WO2025204544A1 - Resin composition, method for producing same, and molded body - Google Patents

Abstract

The purpose of the present invention is to provide a resin composition capable of forming a molded body having excellent solvent resistance and heat sealability. The present invention provides a resin composition containing a crystalline norbornene-based ring-opened polymer hydride and an amorphous cyclic olefin-based polymer, wherein: the norbornene-based ring-opened polymer hydride is a ring-opened polymer hydride containing a norbornene-derived structural unit; the meso-dyad ratio of a cis-structural unit, which is represented by formula (I), contained in the norbornene-derived structural unit is less than 30%; and the mass ratio of the norbornene-based ring-opened polymer hydride to the cyclic olefin-based polymer is 75/25 to 95/5.

Description

Resin composition, method for producing the same, and molded article

The present invention relates to a resin composition, a method for producing the same, and a molded article.

A polymer (hydrogenated norbornene-based ring-opening polymer) obtained by hydrogenating a ring-opening polymer obtained by ring-opening polymerization of a monomer composition containing norbornene has an excellent balance of properties such as heat resistance, transparency, light resistance, low water absorbency, water vapor barrier property, chemical resistance, solvent resistance, dielectric properties, low birefringence, rigidity, and laser resistance, and is therefore used in a wide range of fields, such as optical materials, medical equipment, electrical insulating materials, and equipment for processing electronic components.
Here, studies have been conducted to further improve the performance of resin compositions containing hydrogenated norbornene ring-opening polymers.

For example, Patent Document 1 discloses a polymer composition containing a crystalline cyclic olefin polymer and an amorphous cyclic olefin polymer, each having a predetermined weight-average molecular weight, with the content of the crystalline cyclic olefin polymer falling within a predetermined range. According to Patent Document 1, the polymer composition has excellent transparency and solvent crack resistance.

Japanese Patent Application Laid-Open No. 2007-016102

However, the above-mentioned conventional compositions leave room for further improvement in terms of improving the solvent resistance (solvent resistance) of the resulting molded article, as well as increasing the seal strength of the heat-sealed portion of the molded article (improving heat sealability).

Therefore, an object of the present invention is to provide a resin composition capable of forming a molded article having excellent solvent resistance and heat sealability, and a method for producing the same.
Another object of the present invention is to provide a molded article having excellent solvent resistance and heat sealability.

The present inventors conducted extensive research with the aim of solving the above problems. They discovered that by using a resin composition containing a crystalline hydrogenated norbornene ring-opening polymer having specified properties and an amorphous cyclic olefin polymer in a specified ratio, it is possible to form a molded article with excellent solvent resistance and heat sealability, and thus completed the present invention.

In other words, the object of this invention is to advantageously solve the above problems, and the present invention provides the following resin compositions [1] to [6], the following molded article [7], and the following method for producing the resin composition [8].

[1] A resin composition comprising a crystalline hydrogenated norbornene ring-opening polymer and an amorphous cyclic olefin polymer, wherein the hydrogenated norbornene ring-opening polymer is a hydrogenated ring-opening polymer containing a structural unit derived from norbornene, and the norbornene-derived structural unit contains a compound represented by the following formula (I):
and the mass ratio of the hydrogenated norbornene ring-opening polymer to the cyclic olefin polymer (hydrogenated norbornene ring-opening polymer/cyclic olefin polymer) is 75/25 or more and 95/5 or less.
In this way, by using a resin composition in which the mass ratio of the crystalline norbornene-based hydrogenated ring-opening polymer to the amorphous cyclic olefin polymer is within the above-mentioned range and the ratio of meso-dyads of structural units having a cis-1,3-cyclopentane structure represented by formula (I) (hereinafter, may be referred to as "cis structural units (I)") contained in the norbornene-derived structural units in the norbornene-based hydrogenated ring-opening polymer is less than the above-mentioned value, a molded article having excellent solvent resistance and heat sealability can be obtained.
In the present invention, the "proportion of meso dyads" of the cis structural unit (I) can be obtained as the proportion of the signal intensity of meso dyads to the total signal intensity of meso dyads and racemo dyads observed in ^13C -NMR measurement. More specifically, the "proportion of meso dyads" of the "structural unit having a cis-1,3-cyclopentane structure represented by formula (I)" can be determined using the method described in the Examples of this specification.
In the present invention, a polymer being "crystalline" means that its melting point can be observed by differential scanning calorimetry (DSC) by optimizing the measurement conditions, etc., and a polymer being "amorphous" means that its melting point cannot be observed by differential scanning calorimetry (DSC). The "crystalline" and "amorphous" properties of a polymer are determined by the stereoregularity of the polymer chain.

[2] The resin composition according to [1] above, wherein the hydrogenated norbornene ring-opening polymer contains 90% by mass or more of the structural units derived from norbornene.
When the hydrogenated norbornene ring-opening polymer contains 90% by mass or more of structural units derived from norbornene, the heat resistance can be improved.
In the present invention, the proportion of each structural unit in all structural units of the polymer can be determined by NMR (nuclear magnetic resonance) measurement such as ¹ H-NMR measurement.

[3] The resin composition according to [1] or [2] above, wherein the glass transition temperature of the cyclic olefin polymer is 60°C or higher and 110°C or lower.
When the glass transition temperature of the cyclic olefin polymer is within the above range, the heat sealability of the molded article can be further improved, and the heat resistance of the cyclic olefin polymer can be sufficiently ensured.
In the present invention, the "glass transition temperature" can be measured using the method described in the examples of this specification.

[4] The hydrogenated norbornene ring-opening polymer further has the following formula (II):
The resin composition according to any one of [1] to [3] above, which contains structural units having a trans-1,3-cyclopentane structure represented by the following formula:
When the ratio of the trans structural unit (II) to the total of the cis structural unit (I) and the structural unit having a trans-1,3-cyclopentane structure represented by the above formula (II) (hereinafter, sometimes referred to as the "trans structural unit (II)") (hereinafter, this ratio may be referred to as the "isomerization rate") is within the above-mentioned range, the heat sealability of the molded article can be further improved.
In the present invention, the ratio of the trans structural unit (II) to the total of the cis structural unit (I) and the trans structural unit (II) (isomerization ratio) can be determined by ^13C -NMR measurement. More specifically, the isomerization ratio can be determined by the method described in the Examples of this specification.

[5] The resin composition according to any one of [1] to [4] above, wherein the weight average molecular weight of the hydrogenated norbornene ring-opening polymer is 60,000 or more and 200,000 or less.
When the weight-average molecular weight of the hydrogenated norbornene ring-opening polymer is within the above-mentioned range, the heat-sealability of the molded article can be further improved, and an excessive increase in the viscosity of the resin composition can be suppressed, thereby ensuring sufficient processability of the resin composition.
In the present invention, the "weight average molecular weight" is a value measured by gel permeation chromatography (GPC), and specifically, it can be measured using the method described in the examples of this specification.

[6] The resin composition according to any one of [1] to [5] above, wherein the melting point of the hydrogenated norbornene ring-opening polymer is 110°C or higher and 150°C or lower.
When the melting point of the hydrogenated norbornene ring-opening polymer is within the above-mentioned range, the heat sealability of the molded article can be further improved, and the heat resistance of the hydrogenated norbornene ring-opening polymer can be sufficiently ensured.
In the present invention, the "melting point" can be measured by a differential scanning calorimeter, for example, by the method described in the examples of this specification.

[7] A molded article formed using the resin composition according to any one of [1] to [6] above.
The molded article obtained by molding the above-mentioned resin composition has excellent solvent resistance and heat sealability.

[8] A method for producing the resin composition according to any one of [1] to [6] above, comprising a step of kneading the hydrogenated norbornene ring-opening polymer and the cyclic olefin polymer to obtain the resin composition.
By going through the above-mentioned steps, it is possible to satisfactorily prepare the resin composition of the present invention, which can provide a molded article having excellent solvent resistance and heat sealability.

According to the present invention, it is possible to provide a resin composition capable of forming a molded article having excellent solvent resistance and heat sealability, and a method for producing the same.
Furthermore, according to the present invention, a molded article having excellent solvent resistance and heat sealability can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
The resin composition of the present invention can be used in various fields as a resin material for constituting various molded articles (particularly films, sheets, and bioreactor bags). The resin composition of the present invention can be produced using the method for producing a resin composition of the present invention. The molded article of the present invention can be obtained by molding the resin composition of the present invention.

(Resin composition)
The resin composition of the present invention contains a hydrogenated norbornene ring-opening polymer and a cyclic olefin polymer, and may optionally further contain components (other components) other than the hydrogenated norbornene ring-opening polymer and the cyclic olefin polymer.
The resin composition of the present invention is characterized in that the hydrogenated norbornene ring-opening polymer is crystalline, the cyclic olefin polymer is amorphous, the mass ratio of the hydrogenated norbornene ring-opening polymer to the cyclic olefin polymer is 75/25 or more and 95/5 or less, and the proportion of meso-dyads in the hydrogenated norbornene ring-opening polymer is less than 30%.

<Hydrogenated norbornene ring-opening polymer>
The norbornene-based hydrogenated ring-opening polymer is a hydrogenated ring-opening polymer containing structural units derived from norbornene. The norbornene-based hydrogenated ring-opening polymer must be crystalline. The norbornene-based structural units include at least cis structural units (I) represented by the following formula (I), which are obtained by hydrogenating norbornene units, and optionally trans structural units (II) represented by the following formula (II).

<<Structural units>>
As described above, the hydrogenated norbornene ring-opening polymer contains at least a structural unit derived from norbornene, and may optionally contain a structural unit derived from a monomer other than norbornene (another monomer).

[Structural units derived from norbornene]
The hydrogenated norbornene ring-opening polymer preferably contains norbornene-derived structural units in an amount of 90% by mass or more, more preferably 93% by mass or more, even more preferably 96% by mass or more, and particularly preferably 99% by mass or more, of which total structural units are 100% by mass. When the proportion of norbornene-derived structural units in the total structural units of the hydrogenated norbornene ring-opening polymer is 90% by mass or more, heat resistance can be improved. Furthermore, from the viewpoint of obtaining a crystalline hydrogenated norbornene ring-opening polymer, the proportion of norbornene-derived structural units in the total structural units of the hydrogenated norbornene ring-opening polymer is preferably 90% by mass or more.
The upper limit of the proportion of norbornene-derived structural units in all structural units of the hydrogenated norbornene ring-opening polymer is not particularly limited, and can be 100% by mass or less.

[Other structural units]
The other monomers that can be used to prepare the hydrogenated norbornene ring-opening polymers are not particularly limited as long as they are capable of ring-opening copolymerization with norbornene. Examples of the other monomers include monomers other than norbornene that have a norbornene skeleton (hereinafter referred to as "norbornene monomers"). The other monomers may be used alone or in combination of two or more.

Here, norbornene-based monomers include norbornene-based monomers that do not have a ring fused with a norbornene ring (non-fused ring norbornene-based monomers), and norbornene-based monomers that have a ring fused with a norbornene ring (fused ring norbornene-based monomers).

-Non-condensed ring norbornene monomers-
Examples of the non-condensed ring-forming norbornene monomer include norbornenes having an alkyl group such as 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5-cyclohexylnorbornene, and 5-cyclopentylnorbornene; norbornenes having an alkenyl group such as 5-ethylidenenorbornene, 5-vinylnorbornene, 5-propenylnorbornene, 5-cyclohexenylnorbornene, and 5-cyclopentenylnorbornene; norbornenes having an aromatic ring such as 5-phenylnorbornene; 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, and 5-ethoxycarbonylnorbornene. norbornene having a polar group containing an oxygen atom, such as norbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-methylpropionate, norbornenyl-2-methyloctanate, 5-hydroxymethylnorbornene, 5,6-di(hydroxymethyl)norbornene, 5,5-di(hydroxymethyl)norbornene, 5-hydroxyisopropylnorbornene, 5,6-dicarboxynorbornene, and 5-methoxycarbonyl-6-carboxynorbornene; and norbornenes having a polar group containing a nitrogen atom, such as 5-cyanonorbornene. These may be used alone or in combination of two or more.

-Fused ring-forming norbornene monomers-
Examples of the fused ring-forming norbornene monomer include monomers represented by the following formulae (III) and (IV).

In the above formula (III), ^R1 and ^R2 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent containing a silicon atom, an oxygen atom, or a nitrogen atom (excluding those which fall under the category of hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent), and may be bonded to each other to form a ring. ^R3 is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

In the above formula (IV), ^R4 , ^R5 , ^R6 , and ^R7 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 20 carbon atoms which may have a substituent, or a substituent containing a silicon atom, an oxygen atom, or a nitrogen atom (excluding those which fall under the category of hydrocarbon groups having from 1 to 20 carbon atoms which may have a substituent), and ^R4 and ^R6 may be bonded to each other to form a ring. m is 1 or 2.

Examples of the monomer represented by formula (III) include dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, tricyclo[5.2.1.0 ^2,6 ]dec-8-ene, 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), and 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). These may be used alone or in combination of two or more.

Examples of the monomer represented by formula (IV) above include tetracyclododecenes where m is 1 and hexacycloheptadecenes where m is 2.

Tetracyclododecenes (m = 1) include, for example, tetracyclododecene; tetracyclododecenes having an alkyl group such as 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and 8-cyclopentyltetracyclododecene; tetracyclododecenes having an exocyclic double bond such as 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, and 8-cyclopentenyltetracyclododecene; tetracyclododecenes having an aromatic ring such as 8-phenyltetracyclododecene; 8-methoxycarbonyltetracyclododecene; Examples of suitable tetracyclododecenes include tetracyclododecene having a substituent containing an oxygen atom, such as tetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, and tetracyclododecene-8,9-dicarboxylic anhydride; tetracyclododecenes having a substituent containing a nitrogen atom, such as 8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboxylic imide; tetracyclododecenes having a substituent containing a halogen atom, such as 8-chlorotetracyclododecene; and tetracyclododecenes having a substituent containing a silicon atom, such as 8-trimethoxysilyltetracyclododecene. These may be used alone or in combination of two or more.

Hexacycloheptadecenes (m = 2) include, for example, hexacycloheptadecene; hexacycloheptadecenes having alkyl groups such as 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, and 12-cyclopentylhexacycloheptadecene; 12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene, and Hexacycloheptadecenes having a double bond outside the ring, such as 12-hexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexacycloheptadecene, and 12-cyclopentenylhexacycloheptadecene; hexacycloheptadecenes having an aromatic ring, such as 12-phenylhexacycloheptadecene; 12-methoxycarbonylhexacycloheptadecene, 12-methylhexacycloheptadecene, and 12-methylhexacycloheptadecene; Hexacycloheptadecenes having a substituent containing an oxygen atom, such as 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene-12,13-dicarboxylic acid, and hexacycloheptadecene-12,13-dicarboxylic acid anhydride; hexacycloheptadecenes having a substituent containing a nitrogen atom (excluding those containing an oxygen atom), such as 12-cyanohexacycloheptadecene and hexacycloheptadecene-12,13-dicarboxylic acid imide; hexacycloheptadecenes having a substituent containing a halogen atom, such as 12-chlorohexacycloheptadecene; and hexacycloheptadecenes having a substituent containing a silicon atom (excluding those containing an oxygen atom), such as 12-trimethoxysilylhexacycloheptadecene.

Among these, dicyclopentadiene is preferred. That is, when the hydrogenated ring-opening polymer of the present invention contains structural units derived from other monomers, the structural units derived from the other monomers are preferably structural units derived from dicyclopentadiene.

<<Properties>>
[Meso-Dyad Ratio]
The norbornene-based ring-opening polymer hydrogenation product must have a meso-dyad ratio of the cis structural unit (I) contained in the norbornene-derived structural unit of less than 30%. If the meso-dyad ratio of the cis structural unit (I) is 30% or more, the stereoregularity of the molecular chain portion formed by the cis structural unit (I) in the norbornene-based ring-opening polymer hydrogenation product is reduced (i.e., the molecular chain portion formed by the cis structural unit (I) has an atactic structure). It is presumed that such a reduction in stereoregularity is involved, and if the meso-dyad ratio of the cis structural unit (I) is 30% or more, the heat-sealing property of the resin composition is reduced. On the other hand, if the meso-dyad ratio of the cis structural unit (I) is less than 30% (i.e., the molecular chain portion formed by the cis structural unit (I) has a syndiotactic structure), the resin composition can have excellent heat-sealing property.
The proportion of meso-dyads of the cis structural unit (I) can be, for example, 0% or more, 10% or more, 15% or more, or 20% or more, and can be 29% or less, 28% or less, or 27% or less.
The meso-dyad ratio of the cis structural unit (I) in the hydrogenated norbornene ring-opening polymer can be adjusted by changing the method for producing the hydrogenated norbornene ring-opening polymer, for example, by changing the type of ring-opening polymerization catalyst used in preparing the norbornene ring-opening polymer, which is a precursor of the hydrogenated norbornene ring-opening polymer.

[Isomerization rate]
In the hydrogenated norbornene ring-opening polymer, the proportion of trans structural units (II) in the total of cis structural units (I) and trans structural units (II) (isomerization rate) is preferably 0.5% or more, more preferably 2% or more, even more preferably more than 5%, and is preferably 30% or less, more preferably 25% or less, even more preferably 23% or less, and particularly preferably 20% or less. When the isomerization rate is within the above range, the heat-sealability of the resin composition can be further improved.
The isomerization rate of the hydrogenated norbornene ring-opening polymer can be adjusted by changing the method for producing the hydrogenated norbornene ring-opening polymer, for example, by changing the type and/or amount of the hydrogenation catalyst used when subjecting the precursor norbornene ring-opening polymer to a hydrogenation reaction.

[Weight average molecular weight]
The weight-average molecular weight of the norbornene ring-opening polymer hydrogenated product is preferably 60,000 or more, more preferably 65,000 or more, and even more preferably 70,000 or more, and is preferably 200,000 or less, more preferably 150,000 or less, still more preferably 90,000 or less, and particularly preferably 80,000 or less. If the weight-average molecular weight of the norbornene ring-opening polymer hydrogenated product is 60,000 or more, the heat-sealability of the resin composition can be further improved. On the other hand, if the weight-average molecular weight of the norbornene ring-opening polymer hydrogenated product is 200,000 or less, the viscosity of the resin composition can be prevented from excessively increasing, and the processability of the resin composition can be sufficiently ensured.
The weight-average molecular weight of the hydrogenated norbornene ring-opening polymer can be adjusted by changing the method for producing the hydrogenated norbornene ring-opening polymer, for example, by changing the type and/or amount of a ring-opening polymerization catalyst, a molecular weight modifier, etc., used when preparing the norbornene ring-opening polymer, which is a precursor of the hydrogenated norbornene ring-opening polymer.

[Melting point]
The hydrogenated norbornene ring-opening polymer must be crystalline, i.e., when the hydrogenated norbornene ring-opening polymer is subjected to differential scanning calorimetry (DSC), the melting point must be observable by optimizing the measurement conditions.
The melting point of the hydrogenated norbornene ring-opening polymer is preferably 110° C. or higher, more preferably 120° C. or higher, and even more preferably 130° C. or higher, and is preferably 150° C. or lower, and more preferably 140° C. or lower. If the melting point of the hydrogenated norbornene ring-opening polymer is 110° C. or higher, the heat resistance of the hydrogenated norbornene ring-opening polymer can be sufficiently ensured. On the other hand, if the melting point of the hydrogenated norbornene ring-opening polymer is 150° C. or lower, the heat sealability of the molded article can be further improved.
The melting point of the hydrogenated norbornene ring-opening polymer can be adjusted by changing the method for producing the hydrogenated norbornene ring-opening polymer, for example, by changing the type and/or amount of a monomer having a norbornene skeleton other than norbornene when preparing the norbornene ring-opening polymer, which is a precursor of the hydrogenated norbornene ring-opening polymer.

[Hydrogenation rate]
The hydrogenation rate of the hydrogenated norbornene ring-opening polymer (the proportion of hydrogenated carbon-carbon double bonds in the precursor norbornene ring-opening polymer) is usually 90% or more, preferably 95% or more, and more preferably 99% or more.
In the present invention, the hydrogenation rate of the hydrogenated norbornene ring-opening polymer can be determined by ¹ H-NMR measurement.
The hydrogenation rate of the hydrogenated norbornene ring-opening polymer can be adjusted, for example, by changing the conditions of the hydrogenation reaction.

<<Method for preparing hydrogenated norbornene ring-opening polymer>>
The hydrogenated norbornene ring-opening polymer can be prepared by ring-opening polymerizing a monomer composition containing norbornene and subjecting the resulting norbornene ring-opening polymer to a hydrogenation reaction. After the hydrogenation reaction, post-treatment may be carried out as necessary.

<<Ring-opening polymerization>>
The ring-opening polymerization of the monomer composition containing norbornene can be carried out using a ring-opening polymerization catalyst. During the ring-opening polymerization, a polymerization aid such as a molecular weight modifier may be added to the polymerization system. The ring-opening polymerization may be carried out in the absence of a solvent or in the presence of a solvent.

[Ring-opening polymerization catalyst]
The ring-opening polymerization catalyst is not particularly limited as long as it is capable of ring-opening polymerization of a monomer composition containing norbornene and can produce a norbornene-based ring-opening polymer that can be used as a precursor to a hydrogenated norbornene-based ring-opening polymer having predetermined properties. However, from the viewpoint of efficiently producing a hydrogenated norbornene-based ring-opening polymer having a meso-dyad ratio of less than a predetermined value, a ring-opening polymerization catalyst that can impart stereoregularity to the norbornene-based ring-opening polymer is preferred as the ring-opening polymerization catalyst used to prepare the norbornene-based ring-opening polymer. Examples of ring-opening polymerization catalysts that can impart stereoregularity to norbornene-based ring-opening polymers include complex catalysts containing a transition metal of Group 6 of the periodic table (e.g., those described in JP 2007-137935 A, JP 2002-249553 A, WO 2015/127192 A, and Macromolecules, 2015, 48 (8), pp. 2480-2492).

- Complex catalyst containing transition metals from Group 6 of the periodic table -
Examples of transition metals of Group 6 of the periodic table contained in the complex catalyst (as a central atom) include chromium, tungsten, and molybdenum, with tungsten and molybdenum being preferred.

More specifically, complex catalysts containing transition metals of Group 6 of the periodic table include tungsten(ethylimide)(tetrachloride)(diethyl ether), tungsten(ethylimide)(t-butoxide)(trichloride), tungsten(ethylimide)[di(t-butoxide)](dichloride), tungsten(ethylimide)[tri(t-butoxide)](chloride), tungsten(ethylimide)[tetra(t-butoxide)], tungsten(ethylimide)(phenoxide)(tetrachloride)(diethyl ether), tungsten(n-butylimide)(tetrachloride)(tetrahydrofuran), tungsten(n-hexylimide)(tetrachloride)(diethyl ether), tungsten(n-hexylimide)(tetrachloride)(diethyl ether), tungsten(n-butylimide)(phenoxide)(tetrachloride)(tetrahydrofuran ... Examples include tungsten(i-propylimide)(tetrachloride)(diethyl ether), tungsten(cyclohexylimide)(tetrachloride)(diethyl ether), tungsten(adamantylimide)(tetrachloride)(diethyl ether), tungsten(benzylimide)(tetrachloride)(diethyl ether), tungsten(phenylimide)(tetrachloride)(diethyl ether), tungsten(phenylimide)(tetrachloride)(tetrahydrofuran), tungsten(2,6-dimethylphenylimide)(tetrachloride)(diethyl ether), and tungsten[2,6-di(i-propyl)(phenylimide)](tetrachloride)(diethyl ether).

Furthermore, complex catalysts containing transition metals from Group 6 of the periodic table include bis{3,3'-di(t-butyl)-5,5',6,6'-tetramethyl-2,2'-biphenoxy}oxymolybdenum(VI), bis{3,3',5,5'-tetramethyl-2,2'-biphenoxy}oxymolybdenum(VI), and {3,3'-di(t-butyl)-5,5',6,6'-tetramethyl-2,2'-biphenoxy}oxymolybdenum(VI). dichloride, bis{3,3'-diphenyl-1,1'-binaphthyl-2,2'-dioxy}oxymolybdenum(VI), {3,3'-diphenyl-1,1'-binaphthyl-2,2'-dioxy}oxymolybdenum(VI) dichloride, bis{3,3'-di(t-butyl)-5,5',6,6'-tetramethyl-2,2'-biphenoxy}oxytungsten(VI), {3,3'-di(t-butyl)-5,5',6, 6'-tetramethyl-2,2'-biphenoxy}oxytungsten(VI) dichloride, bis{3,3'-diphenyl-1,1'-binaphthyl-2,2'-dioxy}oxytungsten(VI), {3,3'-diphenyl-1,1'-binaphthyl-2,2'-dioxy}oxytungsten(VI) dichloride, bis{3,3'-di(t-butyl)-5,5',6,6'-tetramethyl-2,2'-biphenoxy}oxytungsten(VI) }tungsten(VI) dichloride, {3,3'-di(t-butyl)-5,5',6,6'-tetramethyl-2,2'-biphenoxy}tungsten(VI) tetrachloride, bis{3,3'-diphenyl-1,1'-binaphthyl-2,2'-dioxy}tungsten(VI) dichloride, {3,3'-diphenyl-1,1'-binaphthyl-2,2'-dioxy}tungsten(VI) tetrachloride.

Furthermore, an example of a complex catalyst containing a transition metal of Group 6 of the periodic table is a complex catalyst represented by the following formula (V):

The complex catalyst containing a transition metal from Group 6 of the periodic table may be used alone or in combination of two or more. Tungsten (phenylimide) (tetrachloride) (tetrahydrofuran) is particularly preferred as a complex catalyst containing a transition metal from Group 6 of the periodic table.

-Cocatalyst-
As the ring-opening polymerization catalyst, it is preferable to use the above-mentioned complex catalyst containing a transition metal of Group 6 of the periodic table in combination with a co-catalyst other than the complex catalyst in order to enhance catalytic activity.

The co-catalyst may be a known organometallic compound. As the organometallic compound, an organometallic compound belonging to any of Groups 1, 2, 12, 13, and 14 of the Periodic Table, having a hydrocarbon group containing from 1 to 20 carbon atoms, is preferred; organolithium compounds, organomagnesium compounds, organozinc compounds, organoaluminum compounds, and organotin compounds are more preferred, with organoaluminum compounds being particularly preferred.

Examples of the organolithium compound include n-butyllithium, methyllithium, phenyllithium, neopentyllithium, and neophyllithium.
Examples of the organic magnesium compound include butylethyl magnesium, butyloctyl magnesium, dihexyl magnesium, ethyl magnesium chloride, n-butyl magnesium chloride, allyl magnesium bromide, neopentyl magnesium chloride, and neophyl magnesium chloride.
The organic zinc compounds include dimethyl zinc, diethyl zinc, and diphenyl zinc.
Examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, diethylaluminum ethoxide, ethylaluminum dichloride, ethylaluminum diethoxide, etc. Among these, diethylaluminum ethoxide is preferred.
Examples of the organotin compound include tetramethyltin, tetra(n-butyl)tin, and tetraphenyltin.

The co-catalyst may be used alone or in combination of two or more types.

[Molecular weight modifier]
Examples of molecular weight modifiers that can be optionally used in the ring-opening polymerization include vinyl compounds and diene compounds.

The vinyl compound is not particularly limited as long as it is an organic compound having a vinyl group and not corresponding to the diene compounds described below. Examples thereof include α-olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene, etc.; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, i-butyl vinyl ether, allyl glycidyl ether, etc.; halogen-containing vinyl compounds such as allyl chloride; oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol, glycidyl methacrylate, etc.; nitrogen-containing vinyl compounds such as acrylamide, etc.; silicon-containing vinyl compounds such as vinyltrimethylsilane, vinyltrimethoxysilane, etc.
Examples of the diene compound include non-conjugated dienes such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, and 2,5-dimethyl-1,5-hexadiene; and conjugated dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene.
The molecular weight modifier may be used alone or in combination of two or more. The molecular weight modifier is preferably an α-olefin, more preferably 1-hexene.

[solvent]
The ring-opening polymerization is preferably carried out in a solvent, particularly an organic solvent, from the viewpoint of being able to well control the reaction.
The organic solvent used is not particularly limited as long as it can dissolve or disperse the resulting norbornene-based ring-opening polymer and is inert to the polymerization reaction. Specific examples include aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindenecyclohexane, and cyclooctane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbon solvents such as dichloromethane, chloroform, and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene; nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene, and acetonitrile; ether solvents such as diethyl ether and tetrahydrofuran; and aromatic ether solvents such as anisole and phenetole. The solvents may be used alone or in combination of two or more. As the solvent, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ether solvents, or aromatic ether solvents are particularly preferred.

[Conditions for ring-opening polymerization]
The conditions for the ring-opening polymerization (such as the amounts of the above-mentioned components used, the polymerization time, and the polymerization temperature) are not particularly limited and can be appropriately set depending on the desired physical properties of the norbornene ring-opening polymer and the hydrogenated norbornene ring-opening polymer.

<<Hydrogenation reaction>>
The norbornene ring-opening polymer obtained through the ring-opening polymerization can be subjected to a hydrogenation reaction to obtain a hydrogenated norbornene ring-opening polymer. Here, the hydrogenation reaction can be carried out, for example, by supplying hydrogen gas to a polymer solution (or polymer dispersion) containing the norbornene ring-opening polymer obtained after the ring-opening polymerization and a solvent in the presence of a hydrogenation catalyst.
The solvent used in the hydrogenation reaction is not particularly limited, and for example, the solvent (particularly the organic solvent) used in the ring-opening polymerization can be used as is.

[Hydrogenation catalyst]
The hydrogenation catalyst is not particularly limited, and those generally used in the hydrogenation reaction of olefin compounds can be used. For example, Ziegler catalysts consisting of a combination of a transition metal compound and an alkali metal compound, such as cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, or tetrabutoxytitanate and dimethylmagnesium; dichlorotris Examples of such catalysts include homogeneous catalysts such as (triphenylphosphine)rhodium and noble metal complex catalysts comprising ruthenium compounds described in JP-A Nos. 7-2929, 7-149823, 11-209460, 11-158256, 11-193323, and 11-209460; and supported heterogeneous catalysts in which a metal such as nickel, palladium, platinum, rhodium, or ruthenium is supported on a carrier such as carbon, silica, diatomaceous earth, alumina, or titanium oxide.

The hydrogenation catalyst may be used alone or in combination of two or more. A supported heterogeneous catalyst is preferred as the hydrogenation catalyst, since the hydrogenation catalyst can be easily removed by filtering the reaction solution after the hydrogenation reaction.
Specific preferred examples of supported heterogeneous catalysts include combinations of nickel/silica, nickel/diatomaceous earth, nickel/alumina, palladium/carbon, palladium/silica, palladium/diatomaceous earth, and palladium/alumina.

[Hydrogenation reaction conditions]
The conditions for the hydrogenation reaction (such as the amount of hydrogenation catalyst used, reaction time, reaction temperature, and hydrogen pressure) are not particularly limited and can be appropriately set depending on the desired physical properties of the hydrogenated norbornene ring-opening polymer (for example, the hydrogenation rate and the isomerization rate).

<<Post-processing>>
After the ring-opening polymerization and hydrogenation reaction described above, post-treatment can be carried out as necessary to satisfactorily isolate the desired hydrogenated norbornene ring-opening polymer. For example, when a heterogeneous catalyst is used, the hydrogenation reaction is filtered to remove the hydrogenation catalyst, followed by coagulation drying or direct drying using a thin-film dryer or the like. When a homogeneous catalyst is used as the hydrogenation catalyst, after the hydrogenation reaction, alcohol or water is added to deactivate the catalyst, making it insoluble in the solvent, and then filtering is carried out to remove the catalyst. The hydrogenated norbornene ring-opening polymer can usually be obtained in the form of a powder or pellets.

<Cyclic olefin polymer>
The cyclic olefin polymer is not particularly limited as long as it is an amorphous polymer obtained by polymerizing a cyclic olefin.

Specific examples of cyclic olefin polymers include copolymers of cyclic olefins and linear olefins, ring-opening polymers of cyclic olefins, and hydrogenated ring-opening polymers of cyclic olefins.

<<Copolymer of Cyclic Olefin and Chain Olefin>>
The copolymer of a cyclic olefin and a chain olefin is usually a polymer obtained by addition copolymerization of a cyclic olefin and a chain olefin.

Specific examples of cyclic olefins include norbornene and norbornene-based monomers described above in the section "Norbornene-based ring-opening polymer hydrogenation products."

Specific examples of chain olefins are not particularly limited as long as they are copolymerizable with the above-mentioned cyclic olefins, and include linear or branched olefins having 2 to 20 carbon atoms, such as ethylene, propylene, butene, pentene, hexene, butadiene, pentadiene, and hexadiene.

The method for preparing the copolymer of a cyclic olefin and a chain olefin is not particularly limited, and any of the known methods for copolymerizing the above-mentioned cyclic olefin and a chain olefin can be used.

<<Ring-opening polymer of cyclic olefin>>
The ring-opening polymer of a cyclic olefin is a polymer obtained by ring-opening polymerization of one or more types of cyclic olefins.
As the cyclic olefin, the same cyclic olefins as those used in the preparation of the above-mentioned copolymer of a cyclic olefin and a chain olefin can be used.
The method for preparing the ring-opening polymer of the cyclic olefin is not particularly limited, and any known method for ring-opening polymerization of the above-mentioned cyclic olefin, such as metathesis polymerization, can be used.

<<Hydrogenated Ring-Opening Polymer of Cyclic Olefin>>
The hydrogenated product of the ring-opening polymer of a cyclic olefin is obtained by hydrogenating the above-mentioned ring-opening polymer of a cyclic olefin.
The method for hydrogenating the ring-opening polymer of a cyclic olefin is not particularly limited, and any known method can be used. For example, a method may be used in which a known hydrogenation catalyst containing a transition metal such as nickel or palladium is added to a solution of the ring-opening polymer of a cyclic olefin to hydrogenate the carbon-carbon double bonds in the ring-opening polymer.

In order to further enhance the solvent resistance and heat sealability of the molded article, the cyclic olefin polymer is preferably a hydrogenated product of a ring-opening polymer of a cyclic olefin, and more preferably a hydrogenated product of a ring-opening polymer containing structural units derived from norbornene and structural units derived from a condensed ring-forming norbornene monomer.

[Structural units derived from norbornene]
The cyclic olefin polymer preferably contains norbornene-derived structural units in an amount of 50% by mass or less, more preferably 48% by mass or less, based on 100% by mass of all structural units. If the proportion of norbornene-derived structural units in all structural units of the cyclic olefin polymer is 50% by mass or less, the transparency of the molded article can be improved while further improving the heat sealability. Furthermore, from the viewpoint of obtaining an amorphous cyclic olefin polymer, the proportion of norbornene-derived structural units in all structural units of the cyclic olefin polymer is preferably 50% by mass or less.
The lower limit of the proportion of norbornene-derived structural units in all structural units of the cyclic olefin polymer is not particularly limited, and can be, for example, 0% by mass or more, 5% by mass or more, or 10% by mass or more.

[Structural units derived from condensed ring-forming norbornene-based monomers]
As the condensed ring-forming norbornene monomer, dicyclopentadiene and tetracyclododecenes are preferred from the viewpoint of excellent moldability.
Furthermore, the cyclic olefin polymer preferably contains structural units derived from condensed ring-forming norbornene monomers in an amount of more than 50% by mass, and more preferably 52% by mass or more, based on 100% by mass of all structural units. When the proportion of structural units derived from condensed ring-forming norbornene monomers in all structural units of the cyclic olefin polymer exceeds 50% by mass, the transparency of the molded article can be improved and the heat sealability can be further enhanced.
The upper limit of the proportion of structural units derived from fused ring-forming norbornene monomers in all structural units of the cyclic olefin polymer is not particularly limited, and can be, for example, 100% by mass or less, 95% by mass or less, or 90% by mass or less.

<<Properties>>
[Glass transition temperature]
The glass transition temperature of the cyclic olefin polymer is preferably 60° C. or higher, more preferably 65° C. or higher, and preferably 150° C. or lower, more preferably 120° C. or lower, even more preferably 110° C. or lower, and particularly preferably 90° C. or lower. If the glass transition temperature of the cyclic olefin polymer is 60° C. or higher, the heat resistance of the cyclic olefin polymer can be sufficiently ensured. On the other hand, if the glass transition temperature of the cyclic olefin polymer is 150° C. or lower, the heat sealability of the molded article can be further improved.
The glass transition temperature of the cyclic olefin polymer can be adjusted, for example, by changing the type and amount of the monomer used in preparing the cyclic olefin polymer.

[Weight average molecular weight]
The weight-average molecular weight of the cyclic olefin polymer is preferably 20,000 or more, more preferably 25,000 or more, and even more preferably 30,000 or more, and is preferably 150,000 or less, more preferably 100,000 or less, and even more preferably 60,000 or less. If the weight-average molecular weight of the cyclic olefin polymer is 20,000 or more, sufficient mechanical strength can be imparted to the molded article. Furthermore, if the weight-average molecular weight of the cyclic olefin polymer is 150,000 or less, molding processing can be easily performed.

<Other ingredients>
The other components are not particularly limited, and examples thereof include polymers other than the above-mentioned hydrogenated norbornene ring-opening polymers and cyclic olefin polymers (such as thermoplastic elastomers), fillers, antioxidants such as tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl], release agents, flame retardants, antibacterial agents, wood flour, coupling agents, plasticizers, colorants, lubricants, silicone oil, foaming agents, surfactants, light stabilizers, dispersing aids, heat stabilizers, ultraviolet absorbers, antistatic agents, dispersants, chlorine scavengers, crystallization nucleating agents, antifogging agents, organic fillers, neutralizing agents, decomposing agents, metal deactivators, and antifouling agents. One type of the other components may be used alone, or two or more types may be used in combination.

The mass ratio of norbornene-based ring-opening polymer hydrogenation to cyclic olefin-based polymer in the resin composition (norbornene-based ring-opening polymer hydrogenation/cyclic olefin-based polymer) is preferably 75/25 or more, more preferably 80/20 or more, even more preferably 85/15 or more, and preferably 95/5 or less, more preferably 90/10 or less. If the norbornene-based ring-opening polymer hydrogenation/cyclic olefin-based polymer ratio is 75/25 or more, the solvent resistance of the molded article can be further improved. On the other hand, if the norbornene-based ring-opening polymer hydrogenation/cyclic olefin-based polymer ratio is 95/5 or less, the heat sealability of the molded article can be further improved and the haze value of the molded article can be reduced.

(Method for producing resin composition)
The method for producing a resin composition of the present invention includes at least a step (kneading step) of kneading a hydrogenated norbornene ring-opening polymer and a cyclic olefin polymer to obtain a resin composition.
The method for producing a resin composition of the present invention may further include a step (other step) other than the kneading step.

<Kneading process>
In the kneading step, the norbornene-based hydrogenated ring-opening polymer and the cyclic olefin polymer are kneaded to obtain a resin composition. The norbornene-based hydrogenated ring-opening polymer and the cyclic olefin polymer are those described above in the "Resin composition" section. During kneading, other components described above in the "Resin composition" section can also be added to the norbornene-based hydrogenated ring-opening polymer and the cyclic olefin polymer.

For kneading, a melt kneader such as a single-screw extruder, twin-screw extruder, Banbury mixer, kneader, or feeder ruder can be used. The kneading temperature is preferably in the range of 200 to 400°C, and more preferably in the range of 240 to 300°C. Furthermore, when kneading, the components may be added all at once and kneaded, or may be added in several portions and kneaded at the same time.

Other processes include, for example, a process of preparing a hydrogenated norbornene ring-opening polymer prior to the kneading process (preparation process), and a process of extruding the resin composition obtained in the kneading process to form pellets (extrusion process).

The method for preparing the hydrogenated norbornene ring-opening polymer in the preparation step can be the method described above in the "Resin Composition" section.

(Molded body)
The molded article of the present invention is formed using the resin composition of the present invention described above. Since the molded article of the present invention is formed by molding the resin composition of the present invention, it has excellent solvent resistance and heat sealability.

The method for producing the molded article is not particularly limited. The resin composition can be molded into a molded article using, for example, known molding methods such as injection molding, compression molding, extrusion molding, blow molding, inflation molding, calendar molding, and solution casting. The shape of the molded article can be selected appropriately depending on the application.

The uses of the molded article of the present invention are not particularly limited, but include, for example:
Optical materials such as optical disks, optical lenses, prisms, light diffusion plates, optical cards, optical fibers, optical mirrors, liquid crystal display element substrates, light guide plates, polarizing films, and retardation films;
Containers for liquid, powder, or solid medicines (liquid medicine containers for injection, ampoules, vials, prefilled syringes, bioreactor bags, infusion bags, inner layers, middle layers, outer layers of multilayer films, sealant films, sealed medicine bags, press-through packages, solid medicine containers, eye drop containers, etc.), sampling containers (blood test sampling test tubes, medicine container caps, blood collection tubes, specimen containers, etc.), medical instruments (syringes, etc.), sterilized containers for medical instruments (for scalpels, forceps, gauze, contact lenses, etc.), laboratory and analytical instruments (beakers, petri dishes, flasks, test tubes, centrifuge tubes, etc.), medical optical components (plastic lenses for medical testing, etc.), piping materials (medical infusion tubes, piping, joints, valves, etc.), artificial organs and their parts (tooth bases, artificial hearts, artificial tooth roots, etc.), and other medical equipment;
Food containers such as bottles, returnable bottles, baby bottles, films, shrink films, etc.;
Equipment for processing electronic components, such as processing or transport containers (tanks, trays, carriers, cases, etc.), protective materials (carrier tapes, separation films, etc.), piping (pipes, tubes, valves, flow meters, filters, pumps, etc.), and liquid containers (sampling containers, bottles, ampoule bags, etc.);
Electrical insulating materials such as coating materials (for electric wires, cables, etc.), housings for consumer and industrial electronic devices (for copying machines, computers, printers, televisions, video decks, video cameras, etc.), structural members (for parabolic antennas, flat antennas, radar domes, etc.);
Circuit boards such as general circuit boards (rigid printed circuit boards, flexible printed circuit boards, multilayer printed wiring boards, etc.), high-frequency circuit boards (circuit boards for satellite communication equipment, etc.); substrates for transparent conductive films (liquid crystal substrates, optical memory, surface heating elements, etc.);
Semiconductor encapsulation materials (transistor encapsulation materials, IC encapsulation materials, LSI encapsulation materials, LED encapsulation materials, etc.), encapsulation materials for electric and electronic parts (motor encapsulation materials, capacitor encapsulation materials, switch encapsulation materials, sensor encapsulation materials, etc.);
Examples include interior materials for automobiles such as room mirrors and meter covers; and exterior materials for automobiles such as door mirrors, fender mirrors, beam lenses, and light covers.

The thickness of the film or sheet used as the molded article of the present invention is not particularly limited, but is typically 1 μm to 20 mm, preferably 5 μm to 5 mm, and more preferably 10 μm to 2 mm.

The film and sheet as the molded article of the present invention may be a laminate having a layer containing the resin composition of the present invention and a layer containing a known polymer that is generally used in the fields of home appliances, food, medicine, etc.
The number of layers to be laminated is usually 2 or 3, but a laminate of more layers can be used. The order of arrangement of layers according to the polymer species in a multilayer structure of 3 or more layers can be determined depending on the purpose and application.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, "%" and "parts" representing amounts are based on mass unless otherwise specified.
In the examples and comparative examples, various measurements and evaluations were carried out using the following methods.

<Copolymerization Composition Ratio of Norbornene Ring-Opening Polymer>
Based on ¹ H-NMR measurement, the ratio of the number of hydrogen atoms derived from norbornene units to the number of hydrogen atoms derived from other monomer units was determined, and the copolymerization composition ratio of the norbornene ring-opening polymer was calculated based on this ratio.
The norbornene ring-opening polymer for measurement was collected by pouring a large amount of acetone into a polymerization reaction solution containing the norbornene ring-opening polymer, filtering the resulting aggregate, washing the filtered product with methanol, and drying it under reduced pressure at 40°C for 24 hours.
<Hydrogenation rate>
Calculation was based on ¹ H-NMR measurement.
<Weight average molecular weight>
The weight average molecular weight of the polymer was measured as a value converted to standard polystyrene by gel permeation chromatography (GPC) using cyclohexane as an eluent. The measuring device used was an HLC8121GPC/HT (manufactured by Tosoh Corporation).
The sample was prepared by dissolving the measurement specimen in cyclohexane at 40° C. under heating so that the sample concentration became 4 mg/ml.
The measurement was performed using three TSKgel (registered trademark) GMHHR·H(20)HT (manufactured by Tosoh Corporation) columns connected in series under conditions of a flow rate of 1.0 ml/min, a sample injection volume of 300 μl, and a column temperature of 40°C.
<Glass transition temperature>
10 mg of a measurement sample was weighed into an aluminum pan, and measurement was carried out using a differential scanning calorimeter (DSC; DSC7000X, manufactured by Hitachi High-Tech Science Corporation) under the conditions specified in JIS Z8703. The sample was heated from 30°C to 200°C at a rate of 10°C/min, cooled to 0°C at a cooling rate of -10°C/min, and then heated to 200°C at a rate of 10°C/min, and a differential scanning calorimetry (DSC) curve was obtained. An empty aluminum pan was used as a reference. The temperature at which the differential signal (DDSC) peaked during this heating process was determined as the glass transition temperature (°C). When multiple peaks were measured, the temperature showing the peak with the largest displacement was taken as the glass transition temperature of the cyclic olefin polymer.
<Melting point>
The melting point of the hydrogenated norbornene ring-opening polymer was measured using a differential scanning calorimeter (DSC; DSC7000X, manufactured by Hitachi High-Tech Science Corporation) in the course of heating from 30°C to 200°C at a rate of 10°C/min, cooling to 0°C at a cooling rate of -10°C/min, and then heating to 200°C at a rate of 10°C/min, regardless of whether the resin had a thermal history. The temperature point at which the endothermic heat was greatest at the peak of the first-order phase transition of crystalline melting was taken as the melting point.
<Proportion of meso-dyads of cis structural units (I)>
The proportion of meso-dyads in the cis structural unit (I) of the hydrogenated norbornene ring-opening polymer was calculated by ^13C -NMR measurement (solvent: deuterated chloroform, measurement temperature: 60°C). Specifically, the signal intensity of the meso-dyad observed at 31.712 ppm in the obtained NMR spectrum was divided by the sum of the signal intensity of the racemo-dyad observed at 31.724 ppm and the signal intensity of the meso-dyad observed at 31.712 ppm, and the result was multiplied by 100 to calculate the proportion (percentage) of the meso-dyads.
When the solubility of the norbornene ring-opening polymer hydrogenated product in a solvent was low and it was necessary to dissolve it at a high temperature, the calculation was performed by ^C -NMR measurement using deuterated tetrachloroethane as the solvent and a measurement temperature of 125° C. Specifically, in such a case, the proportion (percentage) of meso dyads was calculated by dividing the signal intensity of the meso dyad observed at 40.315 ppm in the obtained NMR spectrum by the sum of the signal intensity of the racemo dyad observed at 40.310 ppm and the signal intensity of the meso dyad observed at 40.315 ppm, and multiplying the result by 100.
The chemical shift of each signal in ¹³ C-NMR varies to some extent depending on the measurement environment and analysis process.
<Isomerization rate>
The isomerization rate of the hydrogenated norbornene ring-opening polymer was calculated by ^13C -NMR measurement (solvent: deuterated chloroform, measurement temperature: 60°C). Specifically, the signal intensity of the trans structural unit (II) observed at 32.96 to 33.01 ppm in the obtained NMR spectrum was divided by the sum of the signal intensity of the cis structural unit (I) observed at 31.70 to 31.73 ppm and the signal intensity of the trans structural unit (II) observed at 32.96 to 33.01 ppm, and the resulting value was multiplied by 100 to calculate the isomerization rate (percentage).
When the hydrogenated norbornene ring-opening polymer had low solubility in a solvent and needed to be dissolved at a high temperature, the isomerization rate was calculated by ^C -NMR measurement using deuterated tetrachloroethane as the solvent at a measurement temperature of 125° C. Specifically, in such a case, the signal intensity of the trans structural unit (II) observed at 32.72 ppm in the obtained NMR spectrum was divided by the sum of the signal intensity of the cis structural unit (I) observed at 31.66 ppm and the signal intensity of the trans structural unit (II) observed at 32.72 ppm, and the resulting value was multiplied by 100 to calculate the isomerization rate (percentage).
<Heat sealability>
Test pieces 15 mm wide and 100 mm long were cut out from the monolayer films used as molded articles prepared in the Examples and Comparative Examples, and the seal strength (N/15 mm) of the heat-sealed portion was measured at a pulling rate of 100 mm/min and a width of 15 mm in accordance with JIS Z 0238. The heat-sealing conditions were heating and pressing at a temperature of 150°C and a pressure of 0.3 MPa for 2 seconds. A higher seal strength value indicates better heat-sealability.
<Solvent resistance>
Solvent resistance tests were conducted on the monolayer films used as molded articles produced in the Examples and Comparative Examples. Specifically, the monolayer films were cut into pieces measuring 0.50 cm x 2.00 cm, immersed in vials (5 mL capacity) containing 4 mL of each solvent (n-hexane, xylene, or methanol), and left at 23 °C for 7 days. After leaving the monolayer films to stand, the films were removed, the solvent on the surface was wiped off, and the length of the film in the longitudinal direction was measured with calipers, and this was designated L1 (cm). The dimensional change was calculated using the formula: Dimensional change (%) = {(2.00 - L1) / 2.00} x 100, and evaluated according to the following criteria.
A: Dimensional change is less than 5.0% B: Dimensional change is 5.0% or more but less than 10.0% C: Dimensional change is 10.0% or more or the monolayer film after immersion does not maintain its shape before immersion <Haze>
The haze (%) of the single layer films as molded articles produced in the examples and comparative examples was measured using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

(Production Example 1)
A dried, nitrogen-purged polymerization reactor was charged with 7 parts (1% based on the total amount of monomers used in polymerization) of a monomer mixture of norbornene (hereinafter referred to as "NB"), dicyclopentadiene (hereinafter referred to as "DCPD"), and tetracyclododecene (hereinafter referred to as "TCD") (NB/DCPD/TCD = 18/31/51 (weight ratio)), 1,600 parts of dehydrated cyclohexane, 3.5 parts of 1-hexene as a molecular weight modifier, 1.3 parts of diisopropyl ether, 0.33 parts of isobutyl alcohol, 0.84 parts of triisobutylaluminum, and 30 parts of a 0.66% cyclohexane solution of tungsten hexachloride, and the mixture was stirred at 55°C for 10 minutes.
Next, while maintaining the reaction system at 55°C and stirring, 693 parts of the monomer mixture and 72 parts of a 0.77% cyclohexane solution of tungsten hexachloride were each continuously added dropwise to the polymerization reactor over 150 minutes, and after the completion of the dropwise addition, the mixture was stirred for 30 minutes, and then 1.0 part of isopropyl alcohol was added to terminate the polymerization reaction. When the polymerization reaction solution was measured by gas chromatography, the conversion of the monomer to polymer was 100%.
Next, 300 parts of the polymerization reaction solution containing the polymer was transferred to an autoclave equipped with a stirrer, and 100 parts of cyclohexane and 2.0 parts of a diatomaceous earth-supported nickel catalyst (T8400RL, manufactured by Nikki Chemical Industries, Ltd., nickel loading: 58%) were added. After the atmosphere in the autoclave was replaced with hydrogen, the reaction was carried out at 180°C under a hydrogen pressure of 4.5 MPa for 6 hours.
This solution was filtered using a stainless steel mesh filter with diatomaceous earth (Radiolite #500, manufactured by Showa Chemical Industry Co., Ltd.) as a filter aid to remove the catalyst. The resulting reaction solution was poured into 8,000 parts of isopropyl alcohol with stirring to precipitate a hydride, which was then filtered off. After washing with 500 parts of acetone, the precipitate was dried for 24 hours in a vacuum dryer set at 0.13 × 10 ³ Pa or less and 100°C to obtain a cyclic olefin polymer X.
The resulting cyclic olefin polymer X had a hydrogenation rate of 99.9%, a weight average molecular weight (Mw) of 41,100, a glass transition temperature (Tg) of 100°C, and no melting point was observed (i.e., the cyclic olefin polymer X was amorphous).

(Production Example 2)
Cyclic olefin polymer Y was obtained in the same manner as in Production Example 1, except that the weight ratio of the monomer mixture was changed to NB/TCD=46/54.
The resulting cyclic olefin polymer Y had a hydrogenation rate of 99.9%, a weight average molecular weight (Mw) of 38,500, a glass transition temperature (Tg) of 68°C, and no melting point was observed (i.e., the cyclic olefin polymer Y was amorphous).

(Production Example 3)
Cyclic olefin polymer Z was obtained in the same manner as in Production Example 1, except that the weight ratio of the monomer mixture was changed to DCPD/TCD=35/65.
The resulting cyclic olefin polymer Z had a hydrogenation rate of 99.9%, a weight average molecular weight (Mw) of 37,800, a glass transition temperature (Tg) of 136°C, and no melting point was observed (i.e., the cyclic olefin polymer Z was amorphous).

Example 1
<Preparation of Resin Composition>
[Preparation of hydrogenated norbornene ring-opening polymer A]
Reactor A was charged with 0.15 parts of tungsten(phenylimide)(tetrachloride)(tetrahydrofuran) and 7.42 parts of toluene, and the mixture was stirred. Next, 458 parts of cyclohexane, 0.24 parts of 1-hexene, and a solution of 0.12 parts of diethylaluminum ethoxide dissolved in 0.53 parts of n-hexane were added to another reactor B. Next, the toluene solution of tungsten(phenylimide)(tetrachloride)(tetrahydrofuran) in reactor A and a solution of 100 parts of norbornene dissolved in 100 parts of toluene were added to reactor B over 2.5 hours, and a polymerization reaction was carried out at 45°C for 2.5 hours, yielding a polymerization reaction solution containing a norbornene-based ring-opening polymer. After the polymerization reaction began, the viscosity of the mixture gradually increased.
The polymerization reaction solution obtained above (containing 100 parts of norbornene-based ring-opening polymer) was transferred to an autoclave equipped with a stirrer without precipitation, to which 333 parts of cyclohexane and diatomaceous earth-supported nickel catalyst (manufactured by JGC Chemical Industries, Ltd.; "T8400RL", nickel loading 58 wt%, manufactured by Süd-Chemie Catalysts) 3 parts were added, and the reaction was carried out for 6 hours at 200 ° C. and a hydrogen pressure of 4.5 MPa. This solution was filtered using a filter equipped with a stainless steel wire mesh using 2 parts of separately added diatomaceous earth as a filter aid, and the resulting reaction solution was dried for 48 hours in a vacuum dryer set at 0.13 × 10 ³ Pa or less and 100 ° C. to obtain 100 parts of norbornene-based ring-opening polymer hydrogenated product A. The hydrogenation rate, weight average molecular weight, melting point, meso-dyad ratio and isomerization rate of this norbornene-based ring-opening polymer hydrogenated product A were measured. The results are shown in Table 1. The norbornene ring-opening polymer hydrogenated product A was crystalline according to the definition of the present invention.
To 100 parts of the hydrogenated norbornene ring-opening polymer A obtained above, 0.4 parts of an antioxidant (tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, Irganox 1010, manufactured by BASF) was added, and the mixture was kneaded in a twin-screw kneader (TEM-35B, manufactured by Toshiba Machine Co., Ltd.) and pelletized.
[Mixing and Extrusion]
90 parts of the pellets of the hydrogenated norbornene ring-opening polymer A obtained above and 10 parts of the cyclic olefin polymer X obtained in Production Example 1 were mixed and kneaded using a twin-screw kneader (TEM-35B, manufactured by Toshiba Machine Co., Ltd.) under the following kneading conditions, and then extruded to form pellets.
Screw diameter: 37 mm (L/D = 32)
Screw rotation speed: 175 rpm
Resin temperature: 240℃
Feed rate: 10 kg/hour <Production of molded body>
The pellets of the resin composition obtained above were molded into a monolayer film (thickness 100 μm) using a hanger manifold-type T-die film melt extrusion molding machine equipped with a single-screw extruder equipped with a screw having a screw diameter of 20 mm and a compression ratio of 2.5 (L/D = 30) under the following molding conditions. The heat sealability, solvent resistance, and haze of this monolayer film were evaluated. The results are shown in Table 1.
Die lip: 0.8 mm
Molten resin temperature: 220°C T-die width: 300 mm
Cooling roll: 60°C
Cast roll: 60°C
Film take-up speed: 0.9 m/min

Example 2
A molded article was produced in the same manner as in Example 1, except that the resin composition prepared as follows was used, and evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.
<Preparation of Resin Composition>
[Preparation of hydrogenated norbornene ring-opening polymer B]
A norbornene ring-opening polymer hydrogenated product (norbornene ring-opening polymer hydrogenated product B) was prepared and pelletized in the same manner as in Example 1, except that the amount of the diatomaceous earth-supported nickel catalyst used was changed from 3 parts to 5 parts. Note that the norbornene ring-opening polymer hydrogenated product B was crystalline according to the definition of the present invention.
[Mixing and Extrusion]
95 parts of pellets of the hydrogenated norbornene ring-opening polymer B obtained as described above and 5 parts of the cyclic olefin polymer X were mixed, and the mixture was kneaded and extruded in the same manner as in Example 1 to obtain a pelletized resin composition.

Example 3
Resin compositions and molded articles were prepared or fabricated in the same manner as in Example 2, except that the amount of hydrogenated norbornene ring-opening polymer B used was changed from 95 parts to 85 parts and the amount of cyclic olefin polymer X used was changed from 5 parts to 15 parts during the preparation of the resin compositions. Evaluations were then performed in the same manner as in Example 1. The results are shown in Table 1.

Example 4
A resin composition and a molded article were prepared or produced in the same manner as in Example 2, except that the cyclic olefin polymer Y obtained in Production Example 2 was used instead of the cyclic olefin polymer X as the cyclic olefin polymer when preparing the resin composition.

Example 5
Resin compositions and molded articles were prepared or fabricated in the same manner as in Example 4, except that the amount of hydrogenated norbornene ring-opening polymer B used was changed from 95 parts to 90 parts and the amount of cyclic olefin polymer Y used was changed from 5 parts to 10 parts during the preparation of the resin compositions. Evaluations were then performed in the same manner as in Example 1. The results are shown in Table 1.

Example 6
Resin compositions and molded articles were prepared or fabricated in the same manner as in Example 4, except that the amount of hydrogenated norbornene ring-opening polymer B used was changed from 95 parts to 85 parts and the amount of cyclic olefin polymer Y used was changed from 5 parts to 15 parts during the preparation of the resin compositions. Evaluations were then performed in the same manner as in Example 1. The results are shown in Table 1.

Example 7
Resin compositions and molded articles were prepared or fabricated in the same manner as in Example 4, except that the amount of hydrogenated norbornene ring-opening polymer B used was changed from 95 parts to 75 parts and the amount of cyclic olefin polymer Y used was changed from 5 parts to 25 parts during the preparation of the resin compositions. Evaluations were then performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 8)
A molded article was produced in the same manner as in Example 1, except that the resin composition prepared as follows was used, and evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.
<Preparation of Resin Composition>
[Preparation of hydrogenated norbornene ring-opening polymer C]
A norbornene-based ring-opening polymer hydride (norbornene-based ring-opening polymer hydride C) was prepared and pelletized in the same manner as in Example 1, except that 99 parts of norbornene and 1 part of dicyclopentadiene were used instead of 100 parts of norbornene, and the amount of the diatomaceous earth-supported nickel catalyst used was changed from 3 parts to 5 parts. Note that norbornene-based ring-opening polymer hydride C was crystalline according to the definition of the present invention.
[Mixing and Extrusion]
90 parts of pellets of the hydrogenated norbornene ring-opening polymer C obtained as described above and 10 parts of cyclic olefin polymer Y were mixed, and the mixture was kneaded and extruded in the same manner as in Example 1 to obtain a pelletized resin composition.

Example 9
Resin compositions and molded articles were prepared or fabricated in the same manner as in Example 2, except that the amount of norbornene ring-opening polymer hydride B used was changed from 95 parts to 90 parts, and 10 parts of ring-opening polymer hydride Z obtained in Production Example 3 were used instead of 5 parts of ring-opening polymer hydride X as the cyclic olefin polymer. Evaluations were then performed in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 1)
A resin composition and a molded article were prepared or produced in the same manner as in Example 1, except that cyclic olefin polymer X was not used when preparing the resin composition. Evaluations were then carried out in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 2)
Resin compositions and molded articles were prepared or fabricated in the same manner as in Example 1, except that the amount of hydrogenated norbornene ring-opening polymer A used was changed from 95 parts to 97 parts and the amount of cyclic olefin polymer X used was changed from 5 parts to 3 parts during the preparation of the resin compositions. Evaluations were then performed in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 3)
Resin compositions and molded articles were prepared or fabricated in the same manner as in Example 1, except that the amount of hydrogenated norbornene ring-opening polymer A used was changed from 95 parts to 70 parts and the amount of cyclic olefin polymer X used was changed from 5 parts to 30 parts during the preparation of the resin compositions. Evaluations were then performed in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 4)
A resin composition and a molded article were prepared or produced in the same manner as in Example 2, except that cyclic olefin polymer X was not used when preparing the resin composition. Evaluations were then carried out in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 5)
A resin composition and a molded article were prepared or produced in the same manner as in Example 8, except that cyclic olefin polymer Y was not used when preparing the resin composition. Evaluations were then carried out in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 6)
A molded article was produced in the same manner as in Example 1, except that the resin composition prepared as follows was used, and evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.
<Preparation of Resin Composition>
[Preparation of hydrogenated norbornene ring-opening polymer D]
Under a nitrogen atmosphere, 500 parts of dehydrated cyclohexane were charged into a reactor at room temperature and mixed with 0.55 parts of 1-hexene, 0.40 parts of diisopropyl ether, 0.28 parts of triisobutylaluminum, and 0.10 parts of isobutyl alcohol. Then, while maintaining the temperature at 55°C, 247.5 parts of norbornene, 2.5 parts of dicyclopentadiene, and 20 parts of a 1.0% toluene solution of tungsten hexachloride were continuously added over 2 hours to carry out a polymerization reaction, yielding a polymerization reaction solution containing a norbornene-based ring-opening polymer. The polymerization conversion was nearly 100%. The mass ratio of norbornene units to dicyclopentadiene units in the resulting norbornene-based ring-opening polymer was 99:1.
The polymerization reaction solution obtained above was transferred to a pressure-resistant hydrogenation reactor, and 0.5 parts of a diatomaceous earth-supported nickel catalyst (manufactured by JGC Chemical Industries, Ltd.; "T8400RL", nickel loading 58 wt%, manufactured by Süd-Chemie Catalysts) was added thereto, and the reaction was carried out for 6 hours at 160 ° C. and a hydrogen pressure of 4.5 MPa. This solution was filtered through a filter equipped with a stainless steel wire mesh using 1 part of separately added diatomaceous earth as a filter aid, and the catalyst was removed. The resulting reaction solution was dried for 48 hours in a vacuum dryer set at 0.13 × 10 ³ Pa or less and 100 ° C. to obtain 190 parts of norbornene-based ring-opening polymer hydrogenated product D. Note that norbornene-based ring-opening polymer hydrogenated product D was crystalline according to the definition in the present invention.
To 100 parts of the hydrogenated norbornene ring-opening polymer D obtained above, 0.4 parts of an antioxidant (tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, Irganox 1010, manufactured by BASF) was added, and the mixture was kneaded in a twin-screw kneader (TEM-35B, manufactured by Toshiba Machine Co., Ltd.) and pelletized.
[Mixing and Extrusion]
90 parts of pellets of the hydrogenated norbornene ring-opening polymer D obtained as described above and 10 parts of the cyclic olefin polymer X were mixed, and the mixture was kneaded and extruded in the same manner as in Example 1 to obtain a pelletized resin composition.

In addition, in Tables 1 and 2 shown below,
"Hydrogenated products A to D" respectively represent "Hydrogenated products A to D of norbornene-based ring-opening polymers";
"Polymers X to Z" respectively represent "cyclic olefin polymers X to Z",
"NB" represents a structural unit derived from norbornene,
"DCPD" refers to a structural unit derived from dicyclopentadiene;
"TCD" represents a structural unit derived from tetracyclododecene,
"Mw" indicates the weight average molecular weight;
"Tg" refers to the glass transition temperature.

Tables 1 and 2 show that in Examples 1 to 9, which used resin compositions in which the mass ratio of the hydrogenated norbornene ring-opening polymer to the cyclic olefin polymer was within a predetermined range and the proportion of meso-dyads in the cis structural unit (I) was less than a predetermined value, molded articles with excellent solvent resistance and heat sealability were produced.
On the other hand, in Comparative Examples 1 and 4 to 5, which used resin compositions containing no cyclic olefin polymer, and in Comparative Example 2, which used a resin composition in which the mass ratio of the hydrogenated norbornene ring-opening polymer to the cyclic olefin polymer was outside the specified range, the heat sealability of the molded articles was found to be inferior to that of Examples 1 to 9.
Furthermore, in Comparative Example 3, which used a resin composition in which the mass ratio of the hydrogenated norbornene ring-opening polymer to the cyclic olefin polymer was outside the specified range, it was found that the solvent resistance of the molded body was reduced compared to Examples 1 to 9.
Furthermore, in Comparative Example 6, which uses a resin composition in which the proportion of meso-dyads in the cis structural unit (I) is equal to or greater than a predetermined value, it can be seen that both the solvent resistance and heat sealability of the molded body are reduced compared to Examples 1 to 9.

According to the present invention, it is possible to provide a resin composition capable of forming a molded article having excellent solvent resistance and heat sealability, and a method for producing the same.
Furthermore, according to the present invention, a molded article having excellent solvent resistance and heat sealability can be provided.

Claims (8)

A resin composition comprising a crystalline hydrogenated norbornene ring-opening polymer and an amorphous cyclic olefin polymer,
The hydrogenated norbornene ring-opening polymer is a hydrogenated ring-opening polymer containing a structural unit derived from norbornene,
The norbornene-derived structural unit contains the following formula (I):
The proportion of meso-dyads of structural units having a cis-1,3-cyclopentane structure represented by the formula: is less than 30%;
A resin composition in which the mass ratio of the hydrogenated norbornene ring-opening polymer to the cyclic olefin polymer (hydrogenated norbornene ring-opening polymer/cyclic olefin polymer) is 75/25 or more and 95/5 or less. The resin composition according to claim 1, wherein the norbornene-based hydrogenated ring-opening polymer contains 90% by mass or more of structural units derived from norbornene. The resin composition according to claim 1, wherein the glass transition temperature of the cyclic olefin polymer is 60°C or higher and 110°C or lower. The hydrogenated norbornene ring-opening polymer may further be a compound represented by the following formula (II):
The structural unit has a trans-1,3-cyclopentane structure represented by
2. The resin composition according to claim 1, wherein the proportion of the structural units having the trans-1,3-cyclopentane structure in the total of the structural units having the cis-1,3-cyclopentane structure and the structural units having the trans-1,3-cyclopentane structure is 0.5% or more and 30% or less. The resin composition according to claim 1, wherein the weight-average molecular weight of the hydrogenated norbornene ring-opening polymer is 60,000 or more and 200,000 or less. The resin composition according to claim 1, wherein the melting point of the hydrogenated norbornene ring-opening polymer is 110°C or higher and 150°C or lower. A molded article formed using the resin composition described in any one of claims 1 to 6. A method for producing the resin composition according to any one of claims 1 to 6,
a production method comprising a step of kneading the hydrogenated norbornene ring-opening polymer and the cyclic olefin polymer to obtain the resin composition.