sample is cut from a multilayer film to a size of 150 mm length x 15 mm width, and using a universal tensile compression tester (product name “TCM200”, Shinsei Tsushin Kogyo Co., Ltd.), a tensile speed of 50 mm / min. Under these conditions, a 180 ° peel test was performed. The average load when the load reached equilibrium was defined as the interlayer adhesion strength (unit: N / 15 mm).

[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 the temperature at 55 ° C., 250 parts of 2-norbornene (hereinafter referred to as “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 liquid containing the ring-opening polymer (A) obtained above was transferred to a pressure-resistant hydrogenation reactor, and 0.5 parts of a diatomaceous earth-supported nickel catalyst (T8400, manufactured by Zude Chemie Catalysts Co., Ltd., 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 a ring-opening polymer hydrogenated product (A).
(Polymer physical properties)
The hydrogenation rate of the obtained ring-opening polymer hydrogenated product (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 resin)
100 parts of the ring-opened polymer hydrogenated product (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 was added, and it knead | mixed with the biaxial kneader (product name "TEM-35B", the Toshiba machine company make), and obtained pelletized resin (A).

[Production Example 2]
(Ring-opening copolymerization and hydrogenation reaction)
In Production Example 1, 245 parts of 2-NB and 5 parts of 5-methyl-2-norbornene (hereinafter referred to as “MNB”) were used, 0.40 part of 1-hexene, 0.31 part of diisopropyl ether, and triisobutylaluminum. Ring-opening copolymerization was carried out in the same manner as in Production Example 1 except that 0.20 parts, 0.08 parts of isobutyl alcohol, and 15 parts of a tungsten hexachloride 1.0% toluene solution were used. The polymerization conversion was almost 100%. The resulting ring-opening copolymer (B) had a weight average molecular weight (Mw) of 103,000 and a molecular weight distribution (Mw / Mn) of 1.9. Thereafter, a hydrogenation reaction was carried out in the same manner as in Production Example 1 to obtain 190 parts of a ring-opening copolymer hydride (B).
(Polymer physical properties)
The hydrogenation rate of the obtained ring-opening copolymer hydride (B) was 99.9%, the weight average molecular weight (Mw) was 100,000, the molecular weight distribution (Mw / Mn) was 2.9, and the isomerization rate was It was 8% and the melting point was 136 ° C.
(Preparation of resin)
Except having used the ring-opening copolymer hydride (B), it carried out similarly to manufacture example 1, and obtained pelletized resin (B).

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

[Production Example 4]
(Ring-opening copolymerization)
Under a nitrogen atmosphere, 33.4 parts of a 72% 2-NB toluene solution, 2.27 parts of DCP, 0.020 parts of 1-hexene, and 49.3 parts of cyclohexane were added to an autoclave equipped with a stirrer and stirred. Subsequently, a solution prepared by dissolving 0.023 parts of bis (tricyclohexylphosphine) benzilidineruthenium (IV) dichloride in 8.6 parts of toluene was added and reacted at 60 ° C. for 30 minutes. The polymerization conversion rate was almost 100%. The obtained ring-opening polymer (D) had a weight average molecular weight (Mw) of 81,200 and a molecular weight distribution (Mw / Mn) of 3.5.
(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 (D) was obtained.
(Polymer physical properties)
The hydrogenation rate of the obtained ring-opening copolymer hydride (D) was 99.9%, the weight average molecular weight (Mw) was 84,000, the molecular weight distribution (Mw / Mn) was 3.9, and the melting point was 111 ° 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 hydride (D) was used.

[Production Example 5]
(Ring-opening copolymerization)
Under a nitrogen atmosphere, 33.4 parts of a 70% 2-NB toluene solution, 3.01 parts of DCP, 0.020 parts of 1-hexene, and 49.3 parts of cyclohexane were added to an autoclave equipped with a stirrer and stirred. Subsequently, a solution prepared by dissolving 0.023 parts of bis (tricyclohexylphosphine) benzilidineruthenium (IV) dichloride in 8.6 parts of toluene was added and reacted at 60 ° C. for 30 minutes. The polymerization conversion rate was almost 100%. The resulting ring-opening polymer (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. Met.
(Preparation of resin)
Except having used the ring-opening copolymer hydride (E), it carried out similarly to manufacture example 1, and obtained pelletized resin (E).

[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 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 part 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 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 drier set at 0.13 × 10 ³ Pa or less and 100 ° C. for 48 hours to obtain 130 parts of a ring-opening polymer hydrogenated product (F).
The obtained ring-opening polymer hydrogenated product (F) was not dissolved in the GPC solvent, and the molecular weight could not be measured. The melting point was 273 ° C.
(Preparation of resin)
A pelletized resin (F) was obtained in the same manner as in Production Example 1 except that the ring-opening polymer hydrogenated product (F) was used.

Example 1
70 parts of a pellet of polypropylene (PP1) [propylene homopolymer, melting point 160 ° C., MFR 3 g / 10 min] and hydride of aromatic diene-conjugated diene random copolymer (R1) [aromatic diene is styrene, conjugated diene Is butadiene, styrene unit content 10% by weight, hydrogenation rate of carbon-carbon double bond in structural unit derived from butadiene 99%, hydrogenation rate of aromatic ring derived from styrene 2%, MFR 4 g / 10 min , Density 0.89 g / cm ³ , content of random copolymer part 94%, proportion of 1,2- and 3,4-addition polymerization-derived structural units 79% in butadiene-derived structural units] Parts were mixed with a blender to obtain a polypropylene resin composition.
A polypropylene resin composition using a two-kind, two-layer hanger manifold type T-die film extrusion machine 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 = 28. And the resin (A) obtained in Production Example 1 are co-extruded to form a layer of 50 μm made of a resin composition containing a hydrogenated norbornene monomer ring-opening polymer, and a layer of 100 μm made of a polypropylene resin composition. A multilayer film 1 obtained by directly laminating was obtained. The coextrusion was performed under the conditions of a die lip of 0.8 mm, a temperature of both molten resins of 220 ° C., a T die width of 300 mm, a cast roll temperature of 60 ° C., and a cooling roll temperature of 50 ° C.
The interlayer adhesive strength of the obtained multilayer film was measured. The results are shown in Table 2.
Using a chemical packaging molding machine (product name “FBP-M2”, manufactured by CKD), a cylindrical shape that accommodates tablets (8 mmφ × maximum thickness 4 mm) in the multilayer film 1 under the condition of a mold surface temperature of 130 ° C. A portion (pocket: diameter 9 mm × height 5 mm) was vacuum-formed with an array having a center interval of 15 mm, whereby a processed film 1 was obtained. Next, the concave side (non-projecting side) surface of the pocket of the processed film 1 without filling the contents, and the maleic acid modified polyolefin coated surface of the hard aluminum foil (thickness 20 μm) coated with maleic acid modified polyolefin After stacking and heat sealing at 210 ° C. and slitting at 175 ° C., PTP1 (number of pockets: 5 vertical, 2 horizontal, total 10) was punched into 37 mm width, 94 mm length and 5 mm corner. .
The cross section of the pocket of the obtained PTP1 was observed, and the presence or absence of delamination of the layer made of the resin composition containing the norbornene monomer ring-opening polymer hydrogenated product and the layer made of the polypropylene resin composition was confirmed. . The results are shown in Table 2.

(Example 2)
In the same manner as in Example 1, except that polypropylene (PP2) [polypropylene-ethylene random copolymer (propylene unit 98% by weight), melting point 143 ° C., MFR 3 g / 10 min] was used instead of polypropylene (PP1). Film 2 and PTP2 were obtained. The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Example 3)
PTP3 was obtained in the same manner as in Example 1 except that polypropylene (PP3) [polypropylene-ethylene block copolymer (propylene unit 65% by weight), melting point 162 ° C., MFR 8 g / 10 min] was used instead of polypropylene (PP1). Got. The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

Example 4
PTP4 was obtained in the same manner as in Example 1 except that the amount of polypropylene (PP1) used was changed to 94 parts and the amount of aromatic diene-conjugated diene random copolymer hydride (R1) used was changed to 6 parts. . The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Example 5)
PTP5 was obtained in the same manner as in Example 1 except that the amount of polypropylene (PP1) used was changed to 63 parts and the amount of aromatic diene-conjugated diene random copolymer hydride (R1) used was changed to 37 parts. . The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Example 6)
Instead of hydride (R1) of aromatic diene-conjugated diene random copolymer, hydride (R2) of aromatic diene-conjugated diene random copolymer [aromatic diene is styrene, conjugated diene is butadiene / isoprene ( 6/4), styrene unit content 10% by weight, hydrogenation rate of carbon-carbon double bond in structural unit derived from butadiene 99%, hydrogenation rate of aromatic ring derived from styrene 2%, MFR 4 g / 10 minutes, density 0.89 g / cm ³ , content of random copolymer portion 93%, proportion of structural units derived from 1,2- and 3,4-addition polymerization in structural units derived from butadiene 80%] PTP6 was obtained in the same manner as in Example 1 except that it was used. The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.
(Example 7)
Instead of the hydride of the aromatic diene-conjugated diene random copolymer (R1), the hydride of the aromatic diene-conjugated diene random copolymer (R3) [the aromatic diene is styrene, the conjugated diene is butadiene, Styrene unit content 10% by weight, hydrogenation rate of carbon-carbon double bond in structural unit derived from butadiene 99%, hydrogenation rate of aromatic ring derived from styrene 2%, MFR 4 g / 10 min, density 0.89 g / Cm ³ , content of random copolymer part 94%, ratio of structural units derived from 1,2- and 3,4-addition polymerization in structural units derived from butadiene 62%], Example 1 In the same manner, PTP7 was obtained. The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Examples 8 to 11)
Example except that hydride of aromatic vinyl-conjugated diene block copolymer shown in Table 1 (R6 to R9) was used instead of hydride of aromatic diene-conjugated diene random copolymer (R1) 1 to obtain PTP 8 to 11. The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Examples 12 and 13)
PTP12 and PTP13 were obtained in the same manner as in Example 8 except that polypropylene (PP2) or (PP3) was used instead of polypropylene (PP1). The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Examples 14 to 16)
Instead of the resin (A) obtained in Production Example 1, the same procedures as in Example 1 were conducted except that the resins (B), (C), and (D) obtained in Production Examples 2, 3, and 4 were used. PTP14-16 were obtained. The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Example 17)
PTP20 was obtained in the same manner as in Example 1 except that the amount of polypropylene (PP1) used was changed to 50 parts, and the amount of aromatic diene-conjugated diene random copolymer hydride (R1) used was changed to 50 parts. . The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Example 18)
Instead of hydride (R1) of aromatic diene-conjugated diene random copolymer, hydride (R4) of aromatic vinyl-conjugated diene random copolymer [aromatic diene is styrene, conjugated diene is butadiene, Styrene unit content 10% by weight, hydrogenation rate of carbon-carbon double bond in structural unit derived from butadiene 99%, hydrogenation rate of aromatic ring derived from styrene 2%, MFR 4 g / 10 min, density 0.89 g / Cm ³ , content of random copolymer portion 94%, proportion of structural unit derived from 1,2- and 3,4-addition polymerization in structural unit derived from butadiene 57%], Example 1 In the same manner, PTP21 was obtained. The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Examples 19 to 24)
Example except that hydride (R11 to R16) of aromatic vinyl-conjugated diene block copolymer shown in Table 1 was used instead of hydride (R1) of aromatic diene-conjugated diene random copolymer 1 to obtain PTP26 to PTP31. The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Example 25)
PTP23 was obtained in the same manner as in Example 8 except that the amount of polypropylene (PP1) used was changed to 90 parts and the amount of aromatic vinyl-conjugated diene block copolymer hydride (R6) used was changed to 10 parts. . The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Example 26)
PTP24 was obtained in the same manner as in Example 8, except that the amount of polypropylene (PP1) used was changed to 50 parts, and the amount of aromatic vinyl-conjugated diene block copolymer hydride (R6) used was changed to 50 parts. . The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Comparative Example 1)
PTP17 was obtained in the same manner as in Example 1 except that the hydride (R1) of the aromatic diene-conjugated diene random copolymer was not used. The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Comparative Example 2)
PTP18 was obtained in the same manner as in Example 2 except that the hydride of aromatic diene-conjugated diene random copolymer (R1) was not used. The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Comparative Example 3)
PTP19 was obtained in the same manner as in Example 3 except that the hydride (R1) of the aromatic diene-conjugated diene random copolymer was not used. The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Comparative Example 4)
Instead of hydride (R1) of aromatic diene-conjugated diene random copolymer, (unhydrogenated) aromatic vinyl-conjugated diene random copolymer (R5) [aromatic diene is styrene, conjugated diene is butadiene. Yes, styrene unit content 10% by weight, hydrogenation rate of carbon-carbon double bond in structural unit derived from butadiene 0%, hydrogenation rate of aromatic ring derived from styrene 0%, MFR 4 g / 10 min, density 0 .89 g / cm ³ , content of random copolymer part 94%, proportion of structural units derived from 1,2- and 3,4-addition polymerization in structural units derived from butadiene 63%] PTP22 was obtained in the same manner as in Example 1. The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Comparative Example 5)
Example 1 was used except that the aromatic vinyl-conjugated diene block copolymer (R10) shown in Table 1 was used instead of the hydride of the aromatic diene-conjugated diene random copolymer (R1). PTP25 was obtained. The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Comparative Example 6)
Instead of hydride (R1) of aromatic vinyl-conjugated diene random copolymer, linear low density polyethylene (polymer polymerized with metallocene catalyst, density 0.918 g / cm ³ , MFR 4 g / 10 min (190 ° C. PTP32 was obtained in the same manner as in Example 1 except that the load 21.18N)) was used. The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

(Comparative Examples 7 and 8)
PTP33 to 34 were obtained in the same manner as in Example 1 except that the resins (E) and (F) obtained in Production Examples 5 and 6 were used instead of the resin (A) obtained in Production Example 1. . The interlayer adhesive strength of the obtained multilayer film was measured, and the presence or absence of delamination of the obtained PTP was confirmed. The results are shown in Table 2.

Table 2 shows the following.
When the cross section of the PTP pocket obtained from the multilayer film of the present invention was observed, no delamination was observed between the layer composed of the resin composition (A) and the layer composed of the polypropylene resin composition (B) (implementation) Examples 1 to 26).
On the other hand, when the pocket cross section of PTP obtained from a multilayer film using a layer made of a polypropylene resin composition not containing an aromatic vinyl-conjugated diene copolymer hydride was observed, delamination was observed (Comparative Example). 1-3).
When observing the pocket cross section of PTP obtained from multilayer film using aromatic vinyl-conjugated diene copolymer or linear low density polyethylene instead of hydride of aromatic vinyl-conjugated diene copolymer (unhydrogenated) Delamination was observed (Comparative Example 4: Contrast with Example 7, Comparative Example 5: Contrast with Example 9, Comparative Example 6: Contrast with Examples 1-3, 6-11, and 18-24).
In order to obtain a crystalline norbornene monomer ring-opening polymer hydrogenated product, a polymerizable monomer containing less than 90% by weight of 2-norbornene and more than 10% by weight of substituent-containing norbornene was used. In this case, when the pocket cross section of the obtained PTP was observed, delamination was observed (Comparative Examples 7 and 8: Contrast with Examples 1 and 14 to 16).
When the hydride of the aromatic vinyl-conjugated diene copolymer is contained in the polypropylene resin composition layer (B), delamination of the obtained PTP pocket cross section is not observed, but the aromatic vinyl-conjugated diene copolymer used is By selecting a polymer hydride, between the resin composition layer (A) containing the crystalline norbornene monomer ring-opening polymer hydrogenated product of the multilayer film and the polypropylene resin composition layer (B) It can be seen that the interlaminar bond strengths of the films differ.
In the polypropylene resin composition (B), when the aromatic vinyl-conjugated diene copolymer hydride is a random copolymer, the weight ratio of (polypropylene) / (aromatic vinyl-conjugated diene random copolymer hydride) is When it is in the range of 95/5 to 60/40, the interlayer adhesive strength between the resin composition layer (A) and the polypropylene resin composition layer (B) is high (Examples 1, 4 and 5: Example 17 and comparison) Comparison with Example 1).
When the ratio of the monomer units derived from 1,2- and 3,4-addition polymerization in the monomer units derived from the conjugated diene compound of the aromatic vinyl-conjugated diene random copolymer is 60% by weight or more, The interlayer adhesive strength between the resin composition layer (A) and the polypropylene resin composition layer (B) is high (Examples 1, 6 and 7: comparison with Example 18).
Further, in the polypropylene resin composition (B) comprising a hydrogenated aromatic vinyl-conjugated diene copolymer and polypropylene, the aromatic vinyl-conjugated diene copolymer comprises an aromatic vinyl block (I) and In the case of a block copolymer comprising a conjugated diene block (II), the conjugated diene block (II) is a monomer derived from 1,2- and 3,4-addition polymerization in monomer units derived from a conjugated diene compound. When the proportion of the unit is 40% by weight or more, the interlayer adhesive strength between the resin composition layer (A) and the polypropylene resin composition layer (B) is high (Examples 8 and 11: Comparison with Example 21; Example 9: Contrast with Examples 19 and 20.
When the ratio of the aromatic vinyl block (I) in the aromatic vinyl-conjugated diene block copolymer is in the range of 15 to 55% by weight, the resin composition layer (A) and the polypropylene resin composition layer (B) The interlayer adhesive strength between them is high (Examples 8 and 9: comparison with Examples 22 to 23, Example 11: comparison with Example 24).
When the weight ratio of (polypropylene) / (aromatic vinyl-conjugated diene block copolymer hydride) in the polypropylene resin composition (B) is in the range of 85/15 to 60/40, the resin composition layer (A ) And the polypropylene resin composition layer (B) are high (Example 8: Comparison with Examples 25 and 26).

  The multilayer film of the present invention has a high interlayer adhesive strength between a layer composed of a resin composition containing a crystalline norbornene monomer ring-opening polymer hydrogenated product and a layer composed of a polypropylene resin composition. It can be used as a package or a material of the package.

Claims (5)

  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 monomer ring opening 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 at 0 ° C. A layer comprising a resin composition (A) comprising a polymer hydrogenated product, and a layer comprising a polypropylene resin composition (B) comprising an aromatic vinyl-conjugated diene copolymer hydride and polypropylene. Is a multilayer film having at least one set of directly laminated layers. In the polypropylene resin composition (B),
(1) Aromatic vinyl-conjugated diene copolymer hydride is a hydride of a random copolymer of aromatic vinyl and conjugated diene,
(2) The weight ratio of (polypropylene) / (hydride of aromatic vinyl-conjugated diene random copolymer) in the polypropylene resin composition (B) is in the range of 95/5 to 60/40,
(3) The proportion of structural units derived from 1,2- and 3,4-addition polymerization in the structural units derived from the conjugated diene compound of the aromatic vinyl-conjugated diene random copolymer is 60% by weight or more.
The multilayer film according to claim 1. In a polypropylene resin composition (B) comprising a hydrogenated aromatic vinyl-conjugated diene copolymer and polypropylene,
(1) The aromatic vinyl-conjugated diene copolymer hydride is
(1-1) A hydride of a block copolymer comprising an aromatic vinyl block (I) and a conjugated diene block (II),
(1-2) The proportion of the structural unit derived from 1,2- and 3,4-addition polymerization in the structural unit derived from the conjugated diene compound of the conjugated diene block (II) is 40% by weight or more.
(1-3) The ratio of the aromatic vinyl block (I) in the aromatic vinyl-conjugated diene block copolymer is in the range of 15 to 55% by weight,
(2) The weight ratio of (polypropylene) / (aromatic vinyl-conjugated diene block copolymer hydride) in the polypropylene resin composition (B) is in the range of 85/15 to 60/40.
The multilayer film according to claim 1.   The multilayer film according to claim 1, 2 or 3, wherein the resin composition (A) containing a crystalline norbornene monomer ring-opening polymer hydrogenated product and the polypropylene resin composition (B) are coextruded.   A package comprising the multilayer film according to claim 1, 2, 3 or 4.