JP5810531B2 - Resin composition for extrusion lamination and laminate - Google Patents

Description

  The present invention relates to a resin composition for extrusion lamination containing a crystalline norbornene-based ring-opening polymer hydride, and a laminate obtained by extrusion lamination of this resin composition.

  Cyclic olefin resins are attracting attention as resin materials for food and pharmaceutical packaging films due to their excellent transparency, fluidity during melting, low elution, chemical resistance, and heat resistance. No. 1 has been proposed for use as an extrusion laminating material.

  However, since the cyclic olefin-based resin described in this document is amorphous, depending on its use, water vapor barrier properties, oil resistance, etc. are insufficient, and further improvements in physical properties have been desired.

  In Patent Document 2, a crystalline norbornene-based ring-opening polymer hydride is obtained by ring-opening polymerization of a norbornene-based monomer having 2-norbornene of 90% by weight or more, and then hydrogenating. It is described that a film or sheet obtained by molding a coalescence is excellent in moisture resistance, heat resistance and oil resistance. However, since the polymer disclosed specifically has a linear structure and the extensional viscosity does not show strain rate curability, the extrusion direction of the film called regular surging is called regular in extrusion lamination. Thickness variation will occur.

  Patent Document 3 discloses that a crystalline norbornene-based ring-opening weight obtained by ring-opening polymerization of a norbornene-based monomer having 90% by weight or more of 2-norbornene in the presence of a branching agent and then hydrogenating it. It is described that the combined hydride is excellent in film moldability. However, since the polymer specifically disclosed in this document has a high molecular weight, there is a problem that the melt film is broken when the take-up speed is increased during extrusion lamination molding. Moreover, when the laminated body obtained by extrusion lamination molding is heat-sealed, there is also a problem that the sealing strength is weak and easy to peel off.

JP 2006-123330 A WO2008 / 026733 WO2009 / 107784

  The present invention has been made in view of such a state of the art, and a resin composition for extrusion laminating containing a crystalline norbornene-based ring-opening polymer hydride excellent in moldability and heat sealability, and this It aims at providing the laminated body obtained by carrying out extrusion lamination of the resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that 80% or more of the carbon-carbon double bonds of the ring-opened polymer obtained by ring-opening polymerization of a specific norbornene-based monomer are hydrogenated. A crystalline norbornene-based ring-opening polymer hydrogenated product obtained by addition, having a melting point, a branching index, and a weight average molecular weight having specific values, has been found to be extremely excellent in extrusion laminate processability, and the present invention It came to complete.

Thus, according to the present invention, the following resin compositions for extrusion lamination (1) to (3) and the laminate (4) are provided.
(1) Ring-opening polymerization of a norbornene monomer comprising 90 to 100% by weight of 2-norbornene and 0 to 10% by weight of 2-norbornene having a substituent not containing an aliphatic carbon-carbon double bond. The ring-opened polymer obtained by hydrogenating 80% or more of carbon-carbon double bonds, melting point of 110-145 ° C., branching index of 0.3-0.98, gel permeation chromatography A resin composition for extrusion lamination, comprising a crystalline norbornene-based ring-opening polymer hydride having a weight average molecular weight of 20,000 to 60,000 as measured by lithography.
(2) The resin composition for extrusion lamination according to (1), wherein the ring-opening polymer is obtained by ring-opening polymerization of the norbornene monomer in the presence of a branching agent. object.
(3) The extrusion agent according to (2), wherein the branching agent is an alicyclic structure-containing monomer having a substituent containing an aliphatic carbon-carbon double bond at the terminal. Resin composition.
(4) A laminate obtained by extrusion laminating the resin composition according to any one of (1) to (3) to a base film.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition for extrusion lamination which is excellent in extrusion laminating property is provided. Since the resin composition of the present invention is less prone to surging when extrusion laminate processing and is easy to draw down, a high-quality extrusion laminate laminate can be produced efficiently.

  Hereinafter, the present invention will be described in detail by dividing into 1) a resin composition for extrusion lamination and 2) a laminate.

1) Resin composition for extrusion lamination The resin composition of the present invention is 90 to 100% by weight of 2-norbornene and 0 to 10% of 2-norbornene having a substituent not containing an aliphatic carbon-carbon double bond. % Of a ring-opening polymer obtained by ring-opening polymerization of a norbornene-based monomer comprising 80% of a carbon-carbon double bond, melting point of 110 to 145 ° C., branching index of 0 It is characterized by containing a hydride of a crystalline norbornene-based ring-opening polymer having a weight average molecular weight of 20,000 to 60,000 as measured by gel permeation chromatography.

(Norbornene monomer)
The norbornene-based monomer used in the present invention is a monomer having a norbornene structure that does not generate a branched structure by an olefin and metathesis reaction, and does not contain 2-norbornene and an aliphatic carbon-carbon double bond. It is composed of 2-norbornene having a substituent.

  The norbornene-based monomer used in the present invention is 2-norbornene (bicyclo [2.2.1] hept-2-ene): 90 to 100% by weight, aliphatic when the total amount thereof is 100% by weight. 2-norbornene having a substituent that does not contain a functional carbon-carbon double bond: 10 to 0% by weight. The proportion of 2-norbornene is preferably 95 to 99% by weight, more preferably 97 to 99% by weight, and the proportion of 2-norbornene having a substituent not containing an aliphatic carbon-carbon double bond is Preferably it is 1 to 5 weight%, More preferably, it is 1 to 3 weight%. When the proportion of 2-norbornene is in such a range, the mechanical properties, heat resistance and moisture resistance of the molded article are good.

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

  2-norbornene having a substituent that does not contain an aliphatic carbon-carbon double bond has (a) a substituent that does not contain an aliphatic carbon-carbon double bond in the molecule; It is roughly divided into a norbornene monomer having no ring condensed with the norbornene ring and (b) a polycyclic norbornene monomer having three or more rings having a substituent not containing an aliphatic carbon-carbon double bond. Is done.

Specific examples of the norbornene monomer (a) having a substituent not containing an aliphatic carbon-carbon double bond in the molecule and having no ring condensed with the norbornene ring 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 -Norbornenes having an alkyl group such as bicyclo [2.2.1] hept-2-ene, 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene;
Norbornenes having an aromatic ring such as 5-phenyl-bicyclo [2.2.1] hept-2-ene (5-phenyl-2-norbornene);
5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene (5-methoxycarbonyl-2-norbornene), 5-ethoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5- Methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-ethoxycarbonyl-5-methyl-bicyclo [2.2.1] hept-2-ene, 2-methylpropionic 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] ] Put-2-ene, 5-hydroxyisopropyl-bicyclo [2.2.1] hept-2-ene, 5,6-dicarboxy-bicyclo [2.2.1] hept-2-ene, 6-carboxy- Norbornenes having a polar group containing an oxygen atom such as 5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene;
Norbornene having a polar group containing a nitrogen atom such as 5-cyano-bicyclo [2.2.1] hept-2-ene, 6-carboxy-5-cyano-bicyclo [2.2.1] hept-2-ene And the like.

The polycyclic norbornene monomer having 3 or more rings having a substituent not containing an aliphatic carbon-carbon double bond (b) is obtained by condensing a norbornene ring in the molecule with the norbornene ring. A norbornene monomer having one or more rings.
Specifically, dicyclopentadiene such as tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene), methyldicyclopentadiene, dimethyldicyclopentadiene;
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} . 0 ^4,9 ] pentadeca-4,6,8,13-tetraene (also referred to as “1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene”) and the like. Norbornenes;
Tetracyclododecenes having an unsubstituted or alkyl group such as tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, 8-cyclopentyltetracyclododecene, etc. ;
Tetracyclododecenes having an aromatic ring such as 8-phenyltetracyclododecene;
8-methoxycarbonyltetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid Tetracyclododecenes having a substituent containing an oxygen atom such as tetracyclododecene-8,9-dicarboxylic anhydride;
Tetracyclododecenes having a substituent containing a nitrogen atom such as 8-cyanotetracyclododecene, tetracyclododecene-8,9-dicarboxylic imide;
Tetracyclododecenes having a substituent containing a halogen atom such as 8-chlorotetracyclododecene;
Tetracyclododecenes having a substituent containing a silicon atom, such as 8-trimethoxysilyltetracyclododecene;
Hexacycloheptadecenes having an unsubstituted or alkyl group such as hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, 12-cyclopentylhexacycloheptadecene, etc. ;
Hexacycloheptadecenes having an aromatic ring such as 12-phenylhexacycloheptadecene;
12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene 12,13-dicarboxylic acid, Hexacycloheptadecenes having a substituent containing an oxygen atom such as hexacycloheptadecene 12,13-dicarboxylic anhydride;
Hexacycloheptadecenes having a substituent containing a nitrogen atom such as 12-cyanohexacycloheptadecene, hexacycloheptadecene 12,13-dicarboxylic imide;
Hexacycloheptadecenes having a substituent containing a halogen atom such as 12-chlorohexacycloheptadecene;
And hexacycloheptadecenes having a substituent containing a silicon atom, such as 12-trimethoxysilylhexacycloheptadecene;
Norbornene monomers having a substituent that does not contain an aliphatic carbon-carbon double bond can be used singly or in combination of two or more.

The crystalline norbornene ring-opening polymer hydride used in the present invention has a branched structure. This branched structure can be generated by ring-opening polymerization of a norbornene monomer in the presence of a branching agent.
The branching agent is a substance that contributes to the olefin metathesis reaction in which a combination of two olefins is recombined in the presence of a carbene complex catalyst to generate a new olefin.

  As the branching agent used in the present invention, a compound having a substituent containing an aliphatic carbon-carbon double bond is preferable, and an alicyclic structure having a substituent containing an aliphatic carbon-carbon double bond is contained. More preferably, it is a monomer.

As the substituent containing an aliphatic carbon-carbon double bond, those containing a carbon-carbon double bond at the terminal are preferable.
Examples of the substituent containing an aliphatic carbon-carbon double bond include alkenyl groups having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms. Specific examples include a vinyl group, an allyl group, a 3-butenyl group, a 4-pentenyl group, a 2-methyl-3-butenyl group, and a 5-heptyl group. Among these, a alkenyl group having 2 to 10 carbon atoms containing a carbon-carbon double bond at the terminal is preferable since a hydride of a norbornene-based ring-opening polymer having more excellent fluidity can be obtained. A vinyl group and an allyl group are preferable. Is particularly preferred.

In addition, these alkenyl groups may be bonded to the mother nucleus through an arbitrary group, or may be bonded to the mother nucleus through an arbitrary group to form a ring structure. As an arbitrary group, an alkylene group, —O—, —S—, —O—C (═O) —, —O—CH ₂ —O—C (═O) —, a phenylene group, and the like can be given. The number of elements constituting any group is preferably 10 or less, more preferably 5 or less, and other than alkylene groups, because a norbornene-based ring-opening polymer hydride having better fluidity can be obtained. Those having no divalent group are preferred.
Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure.

Examples of the branching agent used in the present invention include 5-vinyl-bicyclo [2.2.1] hept-2-ene, 5-allyl-bicyclo [2.2.1] hept-2-ene, and 5-vinyloxycarbonyl. -Bicyclo [2.2.1] hept-2-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-allyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . A monomer having a norbornene structure having a substituent capable of undergoing an olefin metathesis reaction, such as 1 ^7,10 ] dodec-3-ene;
exo-trans-exo- pentacyclo [8.2.1.1 ^4,7. 0 ^2,9 . 0 ^3,8 ] tetradeca-5,11-diene (hereinafter sometimes referred to as “NB-dimer”), 4,4a, 4b, 5,8,8a, 9,9a-octahydro-1,4: 5 , 8-bismethano-1H-fluorene, 1α, 4α: 5α, 8α-dimethano-1,4,4a, 5,8,8a, 9,9a, 10,10a-decahydroanthracene, 5,5′-bi ( Norborna-2-ene), tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecane-4,9-diene, 1,4,4a, 5,8,8a, 9,9a, 10,10a-decahydro-1,4: 5,8: 9,10-trimethanoanthracene A monomer having two norbornene structures in the molecule such as
1,2,4-trivinylcyclohexane, 4- (2-propenyl) -1,6-heptadiene, 3-vinyl-1,4-pentadiene, 3-vinyl-1,5-hexadiene, 1,3,5- Monomers having three or more terminal carbon-carbon double bonds in the molecule such as trivinylbenzene, 1,2,4-trivinylbenzene, 1,2,4,5-tetravinylbenzene, etc. Is mentioned.

  For example, as a branching agent, 5-vinyl-bicyclo [2.2.1] hept-2 which is a compound having at least one substituent containing a cycloalkene structure and an aliphatic carbon-carbon double bond in the molecule. When 2-norbornene (2-NB), which is a norbornene-based monomer, is subjected to ring-opening polymerization in the presence of -ene (VNB), a three-branched polymer is generated as shown below.

(In the formula, M represents a transition metal atom such as tungsten, L represents a ligand such as a halogen atom, R represents an alkyl group, and m, n, and p each represents a positive integer.)
That is, 2-norbornene (2-NB) and 5-vinylnorbornene (VNB) undergo a ring-opening metathesis reaction to form a polymer chain (1), and another polymer chain (2-1) undergoes a metathesis reaction. Thus, a three-branched polymer (3) is formed.

  As a branching agent, ring-opening polymerization of 2-norbornene (2-NB), which is a norbornene monomer, in the presence of NB-dimer, which is a compound having two or more cycloalkene structures in the molecule, is as follows. As shown, a 4-branched polymer is produced.

(In the formula, M, L, R, m, n, and p have the same meaning as described above, and q represents a positive integer.)
That is, 2-norbornene (2-NB) and NB-dimer undergo a ring-opening metathesis reaction to produce a polymer chain (4), and another polymer chain (2-1) undergoes a metathesis reaction to form a polymer chain. (5) is generated. Furthermore, 4-norbornene (NB) causes a metathesis reaction to form a 4-branched polymer (6).

  In addition, norbornene is used as a branching agent in the presence of 1,2,4-trivinylcyclohexane (TVC), which is a cycloalkane compound having three or more substituents containing an aliphatic carbon-carbon double bond in the molecule. When ring-opening polymerization of 2-norbornene (2-NB), which is a system monomer, produces a 3-branched polymer as shown below.

(In the formula, M, L, m, n and p have the same meaning as described above.)
That is, the polymer chain (2) obtained from 2-norbornene (2-NB) and the three vinyl groups of 1,2,4-trivinylcyclohexane (TVC) each cause a metathesis reaction to form a three-branched polymer (7) is generated.

  In addition, when the branching agent to be used has a mother nucleus capable of ring-opening metathesis polymerization, this monomer also contributes to the ring-opening polymerization together with a norbornene monomer having no substituent capable of undergoing olefin metathesis reaction.

  As will be described later, the crystalline norbornene-based ring-opening polymer hydride of the present invention is a polymer having a branching index of 0.3 to 0.98. By appropriately adjusting the blending amount of the branching agent in the ring-opening polymerization, a crystalline norbornene-based ring-opening polymer hydride having a desired branching index can be obtained.

  The blending amount of the branching agent can be arbitrarily set depending on the type of the branching agent, but many branching agents are usually 0.01 to 5 when the total amount of norbornene monomers is 100 mol%. It is used in the range of mol%, preferably 0.05 to 5 mol%, more preferably 0.1 to 5 mol%.

(Metathesis polymerization catalyst)
Examples of the metathesis polymerization catalyst used for the ring-opening polymerization of the norbornene monomer include, for example, Japanese Patent Publication No. 41-20111, Japanese Patent Application Laid-Open No. 46-14910, Japanese Patent Publication No. 57-17834, and Japanese Patent Publication No. 57-61044. (I) transition metal compound catalyst component and (ii) metal compound described in JP-A-54-86600, JP-A-58-127728, JP-A-1-240517, etc. General metathesis polymerization catalyst comprising a co-catalyst component; Schrock type polymerization catalyst (Japanese Patent Laid-Open No. 7-179575, Schrock et al., J. Am. Chem. Soc., 1990, 112, 3875-etc.) ) And Grubbs type polymerization catalyst (Fu et al., J. Am. Chem. Soc., 1993, 115, 9856-; Nguye .. Et al, J.Am.Chem.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 (i) a transition metal compound catalyst component and (ii) a metal compound promoter component is preferable in order to adjust the molecular weight distribution of the obtained polymer to a suitable range.

The transition metal compound catalyst component (i) is a compound of a transition metal of Groups 3 to 11 of the periodic table. For example, transition metal halides, oxyhalides, alkoxy halides, alkoxides, carboxylates, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes, derivatives thereof, these or these Examples thereof include a complexed product of a derivative such as P (C ₆ H ₅ ) _{3 with} a complexing agent.
Specific examples include TiCl ₄ , TiBr ₄ , VOCl ₃ , WBr ₃ , WCl ₆ , WOCl ₄ , MoCl ₅ , MoOCl ₄ , WO ₃ , H ₂ WO _{4 and the} like. 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 metal compound promoter component (ii) 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. It is. 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 (i) and (ii), a third component can be added to increase the metathesis polymerization activity. 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 usually in the range of 1: 1 to 1: 100, preferably 1: 2 to 1:10 in terms of the molar ratio of (i) component: (ii) component to metal element. Moreover, (i) component: 3rd component is the range of 1: 0.005 to 1:50, preferably 1: 1 to 1:10 by molar ratio.

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

(Molecular weight regulator)
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 Non-conjugated dienes such as methyl-1,4-pentadiene and 2,5-dimethyl-1,5-hexadiene, or 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1 , 3-butadiene, 1,3-pentadiene, 1,3-hexadiene, etc. 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)
Ring-opening polymerization can be initiated by mixing a norbornene monomer, a branching agent, a metathesis polymerization catalyst, and optionally a molecular weight regulator.

  Ring-opening polymerization is usually performed in a 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 an organic solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, Alicyclic hydrocarbons such as tricyclodecane, hexahydroindenecyclohexane and cyclooctane; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane Halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; diethyl ether and tetrahydrofuran It can be used solvents such as, ethers. These organic solvents can be used alone or in combination of two or more. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and ethers that are widely used in industry are preferable.

  When the polymerization is performed in an organic solvent, the concentration of the monomer (monomer mixture) 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 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 is too high, and the subsequent hydrogenation reaction may be difficult.

Although the temperature which performs ring-opening polymerization is not specifically limited, Usually, -20- + 100 degreeC, Preferably it is 10-80 degreeC. If the polymerization 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 applied pressure is 1 MPa or less normally.
After completion of the reaction, the desired norbornene-based ring-opening polymer can be isolated by ordinary post-treatment operation.

(Hydrogenation reaction)
The obtained norbornene-based ring-opening polymer is subjected to the next hydrogenation reaction step. As will be described later, the hydrogenation reaction can be continuously performed without adding a hydrogenation catalyst to the reaction solution subjected to the ring-opening polymerization and isolating the norbornene-based ring-opening polymer.

  The hydrogenation reaction of the norbornene-based ring-opening polymer is a reaction in which hydrogenation is performed on carbon-carbon double bonds existing in the main chain and / or side chain of the norbornene-based ring-opening polymer.

  This hydrogenation reaction is performed by adding a hydrogenation catalyst to an inert solvent solution of a norbornene-based 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 cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, etc. Catalyst systems comprising combinations of transition metal compounds and alkali metal compounds such as combinations; dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium, bis (tricyclohexylphosphine) And a noble metal complex catalyst such as benzylidine ruthenium (IV) dichloride.

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, titanium oxide or the like can be mentioned.
The usage-amount of a catalyst is 0.05-10 weight part normally with respect to 100 weight part of norbornene-type ring-opening polymers.

  As the inert organic solvent used for the hydrogenation reaction, the same aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons as those exemplified as the organic solvent that can be used in the ring-opening polymerization described above. Halogen-containing aromatic hydrocarbons, nitrogen-containing hydrocarbons, ethers and the like.

  The temperature of the hydrogenation reaction varies depending on the hydrogenation catalyst used, but 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.

  After completion of the hydrogenation reaction, the hydrogenation catalyst and the like are filtered off from the reaction solution, and the target crystalline norbornene-based ring-opening polymer hydrogen is removed by removing volatile components such as a solvent from the polymer solution after the filtration. The compound can be obtained. In addition, in the hydrogenation reaction liquid, an antioxidant (stabilizer), a nucleating agent, a foaming agent, a flame retardant, a compound such as a thermoplastic resin or a soft polymer, a compounding agent such as a lubricant, Other compounding agents usually used in the resin industry field such as dyes, antistatic agents, ultraviolet absorbers, light stabilizers, waxes and the like may be added, followed by heating as necessary, followed by filtration.

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.
As described above, the crystalline norbornene-based ring-opening polymer hydride of the present invention can be obtained.

(Crystalline norbornene ring-opening polymer hydride)
The crystalline norbornene ring-opening polymer hydride used in the present invention has a hydrogenation rate of carbon-carbon double bonds in the norbornene ring-opening polymer of usually 80% or more, preferably 90% or more, more preferably 95 % Or more, more preferably 99% or more, particularly preferably 99.9% or more. When it is in the above range, coloring due to resin burn is suppressed, which is preferable.
The hydrogenation rate of the crystalline norbornene-based ring-opening polymer hydride can be determined by measuring by ¹ H-NMR using deuterated chloroform as a solvent.

  The isomerization rate of the crystalline norbornene ring-opening polymer hydride used in the present invention is usually 25% or less, preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less. If the isomerization rate is too high, the heat resistance of the polymer may be lowered.

The isomerization rate can be calculated from 33.0 ppm peak integrated value / (31.8 ppm peak integrated value + 33.0 ppm peak integrated value) × 100 measured by ¹³ C-NMR using deuterated chloroform as a solvent. ^{In the 13} C-NMR spectrum, the 31.8 ppm peak is derived from a cis isomer of a repeating unit derived from 2-norbornene in the polymer, and the 33.0 ppm peak is a repeating unit derived from 2-norbornene in the polymer. It is derived from the trans form.

  In order to make the isomerization ratio within the above range, in the hydrogenation reaction of the norbornene-based ring-opening polymer, the reaction temperature is preferably 100 to 230 ° C, more preferably 130 to 220 ° C, and particularly preferably 150 to 210 ° C. The amount of the hydrogenation catalyst used is preferably 0.2 to 5 parts by weight, more preferably 0.2 to 2 parts by weight with respect to 100 parts by weight of the norbornene-based ring-opening polymer. Within such a range, the balance between the hydrogenation reaction rate and the heat resistance of the resulting polymer is excellent and suitable.

  The crystalline norbornene ring-opening polymer hydride used in the present invention has a branched structure. The branching index is 0.3 to 0.98, preferably 0.4 to 0.95. If the branching index is too large, the moisture-proof property is increased, but the melt tension of the crystalline norbornene-based ring-opening polymer hydride at the time of film production is lowered, and the film moldability is deteriorated. If the branching index is too small, moisture resistance and heat resistance are lowered, which is not preferable.

The branching index is defined by g = [η] Bra / [η] Lin.
[Η] Bra is the limiting viscosity of the branched crystalline norbornene ring-opening polymer hydride, and [η] Lin is the limit of the linear crystalline norbornene ring-opening polymer hydride having the same weight average molecular weight. Viscosity. Here, the intrinsic viscosity [η] is a value obtained by measuring a sample dissolved in cyclohexane at 60 ° C.

  If the branching coefficient of the crystalline norbornene-based ring-opening polymer hydride is in the above-described range, the melt tension becomes high even with the same weight average molecular weight, which is preferable. If the branching index is too high, the strain rate curability of the extension viscosity is lowered even with the same weight average molecular weight, and regular thickness fluctuations in the film take-off direction called take-up surging occur during extrusion lamination.

  The crystalline norbornene-based ring-opening polymer hydride used in the present invention has a weight average molecular weight (Mw) measured by a square laser light scattering photometric method by gel permeation chromatography (GPC) using cyclohexane as an eluent. And 20,000-60,000, preferably 25,000-55,000, more preferably 30,000-50,000.

  When the Mw of the crystalline norbornene-based ring-opening polymer hydride is in this range, the extrusion laminate processability is excellent. That is, when Mw is too high, the viscosity becomes high and the drawdown property is poor, the molten film is cut during the laminate molding, and the high-speed moldability may be inferior. On the other hand, if Mw is too low, the mechanical properties and heat resistance of the molded product may be reduced, and the polymer hydride is crystalline, so that it is difficult to dissolve in the solution, resulting in deterioration of polymer productivity and polymer. It may be difficult to purify the product.

The crystalline norbornene ring-opening polymer hydride used in the present invention has a molecular weight distribution (Mw / Mn) of preferably 1.5 to 10.0, more preferably 2.0 to 9.0, and still more preferably. 3.0 to 8.0, particularly preferably 4.0 to 7.0.
If Mw / Mn is too narrow, the melt viscosity with respect to the temperature of the polymer tends to change sensitively, so that the workability of molded products such as films and sheets may be deteriorated. Further, if Mw / Mn is too wide, the mechanical properties of the molded product may be deteriorated.

  The melting point of the crystalline norbornene-based ring-opening polymer hydride used in the present invention is usually 110 to 145 ° C, preferably 120 to 145 ° C, more preferably 130 ° C to 145 ° C. When the melting point is in such a range, the molded product has excellent heat resistance and is suitable. In particular, the temperature range of 130 ° C. to 145 ° C. is preferable because it can withstand the steam sterilization performed in medical molded products and food molded products. The melting point of the crystalline norbornene ring-opening polymer hydride varies depending on the molecular weight, molecular weight distribution, isomerization rate, etc. of the norbornene ring-opening polymer hydride.

  The melt flow rate of the crystalline norbornene ring-opened polymer hydride used in the present invention at 230 ° C. and a load of 21.18 N is usually 10 g / 10 min to 100 g / 10 min, preferably 20 g / 10 min to 80 g / 10. Min, more preferably 30 g / 10 min to 60 g / 10 min. If the melt flow rate is too high, the stability during high-speed molding may be deteriorated, and if the melt flow rate is too low, the mechanical strength of the molded product may be reduced.

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

  Since the crystalline norbornene ring-opening polymer hydride used in the present invention is a polymer having a melting point, that is, a polymer that forms a crystal structure, a crystal part is formed (crystallized) inside the molded body, and Combined with the amorphous part, mechanical properties such as tensile elongation at break of the molded product are improved.

  The crystalline norbornene-based ring-opening polymer hydride used in the present invention includes an antioxidant (stabilizer), a nucleating agent, a foaming agent, a flame retardant, other polymers such as a thermoplastic resin and a soft polymer, if desired. A compounding agent such as a lubricant, a compounding agent usually used in the resin industry field such as a dye, an antistatic agent, an ultraviolet absorber, a light stabilizer, and a wax can be added to obtain a resin composition.

  The resin composition for extrusion lamination of the present invention is prepared by uniformly mixing the crystalline norbornene-based ring-opening polymer hydride and, if desired, other compounding agents using a tumbler blender, ribbon blender, V-type blender, Henschel mixer, or the like. Then, it can be prepared by melt-kneading with a single or twin screw extruder, roll, Banbury mixer, kneader, Brabender or the like.

  As will be described later, the resin composition for extrusion lamination of the present invention is useful as a raw material for producing a laminate by extrusion lamination molding.

2) Laminate The laminate of the present invention is obtained by extrusion lamination molding of the resin composition of the present invention to a substrate.
That is, the resin composition for extrusion laminating of the present invention is made into a single layer film by extrusion molding such as T-die cast molding of the resin composition for extrusion laminating of the present invention, for example, or other methods. A method of forming a multilayer coextruded film by coextrusion with a resin, and then laminating the single layer or multilayer film with various substrates by an extrusion coating method, a sandwich lamination method, or the like.
The thickness of the extrusion laminate layer is generally 10 to 100 μm, preferably 15 to 50 μm, and particularly preferably 3 to 40 μm.

Specific examples of the base material include polyolefin resins such as polyethylene and polypropylene, polyethylene terephthalate, polyethylene terephthalate / isophthalate copolymers, polybutylene terephthalate, polyester resins such as polyethylene naphthalate, and nylon 6 Polyamide resin such as nylon 12, nylon 66, nylon MXD6, nylon 6/66, unstretched or stretched film or sheet such as saponified ethylene-vinyl acetate copolymer, or the surface thereof is printed. Examples thereof include: a resin such as a printed film and sheet; a metal foil such as aluminum, copper, and iron; a metal such as a plate having a thickness of about 3 to 1000 μm; and a paper such as paper and paperboard.
The thickness of a base material is 3-2000 micrometers normally, Preferably it is 5-2000 micrometers, More preferably, it is 5-1000 micrometers.

Moreover, you may give an anchor coating agent to the base-material surface. As the anchor coating agent, specifically, reaction of polytitanium compound such as alkyl titanate, titanium acylate, titanium chelate, etc., polyisocyanate compound such as hexamethylene diisocyanate, xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and polyol In general, isocyanate-based ones such as two-component reaction type, one-component reaction type mainly composed of a polyurethane prepolymer, and polyethyleneimine type are preferable. . These are usually used by applying in an amount of about 0.01 to 10 g / m ² .

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

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

In the following Examples and Comparative Examples, various physical properties are measured as follows.
(1) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the norbornene-based ring-opening polymer were measured as standard polystyrene conversion values by gel permeation chromatography (GPC) using toluene as an eluent.
GPC-8020 series (DP8020, SD8022, AS8020, CO8020, RI8020, manufactured by Tosoh Corporation) was used as a measuring apparatus.
As the standard polystyrene, standard polystyrene (Mw of 500, 2630, 10200, 37900, 96400, 427000, 909000, 5480000, a total of 8 points, manufactured by Tosoh Corporation) was used.
The sample was prepared by dissolving the measurement sample in toluene so as to have a sample concentration of 1 mg / ml, and then filtering with a cartridge filter (polytetrafluoroethylene, pore size 0.5 μm).
The measurement was performed using two TSKgel GMHHR · H (manufactured by Tosoh Corporation) connected in series to the column under the conditions of a flow rate of 1.0 ml / min, a sample injection amount of 100 μ1, and a column temperature of 40 ° C.

(2) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the hydride of norbornene-based ring-opening polymer were measured by square laser light scattering by gel permeation chromatography (GPC) using cyclohexane as an eluent. Measured by photometric method.
The sample was prepared by dissolving the measurement sample in cyclohexane at 60 ° C. so that the sample concentration was 1 mg / ml.
As a measuring device, Mode 1350 HTGPC (manufactured by Viscotek) was used.
The measurement was performed under the conditions of using TSKgelG2000HHR, TSKgelG4000HHR, and TSKgelG4000HHR (manufactured by Tosoh Corporation) in series in a column, with a flow rate of 1.0 ml / min, a sample injection amount of 100 μ1, and a column temperature of 60 ° C.

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

(4) The isomerization rate was measured by ¹³ C-NMR using deuterated chloroform as a solvent. Oppm peak integrated value / (31.8 ppm peak integrated value + 33.0 ppm peak integrated value) × 100.
By the way, the 31.8 ppm peak is derived from the cis isomer of 2-norbornene repeating units in the polymer, and the 33.0 ppm peak is derived from the trans isomer of 2-norbornene repeating units in the polymer. is there.

(5) Melting point (Tm) is a cooling rate after heating the sample to 30 ° C. or higher from the melting point based on JIS K 7121 using a differential scanning calorimeter (product name “DSC6220SII”, manufactured by Nanotechnology). The sample was cooled to room temperature at 10 ° C./min, and then measured at a heating rate of 10 ° C./min.

(6) The branching index is the intrinsic viscosity [η] Bra of the branched norbornene ring-opening polymer hydride, and the intrinsic viscosity [η] of the linear norbornene ring-opening polymer hydride having the same weight average molecular weight. Calculated as the value divided by Lin.
Intrinsic viscosity [η] was obtained by measuring the viscosity at four points of concentration adjustment by a multipoint method using a Udehlohde viscometer at 60 ° C. for a sample dissolved in cyclohexane, and extrapolating the relationship between each measurement point to zero concentration .
The intrinsic viscosity of the linear norbornene-based ring-opening polymer hydride having the same weight average molecular weight is the absolute viscosity of the linear norbornene-based ring-opening polymer hydride having a different absolute weight average molecular weight of 4 points or more [η ] Lin = KMwa (where [η] Lin is the intrinsic viscosity, Mw is the absolute average molecular weight, and K and a are constants) and are obtained by interpolation.
A linear norbornene-based ring-opening polymer hydride is identical to a branched norbornene-based ring-opening polymer hydride in the absence of a compound having a substituent capable of olefin metathesis reaction (“branching agent”). The copolymer can be obtained by hydrogenation after copolymerization, and by changing the amount of the molecular weight regulator, linear norbornene-based ring-opening polymers having different weight average molecular weights were obtained.

(7) MFR was measured at 230 ° C. and a load of 21.18 N in accordance with JIS K 7210.

(8) The take-up surging generation speed was measured by measuring the film width at a film length of 1 m at each take-up speed when the take-up speed was increased at the time of extrusion lamination molding, and the variation became ± 3 mm or more. It was set as the take-up speed at the time.

(9) The film cutting speed was set to the pulling speed when the molten film was cut by increasing the drawing speed during extrusion lamination molding.

(10) Heat seal strength is 180 ° peeling at a pulling rate of 200 mm / min using a sample sealed at a temperature = (Tm + 35) ° C., pressure = 0.2 MPa, time = 1 second, and cut out at a width of 15 mm. It was set as the value of the peel strength at the time.

[Example 1]
(Ring-opening polymerization)
Under nitrogen atmosphere, 700 parts by weight of dehydrated cyclohexane was reacted with 0.92 parts by weight of 1-hexene, 1.06 parts by weight of diisopropyl ether, 0.34 parts by weight of triisobutylaluminum, and 0.13 parts by weight of isobutyl alcohol at room temperature. Mix in a bowl. There, 250 parts by weight of 2-norbornene (2-NB), 1.28 parts by weight of 5-vinyl-2-norbornene (hereinafter sometimes referred to as “VNB”) and 1.0% by weight of tungsten hexachloride toluene Polymerization was carried out by continuously adding 26 parts by weight of the solution over 2 hours while maintaining the temperature at 65 ° C. The polymerization conversion rate was almost 100%.
The resulting ring-opening polymer (A) had a weight average molecular weight (Mw) of 33,500 and a molecular weight distribution (Mw / Mn) of 3.5.

(Hydrogenation reaction)
The polymerization reaction liquid obtained above was transferred to a pressure-resistant hydrogenation reactor, and 1.0 part by weight of a diatomaceous earth-supported nickel catalyst (T8400, nickel support rate 58% by weight, manufactured by Zudehemy Catalyst Co., Ltd.) was added. The reaction was carried out at 5 ° C. and a hydrogen pressure of 4.5 MPa for 6 hours. This solution was filtered through 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 by weight of isopropyl alcohol with stirring to precipitate a hydride, which was collected by filtration. Further, after washing with 500 parts by weight of acetone, it was dried in a vacuum dryer set at 0.13 × 10 ³ Pa or less and 100 ° C. for 48 hours to obtain 190 parts by weight of ring-opened polymer hydride (A). It was.

(Polymer physical properties)
The hydrogenation rate of the obtained ring-opened polymer hydride (A) was 99.9%, the weight average molecular weight (Mw) was 38,300, the molecular weight distribution (Mw / Mn) was 3.0, and the isomerization rate was The melting point was 135 ° C., the branching index was 0.82, and the MFR was 36.

(Preparation of resin composition)
Antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, Irga was added to 100 parts by weight of the obtained ring-opened polymer hydride (A). Knox (registered trademark) 1010, manufactured by Ciba Specialty Chemicals Co., Ltd. (hereinafter abbreviated as “antioxidant (A)”) 0.1 part by weight was added, and a biaxial kneader (TEM35, manufactured by Toshiba Machine Co., Ltd.) was used. The mixture was kneaded and pelletized to obtain a resin composition (A).

(Extruded laminate molding)
The obtained resin composition (A) was extruded and laminated on 50 g / m ² kraft paper as a base material using a 65 mmφ extruder and a Sumitomo Heavy Industries laminator having a T die with a die width of 500 mm. A laminate (A) was obtained.
・ Air gap: 130mm
・ Resin temperature: 280 ℃
-Take-off speed: The film thickness was set to 30 μm at 40 m / min.
Table 1 shows the take-up surging generation rate and the film breakage rate, and the heat seal strength of the laminate (A).

[Example 2]
(Ring-opening polymerization)
A ring-opening copolymer (B) was obtained in the same manner as in Example 1, except that 0.55 parts by weight of 1-hexene and 1.91 parts by weight of VNB were used. The polymerization conversion rate was almost 100%.
The weight average molecular weight (Mw) of the ring-opening copolymer (B) was 50,200, and the molecular weight distribution (Mw / Mn) was 4.7.

(Hydrogenation reaction)
In the same manner as in Example 1, the obtained ring-opening copolymer (B) was hydrogenated to obtain a ring-opening polymer hydride (B).

(Polymer physical properties)
The hydrogenation rate of the ring-opening polymer hydride (B) is 99.9%, the weight average molecular weight (Mw) is 56,700, the molecular weight distribution (Mw / Mn) is 4.1, the isomerization rate is 8%, The melting point was 136 ° C., the branching index was 0.73, and the MFR was 14.

(Preparation of resin composition)
A resin composition (B) was obtained from the obtained ring-opened polymer hydride (B) in the same manner as in Example 1.

(Extruded laminate molding)
A laminate (B) was obtained from the obtained resin composition (B) in the same manner as in Example 1. Table 1 shows the take-up surging generation rate and the film breakage rate, and the heat seal strength of the laminate (B).

[Example 3]
(Ring-opening polymerization)
A ring-opening copolymer (C) was obtained in the same manner as in Example 1 except that 3.83 parts by weight of VNB was used in Example 1. The polymerization conversion rate was almost 100%.
The ring-opening copolymer (B) had a weight average molecular weight (Mw) of 35,100 and a molecular weight distribution (Mw / Mn) of 3.6.

(Hydrogenation reaction)
In the same manner as in Example 1, the obtained ring-opening copolymer (C) was hydrogenated to obtain a ring-opening polymer hydride (C).

(Polymer physical properties)
The hydrogenation rate of the ring-opening polymer hydride (C) is 99.9%, the weight average molecular weight (Mw) is 39,200, the molecular weight distribution (Mw / Mn) is 3.1, the isomerization rate is 8%, The melting point was 129 ° C., the branching index was 0.48, and the MFR was 38.

(Preparation of resin composition)
From the obtained ring-opened polymer hydride (C), a resin composition (C) was obtained in the same manner as in Example 1.

(Extruded laminate molding)
A laminate (C) was obtained from the obtained resin composition (C) in the same manner as in Example 1. Table 1 shows the take-up surging generation rate and the film breakage rate, and the heat seal strength of the laminate (C).

[Example 4]
(Ring-opening polymerization)
In Example 1, the monomer was 245 parts by weight of NB, 5 parts by weight of dicyclopentadiene (hereinafter sometimes abbreviated as “DCP”), 1.75 parts by weight of 1-hexene and 1.90 parts by weight of VNB. A ring-opening copolymer (D) was obtained in the same manner as in Example 1 except for using a part. The polymerization conversion rate was almost 100%.
The ring-opening copolymer (D) had a weight average molecular weight (Mw) of 24,000 and a molecular weight distribution (Mw / Mn) of 2.9.

(Hydrogenation reaction)
In the same manner as in Example 1, the obtained ring-opening copolymer (D) was hydrogenated to obtain a ring-opening polymer hydride (D).

(Polymer physical properties)
The hydrogenation rate of the ring-opening polymer hydride (D) is 99.9%, the weight average molecular weight (Mw) is 24,800, the molecular weight distribution (Mw / Mn) is 2.6, the isomerization rate is 7%, The melting point was 126 ° C., the branching index was 0.71, and the MFR was 58.

(Preparation of resin composition)
A resin composition (D) was obtained from the obtained ring-opened polymer hydride (D) in the same manner as in Example 1.

(Extruded laminate molding)
A laminate (D) was obtained from the obtained resin composition (D) in the same manner as in Example 1. Table 1 shows the take-up surging generation rate and the film breakage rate, and the heat seal strength of the laminate (D).

[Example 5]
(Ring-opening polymerization)
In Example 1, a ring-opening copolymer (E) was obtained in the same manner as in Example 1 except that 240 parts by weight of NB, 10 parts by weight of DCP, and 2.52 parts by weight of VNB were used. . The polymerization conversion rate was almost 100%.
The ring-opening copolymer (E) had a weight average molecular weight (Mw) of 37,200 and a molecular weight distribution (Mw / Mn) of 3.5.

(Hydrogenation reaction)
In the same manner as in Example 1, the obtained ring-opening copolymer (E) was hydrogenated to obtain a ring-opening polymer hydride (E).

(Polymer physical properties)
The hydrogenation rate of the ring-opening polymer hydride (E) is 99.9%, the weight average molecular weight (Mw) is 38,500, the molecular weight distribution (Mw / Mn) is 3.0, the isomerization rate is 6%, The melting point was 130 ° C., the branching index was 0.67, and the MFR was 34.

(Preparation of resin composition)
Resin composition (E) was obtained from the obtained ring-opened polymer hydride (E) in the same manner as in Example 1.

(Extruded laminate molding)
A laminate (E) was obtained from the obtained resin composition (E) in the same manner as in Example 1. Table 1 shows the take-up surging generation rate and the film breakage rate, and the heat seal strength of the laminate (E).

[Comparative Example 1]
(Ring-opening polymerization)
A ring-opening copolymer (F) was obtained in the same manner as in Example 1 except that VNB was not added. The polymerization conversion rate was almost 100%.
The ring-opening copolymer (F) had a weight average molecular weight (Mw) of 36,200 and a molecular weight distribution (Mw / Mn) of 2.9.

(Hydrogenation reaction)
In the same manner as in Example 1, the obtained ring-opening copolymer (F) was hydrogenated to obtain a ring-opening polymer hydride (F).

(Polymer physical properties)
The hydrogenation rate of the ring-opening polymer hydride (F) is 99.9%, the weight average molecular weight (Mw) is 37,100, the molecular weight distribution (Mw / Mn) is 2.4, the isomerization rate is 7%, The melting point was 138 ° C., the branching index was 1.0, and the MFR was 48.

(Preparation of resin composition)
A resin composition (F) was obtained from the obtained ring-opening polymer hydride (F) in the same manner as in Example 1.

(Extruded laminate molding)
A laminate (F) was obtained from the obtained resin composition (F) in the same manner as in Example 1. Table 1 shows the take-up surging generation rate and the film breakage rate, and the heat seal strength of the laminate (F).

[Comparative Example 2]
(Ring-opening polymerization)
A ring-opening copolymer (G) was obtained in the same manner as in Example 1, except that 0.43 parts by weight of 1-hexene and 1.60 parts by weight of VNB were used. The polymerization conversion rate was almost 100%.
The ring-opening copolymer (G) had a weight average molecular weight (Mw) of 59,100 and a molecular weight distribution (Mw / Mn) of 6.7.

(Hydrogenation reaction)
In the same manner as in Example 1, the obtained ring-opening copolymer (G) was hydrogenated to obtain a ring-opening polymer hydride (G).

(Polymer physical properties)
The hydrogenation rate of the ring-opening polymer hydride (G) is 99.9%, the weight average molecular weight (Mw) is 68,200, the molecular weight distribution (Mw / Mn) is 5.2, the isomerization rate is 7%, The melting point was 136 ° C., the branching index was 0.77, and the MFR was 3.

(Preparation of resin composition)
A resin composition (H) was obtained from the obtained ring-opened polymer hydride (H) in the same manner as in Example 1.

(Extruded laminate molding)
A laminate (H) was obtained from the obtained resin composition (H) in the same manner as in Example 1. Table 1 shows the take-up surging generation rate and the film breakage rate, and the heat seal strength of the laminate (H).

[Comparative Example 3]
(Ring-opening polymerization)
A ring-opening copolymer (H) was obtained in the same manner as in Example 1 except that 6.38 parts by weight of VNB was used in Example 1. The polymerization conversion rate was almost 100%.
The ring-opening copolymer (H) had a weight average molecular weight (Mw) of 39,500 and a molecular weight distribution (Mw / Mn) of 2.8.

(Hydrogenation reaction)
In the same manner as in Example 1, the obtained ring-opening copolymer (H) was hydrogenated to obtain a ring-opening polymer hydride (H).

(Polymer physical properties)
The hydrogenation rate of the ring-opening polymer hydride (H) is 99.9%, the weight average molecular weight (Mw) is 40,600, the molecular weight distribution (Mw / Mn) is 2.3, the isomerization rate is 8%, The melting point was 126 ° C., the branching index was 0.15, and the MFR was 22.

(Preparation of resin composition)
A resin composition (H) was obtained from the obtained ring-opened polymer hydride (H) in the same manner as in Example 1.

(Extruded laminate molding)
A laminate (H) was obtained from the obtained resin composition (H) in the same manner as in Example 1.
Table 1 shows the take-up surging generation rate and the film breakage rate, and the heat seal strength of the laminate (H).

From Tables 1 and 2, the norbornene-based ring-opening polymer hydrides (A) to (E) in Examples 1 to 5 having a branching index in the range of 0.3 to 0.98 show the take-up surging generation rate and film breakage. It can be seen that the speed is high, the laminate formability is excellent, and the heat seal strength of the laminate is 20 N / 15 mm or more, and the heat seal property is excellent.
On the other hand, the linear ring-opening polymer hydride (F) having a branching index of greater than 0.98 in Comparative Example 1 had a high rate of filming surging but a low rate of take-up surging and was inferior in productivity.
In Comparative Example 2, the ring-opening polymer hydride (G) having a high molecular weight had a low film breaking rate, was inferior in production, and was inferior in heat sealability of the resulting laminate.
In Comparative Example 3, the ring-opened polymer hydride (H) in which the amount of the branching agent was increased and the branching index was reduced to 0.11, had a low film breakage rate and was inferior in laminate processability.
From the above, the resin composition for laminate and the laminate of the examples are excellent in terms of workability and heat sealability required in the recent information field, food field, medical field, civil engineering field, etc. I can say that.

Claims (3)

A norbornene monomer comprising 90 to 100% by weight of 2-norbornene and 0 to 10% by weight of 2-norbornene having a substituent not containing an aliphatic carbon-carbon double bond is used as the norbornene monomer. Melting point obtained by hydrogenating 80% or more of carbon-carbon double bonds of a ring-opening polymer obtained by ring-opening polymerization in the presence of 0.01 to 5 mol% of a branching agent with respect to 100 mol Is a crystalline norbornene ring-opening polymer hydride having a weight average molecular weight of 20,000 to 39,200 measured by gel permeation chromatography A resin composition for extrusion lamination, comprising: The resin composition for extrusion laminating according to claim 1 , wherein the branching agent is an alicyclic structure-containing monomer having a substituent containing an aliphatic carbon-carbon double bond at the terminal. . A laminate obtained by extrusion laminating the resin composition according to claim 1 or 2 to a base film.