JP7426543B2 - Cyclic olefin copolymers, resin compositions, and film-like or sheet-like molded products - Google Patents

Description

The present invention relates to a cyclic olefin copolymer, a resin composition containing the cyclic olefin copolymer, and a film-like or sheet-like molded article formed by molding the cyclic olefin copolymer or the resin composition.

Cyclic olefin homopolymers and cyclic olefin copolymers have low hygroscopicity and high transparency, and are used in various applications including the field of optical materials such as optical disk substrates, optical films, and optical fibers. A copolymer of cyclic olefin and ethylene, which is widely used as a transparent resin, is known as a typical cyclic olefin copolymer. The glass transition temperature (Tg) of a copolymer of cyclic olefin and ethylene can be changed depending on the copolymer composition of cyclic olefin and ethylene. (see, for example, Non-Patent Document 1).

Incoronata, Tritto et al., Coordination Chemistry Reviews, 2006, Vol. 250, p. 212-241

As a cyclic olefin copolymer, for example, there is a chain site of a constitutional unit derived from norbornene monomer, which is a cyclic olefin, and its stereoregularity is known to include meso-type dichain sites and racemo-type dichain sites. It is being The cyclic olefin copolymer obtained by the production method described in Non-Patent Document 1 can be of either meso type or racemo type. On the other hand, in many cyclic olefin copolymers, the stereoregularity is controlled by the catalyst used for copolymerization, and due to such control, most of the chain sites (bichains) of the constituent units derived from norbornene monomers are becomes meso type.

As mentioned above, in the cyclic olefin copolymer formed by copolymerizing norbornene monomer and ethylene, most of the chain sites (diads) of the constituent units derived from norbornene monomer are meso type. It is. Although such cyclic olefin copolymers have excellent mechanical properties such as toughness, they have poor processability due to their high melt viscosity. Furthermore, in the past, it has been possible to produce a cyclic olefin copolymer containing both meso type and racemo type, but the influence of the ratio of meso type and racemo type on physical properties was unknown.

The present invention was made in view of the above conventional problems, and its objects are to provide a cyclic olefin copolymer that is excellent in both processability and mechanical properties, a resin composition containing the cyclic olefin copolymer, and The object of the present invention is to provide a film-like or sheet-like molded product formed by molding the cyclic olefin copolymer or the resin composition.

As a result of intensive studies to solve the above problems, the present inventors have discovered that in a cyclic olefin copolymer formed by copolymerizing norbornene monomer and ethylene, the chain site (two It has been found that the presence of not only the meso type but also the racemo type in a predetermined ratio makes it possible to improve the melt viscosity without sacrificing mechanical properties. Furthermore, they discovered that mechanical properties can be improved by simultaneously satisfying the requirement that the content of chain sites (triads) of constitutional units derived from norbornene monomers be below a predetermined ratio, and have completed the present invention. Ta.

One aspect of the present invention that solves the above problem is as follows.
(1) Contains a constitutional unit derived from norbornene monomer and a constitutional unit derived from ethylene,
The structural unit derived from the norbornene monomer has a meso-type diad site and a racemo-type diad site and triad site,
The value of the ratio of the content (mol%) of the meso-type dilatate site to the content rate (mol%) of the racemo-type dichain site is 0.10 to 3.00, and the triad site A cyclic olefin copolymer having a site content of 2.5 mol% or less.

(2) The cyclic olefin copolymer according to (1) above, which has a glass transition temperature of 110°C or lower.

(3) The cyclic olefin copolymer according to (1) or (2) above, which is obtained by copolymerizing norbornene monomer and ethylene in the presence of a catalyst having a phosphineimide group.

(4) The catalyst having a phosphineimide group has a cyclopentadiene ring, and the cyclopentadiene ring is unsubstituted or has at least one of a methyl group and a trimethylsilyl group as a substituent, as described in (3) above. Cyclic olefin copolymer.

(5) A resin composition containing the cyclic olefin copolymer according to any one of (1) to (4) above.

(6) A film-like or sheet-like molded article obtained by molding the cyclic olefin copolymer according to any one of (1) to (4) above or the resin composition according to (5) above.

According to the present invention, a cyclic olefin copolymer having excellent processability and mechanical properties, a resin composition containing the cyclic olefin copolymer, and molding of the cyclic olefin copolymer or the resin composition are provided. A film-like or sheet-like molded product can be provided.

<Cyclic olefin copolymer>
The cyclic olefin copolymer of this embodiment includes a constitutional unit derived from a norbornene monomer and a constitutional unit derived from ethylene. The constituent unit derived from the norbornene monomer has a meso-type diad site and a racemo-type diad site and a triad site, and the content of the racemo-type diad site (mol% ) is 0.10 to 3.00, and the content of the triplet moiety is 2.5 mol% or less.

As mentioned above, in the cyclic olefin copolymer formed by copolymerizing norbornene monomer and ethylene, meso-type diad sites account for most of the chain sites of the constituent units derived from norbornene monomer. Although it has excellent mechanical properties, it has poor processability due to its high melt viscosity. Therefore, in the cyclic olefin copolymer of the present embodiment, meso type and racemo type are included in a predetermined ratio as diad moieties of the constitutional unit derived from norbornene monomer, and triplet moieties are included in a predetermined ratio. We aim to achieve both mechanical properties and processability as follows.

The meso type, racemo type, and triad type as diad sites of the constituent unit derived from norbornene monomer are shown in the following structures.

In the cyclic olefin copolymer of the present embodiment, the ratio of the content (mol%) of meso-type diadic sites to the content (mol%) of racemo-type diadic sites is 0.10 to It is 3.00. If the value of the ratio is less than 0.10, the mechanical properties, that is, toughness, will decrease, and if it exceeds 3.00, the melt viscosity will increase and the processability will decrease. The value of the ratio is preferably 0.20 to 2.5, more preferably 0.20 to 2.0, even more preferably 0.20 to 1.5, even more preferably 0.20 to 1.0, and .20 to 0.90 is particularly preferred, and 0.20 to 0.60 is most preferred.
In addition, the total content of the racemo-type two-part moiety and the meso-type two-part part is preferably 0.1 to 10 mol%, more preferably 0.2 to 8 mol%, and even more preferably 0.3 to 7 mol%. preferable.
Furthermore, the content of the triad moiety of the structural unit derived from the norbornene monomer in the cyclic olefin copolymer is 2.5 mol% or less. If the content exceeds 2.5 mol%, mechanical properties, that is, toughness, and workability will decrease. The content is preferably 2.3 mol% or less, more preferably 2.0 mol% or less. Further, the lower limit of the content of the triad site is preferably 0 mol%.
In addition, in the cyclic olefin copolymer of the present embodiment, the value of the ratio of the content (mol%) of meso-type diadic sites to the content (mol%) of racemo-type diadic sites is: ^13C - It is obtained by identifying each site by NMR, calculating the ratio (mol%), and dividing the ratio of meso-type two-part sites by the ratio of racemo-type two-part sites. In addition, in the cyclic olefin copolymer of the present embodiment, the content of the triad moiety of the structural unit derived from the norbornene monomer can be determined by identifying the triad moiety by ¹³ C-NMR and calculating the ratio (mol%). Obtained by calculating.

In addition, the value of the ratio of the content rate (mol%) of the meso type diad site to the content rate (mol%) of the racemo type diad site is 0.10 to 3.00, and Setting the content to 2.5 mol% or less based on the cyclic olefin copolymer can be achieved, for example, by copolymerizing norbornene monomer and ethylene using a predetermined catalyst having a phosphine imide group. , which will be discussed later.

In the cyclic olefin copolymer of the present embodiment, the ratio of the content (mol%) of meso-type diadic sites to the content (mol%) of racemo-type diadic sites is 0.10 to 3.00, and the ratio of meso-type two-part sites tends to be smaller than the ratio of racemo-type two-part sites. Although such a structure is considered to be sterically disadvantageous in terms of mechanical properties, the mechanical properties are no different from those of conventional cyclic olefin copolymers in which meso-type diad sites occupy the majority. This is considered to be due to the fact that the glass transition temperature of the cyclic olefin copolymer of this embodiment is 110° C. or lower. That is, when the glass transition temperature of the cyclic olefin copolymer is 110° C. or lower, the amount of norbornene in the copolymer is small and the amount of flexible ethylene units is sufficiently large. Therefore, although it has a structure that is sterically disadvantageous for mechanical properties, it is thought that the influence on mechanical properties is small due to the flexibility of the sufficient content of ethylene units. Therefore, the glass transition temperature of the cyclic olefin copolymer of this embodiment is preferably 110°C or lower, more preferably 10 to 100°C. On the other hand, in the cyclic olefin copolymer of this embodiment, the content of the triad moiety of the structural unit derived from the norbornene monomer is 2.5 mol% or less with respect to the cyclic olefin copolymer. As mentioned above, the value of the ratio of the content (mol%) of the meso-type two-part moiety to the content (mol%) of the racemo-type two-part part is 0.10 to 3.00, and Since the content of the triad moiety is 2.5 mol % or less, the cyclic olefin copolymer of this embodiment has excellent mechanical properties.

The constituent unit derived from norbornene monomer as described above has a meso-type diadic site and a racemo-type diadic site at a predetermined ratio, and a triad site at a predetermined ratio. The cyclic olefin copolymer contained can be obtained by the following manufacturing method. The production method includes at least a step of charging norbornene monomer and ethylene as monomers into a polymerization container (hereinafter referred to as the "charging step"), and a step of charging the monomers in the polymerization container to a catalyst having a phosphine imide group. (hereinafter referred to as "polymerization step").
Each step will be explained in detail below.

[Preparation process]
In the charging step, at least norbornene monomer and ethylene are charged as monomers into the polymerization vessel. The norbornene monomer and other monomers other than ethylene may be charged in the polymerization container as long as they do not adversely affect the production method of this embodiment. In the cyclic olefin copolymer, the total ratio of the structural units derived from the norbornene monomer and the ratio of the structural units derived from ethylene is typically 80% by mass or more based on the total structural units. It is preferably 95% by mass or more, more preferably 98% by mass or more.

The method for charging ethylene into the polymerization solution is not particularly limited as long as a desired amount of ethylene can be charged into the polymerization container. Typically, ethylene is charged into the polymerization vessel such that the pressure of ethylene in the polymerization vessel is 0.5 MPa or higher. The charging pressure of ethylene is preferably 0.55 MPa or more, more preferably 0.6 MPa or more. By increasing the ethylene charging pressure, the amount of catalyst used per produced polymer can be reduced. Regarding the upper limit, the ethylene charging pressure is preferably 10 MPa or less, more preferably 5 MPa or less, and even more preferably 3 MPa or less.

A solvent may be charged into the polymerization vessel together with the norbornene monomer and ethylene. The solvent is not particularly limited as long as it does not inhibit the polymerization reaction. Examples of solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), benzene, toluene, and xylene, as well as chloroform and methylene chloride. , dichloromethane, dichloroethane, and chlorobenzene.

The lower limit of the concentration of norbornene monomer in the case where the norbornene monomer is introduced into the solvent is preferably, for example, 0.5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably, for example, 50% by mass or less, and more preferably 35% by mass or less.

The norbornene monomer will be explained in detail below.

[Norbornene monomer]
Examples of the norbornene monomer include norbornene and substituted norbornene, with norbornene being preferred. Norbornene monomers can be used alone or in combination of two or more.

The above-mentioned substituted norbornene is not particularly limited, and examples of the substituent that this substituted norbornene has include a halogen atom and a monovalent or divalent hydrocarbon group. Specific examples of substituted norbornene include compounds represented by the following general formula (I).

［一般式（Ｉ）中、Ｒ^１～Ｒ^１２は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、炭化水素基からなる群より選ばれるものであり、
Ｒ^９とＲ^１０、Ｒ^１１とＲ^１２は、一体化して２価の炭化水素基を形成してもよく、
Ｒ^９又はＲ^１０と、Ｒ^１１又はＲ^１２とは、互いに環を形成していてもよい。
また、ｎは、０又は正の整数を示し、
ｎが２以上の場合には、Ｒ^５～Ｒ^８は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよい。
ただし、ｎ＝０の場合、Ｒ^１～Ｒ^４及びＲ^９～Ｒ^１２の少なくとも１個は、水素原子ではない。］

[In general formula (I), R ¹ to R ¹² may be the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group,
R ⁹ and R ¹⁰ , R ¹¹ and R ¹² may be combined to form a divalent hydrocarbon group,
R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may mutually form a ring.
Further, n represents 0 or a positive integer,
When n is 2 or more, R ⁵ to R ⁸ may be the same or different in each repeating unit.
However, when n=0, at least one of R ¹ to R ⁴ and R ⁹ to R ¹² is not a hydrogen atom. ]

The substituted norbornene represented by the general formula (I) will be explained. R ¹ to R ¹² in general formula (I) may be the same or different, and are selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups.

Specific examples of R ¹ to R ⁸ include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine, and bromine; an alkyl group having 1 to 20 carbon atoms, and these may be different from each other. , may be partially different, or may be entirely the same.

Further, specific examples of R ⁹ to R ¹² include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine, and bromine; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group such as a cyclohexyl group; a phenyl group, and a tolyl group. Substituted or unsubstituted aromatic hydrocarbon groups such as ethylphenyl group, isopropylphenyl group, naphthyl group, anthryl group; examples include benzyl group, phenethyl group, and other aralkyl groups in which an alkyl group is substituted with an aryl group. These may be different from each other, may be partially different, or may be entirely the same.

Specific examples of the case where R ⁹ and R ¹⁰ or R ¹¹ and R ¹² are combined to form a divalent hydrocarbon group include alkylidene groups such as ethylidene group, propylidene group, isopropylidene group, etc. can be mentioned.

When R ⁹ or R ¹⁰ and R ¹¹ or R ¹² mutually form a ring, the ring formed may be monocyclic or polycyclic, or may be a polycyclic ring having a bridge. , a double bond, or a combination of these rings. Further, these rings may have a substituent such as a methyl group.

Specific examples of the substituted norbornene represented by the general formula (I) include 5-methyl-bicyclo[2.2.1]hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hept- 2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2. 1] Hept-2-ene, 5-hexyl-bicyclo[2.2.1]hept-2-ene, 5-octyl-bicyclo[2.2.1]hept-2-ene, 5-octadecyl-bicyclo[ 2.2.1] hept-2-ene, 5-methylidene-bicyclo[2.2.1] hept-2-ene, 5-vinyl-bicyclo[2.2.1] hept-2-ene, 5- 2-ring cyclic olefin such as propenyl-bicyclo[2.2.1]hept-2-ene;
Tricyclo[4.3.0.1 ^2,5 ]dec-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 ^2,5 ]dec-3-ene; tricyclo[ 4.4.0.1 ^2,5 ]undec-3,7-diene or tricyclo[4.4.0.1 ^2,5 ]undec-3,8-diene or partially hydrogenated products thereof (or cyclopentadiene and cyclohexene), tricyclo[4.4.0.1 ^2,5 ]undec-3-ene; 5-cyclopentyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] Hept-2-ene, 5-cyclohexenylbicyclo[2.2.1]hept-2-ene, 5-phenyl-bicyclo[2.2.1]hept-2-ene, etc. Cyclic olefin of the ring;
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (also simply called tetracyclododecene), 8-methyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyltetracyclo[4,4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] 4-ring cyclic olefin such as dodec-3-ene;
8-Cyclopentyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-cyclohexyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-cyclohexenyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene; tetracyclo[7.4.1 ^3,6 . 0 ^1,9 . 0 ^2,7 ]tetradeca-4,9,11,13-tetraene (also referred to as 1,4-methano-1,4,4a,9a-tetrahydrofluorene), tetracyclo[8.4.1 ^4,7 . 0 ^{1, 10} . 0 ^3,8 ] Pentadeca-5,10,12,14-tetraene (also referred to as 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene); Pentacyclo[6.6.1. 1 ^{3, 6} . 0 ^2,7 . 0 ^9,14 ]-4-hexadecene, pentacyclo[6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ]-4-pentadecene, pentacyclo[7.4.0.0 ^2,7 . 1 ^{3, 6} . 1 ^10,13 ]-4-pentadecene; heptacyclo[8.7.0.1 ^2,9 . 1 ^{4, 7} . 1 ^{11, 17} . 0 ^3,8 . 0 ^12,16 ]-5-eicosene, heptacyclo[8.7.0.1 ^2,9 . 0 ^3,8 . 1 ^{4, 7} . 0 ^{12, 17} . 1 ^13,l6 ]-14-eicosene; Polycyclic cyclic olefins such as a cyclopentadiene tetramer can be mentioned.

Among them, alkyl-substituted norbornene (e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups), alkylidene-substituted norbornene (e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkylidene groups), [2.2.1]hept-2-ene) is preferred, and 5-ethylidene-bicyclo[2.2.1]hept-2-ene (common name: 5-ethylidene-2-norbornene, or simply ethylidenenorbornene) is preferred. ) is particularly preferred.

Monomers other than norbornene monomer and ethylene are not particularly limited as long as they are copolymerizable with norbornene monomer and ethylene. Typical examples of such other monomers include α-olefins. The α-olefin may be substituted with at least one substituent such as a halogen atom.

As the α-olefin, C3 to C12 α-olefins are preferred. C3 to C12 α-olefins are not particularly limited, but include, for example, propylene, 1-butene, 1-pentene, 1-hexene, 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-pentene, 4-ethyl-1-hexene, 3-ethyl Examples include -1-hexene, 1-octene, 1-decene, and 1-dodecene. Among these, 1-hexene, 1-octene, and 1-decene are preferred.

[Polymerization process]
As mentioned above, in this embodiment, in order to obtain a cyclic olefin copolymer in which the constituent unit derived from norbornene monomer has a meso type diad site and a racemo type diad site in a predetermined ratio, During the copolymerization, a predetermined catalyst having a phosphine imide group is used.

In the polymerization step, monomers in the polymerization container are polymerized in the presence of a specific catalyst having a phosphineimide group.
The temperature during polymerization is not particularly limited. Since the yield of the cyclic olefin copolymer is good, the temperature during polymerization is preferably 20°C or higher, more preferably 30°C or higher, even more preferably 50°C or higher, and even more preferably 60°C or higher. A temperature of 70°C or higher is particularly preferred. The temperature during polymerization may be 80°C or higher, or may be 85°C or higher.
The upper limit of the temperature during polymerization is not particularly limited, and may be, for example, 200°C or lower, 140°C or lower, or 120°C or lower.

(Catalyst with phosphineimide group)
As the catalyst having a phosphineimide group (hereinafter referred to as "catalyst A"), it is preferable to use a metal-containing compound represented by the following formula (a1). By using such a catalyst, the structural unit derived from the norbornene monomer contains meso-type diadic sites and racemo-type diadic sites in a predetermined ratio, and triplet sites in a predetermined ratio. It is possible to produce a cyclic olefin copolymer in a proportion below.

In formula (a1), M is Ti, Zr, or Hf, and Ti and Zr are particularly preferred from the viewpoint of ease of obtaining and manufacturing the catalyst A and the activity of the catalyst.
When M is Zr, from the viewpoint of improving catalyst activity, it is preferable that the catalyst and the alkyl aluminum compound be brought into contact with each other (mixed) beforehand and then added to the polymerization system.
As the alkyl aluminum compound, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, MAO (generally containing alkylaluminum), etc. are preferably used.
The amount of the alkyl aluminum compound mixed with the catalyst is preferably 1 to 100 equivalents, more preferably 2 to 50 equivalents, and even more preferably 2 to 10 equivalents.
X is an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or a halogen atom.
L ¹ is a group represented by the following formula (a1a) or formula (a1b). Moreover, L ² is a group represented by the following formula (a1b). In formula (a1), when L ¹ and L ² are both groups represented by formula (a1b), L ¹ and L ² may be the same group or different groups, and are preferably the same group. .

In formula (a1a), R ^a1 to R ^a5 may each independently be the same or different, and may be a hydrogen atom, an organic substituent having 1 to 3 carbon atoms which may contain a hetero atom, or an inorganic substituent. It is the basis. Two adjacent groups on the five-membered ring among R ^a1 to R ^a5 may be bonded to each other to form a ring.
In formula (a1b), R ^a6 to R ^a8 may each independently be the same or different, and may be a hydrogen atom, an organic substituent having 1 to 20 carbon atoms which may contain a hetero atom, or an inorganic substituent. It is the basis. Two groups selected from R ^a6 to R ^a8 may be bonded to each other to form a ring.

In formula (a1), X is an organic substituent having 1 to 20 carbon atoms, which may contain a heteroatom, or a halogen atom.
Regarding the organic substituent having 1 to 20 carbon atoms which may contain a hetero atom, when the organic substituent contains a hetero atom, the type of the hetero atom is particularly determined within the range that does not impede the effect of the production method of this embodiment. Not limited. Specific examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, selenium atoms, and halogen atoms.

The organic substituent is not particularly limited as long as it does not inhibit the formation reaction of the metal-containing compound represented by the above formula (a1). For example, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aliphatic acyl group having 2 to 20 carbon atoms, a benzoyl group, an α- Naphthylcarbonyl group, β-naphthylcarbonyl group, aromatic hydrocarbon group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, trialkylsilyl group having 3 to 20 carbon atoms, 3 to 20 carbon atoms 20 triarylsilyl groups, monosubstituted amino groups substituted with hydrocarbon groups having 1 to 20 carbon atoms, and disubstituted amino groups substituted with hydrocarbon groups having 1 to 20 carbon atoms.

Among these organic substituents, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, aliphatic acyl groups having 2 to 6 carbon atoms, A benzoyl group, a phenyl group, a benzyl group, a phenethyl group, a trialkylsilyl group having 3 to 10 carbon atoms, and a triarylsilyl group having 3 to 10 carbon atoms are preferred.

Among the organic substituents, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, adamantyl group, methoxy group, ethoxy group, n- Propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, acetyl group, propionyl group, butanoyl group, phenyl group, trimethylsilyl group, triethylsilyl group, tert-butyldimethyl More preferred are a silyl group, a triphenylsilyl group, and a trispentafluorophenylsilyl group.

As X, a halogen atom is preferable, a chlorine atom and a bromine atom are more preferable, and a chlorine atom is particularly preferable.

In formula (a1a), R ^a1 to R ^a5 may each independently be the same or different, and may be a hydrogen atom, an organic substituent having 1 to 3 carbon atoms which may contain a hetero atom, or an inorganic substituent. It is the basis. Further, two adjacent groups on the five-membered ring among R ^a1 to R ^a5 may be bonded to each other to form a ring.
Specific examples and preferred examples of organic substituents having 1 to 3 carbon atoms which may contain a hetero atom as R ^a1 to R ^a5 are respectively carbon atoms which may contain a hetero atom as X Specific examples and preferred examples of organic substituents in numbers 1 to 3 are the same.

The inorganic substituent is not particularly limited as long as it does not inhibit the formation reaction of the metal-containing compound represented by the above formula (a1).
Specific examples of the inorganic substituent include a halogen atom, a nitro group, an unsubstituted amino group, and a cyano group.

In formula (a1b), R ^a6 to R ^a8 may each independently be the same or different, and may be a hydrogen atom, an organic substituent having 1 to 20 carbon atoms which may contain a hetero atom, or an inorganic substituent. It is the basis. Furthermore, two groups selected from R ^a6 to R ^a8 may be bonded to each other to form a ring.
Specific examples and preferred examples of the organic substituent having 1 to 20 carbon atoms which may contain a hetero atom as R ^a6 to R ^a8 are respectively the carbon atom which may contain a hetero atom as X; It is the same as the specific examples and preferred examples of organic substituents numbered 1 to 20. Further, as the organic substituent having 1 to 20 carbon atoms which may contain a hetero atom as R ^a6 to R ^a8 , an adamantyl group and an o-tolyl group are also mentioned as preferable examples.
In addition, as R ^a6 to R ^a8 , the organic substituent having 1 to 20 carbon atoms which may contain a hetero atom is a group represented by formula (a1b), and R ^a6 to R ^a8 However, groups each independently being a hydrocarbon group having 1 to 20 carbon atoms are also preferred.
When the organic substituent having 1 to 20 carbon atoms which may contain a hetero atom as R ^a6 to R ^a8 is a group represented by formula (a1b), -N=P is a preferable example. (Me) ₃ , -N=P(Et) ₃ , -N=P(n-Pr) ₃ , -N=P(iso-Pr) ₃ , -N=P(n-Bu) ₃ , -N= P(iso-Bu) ₃ , -N=P(sec-Bu) ₃ , -N=P(tert-Bu) ₃ , -N=P(-N=P(tert-Bu) ₃ )Ph ₂ , and -N=P(Ph) ₃ is mentioned. Among these, -N=P(tert-Bu) ₃ and -N=P(iso-Pr) ₃ are preferred, and -N=P(tert-Bu) ₃ is more preferred. In addition, Me is a methyl group, Et is an ethyl group, n-Pr is an n-propyl group, iso-Pr is an iso-propyl group, n-Bu is an n-butyl group, and iso -Bu is an isobutyl group, sec-Bu is a sec-butyl group, tert-Bu is a tert-butyl group, and Ph is a phenyl group.
Further, specific examples of the inorganic substituents as R ^a6 to R ^a8 are the same as those of the inorganic substituents as R ^a1 to R ^a5 .
R ^a6 to R ^a8 are preferably cyclic or non-cyclic tertiary alkyl groups, or aromatic ring groups having at least one alkyl group at the ortho position. Examples of the cyclic tertiary alkyl group include an adamantyl group, and examples of the non-cyclic tertiary alkyl group include a tert-butyl group. Examples of the aromatic ring group having at least one alkyl group at the ortho position include an o-tolyl group and a mesityl group.

Preferred examples of the group represented by formula (a1b) include -N=P(Me) ₃ , -N=P(Et) ₃ , -N=P(n-Pr) ₃ , -N=P(iso -Pr) ₃ , -N=P(n-Bu) ₃ , -N=P(iso-Bu) ₃ , -N=P(sec-Bu) ₃ , -N=P(tert-Bu) ₃ , - N=P(Ph) ₃ , -N=P(-N=P(tert-Bu) ₃ )Ph ₂ , and -N=P(-N=P(iso-Pr) ₃ )Ph ₂ . Among these, -N=P(tert-Bu) ₃ and -N=P(iso-Pr) ₃ are preferred, and -N=P(tert-Bu) ₃ is more preferred.

Preferred specific examples of the metal-containing compound represented by formula (a1) described above include the following metal-containing compounds. Note that M in the following formula is the same as M in formula (a1).
Further, in the following formula, Si(Me) ₃ is a trimethylsilyl group, and Si(Me) ₂ tert-butyl is a tert-butyldimethylsilyl group.

The above catalyst having a phosphineimide group preferably has a cyclopentadiene ring, and the cyclopentadiene ring is unsubstituted or has at least one of a methyl group and a trimethylsilyl group as a substituent. For example, in formula (a1), L ¹ includes a group represented by formula (a1a), and R ^a1 to R ^a5 in formula (a1a) are at least one of a hydrogen atom, a methyl group, and a trimethylsilyl group. This applies to things that have seeds.

The monomer polymerization is preferably carried out in the presence of the catalyst A and a co-catalyst. As the co-catalyst, compounds generally used as co-catalysts in olefin polymerization can be used without particular limitation. Suitable examples of co-catalysts include aluminoxane and ionic compounds. From the viewpoint that the polymerization reaction tends to proceed well, it is particularly preferable that the monomer polymerization is carried out using at least one of aluminoxane and a borate compound as an ionic compound as a cocatalyst.

For this reason, it is preferable that the catalyst A is mixed with aluminoxane and/or an ionic compound to form a catalyst composition.
Here, the ionic compound is a compound that generates a cationic transition metal compound by reaction with catalyst A.

Preferably, the catalyst composition is prepared using a solution of catalyst A. The solvent contained in the solution of catalyst A is not particularly limited. Preferred solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), mineral oil, benzene, toluene, and xylene; chloroform; Examples include halogenated hydrocarbon solvents such as methylene chloride, dichloromethane, dichloroethane, and chlorobenzene.

The amount of solvent used is not particularly limited as long as a catalyst composition with desired performance can be produced. Typically, the concentration of catalyst A, aluminoxane, and ionic compound is preferably 0.00000001 to 100 mol/L, more preferably 0.00000005 to 50 mol/L, particularly preferably 0.0000001 to 20 mol/L. amount of solvent used.

When mixing the liquid containing the raw materials for the catalyst composition, the number of moles of the transition metal element in catalyst A is M _a , the number of moles of aluminum in aluminoxane is M _b1 , and the number of moles of the ionic compound is M _b2 . In this case, the liquid containing the raw materials for the catalyst composition is mixed so that the value of (M _b1 +M _b2 )/M _a is preferably 1 to 200,000, more preferably 5 to 100,000, particularly preferably 10 to 80,000. Preferably.

The temperature at which the liquid containing the raw materials for the catalyst composition is mixed is not particularly limited, but is preferably -100 to 100°C, more preferably -50 to 50°C.

The solution of catalyst A for preparing the catalyst composition, and the aluminoxane and/or ionic compound may be mixed before polymerization in a device separate from the polymerization container, and in the polymerization container, the It may be carried out before or during the polymerization.

The materials used for preparing the catalyst composition and the conditions for preparing the catalyst composition will be explained below.

[Aluminoxane]
As the aluminoxane, various aluminoxanes that have been conventionally used as cocatalysts and the like in the polymerization of various olefins can be used without particular limitation. Typically, the aluminoxane is an organic aluminoxane.
In producing the catalyst composition, one type of aluminoxane may be used alone, or two or more types may be used in combination.

As the aluminoxane, alkylaluminoxane is preferably used. Examples of the alkylaluminoxane include compounds represented by the following formula (b1-1) or (b1-2). The alkylaluminoxane represented by the following formula (b1-1) or (b1-2) is a product obtained by the reaction of trialkylaluminum and water.

［式（ｂ１－１）及び式（ｂ１－２）中、Ｒは炭素原子数１～４のアルキル基、ｎは０～４０、好ましくは２～３０の整数を示す。］

[In formula (b1-1) and formula (b1-2), R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 40, preferably 2 to 30. ]

Examples of the alkylaluminoxane include methylaluminoxane and modified methylaluminoxane in which a part of the methyl group of methylaluminoxane is substituted with another alkyl group. As the modified methylaluminoxane, for example, a modified methylaluminoxane having an alkyl group having 2 to 4 carbon atoms such as an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group as a substituted alkyl group is preferable, and in particular, More preferred is a modified methylaluminoxane in which some of the methyl groups are substituted with isobutyl groups. Specific examples of alkylaluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane, and the like, with methylaluminoxane and methylisobutylaluminoxane being preferred.

Alkylaluminoxanes can be prepared by known methods. Furthermore, as the alkylaluminoxane, commercially available products may be used. Commercially available alkylaluminoxane products include, for example, MMAO-3A, TMAO-200 series, TMAO-340 series, solid MAO (all manufactured by Tosoh Finechem Corporation), and methylaluminoxane solution (manufactured by Albemarle). .

[Ionic compound]
The ionic compound is a compound that produces a cationic transition metal compound upon reaction with catalyst A.
Such ionic compounds include the anion of tetrakis(pentafluorophenyl)borate, the amine cation with an active proton such as the dimethylphenylammonium cation ((CH ₃ ) ₂ N(C ₆ H ₅ )H ⁺ ), (C ₆ H ₅ ) An ionic compound containing an ion such as a trisubstituted carbonium cation such as _3C ⁺ , a carborane cation, a metalcarborane cation, or a ferrocenium cation having a transition metal can be used.

A suitable example of the ionic compound is borate. Preferred specific examples of the borate include tetrakis(pentafluorophenyl)tritylborate, dimethylphenylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, and N-methyldinormaldecyl. Examples include N-methyldialkyl ammonium tetrakis(pentafluorophenyl)borate such as ammonium tetrakis(pentafluorophenyl)borate.

In order to easily produce a cyclic olefin copolymer with good yield, an aluminoxane or an alkyl aluminum compound is added to the polymerization vessel before adding catalyst A or a catalyst composition containing catalyst A. Preferably, one or more types are present.

The aluminoxane is as explained in the method for producing the catalyst composition.
As the alkyl aluminum compound, compounds conventionally used for polymerization of olefins, etc. can be used without particular limitation. Examples of the alkylaluminum compounds include compounds represented by the following general formula (II).
(R ¹⁰ ) _z AlX _3-z (II)
(In the general formula (II), R ¹⁰ is an alkyl group having 1 to 15 carbon atoms, preferably 1 to 8 carbon atoms, X is a halogen atom or a hydrogen atom, and z is an integer of 1 to 3. )

Examples of the alkyl group having 1 to 15 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-octyl group, and the like.

Specific examples of the alkylaluminium compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-n-octylaluminium; dimethyl Examples include dialkyl aluminum halides such as aluminum chloride and diisobutyl aluminum chloride; dialkyl aluminum hydrides such as diisobutyl aluminum hydride; and dialkyl aluminum alkoxides such as dimethyl aluminum methoxide.

When adding aluminoxane into the polymerization vessel before adding catalyst A or a catalyst composition containing catalyst A, the amount used is preferably 1 to 1,000,000 moles, as the number of moles of aluminum in aluminoxane per mole of catalyst A, and 10 More preferably, the amount is between 100,000 mol and 100,000 mol.
When adding an alkyl aluminum compound into the polymerization vessel before adding catalyst A or a catalyst composition containing catalyst A, the amount used is preferably 1 to 500,000 moles, and 10 to 500,000 moles of aluminum per mole of catalyst A. More preferably 50,000 moles.

The polymerization is preferably carried out in the presence of catalyst A and an aluminoxane or in the presence of catalyst A, an ionic compound and an alkyl aluminum.

The polymerization conditions are not particularly limited as long as they provide a cyclic olefin copolymer with desired physical properties, and known conditions can be used.
The amount of catalyst composition used is derived from the amount of metal-containing compound used in its preparation. The amount of the catalyst composition to be used is preferably 0.000000001 to 0.005 mol, and 0.00000001 to 0.0005 mol per 1 mol of norbornene monomer as the mass of the metal-containing compound used for its preparation. More preferred.

The polymerization time is not particularly limited, and the polymerization is carried out until a desired yield is reached or the molecular weight of the polymer increases to a desired degree.
The polymerization time varies depending on the temperature, catalyst composition, and monomer composition, but is typically 0.01 to 120 hours, preferably 0.1 to 80 hours, and 0.2 to 80 hours. 10 hours is more preferred.

Preferably, at least a portion, preferably all, of the catalyst composition is added continuously to the polymerization vessel.
By continuously adding the catalyst composition, it becomes possible to continuously produce the cyclic olefin copolymer, and it becomes possible to reduce the production cost of the cyclic olefin copolymer.

The cyclic olefin copolymer produced by the above method has excellent processability and mechanical properties (toughness). Therefore, the cyclic olefin copolymer produced by the above method can be used as a functional packaging film or sheet for packaging materials such as optical films or sheets, shrink packaging films, pharmaceutical packaging, medical device packaging, food packaging, etc. It is particularly preferably used for materials such as

On the other hand, when molding using the cyclic olefin copolymer of this embodiment, in order to improve film processability, polyolefins such as polyethylene and polypropylene, elastomers such as styrene elastomers, etc. are added in plants or during compounding. They may be blended using various methods and subjected to processing such as molding.

<Resin composition>
The resin composition of this embodiment contains the above-described cyclic olefin copolymer of this embodiment. Since the resin composition of this embodiment contains the cyclic olefin copolymer of this embodiment, the resin composition and the molded product obtained by molding the same can have excellent processability and mechanical properties. can get.

It is preferable that the resin composition of this embodiment further contains an antioxidant. By containing an antioxidant, it is possible to suppress decomposition, deterioration, and yellowing of the resin composition during processing.

Antioxidants can be used alone or in combination of two or more. Examples of the antioxidant include hindered phenolic antioxidants, phenolic antioxidants, and the like. Furthermore, it may be used in combination with an antioxidant such as a hindered amine antioxidant or a sulfur compound. Specifically, the hindered phenolic antioxidants include, for example, 2,6-di-tert-butyl-p-cresol, stearyl-(3,5-dimethyl-4-hydroxybenzyl)thioglycolate, stearyl- β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate, distearyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, distearyl(4-hydroxy-3-methyl- 5-tert-butyl)benzylmalonate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2' -Methylenebis[6-(1-methylcyclohexyl)-p-cresol], bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid] glycol ester, 4,4'-butylidenebis( 6-tert-butyl-m-cresol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-tris(3,5-di- tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 1,3,5 -Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate Nurate, 2-octylthio-4,6-di(4-hydroxy-3,5-di-tert-butyl)phenoxy-1,3,5-triazine, 4,4'-thiobis(6-tert-butyl-m -cresol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexyldiol-bis[3-(3,5-di-tert) -butyl-4-hydroxyphenyl)propionate], 2,4-bis-octylthio-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, 2,2-thio -diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate) 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4 -hydroxybenzyl)benzene, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2 , 4-bis[(octylthio)methyl]-o-cresol and the like.

In the present embodiment, the antioxidant is preferably contained in the resin composition in an amount of 0.01 to 5% by mass, more preferably 0.1 to 1% by mass.

In addition to the above-mentioned components, the resin composition of the present embodiment is generally added to thermoplastic resins and thermosetting resins in order to impart desired properties according to the purpose, within a range that does not impair its effects. Known additives, such as mold release agents, lubricants, plasticizers, flame retardants, colorants such as dyes and pigments, crystallization promoters, crystal nucleating agents, heat stabilizers, weathering stabilizers, corrosion inhibitors, etc. may also be blended.

<Film-like or sheet-like molded products>
The film-like or sheet-like molded product of this embodiment is formed by molding the above-described cyclic olefin copolymer of this embodiment or the resin composition of this embodiment. As described above, the cyclic olefin copolymer of this embodiment has excellent processability and mechanical properties (toughness). Therefore, it is easy to mold it into a film or sheet shape. Moreover, the film-like or sheet-like molded product obtained has excellent mechanical properties (toughness).

The film-like or sheet-like molded product of this embodiment is produced by using a T-shaped die to produce the above-described cyclic olefin copolymer of this embodiment alone or a composition to which other resin components or additives are added as necessary. It can be obtained by molding into a film or sheet by known extrusion molding such as extrusion molding.

The present embodiment will be described in more detail below with reference to examples, but the present embodiment is not limited to the following examples.

[Examples 1 to 7, Comparative Examples 1 to 2]
In each of the Examples and Comparative Examples, 157 kg of decalin and 23 kg of norbornene were added to a 1 m ³ SUS polymerization machine that had been sufficiently purged with nitrogen under a nitrogen atmosphere. Co., Ltd.) / toluene solution (1 mol/L)) was added in the amount shown in Table 1 (excluding Example 4 and Comparative Examples 1 and 2). Next, ethylene was passed through the polymerization machine to saturate it. The temperature and pressure of the polymerization machine were increased to 90°C and gauge pressure of 0.9MPa, and after confirming that the temperature inside the polymerization machine was sufficiently stabilized, the catalysts (toluene solutions) shown in Table 1 and Added in catalytic amounts. However, Examples 6 and 7 were conducted as follows. That is, in Example 6, TMAO (see below) was slowly added dropwise to catalyst 6 (toluene solution) so that the amount of trimethylaluminum added was 3 equivalents relative to the amount of catalyst, and then stirred at room temperature for 1 hour. were added in the amounts of catalyst shown in Table 1. In addition, in Example 7, a toluene solution of trimethylaluminum was slowly dropped into catalyst 7 (toluene solution) so that the amount of trimethylaluminum added was 3 equivalents relative to the amount of catalyst, and then stirred at room temperature for 1 hour. were added in the amounts of catalyst shown in Table 1. Furthermore, in each of the Examples and Comparative Examples, after adding 3 g of co-catalyst 2 shown in Table 1 and allowing the reaction to proceed for 15 minutes, 2-propanol was added to the polymerization solution to stop the polymerization. In co-catalyst 2 shown in Table 1, "borate" is N-methyldialkylammonium tetrakis(pentafluorophenyl)borate (alkyl: C14 to C18 (average: C17.5)) (manufactured by Tosoh Finechem Co., Ltd.) )). In addition, "TMAO" is a TMAO-211 toluene solution (9.0% by mass (as Al atom content) solution of methylaluminoxane, manufactured by Tosoh Finechem Co., Ltd., and 26mol% of trimethylaluminum based on total Al). "MMAO" means MMAO-3A toluene solution (6.5% by mass (as Al atom content) [(CH ₃ ) _0.7 (iso-C ₄ H ₉ ) _0.3 AlO] A toluene solution of methylisobutylaluminoxane represented by _n (manufactured by Tosoh FineChem Co., Ltd., containing 6 mol% trimethylaluminum based on total Al) was used. Further, the structure of the catalyst used in each example and comparative example is shown below.

With respect to the cyclic olefin copolymers obtained in each example and comparative example, racemo-type diadic sites, meso-type diadic sites, and triad sites were identified by ¹³ C-NMR, The abundance (mol%) of each was calculated. The central peak of the measurement solvent (C ₂ D ₂ Cl ₄ ) was set at 74 ppm. In addition, the value of the ratio of the meso-type two-part site (mol%) to the racemo-type two-part site (mol%) was calculated. The calculation results are shown in Table 1. In addition, in Comparative Example 3, all of the samples were meso-type, so they are written as "∞". Furthermore, the measurement conditions for ¹³ C-NMR measurement are as follows.
・Measuring equipment: AVANCE400III III manufactured by BRUKER
-Measurement solvent: C ₂ D ₂ Cl ₄ (1,1,2,2-Tetrachloroethane-d ₂ )
・Measurement temperature: 100℃

<Molecular weight measurement>
The number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by gel permeation chromatography according to the following measurement conditions. Standard sample: Monodisperse polystyrene was used.
・Measuring equipment: Malvern Viscotek TDA302 detector + Pump autosampler device ・Detector: RI
・Measurement solvent: Toluene ・Measurement temperature: 75℃

[evaluation]
(1) Melt viscosity For the cyclic olefin copolymers obtained in each example and comparative example, a Capillograph manufactured by Toyo Seiki Seisakusho Co., Ltd. was used, a flat die of 1 mmφ x 10 mmL was used as the capillary, and the cylinder temperature was 180. The melt viscosity at , 220 and 260°C was measured, and the melt viscosity at 230°C was determined.
(2) Tensile elongation Using the cyclic olefin copolymer obtained in each Example and Comparative Example, molding was performed using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name: SE75D) at a cylinder temperature of 220°C. A test piece was obtained by molding a flat plate of 70 mm x 70 mm x 2 mm thickness at a mold temperature of 50° C. and an injection speed of 80 mm/sec. Using this test piece, the tensile elongation (%) was measured according to ISO527-1, 2, and the tensile elongation at the yield point and the tensile elongation at break were determined. The measurement results are shown in Table 1.

From Table 1, it can be seen that the cyclic olefin copolymers of Examples 1 to 7 have low melt viscosity, high tensile elongation at yield and high tensile elongation at break, and excellent toughness (mechanical properties). That is, the cyclic olefin copolymers of Examples 1 to 7 are excellent in both processability and mechanical properties. In particular, in Examples 1 to 3 and 6 to 7, the value of the ratio of the content (mol%) of the meso-type two-part moiety to the content (mol%) of the racemo-type two-part part is in a particularly preferable range. (0.20 to 0.90), and a better balance between melt viscosity (processability) and toughness (mechanical properties) was obtained than in Examples 4 and 5, which were not within this range. On the other hand, the cyclic olefin copolymers of Comparative Examples 1 and 2 did not give good results in either melt viscosity, tensile elongation at yield, or tensile elongation at break. Specifically, in Comparative Example 1 in which the value of the ratio was less than 0.10, the tensile elongation at break was poor. In addition, in Comparative Example 2, the ratio of the content (mol%) of the meso-type dilatation site to the content rate (mol%) of the racemo-type dilatation site was more than 3.00, and the melting The viscosity was high.

Claims (5)

Contains a constitutional unit derived from norbornene monomer and a constitutional unit derived from ethylene,
The structural unit derived from the norbornene monomer has a meso-type diad site and a racemo-type diad site and triad site,
The value of the ratio of the content (mol%) of the meso-type dilatate site to the content rate (mol%) of the racemo-type dichain site is 0.10 to 3.00, and the triad site The content of the part is 2.5 mol% or less,
A cyclic olefin copolymer having a glass transition temperature of 110°C or less. Contains a constitutional unit derived from norbornene monomer and a constitutional unit derived from ethylene,
The structural unit derived from the norbornene monomer has a meso-type diad site and a racemo-type diad site and triad site,
The value of the ratio of the content (mol%) of the meso-type dilatate site to the content rate (mol%) of the racemo-type dichain site is 0.10 to 3.00, and the triad site A cyclic olefin copolymer having a content of 2.5 mol % or less of moieties, and a total content of racemo-type diad sites and meso-type diad sites of 0.1 to 10 mol %. A resin composition containing the cyclic olefin copolymer according to claim 1 or 2. A film-like or sheet-like molded article formed by molding the cyclic olefin copolymer according to claim 1 or 2. A film-like or sheet-like molded article formed by molding the resin composition according to claim 3.