Cyclic olefin copolymer, resin composition, and film-shaped or sheet-shaped molded article

Abstract

The present invention provides a cycloolefin copolymer, a resin composition containing the cycloolefin copolymer, and a film-shaped or sheet-shaped molded article obtained by molding the cycloolefin copolymer or the resin composition. The cycloolefin copolymer contains structural units derived from a norbornene monomer and structural units derived from ethylene, wherein the structural units derived from the norbornene monomer have a meso-type diad site, a racemic-type diad site, and a triad site, wherein the ratio of the content (mol %) of the meso-type diad site to the content (mol %) of the racemic-type diad site is 0.10 to 3.00, and the content of the triad site is 2.5 mol % or less.

Description

Technical Field

[0001] The present invention relates to a cycloolefin copolymer, a resin composition containing the cycloolefin copolymer, and a film-shaped or sheet-shaped molded article obtained by molding the cycloolefin copolymer or the resin composition. Background Art

[0002] Cyclic olefin homopolymers and cycloolefin copolymers have low hygroscopicity and high transparency and are used in various applications, particularly in the fields of optical materials such as optical disc substrates, optical films, and optical fibers. As a representative cycloolefin copolymer, a copolymer of a cycloolefin and ethylene, which is widely used as a transparent resin, is known. Since the glass transition temperature (Tg) of a cycloolefin and ethylene copolymer can be changed according to the copolymerization composition of the cycloolefin and ethylene, it is possible to manufacture a copolymer that can adjust the glass transition temperature in a wide temperature range (e.g., with reference to non-patent literature 1).

[0003] Prior art literature

[0004] Non-patent literature

[0005] Non-patent document 1: Incoronata, Tritto et al., Coordination Chemistry Reviews, 2006, Vol. 250, pp. 212-241 Summary of the Invention

[0006] Problems to be solved by the invention

[0007] Cyclic olefin copolymers, for example, have chain positions of structural units derived from norbornene monomers as cyclic olefins, and their stereoregularity is known to include meso-type diad sites and racemic-type diad sites. Furthermore, the cycloolefin copolymers obtained by the method described in Non-Patent Document 1 can be either meso-type or racemic-type. On the other hand, the stereoregularity of cycloolefin copolymers is often controlled by the catalyst used in the copolymerization. This control results in a majority of the chain positions (diads) of structural units derived from norbornene monomers becoming meso-type.

[0008] As mentioned above, in cycloolefin copolymers obtained by copolymerizing norbornene monomers with ethylene, a large portion of the chain positions (dyads) of the structural units derived from the norbornene monomer have traditionally been meso-type. Such cycloolefin copolymers have excellent mechanical properties such as toughness, but high melt viscosity, resulting in poor processability. Furthermore, cycloolefin copolymers containing both meso and racemic forms have been produced, but the effect of the ratio of meso to racemic forms on physical properties has been unclear.

[0009] The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to provide a cycloolefin copolymer having excellent processability and mechanical properties, a resin composition containing the cycloolefin copolymer, and a film- or sheet-shaped molded article obtained by molding the cycloolefin copolymer or the resin composition.

[0010] Solutions to Problems

[0011] The present inventors conducted intensive research to address the aforementioned issues and have discovered that, in a cycloolefin copolymer obtained by copolymerizing a norbornene monomer and ethylene, the presence of not only meso but also racemic forms at a predetermined ratio of the chain positions (diads) of the structural units derived from the norbornene monomer can improve the melt viscosity without sacrificing mechanical properties. Furthermore, the present inventors have discovered that, by simultaneously maintaining the content of the chain positions (triads) of the structural units derived from the norbornene monomer at a predetermined ratio or less, excellent mechanical properties can be achieved, thereby arriving at the present invention.

[0012] One aspect of the present invention for solving the aforementioned problems is as follows.

[0013] (1) A cycloolefin copolymer comprising a structural unit derived from a norbornene monomer and a structural unit derived from ethylene,

[0014] The structural unit derived from the norbornene monomer has a meso-type diad site, a racemic diad site, and a triad site,

[0015] The ratio of the content (mol%) of the meso diad site to the content (mol%) of the racemic diad site is 0.10 to 3.00, and the content of the triad site is 2.5 mol% or less.

[0016] (2) The cycloolefin copolymer according to (1) above, which has a glass transition temperature of 110°C or lower.

[0017] (3) The cycloolefin copolymer according to (1) or (2) above, which is obtained by copolymerizing a norbornene monomer and ethylene in the presence of a catalyst having a phosphinimido group.

[0018] (4) The cycloolefin copolymer according to (3) above, wherein the catalyst having the phosphinimido 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.

[0019] (5) A resin composition comprising the cycloolefin copolymer described in any one of (1) to (4) above.

[0020] (6) A film-shaped or sheet-shaped molded article obtained by molding the cycloolefin copolymer described in any one of (1) to (4) above or the resin composition described in (5) above.

[0021] Effects of the Invention

[0022] According to the present invention, there are provided a cycloolefin copolymer having excellent processability and mechanical properties, a resin composition containing the cycloolefin copolymer, and a film-shaped or sheet-shaped molded article obtained by molding the cycloolefin copolymer or the resin composition. DETAILED DESCRIPTION

[0023] <Cyclic olefin copolymer>

[0024] The cycloolefin copolymer of this embodiment comprises structural units derived from a norbornene monomer and structural units derived from ethylene. Furthermore, the structural units derived from the norbornene monomer have a meso-type diad site, a racemic diad site, and a triad site. The ratio of the content (mol%) of the meso-type diad site to the content (mol%) of the racemic diad site is 0.10 to 3.00, and the content of the triad site is 2.5 mol% or less.

[0025] As described above, in a cycloolefin copolymer obtained by copolymerizing a norbornene monomer and ethylene, when meso-type diad sites account for a majority of the chain positions of the structural units derived from the norbornene monomer, the copolymer exhibits excellent mechanical properties, but suffers from poor processability due to high melt viscosity. Therefore, in the cycloolefin copolymer of this embodiment, the diad sites of the structural units derived from the norbornene monomer contain meso-type and racemic-type sites at a predetermined ratio, and the triad sites are at a predetermined ratio or less, thereby achieving both mechanical properties and processability.

[0026] As a diad site of a structural unit derived from a norbornene monomer, a meso type and a racemic type, and a triad site are represented by the following structures.

[0027] [Chemical Formula 1]

[0028]

[0029] [Chemical Formula 2]

[0030]

[0031] In the cycloolefin copolymer of this embodiment, the ratio of the content (mol%) of meso-type diad sites to the content (mol%) of racemic-type diad sites is 0.10 to 3.00. If this ratio is less than 0.10, mechanical properties, namely, toughness, are reduced. If it exceeds 3.00, melt viscosity increases, and processability is reduced. This 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, particularly preferably 0.20 to 0.90, and most preferably 0.20 to 0.60.

[0032] The total content of the racemic diad site and the meso diad site is preferably 0.1 to 10 mol %, more preferably 0.2 to 8 mol %, and even more preferably 0.3 to 7 mol %.

[0033] Furthermore, the content of triad sites in the structural units derived from norbornene monomers in the cycloolefin copolymer is 2.5 mol% or less. If this content exceeds 2.5 mol%, mechanical properties, namely toughness, deteriorate, and processability decreases. This content is preferably 2.3 mol% or less, and more preferably 2.0 mol% or less. Furthermore, the lower limit of the triad site content is preferably 0 mol%.

[0034] In the cycloolefin copolymer of the present embodiment, the ratio of the content (mol%) of the meso diad site to the content (mol%) of the racemic diad site is obtained by 13 C-NMR is used to identify each site and calculate the ratio (mol%), which is obtained by dividing the ratio of the meso diad site by the ratio of the racemic diad site. In the cycloolefin copolymer of this embodiment, the content of the triad site of the structural unit derived from the norbornene monomer is calculated by 13 The triad sites were identified by C-NMR and the ratio (mol %) was calculated.

[0035] Furthermore, the ratio of the content (mol %) of the meso diad site to the content (mol %) of the racemic diad site is 0.10 to 3.00, and the content of the triad site is 2.5 mol % or less relative to the cycloolefin copolymer. This can be achieved, for example, by copolymerizing a norbornene monomer and ethylene using a predetermined catalyst having a phosphinimido group, as will be described later.

[0036] In the cycloolefin copolymer of this embodiment, the ratio of the content (mol%) of meso diad sites to the content (mol%) of racemic diad sites is 0.10 to 3.00, with a tendency for the ratio of meso diad sites to be lower than that of racemic diad sites. This structure is considered to be detrimental to stereomechanical properties, but the mechanical properties are the same as those of conventional cycloolefin copolymers in which meso diad sites account for a majority of the copolymer. This is believed to be due to the glass transition temperature of the cycloolefin copolymer of this embodiment being 110°C or lower. In other words, when the glass transition temperature of the cycloolefin copolymer is 110°C or lower, the amount of norbornene in the copolymer is low, and the number of flexible ethylene units is sufficient. Therefore, despite having a structure that is detrimental to stereomechanical properties, the flexibility of the sufficient content of ethylene units is believed to have a minimal impact on the mechanical properties. Therefore, the glass transition temperature of the cycloolefin copolymer of this embodiment is preferably 110°C or lower, and more preferably 10 to 100°C. On the other hand, in the cycloolefin copolymer of this embodiment, the content of triad sites in the structural units derived from norbornene monomers is 2.5 mol% or less relative to the cycloolefin copolymer. As described above, the cycloolefin copolymer of this embodiment exhibits excellent mechanical properties due to the ratio of the content (mol%) of meso-type diad sites to the content (mol%) of racemic-type diad sites being 0.10 to 3.00 and the triad site content being 2.5 mol% or less.

[0037] A cycloolefin copolymer in which the structural units derived from a norbornene monomer have meso-type diad sites and racemic-type diad sites at a predetermined ratio and triad sites at a predetermined ratio can be obtained by the following production method. This production method comprises the steps of charging at least norbornene monomer and ethylene as monomers into a polymerization vessel (hereinafter referred to as the "charging step") and polymerizing the monomers in the polymerization vessel in the presence of a catalyst having a phosphinimido group (hereinafter referred to as the "polymerization step").

[0038] Each step is described in detail below.

[0039] [Loading process]

[0040] In the charging step, at least norbornene monomer and ethylene are charged as monomers into the polymerization vessel. Norbornene monomer and monomers other than ethylene may be charged into the polymerization vessel as long as they do not adversely affect the production method of this embodiment. The total ratio of the structural units derived from the norbornene monomer and the structural units derived from ethylene in the cycloolefin copolymer is typically preferably 80% by mass or greater, more preferably 95% by mass or greater, and even more preferably 98% by mass or greater, relative to the total structural units.

[0041] The method for charging ethylene into the polymerization solution is not particularly limited as long as the desired amount of ethylene is charged into the polymerization vessel. Typically, ethylene is charged into the polymerization vessel in such a manner that the charging pressure of ethylene into the polymerization vessel is 0.5 MPa or higher. The charging pressure of ethylene is preferably 0.55 MPa or higher, more preferably 0.6 MPa or higher. When the charging pressure of ethylene is increased, the amount of catalyst used per polymer produced can be reduced. As for the upper limit, the charging pressure of ethylene is preferably, for example, 10 MPa or lower, more preferably 5 MPa or lower, and even more preferably 3 MPa or lower.

[0042] A solvent may also be placed in the polymerization vessel together with the norbornene monomer and ethylene. The solvent is not particularly limited as long as it does not interfere with the polymerization reaction. Examples of the solvent include hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene, benzene, toluene, and xylene, and halogenated hydrocarbon solvents such as chloroform, methylene chloride, dichloromethane, dichloroethane, and chlorobenzene.

[0043] When the norbornene monomer is added to the solvent, the lower limit of the norbornene monomer concentration is preferably 0.5 mass % or more, more preferably 10 mass % or more, and the upper limit is preferably 50 mass % or less, more preferably 35 mass % or less.

[0044] The norbornene monomer is described in detail below.

[0045] [Norbornene monomer]

[0046] Examples of the norbornene monomer include norbornene and substituted norbornene, with norbornene being preferred. The norbornene monomer may be used alone or in combination of two or more.

[0047] The substituted norbornene is not particularly limited. Examples of the substituent of the substituted norbornene include a halogen atom and a monovalent or divalent hydrocarbon group. Specific examples of the substituted norbornene include compounds represented by the following general formula (I).

[0048] [Chemical Formula 3]

[0049]

[0050] [In the general formula (I), R 1 ~R 12 are each the same or different and selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group,

[0051] R 9 and R 10 、R 11 and R 12 Can form a divalent hydrocarbon group integrally,

[0052] R 9 or R 10 With R 11 or R 12 Can form a loop with each other.

[0053] In addition, n represents 0 or a positive integer,

[0054] When n is 2 or more, R 5 ~R 8 In each repeating unit, they may be the same or different.

[0055] However, when n=0, R 1 ~R 4 and R 9 ~R 12 At least one of them is not a hydrogen atom.]

[0056] The substituted norbornene represented by the general formula (I) is described. 1 ~R 12 are each the same or different and selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group.

[0057] As R 1 ~R 8 Specific examples include hydrogen atoms; halogen atoms such as fluorine, chlorine, and bromine; and alkyl groups having 1 to 20 carbon atoms. These may be different from each other, may be partially different from each other, or may be all the same.

[0058] In addition, as R 9 ~R 12 Specific examples include hydrogen atoms; halogen atoms such as fluorine, chlorine, and bromine; alkyl groups having 1 to 20 carbon atoms; cycloalkyl groups such as cyclohexyl; substituted or unsubstituted aromatic hydrocarbon groups such as phenyl, tolyl, ethylphenyl, isopropylphenyl, naphthyl, and anthracenyl; benzyl, phenethyl, and other aralkyl groups in which an aryl group is substituted with an alkyl group, and these groups may be different from each other, may be partially different, or may be all the same.

[0059] As R 9 With R 10 , or R 11 With R 12 Specific examples of the case where the groups are integrated to form a divalent hydrocarbon group include alkylene groups such as ethylene, propylene, and isopropylene.

[0060] In R 9 or R 10 With R 11 or R 12 When the rings are formed, the rings formed may be monocyclic or polycyclic, may be cross-linked polycyclic, may be rings with double bonds, or may be rings composed of combinations of these rings. In addition, these rings may also have substituents such as methyl groups.

[0061] Specific examples of the substituted norbornene represented by the general formula (I) include bicyclic cyclic olefins such as 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-methylene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, and 5-propenyl-bicyclo[2.2.1]hept-2-ene.

[0062] Three Rings [4.3.0.1 2,5 ]Deca-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 2,5 ]De-3-ene; tricyclo[4.4.0.1 2,5 ] undec-3,7-diene or tricyclo[4.4.0.1 2,5 ] 11-3,8-diene or its partial hydrogenation products (or adducts of cyclopentadiene and cyclohexene), namely tricyclo[4.4.0.1 2,5 ] undec-3-ene; tricyclic cyclic olefins such as 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, and 5-phenyl-bicyclo[2.2.1]hept-2-ene;

[0063] Four Rings [4.4.0.1 2,5 .1 7,10 ] dodec-3-ene (abbreviated as tetracyclododecene), 8-methyltetracyclo[4.4.0.1 2, 5 .1 7,10 ] dodeca-3-ene, 8-ethyltetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-methylenetetracyclo[4.4.0.1 2,5 .1 7,10 ] dodec-3-ene, 8-ethylenetetracyclo[4.4.0.1 2,5 .1 7,10 ] dodeca-3-ene, 8-vinyltetracyclo[4,4.0.1 2,5 .1 7 ,10 ] dodeca-3-ene, 8-propenyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ] Four-ring cyclic olefins such as dodec-3-ene;

[0064] 8-Cyclopentyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ] dodeca-3-ene, 8-cyclohexyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ] dodeca-3-ene, 8-cyclohexenyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ] dodeca-3-ene, 8-phenyl-cyclopentyl-tetracyclo[4.4.0.1 2 ,5 .1 7,10 ] dodeca-3-ene; tetracyclo[7.4.1 3,6 .0 1,9 .0 2,7 ]Tetradeca-4,9,11,13-tetraene (also known 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 known as 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene); pentacyclic [6.6.1.1 3,6 .0 2,7 .0 9,14 ]-4-hexadecene, pentacyclic [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-pentadecen; heptacyclic [8.7.0.1 2,9 .1 4,7 .1 11 ,17 .0 3,8 .0 12,16 ]-5-eicosene, heptacyclic [8.7.0.1 2,9 .0 3,8 .1 4,7 .012,17 .1 13,l6 ]-14-eicosene; a polycyclic cyclic olefin such as a tetramer of cyclopentadiene.

[0065] Among them, alkyl-substituted norbornenes (e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups) and alkylene-substituted norbornenes (e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkylene groups) are preferred, and 5-ethylidene-bicyclo[2.2.1]hept-2-ene (common name: 5-ethylidene-2-norbornene or simply ethylidene norbornene) is particularly preferred.

[0066] There are no particular limitations on other monomers other than norbornene monomer and ethylene, as long as they are copolymerizable with norbornene monomer and ethylene. Typical examples of such other monomers include α-olefins. α-olefins may be substituted with at least one substituent such as a halogen atom.

[0067] The α-olefin is preferably a C3 to C12 α-olefin. The C3 to C12 α-olefin is not particularly limited, and examples thereof include 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-1-hexene, 1-octene, 1-decene, and 1-dodecene. Among them, 1-hexene, 1-octene, and 1-decene are preferred.

[0068] [Polymerization process]

[0069] As described above, in this embodiment, a predetermined catalyst having a phosphonimide group is used during copolymerization to obtain a cycloolefin copolymer in which the structural unit derived from a norbornene monomer has a meso-type diad site and a racemic-type diad site at a predetermined ratio.

[0070] In the polymerization step, the monomers in the polymerization vessel are polymerized in the presence of a specific catalyst having a phosphinimido group.

[0071] The polymerization temperature is not particularly limited. Since the yield of the cycloolefin copolymer is good, the polymerization temperature is preferably 20°C or higher, more preferably 30°C or higher, even more preferably 50°C or higher, even more preferably 60°C or higher, and particularly preferably 70°C or higher. The polymerization temperature may be 80°C or higher, or 85°C or higher.

[0072] 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.

[0073] (Catalyst having a phosphinimide group)

[0074] A metal-containing compound represented by the following formula (a1) is preferably used as a catalyst having a phosphinimido group (hereinafter referred to as "catalyst A"). Use of this catalyst allows production of a cycloolefin copolymer in which the structural units derived from a norbornene monomer contain meso-type diad sites and racemic-type diad sites at a predetermined ratio, and triad sites are present in a predetermined ratio or less.

[0075] [Chemical Formula 4]

[0076]

[0077] In formula (a1), M is Ti, Zr, or Hf, and Ti and Zr are particularly preferred from the viewpoints of easy availability and production of the catalyst A and catalytic activity.

[0078] When M is Zr, from the viewpoint of improving catalyst activity, it is preferred to bring the catalyst into contact with (mix with) the alkylaluminum compound in advance and then add the catalyst to the polymerization system.

[0079] As the alkylaluminum compound, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, MAO (usually containing an alkylaluminum), etc. are preferably used.

[0080] The amount of the alkylaluminum compound to be mixed with the catalyst is preferably 1 to 100 equivalents, more preferably 2 to 50 equivalents, and even more preferably 2 to 10 equivalents relative to the catalyst.

[0081] X is an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or a halogen atom.

[0082] L 1 is a group represented by the following formula (a1a) or formula (a1b). 2 is a group represented by the following formula (a1b). In formula (a1), L 1 and L 2 When both are groups represented by formula (a1b), L 1 and L 2 They may be the same group or different groups, but are preferably the same group.

[0083] [Chemical Formula 5]

[0084]

[0085] In formula (a1a), R a1 ~R a5 Each independently represents a hydrogen atom which may be the same or different, an organic substituent having 1 to 3 carbon atoms which may contain a heteroatom, or an inorganic substituent. a1 ~R a5 Two adjacent groups on the 5-membered ring can combine with each other to form a ring.

[0086] In formula (a1b), R a6 ~R a8 Each independently represents a hydrogen atom, an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or an inorganic substituent, which may be the same or different. a6 ~R a8 The two groups can be combined with each other to form a ring.

[0087] In formula (a1), X is an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or a halogen atom.

[0088] Regarding the organic substituent having 1 to 20 carbon atoms that may contain a heteroatom, when the organic substituent contains a heteroatom, the type of the heteroatom is not particularly limited as long as it does not hinder the effect of the production method of this embodiment. Specific examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, selenium atoms, and halogen atoms.

[0089] 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). Examples thereof include 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, a β-naphthylcarbonyl group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a trialkylsilyl group having 3 to 20 carbon atoms, a triarylsilyl group having 3 to 20 carbon atoms, a monosubstituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms, and a disubstituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms.

[0090] Among these organic substituents, preferred are an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aliphatic acyl group 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.

[0091] Among the organic substituents, more preferred are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, adamantyl, methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, acetyl, propionyl, butyryl, phenyl, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, triphenylsilyl, and trispentafluorophenylsilyl.

[0092] X is preferably a halogen atom, more preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.

[0093] In formula (a1a), R a1 ~R a5 Each independently represents a hydrogen atom which may be the same or different, an organic substituent having 1 to 3 carbon atoms which may contain a heteroatom, or an inorganic substituent. a1 ~R a5 Two adjacent groups on the 5-membered ring can combine with each other to form a ring.

[0094] As R a1 ~R a5 Specific examples and preferred examples of the organic substituent having 1 to 3 carbon atoms and optionally containing a hetero atom are the same as the specific examples and preferred examples of the organic substituent having 1 to 3 carbon atoms and optionally containing a hetero atom as X, respectively.

[0095] 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).

[0096] Specific examples of the inorganic substituent include a halogen atom, a nitro group, an unsubstituted amino group, and a cyano group.

[0097] In formula (a1b), R a6 ~R a8 Each independently represents a hydrogen atom which may be the same or different, an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or an inorganic substituent. a6 ~R a8 The two groups can be combined with each other to form a ring.

[0098] As R a6 ~R a8 Specific examples and preferred examples of the organic substituent having 1 to 20 carbon atoms and optionally containing a hetero atom are the same as the specific examples and preferred examples of the organic substituent having 1 to 20 carbon atoms and optionally containing a hetero atom as X. a6 ~R a8The organic substituent having 1 to 20 carbon atoms and optionally containing a heteroatom can be exemplified by adamantyl and o-tolyl.

[0099] In addition, as R a6 ~R a8 The organic substituent having 1 to 20 carbon atoms and optionally containing a heteroatom is preferably a group represented by formula (a1b), that is, R a6 ~R a8 Each of the groups is independently a hydrocarbon group having 1 to 20 carbon atoms.

[0100] As R a6 ~R a8 Preferred examples of the case where the organic substituent having 1 to 20 carbon atoms and optionally containing a heteroatom is a 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(-N=P(tert-Bu)3)Ph2, and -N=P(Ph)3. Among them, -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 isopropyl group, n-Bu is an n-butyl group, 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.

[0101] In addition, as R a6 ~R a8 Specific examples of inorganic substituents are as follows: a1 ~R a5 The specific examples of the inorganic substituent are the same as those of .

[0102] As R a6 ~R a8 Preferred are cyclic or acyclic tertiary alkyl groups or aromatic ring groups having at least one alkyl group at the ortho position. Examples of cyclic tertiary alkyl groups include adamantyl groups, and examples of acyclic tertiary alkyl groups include tert-butyl groups. Examples of aromatic ring groups having at least one alkyl group at the ortho position include o-tolyl groups and mesityl groups.

[0103] 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)Ph2, and -N=P(-N=P(iso-Pr)3)Ph2. Among them, -N=P(tert-Bu)3 and -N=P(iso-Pr)3 are preferred, and -N=P(tert-Bu)3 is more preferred.

[0104] Preferred specific examples of the metal-containing compound represented by the above-described formula (a1) include the following metal-containing compounds: In the following formula, M is the same as M in the formula (a1).

[0105] In the following formula, Si(Me)3 is trimethylsilyl, and Si(Me)2tert-butyl is tert-butyldimethylsilyl.

[0106] [Chemical Formula 6]

[0107]

[0108] [Chemical Formula 7]

[0109]

[0110] [Chemical Formula 8]

[0111]

[0112] The catalyst having the above phosphinimide group has a cyclopentadiene ring, and the cyclopentadiene ring is preferably unsubstituted or has at least one of a methyl group and a trimethylsilyl group as a substituent. For example, in the above formula (a1), L 1 Contains a group represented by formula (a1a), and R in formula (a1a) a1 ~R a5 It has at least one of a hydrogen atom, a methyl group, and a trimethylsilyl group.

[0113] The polymerization of the monomers is preferably carried out in the presence of the above-mentioned catalyst A and a co-catalyst. As the co-catalyst, compounds commonly used as co-catalysts in the polymerization of olefins can be used without particular limitation. Preferred examples of the co-catalyst include aluminoxane and ionic compounds. From the perspective of facilitating smooth progress of the polymerization reaction, it is particularly preferred to use at least one of aluminoxane and a borate compound as a co-catalyst for the polymerization of the monomers.

[0114] Therefore, the above-mentioned catalyst A is preferably mixed with aluminoxane and / or an ionic compound to form a catalyst composition.

[0115] Here, the ionic compound is a compound that generates a cationic transition metal compound by reacting with the catalyst A.

[0116] The catalyst composition is preferably 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, decalin (decahydronaphthalene), mineral oil, benzene, toluene, and xylene, and halogenated hydrocarbon solvents such as chloroform, methylene chloride, dichloromethane, dichloroethane, and chlorobenzene.

[0117] The amount of solvent used is not particularly limited as long as a catalyst composition having the desired performance can be produced. Typically, the solvent can be used in an amount such that 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, and particularly preferably 0.0000001 to 20 mol / L.

[0118] When the liquid containing the raw material of the catalyst composition is mixed, it is preferred that the number of moles of the transition metal element in the catalyst A is M a The number of moles of aluminum in aluminoxane is M b1 The number of moles of the ionic compound is M b2 In the case of (M b1 +M b2 ) / M a The liquid containing the raw material of the catalyst composition is mixed so that the value of is preferably 1 to 200,000, more preferably 5 to 100,000, and particularly preferably 10 to 80,000.

[0119] The temperature of the liquid in which the raw materials containing the catalyst composition are mixed is not particularly limited, but is preferably -100 to 100°C, more preferably -50 to 50°C.

[0120] The mixing of the solution of Catalyst A and the aluminoxane and / or ionic compound for preparing the catalyst composition may be carried out in a device separate from the polymerization vessel before polymerization, or may be carried out in the polymerization vessel before or during polymerization.

[0121] Hereinafter, the materials used in the preparation of the catalyst composition and the conditions for preparing the catalyst composition will be described.

[0122] [Aluminoxane]

[0123] As the aluminoxane, various aluminoxanes that have been used as co-catalysts in the polymerization of various olefins can be used without particular limitation. Typically, the aluminoxane is an organoaluminoxane.

[0124] When producing the catalyst composition, the aluminoxane may be used alone or in combination of two or more.

[0125] Alkyl aluminoxane is preferably used as the aluminoxane. Examples of the alkyl aluminoxane include compounds represented by the following formula (b1-1) or (b1-2). The alkyl aluminoxane represented by the following formula (b1-1) or (b1-2) is a product obtained by the reaction of trialkylaluminum and water.

[0126] [Chemical Formula 9]

[0127]

[0128] [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.]

[0129] Examples of the alkylaluminoxane include methylaluminoxane and modified methylaluminoxane (MMAO) in which a portion of the methyl groups of methylaluminoxane are substituted with other alkyl groups. As the modified methylaluminoxane, for example, a modified methylaluminoxane having an alkyl group having 2 to 4 carbon atoms, such as an ethyl group, propyl group, isopropyl group, butyl group, or isobutyl group, is preferably a modified methylaluminoxane in which a portion of the methyl groups are substituted with an isobutyl group. Specific examples of the alkylaluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, and methylisobutylaluminoxane. Among these, methylaluminoxane and methylisobutylaluminoxane are preferred.

[0130] Alkyl aluminoxane can be prepared by a known method. In addition, commercially available products can be used as alkyl aluminoxane. Examples of commercially available alkyl aluminoxanes include MMAO-3A, ​​TMAO-200 series, TMAO-340 series, solid MAO (all manufactured by Tosoh Finechem Co., Ltd.), and methyl aluminoxane solution (manufactured by Albemarle).

[0131] [Ionic compounds]

[0132] The ionic compound is a compound that generates a cationic transition metal compound by reacting with the catalyst A.

[0133] As the ionic compounds involved, anions containing tetrakis(pentafluorophenyl)borate, dimethylphenylammonium cations ((CH3)2N(C6H5)H + ) such as amine cations with active protons, (C6H5)3C + Such ionic compounds include trisubstituted carbocations, carborane cations, metallocarborane cations, and ferrocenium cations having transition metals.

[0134] Preferred examples of ionic compounds include borates. Preferred specific examples of borates include tetrakis(pentafluorophenyl)trityl borate, dimethylphenylammonium tetrakis(pentafluorophenyl)borate, and N-methyldialkylammonium tetrakis(pentafluorophenyl)borate, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and N-methyldi-n-decylammonium tetrakis(pentafluorophenyl)borate.

[0135] Furthermore, from the viewpoint of easily producing the cycloolefin copolymer in good yield, it is preferred that at least one compound selected from aluminoxanes and alkylaluminum compounds be present in the polymerization vessel before the catalyst A or the catalyst composition containing the catalyst A is added.

[0136] Aluminoxane is as described in the method for producing the catalyst composition.

[0137] As the alkylaluminum compound, any compound conventionally used in olefin polymerization, etc. can be used without particular limitation. Examples of the alkylaluminum compound include compounds represented by the following general formula (II).

[0138] (R 10 ) z AlX 3-z (II)

[0139] (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.

[0140] Examples of the alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and an n-octyl group.

[0141] Specific examples of the alkylaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, and tri-n-octylaluminum; dialkylaluminum halides such as dimethylaluminum chloride and diisobutylaluminum chloride; dialkylaluminum hydrides such as diisobutylaluminum hydride; and dialkylaluminum alkoxides such as dimethylaluminum methoxide.

[0142] When aluminoxane is added to the polymerization vessel before adding Catalyst A or a catalyst composition containing Catalyst A, the amount thereof is preferably 1 to 1,000,000 mol, more preferably 10 to 100,000 mol, as the number of moles of aluminum in the aluminoxane per 1 mol of Catalyst A.

[0143] When the alkylaluminum compound is added to the polymerization vessel before adding the catalyst A or the catalyst composition containing the catalyst A, the amount thereof is preferably 1 to 500,000 mol, more preferably 10 to 50,000 mol, as a mole of aluminum per 1 mol of the catalyst A.

[0144] The polymerization is preferably carried out in the presence of catalyst A and aluminoxane or in the presence of catalyst A, an ionic compound and an aluminum alkyl.

[0145] The polymerization conditions are not particularly limited as long as a cycloolefin copolymer having desired physical properties can be obtained, and known conditions can be used.

[0146] The amount of the catalyst composition used can be deduced from the amount of the metal-containing compound used in its preparation. The amount of the catalyst composition used, as the mass of the metal-containing compound used in its preparation, is preferably 0.000000001 to 0.005 mol, more preferably 0.00000001 to 0.0005 mol, per 1 mol of norbornene monomer.

[0147] The polymerization time is not particularly limited, and the polymerization is carried out until a desired yield is achieved or the molecular weight of the polymer rises to a desired level.

[0148] The polymerization time varies depending on the temperature, the composition of the catalyst, and the composition of the monomers, but is typically 0.01 to 120 hours, preferably 0.1 to 80 hours, and more preferably 0.2 to 10 hours.

[0149] Preferably, at least a portion, preferably all, of the catalyst composition is added continuously to the polymerization vessel.

[0150] By continuously adding the catalyst composition, the cycloolefin copolymer can be produced continuously, thereby reducing the production cost of the cycloolefin copolymer.

[0151] The cycloolefin copolymer produced by the above method has excellent processability and mechanical properties (toughness). Therefore, the cycloolefin copolymer produced by the above method is particularly suitable for use as a material for functional packaging films or sheets for packaging materials such as optical films or sheets, shrink wrap films, and pharmaceutical packaging, medical device packaging, and food packaging.

[0152] On the other hand, when the cycloolefin copolymer of this embodiment is used for molding, in order to improve the processability of the film, polyolefins such as polyethylene and polypropylene, elastomers such as styrene elastomers, etc. can also be mixed by various methods such as adding them to production equipment and adding them during synthesis, and then provided for processing such as molding.

[0153] <Resin composition>

[0154] The resin composition of this embodiment contains the cycloolefin copolymer of this embodiment described above. Since the resin composition of this embodiment contains the cycloolefin copolymer of this embodiment, the resin composition and the molded article formed therefrom can have excellent processability and mechanical properties.

[0155] The resin composition of this embodiment preferably further contains an antioxidant. By containing an antioxidant, decomposition / deterioration and yellowing of the resin composition during processing can be suppressed.

[0156] Antioxidants can be used alone or in combination of two or more. Examples of antioxidants include hindered phenol antioxidants and phenol antioxidants. Furthermore, they can be used in combination with antioxidants such as hindered amine antioxidants and sulfides. As hindered phenol antioxidants, specifically, 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) benzyl malonate, 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) butyrate] ethylene glycol ester, 4,4'-butylenebis(6-tert-butyl-m-cresol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, tetra[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, 2-octylthio-4,6-bis(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-hexyl glycol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bisoctylthio-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, 2, 2-Thio-divinylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid), 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, etc.

[0157] In the present embodiment, the antioxidant is contained in the resin composition in an amount of preferably 0.01 to 5% by mass, more preferably 0.1 to 1% by mass.

[0158] The resin composition of this embodiment may also contain, in addition to the above-mentioned components, known additives commonly added to thermoplastic resins and thermosetting resins, such as mold release agents, lubricants, plasticizers, flame retardants, colorants such as dyes and pigments, crystallization accelerators, crystallization nucleating agents, heat stabilizers, weathering stabilizers, preservatives, etc., in order to impart desired properties corresponding to its purpose, within the scope of not impairing its effects.

[0159] <Film or sheet molded products>

[0160] The film-like or sheet-like molded article of this embodiment is formed by molding the cycloolefin copolymer of this embodiment or the resin composition of this embodiment. As described above, the cycloolefin copolymer of this embodiment has excellent processability and mechanical properties (toughness). Therefore, it is easy to mold into a film-like or sheet-like shape. In addition, the resulting film-like or sheet-like molded article has excellent mechanical properties (toughness).

[0161] The film or sheet molded product of this embodiment can be obtained by molding the cycloolefin copolymer of this embodiment alone or a composition to which other resin components or additives are added as needed into a film or sheet by known extrusion molding such as extrusion molding using a T-die.

[0162] Example

[0163] Hereinafter, this embodiment will be described in more detail with reference to examples, but this embodiment is not limited to the following examples.

[0164] [Examples 1 to 7, Comparative Examples 1 and 2]

[0165] In each embodiment / comparative example, under nitrogen atmosphere, 1m 3In a SUS-made polymerization machine, after adding 157 kg of decahydronaphthalene and 23 kg of norbornene, TIBA (triisobutylaluminum (manufactured by Tosoh Fine Chemicals Co., Ltd.) / toluene solution (1 mol / L)) was added as a co-catalyst 1 in the amount shown in Table 1 (except Example 4, Comparative Examples 1 and 2). Next, ethylene was circulated in the polymerization machine and saturated. The temperature and pressure of the polymerization machine were raised to 90°C and a gauge pressure of 0.9 MPa. After confirming that the temperature in the polymerization machine was sufficiently stable, the catalyst (toluene solution) and the amount of catalyst shown in Table 1 of each Example / Comparative Example were added. However, with respect to Example 6 and Example 7, the following procedure was followed. That is, in Example 6, TMAO (see below) was slowly added dropwise to Catalyst 6 (Toluene Solution) so that the amount of trimethylaluminum added became 3 equivalents relative to the amount of the catalyst, and then the substance stirred at room temperature for 1 hour was added in the amount of the catalyst shown in Table 1. In Example 7, a toluene solution of trimethylaluminum was slowly added dropwise to Catalyst 7 (toluene solution) to a concentration of 3 equivalents of trimethylaluminum relative to the catalyst amount. The mixture was then stirred at room temperature for one hour before the catalyst was added in the amounts shown in Table 1. Furthermore, in each Example / Comparative Example, 3 g of Co-catalyst 2 shown in Table 1 was added, and after 15 minutes of reaction, 2-propanol was added to the polymerization solution to terminate the polymerization. In the Co-catalyst 2 shown in Table 1, "borate" refers to N-methyldialkylammonium tetrakis(pentafluorophenyl)borate (alkyl group: C14-C18 (average: C17.5)) (manufactured by Tosoh Fine Chemicals Co., Ltd.). In addition, “TMAO” used a TMAO-211 toluene solution (a solution of 9.0% by mass (as content of Al atoms) methylaluminoxane, manufactured by Tosoh Fine Chemicals Co., Ltd., and containing 26 mol% of trimethylaluminum relative to the total Al), and “MMAO” used a MMAO-3A toluene solution (6.5% by mass (as content of Al atoms) [(CH3) 0.7 (iso-C4H9) 0.3 AlO] n (a toluene solution of methyl isobutyl aluminoxane represented by EMI15.1, manufactured by Tosoh Fine Chemicals Co., Ltd., and containing 6 mol% of trimethylaluminum relative to the total Al.) The structures of the catalysts used in each of the Examples and Comparative Examples are shown below.

[0166] [Chemical Formula 10]

[0167]

[0168] [Chemical Formula 11]

[0169]

[0170] With respect to the cycloolefin copolymers obtained in each example / comparative example, 13 C-NMR is used to identify the racemic diad site, the meso diad site and the triad site, and the amount of each present (mol%) is calculated. The central peak of the solvent (C2D2Cl4) is determined to be 74ppm. At the same time, the ratio of the meso diad site (mol%) to the racemic diad site (mol%) is calculated. The calculation results are shown in Table 1. In addition, in Comparative Example 3, since all are meso, they are expressed as "∞". In addition, 13 The measurement conditions of C-NMR measurement are as follows.

[0171] Measuring machine: AVANCE400III III manufactured by BRUKER

[0172] ·Determination solvent: C2D2Cl4 (1,1,2,2-Tetrachloroethane-d2)

[0173] ·Measurement temperature: 100℃

[0174] <Molecular weight determination>

[0175] The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by gel permeation chromatography under the following measurement conditions: Standard sample: Monodisperse polystyrene was used.

[0176] ·Measurement instrument: Viscotek TDA302 detector + pump autosampler device manufactured by Malvern

[0177] Detector: RI

[0178] ·Measurement solvent: toluene

[0179] ·Measurement temperature: 75℃

[0180] [evaluate]

[0181] (1) Melt viscosity

[0182] The cycloolefin copolymers obtained in each example / comparative example were measured using a capillary analyzer (capillograph) manufactured by Toyo Seiki Seisaku-sho, Ltd., using a capillary. The melt viscosity at cylinder temperatures of 180, 220, and 260°C was measured using a flat die, and the melt viscosity at 230°C was determined.

[0183] (2) Tensile elongation

[0184] The cycloolefin copolymers obtained in each of the Examples and Comparative Examples were molded into 70 mm x 70 mm x 2 mm thick flat plates using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name: SE75D) at a cylinder temperature of 220°C, a mold temperature of 50°C, and an injection speed of 80 mm / sec to produce test specimens. The tensile elongation (%) of these specimens was measured in accordance with ISO 527-1 and 2, with the tensile elongation at yield point and the tensile elongation at break being determined. The results are shown in Table 1.

[0185] [Table 1]

[0186]

[0187] As shown in Table 1, the cycloolefin copolymers of Examples 1 to 7 have low melt viscosities, high tensile elongation at yield and tensile elongation at break, and excellent toughness (mechanical properties). That is, the cycloolefin copolymers of Examples 1 to 7 have excellent both processability and mechanical properties. In particular, in Examples 1 to 3 and 6 to 7, the ratio of the content (mol%) of the meso-type diad site to the content (mol%) of the racemic-type diad site is within a particularly preferred range (0.20 to 0.90), achieving a balanced result between melt viscosity (processability) and toughness (mechanical properties) compared to Examples 4 and 5, which are outside this range. On the other hand, the cycloolefin copolymers of Comparative Examples 1 to 2 did not achieve good results in terms of melt viscosity, tensile elongation at yield, and tensile elongation at break. Specifically, in Comparative Example 1, where the ratio is less than 0.10, the tensile elongation at break is poor. Furthermore, in Comparative Example 2, the ratio of the content (mol%) of the meso dyad site to the content (mol%) of the racemic dyad site exceeded 3.00, and the melt viscosity was high.

Claims

1. A resin composition, characterized in that It contains a cyclic olefin copolymer containing a structural unit derived from a norbornene monomer and a structural unit derived from ethylene, The structural unit derived from the norbornene monomer has a meso-type diad site, a racemic diad site, and a racemic triad site, The ratio of the molar percentage of the meso diad site to the molar percentage of the racemic diad site is 0.10 to 3.00, and the content of the triad site is 2.5 mol% or less. The glass transition temperature is 110°C or lower.

2. A resin composition, characterized in that It contains a cyclic olefin copolymer containing a structural unit derived from a norbornene monomer and a structural unit derived from ethylene, The structural unit derived from the norbornene monomer has a meso-type diad site, a racemic diad site, and a racemic triad site, The ratio of the molar percentage of the meso diad site to the molar percentage of the racemic diad site is 0.10 to 3.00, the content of the triad site is 2.5 mol% or less, and the total content of the racemic diad site and the meso diad site is 0.1 to 10 mol%.

3. A film-shaped or sheet-shaped molded product, characterized in that: is obtained by molding a cyclic olefin copolymer containing a structural unit derived from a norbornene monomer and a structural unit derived from ethylene, The structural unit derived from the norbornene monomer has a meso-type diad site, a racemic diad site, and a racemic triad site, The ratio of the molar percentage of the meso diad site to the molar percentage of the racemic diad site is 0.10 to 3.00, and the content of the triad site is 2.5 mol% or less. The glass transition temperature is 110°C or lower.

4. A film-shaped or sheet-shaped molded product, characterized in that: is obtained by molding a cycloolefin copolymer containing a structural unit derived from a norbornene monomer and a structural unit derived from ethylene, The structural unit derived from the norbornene monomer has a meso-type diad site, a racemic diad site, and a racemic triad site, The ratio of the molar percentage of the meso diad site to the molar percentage of the racemic diad site is 0.10 to 3.00, the content of the triad site is 2.5 mol% or less, and the total content of the racemic diad site and the meso diad site is 0.1 to 10 mol%.

5. A film-shaped or sheet-shaped molded product, characterized in that: The invention is obtained by molding the resin composition according to claim 1 or 2.

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