JP2020105333A - Polyolefin-based polymer, resin composition and compact - Google Patents

Abstract

To provide a polyolefin-based polymer that may be a material of a compact provided with excellent flex resistance and oxygen permeability, while having a large phase difference.SOLUTION: A polyolefin-based polymer having a cycloolefin unit of a formula (I) and an α-olefin unit. R1 to R16 each may be independently bound with H, a hydrocarbon group, a hydroxyl group, other group, and R1 and R3 to form a ring, R1 and R2, or R3 and R4 together may form an alkylidene group, n and m each is 1 to 3, and n+m is 2 to 4.SELECTED DRAWING: None

Description

The present invention relates to a polyolefin-based polymer, a resin composition, and a molded product of the resin composition.

In recent years, a polyolefin-based polymer obtained by addition-polymerizing an α-olefin and a cycloolefin has attracted attention as a material for a molded product made of a resin composition.

For example, in Patent Document 1, a copolymer containing a structural unit derived from ethylene and a structural unit derived from norbornene having a predetermined chemical structure, and having a molecular weight distribution and a glass transition temperature within a predetermined range, respectively. Coalescence is listed. And according to patent document 1, the optical film which has the outstanding in-plane retardation etc. can be obtained by extending|stretching the resin composition containing the said copolymer.

JP, 2017-58487, A

Here, in recent years, not only a large retardation but also excellent flex resistance and oxygen permeability are demanded for a molded product obtained by using a polyolefin-based polymer.

However, even if a resin composition containing the above-mentioned conventional polyolefin-based polymer is molded, it is not possible to obtain a molded product having a large retardation and excellent flex resistance and oxygen permeability.

Therefore, an object of the present invention is to provide a polyolefin-based polymer which can be a material for a molded article having excellent flex resistance and oxygen permeability while having a large retardation.
Another object of the present invention is to provide a resin composition capable of forming a molded article having excellent flex resistance and oxygen permeability while having a large retardation.
And an object of the present invention is to provide a molded product having a large retardation and excellent flex resistance and oxygen permeability.

The present inventor has made earnest studies for the purpose of solving the above problems. Then, the present inventor has a large phase difference and is excellent in bending resistance and oxygen permeability when a polyolefin-based polymer obtained by addition-polymerizing a cycloolefin having a predetermined structure and an α-olefin is used. The inventors have newly found that a molded product can be produced and completed the present invention.

〔式（Ｉ）中、Ｒ_１〜Ｒ_１６は、それぞれ独立して、水素原子、置換基を有していてもよい炭化水素基、水酸基、ニトロ基、エーテル基、エステル基、カルボニル基、アミノ基、アミド基、イミド基、複素環基、またはケイ素含有基を示し、ここで、Ｒ_１とＲ_３は結合して環を形成していてもよく、また、Ｒ^１とＲ^２は一緒になってアルキリデン基を形成していてもよく、Ｒ^３とＲ^４は一緒になってアルキリデン基を形成していてもよく、ｎとｍは、それぞれ１以上３以下の整数であり、且つ、ｎ＋ｍは２以上４以下である。〕で示されるシクロオレフィン由来の構造単位と、α−オレフィン由来の構造単位とを含有する、ことを特徴とする。このように、上記所定の構造単位２種を少なくとも含有するポリオレフィン系重合体を用いれば、大きな位相差を有しつつ、優れた耐屈曲性および酸素透過性を備える成形体を得ることができる。
なお、本発明において、「置換基を有していてもよい」は、「無置換の、または、置換基を有する」の意味である。 That is, the present invention is intended to advantageously solve the above problems, and the polyolefin-based polymer of the present invention has the following formula (I):

[In formula (I), R _{1 to} R ₁₆ are each independently a hydrogen atom, a hydrocarbon group which may have a substituent, a hydroxyl group, a nitro group, an ether group, an ester group, a carbonyl group, or an amino group. Represents a group, an amide group, an imide group, a heterocyclic group, or a silicon-containing group, wherein R ₁ and R ₃ may be combined to form a ring, and R ¹ and R ² are taken together. May form an alkylidene group, R ³ and R ⁴ may together form an alkylidene group, and n and m are each an integer of 1 or more and 3 or less, and n+m Is 2 or more and 4 or less. ] The structural unit derived from the cycloolefin shown by these, and the structural unit derived from (alpha)- olefin are contained, It is characterized by the above-mentioned. Thus, by using a polyolefin-based polymer containing at least two kinds of the above-mentioned predetermined structural units, it is possible to obtain a molded product having a large retardation and excellent flex resistance and oxygen permeability.
In the present invention, “which may have a substituent” means “unsubstituted or having a substituent”.

Here, in the polyolefin-based polymer of the present invention, the content of the structural unit derived from the cycloolefin represented by the formula (I) is 5 mol% or more and 50 mol% or less, and the structural unit derived from the α-olefin is The content ratio is preferably 50 mol% or more and 95 mol% or less. If the content ratio of the structural unit derived from the cycloolefin represented by the formula (I) and the structural unit derived from the α-olefin in the polyolefin-based polymer is within the above ranges, the resin composition is obtained. The retardation, bending resistance and oxygen permeability of the molded product can be further improved. In addition, the ease of polymerization of the polyolefin-based polymer and the moldability of the resin composition containing the polyolefin-based polymer can be ensured.
In addition, in this invention, "content ratio of a structural unit" can be measured using nuclear magnetic resonance (NMR) methods, such as < ¹ >H-NMR and < ¹³ >C-NMR.

Further, in the polyolefin-based polymer of the present invention, the α-olefin-derived structural unit is preferably an ethylene-derived structural unit. If ethylene is used as the α-olefin in the preparation of the polyolefin-based polymer, the ease of polymerization of the polyolefin-based polymer can be ensured.

In addition, in the polyolefin-based polymer of the present invention, the structural unit derived from the cycloolefin represented by the formula (I) is a structural unit derived from tricyclo[6.2.1.0 ^2,7 ]undec-4-ene. Is preferred. When tricyclo[6.2.1.0 ^2,7 ]undec-4-ene is used as the cycloolefin represented by the formula (I) in the preparation of the polyolefin-based polymer, a resin composition containing the polyolefin-based polymer is obtained. It is possible to further improve the retardation, bending resistance and oxygen permeability of the molded product obtained by using.

Moreover, this invention aims at solving the said subject advantageously, and the resin composition of this invention is characterized by including any of the above-mentioned polyolefin polymers. A molded product obtained by molding a resin composition containing any of the above-described polyolefin-based polymers has a large retardation and excellent flex resistance and oxygen permeability.

Moreover, this invention aims at solving the said subject advantageously, and the molded object of this invention is characterized by shape|molding the resin composition mentioned above. A molded product obtained by molding the above-mentioned resin composition has a large retardation and excellent flex resistance and oxygen permeability.

According to the present invention, it is possible to provide a polyolefin-based polymer which can be a material for a molded article having excellent flex resistance and oxygen permeability while having a large retardation.
Further, according to the present invention, it is possible to provide a resin composition capable of forming a molded article having excellent flex resistance and oxygen permeability while having a large retardation.
Further, according to the present invention, it is possible to provide a molded product having a large retardation and excellent flex resistance and oxygen permeability.

Hereinafter, embodiments of the present invention will be described in detail.
Here, the polyolefin-based polymer of the present invention has a large retardation, excellent bending resistance, and excellent oxygen permeability, and is suitable as a material for various molded products such as optical films and medical packaging materials. Can be used for. The resin composition of the present invention contains the polyolefin-based polymer of the present invention, and can be suitably used, for example, as a material for the molded article of the present invention.

(Polyolefin polymer)
The polyolefin-based polymer of the present invention comprises a structural unit derived from a cycloolefin represented by a predetermined formula (I) (hereinafter sometimes referred to as cycloolefin (I)) and a structural unit derived from α-olefin. It contains, and optionally further contains structural units other than the above-mentioned structural units (hereinafter referred to as “other structural units”).
Since the polyolefin-based polymer of the present invention contains the structural unit derived from cycloolefin (I) and the structural unit derived from α-olefin, if the polyolefin-based polymer of the present invention is used, It is possible to obtain a molded product having excellent flex resistance and oxygen permeability while having a large retardation.

<Structural unit derived from cycloolefin (I)>
The cycloolefin (I) capable of forming a structural unit derived from the cycloolefin (I) is represented by the following formula (I).

In the above formula (I), n and m are each an integer of 1 or more and 3 or less, and n+m is 2 or more and 4 or less. That is, the combination (n,m) of n and m is (1,1), (1,2), (1,3), (2,1), (2,2), (3,1). Is mentioned. It is preferable that both n and m are 1 (that is, n+m=2).

In the above formula (I), R _{1 to} R ₁₆ are each independently a hydrogen atom, a hydrocarbon group which may have a substituent, a hydroxyl group, a nitro group, an ether group, an ester group, a carbonyl group or an amino group. Represents a group, an amide group, an imide group, a heterocyclic group, or a silicon-containing group. When m is 2 or 3, a plurality of R _{11 s} in the formula (I) may be the same or different from each other, and a plurality of R _{12 s} in the formula (I) may be the same or different from each other. Good. When n is 2 or 3, a plurality of R _{13 s} in the formula (I) may be the same or different from each other, and a plurality of R _{14 s} in the formula (I) are the same or different from each other. Good.

The (unsubstituted) hydrocarbon group constituting the hydrocarbon group which may have a substituent of R _{1 to} R ₁₆ is not particularly limited, and examples thereof include a hydrocarbon group having 1 to 30 carbon atoms. .. Examples of the hydrocarbon group having 1 to 30 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, an octyl group, a nonyl group, a dodecyl group, an eicosyl group, a norbornyl group, and an adamantyl group. Aryl groups such as benzyl group, cumyl group, phenylethyl group, phenylpropyl group, diphenylethyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, An aryl group such as a biphenyl group, a naphthyl group, a methylnaphthyl group, an anthracenyl group, and a phenanthryl group; and a cyclopentadienyl group.
Then, the substituent which the above-described hydrocarbon group optionally has is not particularly limited, but for example, a halogen atom (chlorine atom, fluorine atom, etc.), a hydroxyl group, and a nitro group, and an ether group, an ester group described later, Examples include carbonyl group, amino group, amide group, imide group, heterocyclic group, and silicon-containing group. The hydrocarbon group may have only one type of these substituents, or may have two or more types. Further, the hydrocarbon group may have one substituent or may have two or more substituents.

The ether group of R _{1 to} R _{16 is} a group represented by —O—R _A , and examples of R _A include the hydrocarbon groups having 1 to 30 carbon atoms described above.

The ester group of R _{1 to} R _{16 is} a group represented by —CO—OR _B , and examples of R _B include the hydrocarbon groups having 1 to 30 carbon atoms described above.

The carbonyl group of R _{1 to} R _{16 is} a group represented by —CO— _RC , and examples of R _C include a hydrogen atom, a hydroxyl group, and the above-described hydrocarbon group having 1 to 30 carbon atoms.

The amino group of R _{1 to} R _{16 is} a group represented by —NR _D R _E , and examples of R _D and R _E include a hydrogen atom and the above-described hydrocarbon group having 1 to 30 carbon atoms. .. Note that R _D and R _E may be the same or different.

The amide group of R _{1 to} R _{16 is} a group represented by —CO—NR _F R _G , and examples of R _F and R _G include a hydrogen atom and the above-described hydrocarbon group having 1 to 30 carbon atoms. Can be mentioned. Note that R _F and R _G may be the same or different.

The imide group of R _{1 to} R _{16 is} a group represented by —N(COR _H )(COR _I ), and examples of R _H and R _I include the above-described hydrocarbon groups having 1 to 30 carbon atoms. Can be mentioned. In addition, R _H and R _I may be the same or different.

The heterocyclic group of R _{1 to} R ₁₆ is not particularly limited, but is a furan ring group, thiophene ring group, pyrrole ring group, pyrazole ring group, imidazole ring group, pyridine ring group, pyridazine ring group, pyrimidine ring group, pyrazine. Examples thereof include a ring group.

The silicon-containing group of R _{1 to} R ₁₆ is not particularly limited, and examples thereof include silyl groups such as trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, triisopropylsilyl group, and tert-butyldiphenylsilyl group.

Further, in the above formula (I), R ₁ and R ₃ may be bonded to each other to form a ring. The ring formed by combining R ₁ and R ₃ in this way may have a monocyclic structure or a polycyclic structure. The ring formed by combining R ₁ and R ₃ is preferably a hydrocarbon ring which may have a substituent. Such a substituent is not particularly limited, but examples thereof include a halogen atom (chlorine atom, fluorine atom, etc.), a hydroxyl group, and a nitro group, and the above-mentioned hydrocarbon group having 1 to 30 carbon atoms and an ether group. , An ester group, a carbonyl group, an amino group, an amide group, an imide group, a heterocyclic group, a silicon-containing group, and an alkylidene group described later. The hydrocarbon ring formed by combining R ₁ and R ₃ may have only one type of these substituents, or may have two or more types thereof. Further, the hydrocarbon ring formed by combining R ₁ and R ₃ may have one substituent or may have two or more substituents.

In addition, in the above formula (I), R ¹ and R ² may be combined to form an alkylidene group, and R ³ and R ⁴ may be combined to form an alkylidene group. The alkylidene group is not particularly limited, for example, ethylidene (= CH-CH ₃₎ may be mentioned.

Specific examples of cycloolefin (I) are shown below as formulas (1-1) to (I-8).

Then, as the cycloolefin (I), from the viewpoint of further improving the retardation, bending resistance and oxygen permeability of the obtained molded product, tricyclo[6.2.1] represented by the above formula (I-1). .0 ^2,7 ]Undec-4-ene is preferred. That is, the polyolefin-based polymer preferably contains a structural unit derived from tricyclo[6.2.1.0 ^2,7 ]undec-4-ene.
In addition, cycloolefin (I) may be used individually by 1 type, and may be used in combination of 2 or more type.

Here, the content ratio of the structural unit derived from cycloolefin (I) in the polyolefin-based polymer is preferably 5 mol% or more, more preferably 15 mol% or more, and 25 mol% or more. It is more preferable that the content is 35 mol% or more, particularly preferably 50 mol% or less. When the content of the structural unit derived from cycloolefin (I) is 5 mol% or more, the retardation, bending resistance and oxygen permeability of the obtained molded product can be further improved. On the other hand, when the content ratio of the structural unit derived from cycloolefin (I) is 50 mol% or less, the glass transition temperature of cycloolefin (I) does not excessively increase, and the resin composition containing cycloolefin (I) The moldability of can be secured.

<Structural unit derived from α-olefin>
The α-olefin capable of forming a structural unit derived from α-olefin is not particularly limited, and examples thereof include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 3-methyl-1-butene. , 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1. Examples include α-olefins having 1 to 20 carbon atoms such as -pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene and 1-decene. Among these, ethylene is preferable from the viewpoint of ensuring the ease of polymerization of the polyolefin-based polymer.
The α-olefins may be used alone or in combination of two or more.

The content ratio of the α-olefin-derived structural unit in the polyolefin polymer is preferably 50 mol% or more, preferably 95 mol% or less, and more preferably 85 mol% or less. It is more preferably 75 mol% or less, further preferably 65 mol% or less. When the content ratio of the α-olefin-derived structural unit is 50 mol% or more, the ease of polymerization of the polyolefin-based polymer can be ensured. Further, the glass transition temperature of cycloolefin (I) does not excessively increase, and the moldability of the resin composition containing cycloolefin (I) can be secured. On the other hand, when the content of the structural unit derived from α-olefin is 95 mol% or less, the retardation, bending resistance and oxygen permeability of the obtained molded article can be sufficiently improved.

<Other structural units>
The compound capable of forming another structural unit is not particularly limited, and examples thereof include norbornene compounds (norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decyl. Norbornene, 5-cyclohexylnorbornene, 5-cyclopentylnorbornene, 5-methyl-5-phenyl-bicyclo[2.2.1]hept-2-ene, etc.), acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylic acid Examples thereof include esters and methacrylic acid esters. These may be used alone or in combination of two or more.

The content of the other structural unit is not particularly limited and is preferably 10 mol% or less, more preferably 5 mol% or less, and further preferably 1 mol% or less. , 0 mol% (that is, the polyolefin-based polymer does not include any other structural unit).

<Properties of polyolefin polymer>
[Glass-transition temperature]
The glass transition temperature of the polyolefin-based polymer is preferably 70° C. or higher, more preferably 80° C. or higher, even more preferably 90° C. or higher, and preferably 180° C. or lower, 170 It is more preferable that the temperature is not higher than °C. If the glass transition temperature of the polyolefin-based polymer is 70° C. or higher, the heat resistance of the molded product formed from the resin composition containing the polyolefin-based polymer can be ensured, and if it is 180° C. or lower, the polyolefin-based polymer is The moldability of the resin composition containing the polymer can be ensured.
In the present invention, the "glass transition temperature" can be measured by using a differential scanning calorimeter according to JIS K6911.

[Weight average molecular weight]
The weight average molecular weight of the polyolefin-based polymer is preferably 10,000 or more, more preferably 50,000 or more, further preferably 100,000 or more, and 120,000 or more. It is particularly preferable that it is 1,000,000 or less. When the weight average molecular weight of the polyolefin-based polymer is 10,000 or more, the bending resistance of the molded product formed from the resin composition containing the polyolefin-based polymer can be further enhanced. On the other hand, when the weight average molecular weight of the polyolefin-based polymer is 1,000,000 or less, the moldability of the resin composition containing the polyolefin-based polymer can be secured.

[Molecular weight distribution]
Further, the molecular weight distribution of the polyolefin-based polymer is preferably 1.30 or more, more preferably 5.00 or less, and even more preferably 4.00 or less.
The "molecular weight distribution (Mw/Mn)" can be calculated from the weight average molecular weight (Mw) and number average molecular weight (Mn) obtained as standard polyisoprene conversion values using gel permeation chromatography (GPC). it can.

<Method for preparing polyolefin-based polymer>
The above-mentioned polyolefin-based polymer comprises, for example, a cycloolefin (I) capable of forming a cycloolefin (I)-derived structural unit in the presence of a catalyst in a hydrocarbon solvent, and an α-olefin-derived structural unit. It can be produced by copolymerizing (addition polymerization) a monomer composition containing a α-olefin that can be formed and optionally further containing a compound that can form another structural unit. The copolymerization may be carried out in the presence of the organoaluminum compound.
Here, examples of the hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and dodecane, and their halogen derivatives; cycloaliphatic hydrocarbons such as cyclohexane, methylcyclopentane, and methylcyclohexane, and their derivatives. Halogen derivatives; and aromatic hydrocarbons such as benzene, toluene, xylene, and halogen derivatives thereof (eg, chlorobenzene); and the like can be used. These hydrocarbon solvents may be mixed and used.
As the ^{_{catalyst, CpTi ((t-Bu)}} 2 C = N) Cl 2, Cp * Ti ((t-Bu) 2 C = N) Cl 2, 1,3-Me 2 CpTi ((t-Bu ) ₂ C=N)Cl ₂ and 1,3-Me ₂ CpTi((Me ₃ Si)(t-Bu)C=N)Cl _{2 and the} like. These may be used alone or in combination. Here, “Cp” represents a cyclopentadienyl group, “Cp ^* ” represents a η5-pentamethylcyclopentadienyl group, “t-Bu” represents a tert-butyl group, and “Me” represents methyl. Represents a group. The catalyst can be supplied to the polymerization system in the state of a catalyst solution dissolved in a hydrocarbon solvent.
Here, the above-mentioned catalyst includes, for example, (A) a transition metal compound and (B) one or more activators selected from the group consisting of an alkylaluminumoxy compound and an organoboron compound, in any order, and , Can be manufactured by combining them by any method.
As the alkylaluminum oxy compound, conventionally known aluminoxane, those exemplified in JP-A-2-78687, and the like can be used. Here, the alkylaluminum oxy compound may contain, as an impurity, an alkylaluminum compound such as trimethylaluminum, triethylaluminum, triisobutylaluminum used as a raw material for its synthesis.
Further, as the organic boron compound, trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate And so on. Among them, triphenylcarbenium tetrakis(pentafluorophenyl)borate can be preferably used. These organic boron compounds may be mixed and used.
Then, the ratio of the amounts of the (A) transition metal compound and the (B) activator used when preparing the catalyst is a molar ratio (transition metal compound:activator), preferably 1:0.01 to. It is 1:10000, and more preferably 1:100 to 1:3000.
The catalyst may be prepared by (1) mixing the transition metal compound (A) and the activator (B) in a solvent under an atmosphere of an inert gas such as nitrogen or argon, or (2) ) It may be carried out in the reactor by separately introducing (A) the transition metal compound and (B) the activation into the reactor in which the monomers coexist. Here, the temperature for preparing the catalyst is preferably −20° C. or higher and 150° C. or lower. Further, as the solvent, an alkane such as hexane or cyclohexane, or an aromatic compound such as toluene, benzene or ethylbenzene can be used. Then, it is preferable that the solvent to be used has water and the like removed in the pretreatment.

Furthermore, examples of the organoaluminum compound that can be used in the copolymerization include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane and methylisobutylaluminoxane. Among them, methylaluminoxane, isobutylaluminoxane and methylisobutylaluminoxane can be preferably used. You may mix and use these organoaluminum compounds.
The copolymerization can be performed by any of bulk polymerization, solution polymerization and slurry polymerization under any of reduced pressure, atmospheric pressure and increased pressure.
The temperature for copolymerization is preferably -30°C or higher and 260°C or lower, and more preferably 0°C or higher and 200°C or lower.
Further, the copolymerization may be carried out in an atmosphere of an inert gas such as nitrogen or argon, or when a monomer such as an olefin (eg ethylene) is supplied in a gas state, the monomer It may be carried out in a gas atmosphere or in a mixed atmosphere of an inert gas and a monomer gas.
Further, hydrogen may be allowed to coexist in the above atmosphere gas in order to adjust the molecular weight. Further, the catalyst component may be supported on a carrier such as alumina, magnesium chloride or silica before use.

The amount of the catalyst used in the copolymerization is preferably such that the amount of the produced copolymer is 10 kg or more and 1,000,000 kg or less with respect to 1 mol of the catalyst. As a method for separating and recovering the copolymer obtained after the copolymerization, for example, (1) the copolymer is prepared by adding a polar solvent which is a poor solvent such as alcohol or an alcohol mixed with an acid or an alkali to the reaction solution. A method of precipitating and collecting, (2) a method in which the reaction solution is poured into hot water with stirring and then distilled and recovered together with a solvent, or (3) a method in which the reaction solution is directly heated to distill off the solvent Can be mentioned.

(Resin composition)
The resin composition of the present invention contains the above-mentioned polyolefin-based polymer, and optionally further contains a component other than the polyolefin-based polymer (hereinafter referred to as “other component”).
Since the resin composition of the present invention contains the above-mentioned polyolefin-based polymer, by molding the resin composition, while having a large phase difference, excellent flex resistance and oxygen permeability. It is possible to obtain a molded body that is provided with.

<Other ingredients>
Other components that the resin composition may optionally include are not particularly limited, and known additives can be used. Examples of such additives include antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, colorants such as dyes and pigments, and antistatic agents. These other components may be used alone or in combination of two or more. The content of the other components in the resin composition can be appropriately selected within the range that does not impair the object of the present invention.
The polyolefin-based polymer and the other components can be mixed using a known mixing method.

(Molded body)
The molded product of the present invention is formed by molding the above resin composition. Then, the molded product of the present invention is formed by molding the above-mentioned resin composition and contains the above-mentioned polyolefin-based polymer, so that it has a large phase difference and excellent flex resistance and oxygen permeability. .. The molded product of the present invention can be advantageously used as, for example, an optical film or a medical packaging material. Hereinafter, the molded product of the present invention will be described by taking the case where the molded product is an optical film or a medical packaging material as an example, but the present invention is not limited thereto.

<Optical film>
Since the molded product of the present invention has a large retardation and excellent bending resistance, it can be advantageously used as an optical film.
The average thickness of the optical film as the molded product of the present invention is not particularly limited and can be, for example, 10 μm or more and 500 μm or less.
In the present invention, the “average thickness” of the film can be calculated as an average value at any 5 points on the film.
And the manufacturing method of the optical film as a molded body of the present invention is not particularly limited as long as the resin composition of the present invention can be molded into a film shape, and a known method can be adopted. As such a method, for example, the method described in International Publication No. 2016/060070 can be used.

<Medical packaging material>
Further, since the molded product of the present invention is excellent in oxygen permeability and bending resistance, it can be advantageously used in the medical field, for example, as a medical packaging material.
When the film as the molded body of the present invention is used as a medical packaging material, the average thickness thereof is not particularly limited and can be, for example, 1 μm or more and 500 μm or less.
And the manufacturing method of the medical packaging material as a molded object of this invention will not be specifically limited if the resin composition of this invention can be shape|molded in a film form, and a well-known method can be employ|adopted.

<Other uses>
Further, for example, the molded article of the present invention, in addition to the optical film and the medical packaging material described above, various fields such as food field, energy field, electric and electronic field, communication field, automobile field, consumer field, civil engineering and construction field. It can be used for various purposes. Among them, it is suitable for applications in the food field, energy field and the like.
In the food field, for example, it can be used as a wrap film, a shrink film, a film for blister packaging, and the like. The food for which such a film is used is not particularly limited, and examples thereof include ham, sausage, retort food, frozen food, dried food, specified insurance food, cooked rice, confectionery and meat.
In the energy field, for example, 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.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The measurement and evaluation in each example were performed by the following methods. Further, in the following description, “parts” and “%” representing amounts are based on mass unless otherwise specified.

(1) Glass transition temperature The glass transition temperature (Tg) of the polymer was determined by using a differential scanning calorimeter (manufactured by Nanotechnology Co., product name "DSC6220SII") based on JIS K6911 and a heating rate of 10°C/min. It was measured under the conditions.
(2) Composition of polymer The ratio of structural units contained in the polymer was measured by ¹³ C-NMR.
(3) Weight average molecular weight (Mw) and molecular weight distribution (Mn)
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured by gel permeation chromatography (GPC) using cyclohexane as an eluent, and determined as standard polyisoprene conversion values. Then, the molecular weight distribution (Mw/Mn) was calculated.
As the standard polyisoprene, standard polyisoprene (Mw=602, 1390, 3920, 8050, 13800, 22700, 58800, 71300, 109000, 280000) manufactured by Tosoh Corporation was used.
The measurement was carried out using three Tosoh columns (TSKgel G5000HXL, TSKgel G4000HXL and TSKgel G2000HXL) connected in series under the conditions of a flow rate of 1.0 mL/min, a sample injection amount of 100 μL and a column temperature of 40°C.
(4) Average thickness of film Using a film thickness meter (manufactured by Meitan Co., Ltd., product name "RC-1 ROTARY CALIPER"), the thickness of five places was measured at equal intervals in the width direction of the film, and the average thereof was measured. The value was calculated.
(5) In-plane retardation (Re) value of film Using a retarder (manufactured by Oji Scientific Instruments Co., Ltd., product name "KOBRA-21ADH"), the wavelength is 590 nm and the width is 5 at equal intervals. The in-plane retardation value was measured and the average value was calculated. A larger average value means that the film has a larger retardation.
(6) Bending resistance When both ends of the film were gripped and bent at 90°, those that were not cracked were evaluated as "good" in bending resistance, and those that were cracked were evaluated as "defective" in bending resistance.
(7) Oxygen Permeability The resin composition was molded into a plate shape of 9 cm×5.5 cm×0.1 cm by using an injection molding machine (manufactured by Fanuc, product name “ROBOSHOT S-2000i100A”). The oxygen permeability of this plate was measured under the conditions of 30° C. and relative humidity of 85% by using an oxygen permeability measuring device (MOCON, product name “OX-TRAN”) according to JIS K7126-2. Then, the value was converted to a thickness of 100 μm (unit: cc/m ² ·day (100 μm)). The larger this value is, the better the oxygen permeability of the molded article made of the resin composition is.

(Example 1)
<Preparation of polyolefin polymer and resin composition>
The tank type reactor with an agitator having an internal volume of 1.0 L was sufficiently replaced with nitrogen. To this reactor, 960 parts of toluene and 220 parts of tricyclo[6.2.1.0 ^2,7 ]undec-4-ene as cycloolefin (I) were charged, and while stirring at a rotation speed of 300 to 350 rpm, 25 C was maintained. After adding 8.5 parts of a methylaluminoxane 9.0% toluene solution (manufactured by Tosoh Finechem Co., Ltd.: TMAO-200 series), a catalyst solution (CpTi((t-Bu) ₂ C=N)Cl ₂ as a catalyst was added. Was added (100 mL of a toluene solution containing 0.25 μmol). Immediately after the addition of the catalyst solution, ethylene gas as an α-olefin was introduced so that the pressure became 0.1 MPa to start the addition polymerization reaction. Then, the addition polymerization reaction was carried out for 4 hours while maintaining the temperature and ethylene pressure in the reactor. After depressurization, the contents of the reactor were transferred into a large amount of hydrochloric acid acidic 2-propanol to precipitate an addition polymer. The precipitated polymer was collected and washed to obtain a polyolefin polymer.
Then, 100 parts of the polyolefin-based polymer was added to pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] which is an antioxidant (manufactured by Ciba Specialty Chemicals, product Name "Irganox (registered trademark) 1010")], and 2.0 parts of a xylene solution in which 0.1 part was dissolved was added. Then, the resin composition was obtained by drying under reduced pressure at 150° C. for 15 hours. Using the obtained resin composition, the composition and glass transition temperature of the polyolefin polymer, and the weight average molecular weight and molecular weight distribution were measured. Moreover, the obtained resin composition was molded and the oxygen permeability was measured. The results are shown in Table 1.
<Production of film>
The resin composition was heat-treated at 70° C. for 4 hours using a hot air dryer in which air was passed. The resin composition from which dissolved air has been removed by heat treatment is equipped with a T-die type film melt extrusion molding machine (T-die width: 300 mm) having a twin-screw kneader equipped with a 37 mmφ screw, a cast roll, and a film take-up device. Using an extrusion film molding machine, the resin composition was extruded under the molding conditions of molten resin temperature: 200° C., T die temperature: 200° C., cast roll temperature: 80° C., and cooled without stretching. An unstretched film (average thickness: 100 μm, width: 230 mm) was formed. The flex resistance of this unstretched film was evaluated. The results are shown in Table 1.
The unstretched film collected by winding is supplied to a longitudinal uniaxial stretching machine (uniaxially stretching by utilizing the difference in peripheral speed between rolls) installed in a clean room, and heated to 138°C (Tg+10°C). Heated. Next, the film was uniaxially stretched in the extrusion direction at a stretching ratio of 1.5 times at a stretching speed (pulling speed) of 40 mm/sec while passing through a first roll and a second roll having different rotation speeds in this order. The stretched film was cooled to 35° C. with a cooling roll and then wound and collected. The average thickness of the obtained stretched film was 61 μm. Then, the in-plane retardation (Re) value of the obtained stretched film was evaluated. The results are shown in Table 1.

(Example 2)
<Preparation of polyolefin polymer and resin composition>
When the amount of tricyclo[6.2.1.0 ^2,7 ]undec-4-ene as the cycloolefin (I) was changed from 220 parts to 180 parts and ethylene gas as the α-olefin was introduced, A polyolefin polymer and a resin composition were prepared in the same manner as in Example 1 except that the pressure was changed from 0.1 MPa to 0.15 MPa. Then, the composition and glass transition temperature of the obtained polyolefin-based polymer, and the weight average molecular weight and molecular weight distribution were measured. Moreover, the obtained resin composition was molded and the oxygen permeability was measured. The results are shown in Table 1.
<Production of film>
An unstretched film (average thickness: 100 μm, width: 230 mm) made of the resin composition was formed in the same manner as in Example 1 except that the above resin composition was used. The flex resistance of this unstretched film was evaluated. The results are shown in Table 1.
A stretched film (average thickness: 63 μm) was obtained in the same manner as in Example 1 except that the temperature of the heating roll was changed to 115° C. (Tg+10° C.) for the unstretched film collected by winding. Then, the in-plane retardation (Re) value of the obtained stretched film was evaluated. The results are shown in Table 1.

(Example 3)
<Preparation of polyolefin polymer and resin composition>
When the amount of tricyclo[6.2.1.0 ^2,7 ]undec-4-ene as the cycloolefin (I) was changed from 220 parts to 140 parts and ethylene gas as the α-olefin was introduced, A polyolefin polymer and a resin composition were prepared in the same manner as in Example 1 except that the pressure was changed from 0.1 MPa to 0.15 MPa. Then, the composition and glass transition temperature of the obtained polyolefin-based polymer, and the weight average molecular weight and molecular weight distribution were measured. Moreover, the obtained resin composition was molded and the oxygen permeability was measured. The results are shown in Table 1.
<Production of film>
An unstretched film (average thickness: 100 μm, width: 230 mm) made of the resin composition was formed in the same manner as in Example 1 except that the above resin composition was used. The flex resistance of this unstretched film was evaluated. The results are shown in Table 1.
A stretched film (average thickness: 63 μm) was obtained in the same manner as in Example 1 except that the temperature of the heating roll was changed to 95° C. (Tg+10° C.) for the unstretched film collected by winding. Then, the in-plane retardation (Re) value of the obtained stretched film was evaluated. The results are shown in Table 1.

(Comparative Example 1)
<Preparation of polyolefin polymer and resin composition>
The tank type reactor with an agitator having an internal volume of 1.0 L was sufficiently replaced with nitrogen. The reactor 960 parts of toluene, tetracyclododecene (tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodeca-3-ene) were charged 180 parts of stirring at a rotation speed of 300~350rpm While raising the solvent temperature to 70°C. Toluene 23.5 parts, cyclohexylidene (cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium dichloride 0.05 part, methylaluminoxane 9.0% toluene solution 6.22 parts in a glass container. And mixed to obtain a catalyst. When the temperature of the solvent in the reactor reached 70° C., the catalyst was added to the reactor, and immediately thereafter, 0.08 MPa ethylene gas was introduced into the liquid phase to start polymerization. After 20 minutes, the introduction of ethylene gas was stopped, the pressure was released, and then 5 parts of methanol was added to stop the polymerization reaction. This solution was filtered through a filter aid (product name "Radiolite (registered trademark) #800") and transferred into acidic 2-propanol hydrochloride to precipitate an addition polymer. The precipitated polymer was collected and washed to obtain a polyolefin polymer.
Then, 100 parts of the polyolefin-based polymer was added to pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] which is an antioxidant (manufactured by Ciba Specialty Chemicals, product Name "Irganox (registered trademark) 1010")], and 2.0 parts of a xylene solution in which 0.1 part was dissolved was added. Then, it was dried under reduced pressure at 150° C. for 15 hours to obtain a resin composition. Using the obtained resin composition, the composition and glass transition temperature of the polyolefin polymer, and the weight average molecular weight and molecular weight distribution were measured. Moreover, the obtained resin composition was molded and the oxygen permeability was measured. The results are shown in Table 1.
<Production of film>
An unstretched film (average thickness: 100 μm, width: 230 mm) made of the resin composition was formed in the same manner as in Example 1 except that the above resin composition was used. The flex resistance of this unstretched film was evaluated. The results are shown in Table 1.
A stretched film (average thickness: 63 μm) was obtained in the same manner as in Example 1 except that the temperature of the heating roll was changed to 145° C. (Tg+10° C.) for the unstretched film collected by winding. Then, the in-plane retardation (Re) value of the obtained stretched film was evaluated. The results are shown in Table 1.

In Table 1 below,
"Ethylene unit" indicates a structural unit derived from ethylene,
“TCUE unit” represents a structural unit derived from tricyclo[6.2.1.0 ^2,7 ]undec-4-ene,
“TCD unit” refers to a structural unit derived from tetracyclododecene.

From Table 1, it contains a structural unit derived from tricyclo[6.2.1.0 ^2,7 ]undec-4-ene as a cycloolefin (I) and a structural unit derived from ethylene as an α-olefin. In Examples 1 to 3 using the polyolefin-based polymer, it can be seen that a molded product having a large retardation and excellent flex resistance and oxygen permeability can be produced.
On the other hand, in Comparative Example 1 using a polyolefin-based polymer containing a structural unit derived from tetracyclododecene not corresponding to cycloolefin (I) and a structural unit derived from ethylene as an α-olefin, Example 1 was used. It can be seen that the retardation of the molded product is smaller and the flex resistance and oxygen permeability are inferior as compared with those of Nos.

According to the present invention, it is possible to provide a polyolefin-based polymer which can be a material for a molded article having excellent flex resistance and oxygen permeability while having a large retardation.
Further, according to the present invention, it is possible to provide a resin composition capable of forming a molded article having excellent flex resistance and oxygen permeability while having a large retardation.
Further, according to the present invention, it is possible to provide a molded product having a large retardation and excellent flex resistance and oxygen permeability.

Claims (6)

Formula (I) below:

[In the formula (I),
R _{1 to} R ₁₆ are each independently a hydrogen atom, a hydrocarbon group which may have a substituent, a hydroxyl group, a nitro group, an ether group, an ester group, a carbonyl group, an amino group, an amide group or an imide group. , A heterocyclic group, or a silicon-containing group, wherein R ₁ and R ₃ may combine to form a ring, and R ¹ and R ² together form an alkylidene group. And R ³ and R ⁴ may together form an alkylidene group,
n and m are each an integer of 1 or more and 3 or less, and n+m is 2 or more and 4 or less. ]
And a structural unit derived from a cycloolefin,
A polyolefin-based polymer containing a structural unit derived from α-olefin. When the content ratio of the structural unit derived from the cycloolefin represented by the formula (I) is 5 mol% or more and 50 mol% or less, and the content ratio of the structural unit derived from the α-olefin is 50 mol% or more and 95 mol% or less. The polyolefin polymer according to claim 1, which is present. The polyolefin-based polymer according to claim 1 or 2, wherein the α-olefin-derived structural unit is an ethylene-derived structural unit. The structural unit derived from the cycloolefin represented by the formula (I) is a structural unit derived from tricyclo[6.2.1.0 ^2,7 ]undec-4-ene. The polyolefin-based polymer described. A resin composition comprising the polyolefin polymer according to claim 1. A molded body obtained by molding the resin composition according to claim 5.