Solution composition and film

Abstract

To provide a solution composition comprising a cyclic olefin copolymer which is a copolymer of a cyclic olefin monomer and an α-olefin having 3 or more and 20 or less carbon atoms and can form a film having both excellent breaking strain and toughness and having excellent bending resistance and to provide a film formed using the solution composition.SOLUTION: There is provided a solution composition comprising (A) a cyclic olefin copolymer and (B) an organic solvent, wherein the amount of the structural unit derived from the α-olefin in the cyclic olefin copolymer (A) is adjusted to be 10 mol% or more and 40 mol% or less based on the total structural units and the cyclic olefin copolymer (A) is adjusted to have two or more glass transition temperatures in the range of 0°C to 300°C as determined by solid viscoelasticity measurement by using a copolymer of a cyclic olefin monomer and an α-olefin having 3 or more and 20 or less carbon atoms as the cyclic olefin copolymer (A).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a solution composition and a film. [Background technology]

[0002] Cyclic olefin polymers and cyclic olefin copolymers (also referred to as "COP" and "COC," respectively) have low moisture absorption and high transparency. For this reason, COPs and COCs are used in a variety of applications, including optical materials such as optical disk substrates, optical films, and optical fibers. A typical COC is a copolymer of cyclic olefin and ethylene. The glass transition temperature of such a copolymer can be changed by the copolymerization composition of the cyclic olefin and ethylene. Therefore, a copolymer of cyclic olefin and ethylene can be produced as a copolymer with a higher glass transition temperature (Tg) than COPs, and it is even possible to achieve a Tg of over 200°C, which is difficult to achieve with COPs. However, such copolymers are hard and brittle. Therefore, such copolymers have problems such as low mechanical strength and poor handling and processability.

[0003] One method for improving the mechanical strength of high TgCOC is to copolymerize cyclic olefins with α-olefins other than ethylene (hereinafter referred to as "specific α-olefins"). Various studies have been conducted on the copolymerization of cyclic olefins with specific α-olefins.

[0004] The copolymerization of a cyclic olefin and a specific α-olefin is significantly different from the copolymerization of a cyclic olefin and ethylene. Under the conditions under which a high molecular weight material can be obtained by copolymerization of a cyclic olefin and ethylene, a chain transfer reaction caused by the specific α-olefin occurs in the copolymerization of a cyclic olefin and a specific α-olefin, making it difficult to obtain a high molecular weight material. Therefore, copolymers of a cyclic olefin and a specific α-olefin have been considered unsuitable for use as molding materials (see, for example, Non-Patent Document 1).

[0005] For this reason, various studies have been conducted to improve the molding processability of copolymers of cyclic olefins and specific α-olefins.For example, as a method for producing a copolymer of cyclic olefins and specific α-olefins that has a relatively high molecular weight and can be molded into a film, a method has been proposed in which a cyclic olefin and a specific α-olefin are copolymerized in the presence of a titanocene catalyst having a specific structure and triphenylmethylium tetrakis(pentafluorophenyl)borate (see Patent Document 1).

[0006] Norbornene-based polymers such as COP and COC are also used as materials for the resin layer in metal laminates obtained by laminating a resin layer and a metal foil layer. For example, Patent Documents 2 to 4 disclose metal resin laminates having a resin layer obtained from a solution containing a norbornene-based polymer. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-56275 [Patent Document 2] International Publication No. 98 / 56011 Brochure [Patent Document 3] Japanese Patent Application Laid-Open No. 2005-103949 [Patent Document 4] Japanese Patent Application Laid-Open No. 2016-37045 [Non-patent literature]

[0008] [Non-Patent Document 1] Jung, HY et al., Polyhedron, 2005, Vol. 24, pp. 1269-1273 Summary of the Invention [Problem to be solved by the invention]

[0009] However, it is difficult to produce a copolymer of a cyclic olefin and a specific α-olefin that has both excellent breaking strain and toughness as a cyclic olefin copolymer, even by the method described in Patent Document 1. For these reasons, no cyclic olefin copolymer solution has been obtained that can form a film that has both excellent breaking strain and toughness and excellent bending resistance.

[0010] The present invention has been made in view of the above circumstances, and aims to provide a solution composition containing a cyclic olefin copolymer, which is a copolymer of a cyclic olefin monomer and an α-olefin having from 3 to 20 carbon atoms, capable of forming a film having both excellent breaking strain and excellent toughness and excellent bending resistance, and a film formed using the solution composition. [Means for solving the problem]

[0011] The present inventors have found that the above-mentioned problems can be solved by using, in a solution composition comprising (A) a cyclic olefin copolymer and (B) an organic solvent, a copolymer of a cyclic olefin monomer and an α-olefin having from 3 to 20 carbon atoms as the cyclic olefin copolymer, adjusting the amount of structural units derived from the α-olefin in the cyclic olefin copolymer to from 10 mol % to 40 mol % of all structural units, and allowing the cyclic olefin copolymer to have two or more glass transition temperatures within the range of 0°C to 300°C as determined by solid viscoelasticity measurement, and have thus completed the present invention. More specifically, the present invention provides the following.

[0012] (I) A solution composition comprising (A) a cyclic olefin copolymer and (B) an organic solvent, (A) The cyclic olefin copolymer is an addition polymer of a cyclic olefin monomer and an α-olefin having 3 to 20 carbon atoms, (A) the ratio of the number of moles of structural units derived from α-olefin to the number of moles of all structural units of the cyclic olefin copolymer is 10 mol % or more and 40 mol % or less, (A) A solution composition, wherein the cyclic olefin copolymer is a cyclic olefin copolymer having two or more glass transition temperatures within the range of 0°C to 300°C as determined by viscoelasticity measurement.

[0013] (II) The solution composition according to (I), wherein the cyclic olefin copolymer (A) has at least one glass transition temperature within the range of 0°C to 100°C and at least one glass transition temperature within the range of 160°C to 300°C.

[0014] (III) The solution composition according to (I) or (II), wherein the cyclic olefin copolymer (A) has at least one glass transition temperature in the range of less than 0°C, in the range of 0°C to 100°C, and in the range of 160°C to 300°C.

[0015] (VI) A film obtained from the solution composition according to any one of (I) to (III).

[0016] (V) The film according to (IV), which has a folding endurance of 100 or more times as measured in accordance with JIS P8115. [Effects of the Invention]

[0017] According to the present invention, it is possible to provide a solution composition containing a cyclic olefin copolymer, which is a copolymer of a cyclic olefin monomer and an α-olefin having from 3 to 20 carbon atoms, which can form a film having both excellent breaking strain and excellent toughness and excellent bending resistance, and a film formed using the solution composition. DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0019] <Solution composition> The solution composition contains (A) a cyclic olefin copolymer and (B) an organic solvent. The solution composition may contain various additives within the range that does not impair the desired effects. When the solution composition contains the following (A) cyclic olefin copolymer, it is possible to form a film having excellent breaking strain, excellent toughness, and excellent bending resistance using the solution composition. The use of the solution composition is not limited to film formation. The solution composition may be used as a so-called paint or a varnish used for coating metal wiring or the like, or may be used for spinning to produce fibers of the cyclic olefin copolymer.

[0020] <(A) Cyclic olefin copolymer> (A) Cyclic olefin copolymer is an addition polymer of a cyclic olefin monomer and an α-olefin having 3 to 20 carbon atoms. In (A) cyclic olefin copolymer, the ratio of the number of moles of structural units derived from α-olefin to the number of moles of all structural units is 10 to 40 mol %. In addition, (A) cyclic olefin copolymer has two or more glass transition temperatures within the range of 0 to 300°C as determined by viscoelasticity measurement.

[0021] Although the detailed mechanism is unknown, the cyclic olefin copolymer (A) has both excellent breaking strain and excellent toughness. Specifically, the (A) cyclic olefin copolymer exhibits a tensile strength of preferably 25 MPa or more, more preferably 30 MPa or more, and even more preferably 40 MPa or more, as measured in a tensile test performed at 23°C using a No. 2 dumbbell test piece having a thickness of 50 μm according to a method in accordance with ISO 527-3. Furthermore, the cyclic olefin copolymer (A) preferably exhibits a breaking strain of 3.5% or more, more preferably 5% or more, as measured by the tensile test according to the above method. Furthermore, the cyclic olefin copolymer (A) preferably exhibits a tensile modulus of elasticity of 1000 MPa or more, more preferably 1100 MPa or more, and even more preferably 1500 MPa or more, as measured by the tensile test according to the above method. Therefore, when the solution composition is used, a film having both excellent breaking strain and excellent toughness can be formed.

[0022] In the (A) cyclic olefin copolymer, the ratio of the number of moles of structural units derived from α-olefin to the number of moles of all structural units is 10 mol% or more and 40 mol% or less, and preferably 20 mol% or more and 30 mol% or less. If the ratio of the number of moles of structural units derived from α-olefin is too high, it is difficult to obtain a (A) cyclic olefin copolymer with high tensile strength and tensile modulus. If the ratio of the number of moles of structural units derived from α-olefin is too high, it is difficult to obtain a (A) cyclic olefin copolymer with high glass transition temperature and excellent heat resistance. The ratio of the number of moles of structural units derived from α-olefins is 13 It can be calculated by measuring the C-NMR spectrum.

[0023] (A) The cyclic olefin copolymer may contain structural units other than the structural units derived from the cyclic olefin monomer and the structural units derived from an α-olefin having from 3 to 20 carbon atoms, provided that the object of the present invention is not impaired. As the other structural units, structural units derived from a compound copolymerizable with the cyclic olefin monomer and the α-olefin having from 3 to 20 carbon atoms and having a carbon-carbon unsaturated double bond may be used. Typically, structural units derived from ethylene are preferred as the other structural units.

[0024] In the (A) cyclic olefin copolymer, the sum of the ratio of the number of moles of structural units derived from cyclic olefin monomers and the ratio of the number of moles of structural units derived from α-olefins to the number of moles of all structural units is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and most preferably 100 mol%.

[0025] (A) The cyclic olefin copolymer has two or more glass transition temperatures within the range of 0°C to 300°C as determined by viscoelasticity measurement. The glass transition temperature can be measured by observing the viscoelastic behavior of a 50 μm-thick film-shaped molded product with a solid rheometer at −100° C. to 300° C. Specifically, the glass transition temperature is determined as the peak top temperature in the tan δ chart obtained by the above-mentioned measurement.

[0026] The (A) cyclic olefin copolymer preferably has at least one glass transition temperature within the range of 0°C to 100°C and at least one glass transition temperature within the range of 160°C to 300°C, as this provides good mechanical properties measured by the above tensile test. In particular, since the breaking strain measured by the above-mentioned tensile test is large, it is preferable that (A) cyclic olefin copolymer has at least one glass transition temperature in the range below 0°C, in the range of 0°C to 100°C, and in the range of 160°C to 300°C. Within the above range of 0°C to 100°C, the range of 30°C to 80°C is preferred, and the range of 40°C to 70°C is more preferred. Within the above range of 160°C to 300°C, 170°C to 280°C is preferred, and 180°C to 270°C is more preferred. Within the above range of less than 0°C, -50°C to 0°C is preferred, and -40°C to -10°C is more preferred.

[0027] Typically, the (A) cyclic olefin copolymer has one glass transition temperature in the range of 0°C to 100°C and one glass transition temperature in the range of 160°C to 300°C, or has one glass transition temperature in the range below 0°C, one glass transition temperature in the range of 0°C to 100°C, and one glass transition temperature in the range of 160°C to 300°C.

[0028] The molecular weight of the (A) cyclic olefin copolymer is not particularly limited. The weight average molecular weight (Mw) of the (A) cyclic olefin copolymer is preferably 5,000 or more and 200,000 or less, and more preferably 10,000 or more and 100,000 or less, as a polystyrene-equivalent value measured by gel permeation chromatography (GPC). The number average molecular weight (Mn) of the (A) cyclic olefin copolymer is preferably 5,000 or more and 200,000 or less, more preferably 10,000 or more and 100,000 or less, in terms of polystyrene, measured by gel permeation chromatography (GPC). The dispersion ratio (Mw / Mn) is preferably 1.2 or more, and more preferably 1.3 or more.

[0029] [Cyclic olefin monomer] The cyclic olefin monomer is not particularly limited as long as it does not impair the object of the present invention. Typically, norbornene and substituted norbornene are preferably used as the cyclic olefin monomer. Norbornene is particularly preferred as the cyclic olefin monomer in terms of a good balance between cost, polymerizability, and the physical properties of the resulting cyclic olefin copolymer (A). The cyclic olefin monomer may be used alone or in combination of two or more.

[0030] The substituted norbornene is not particularly limited. Examples of the substituents on the substituted norbornene include halogen atoms and monovalent or divalent hydrocarbon groups. Specific examples of the substituted norbornene include compounds represented by the following formula (I):

[0031] [ka]

[0032] In formula (I), R a1 ~R a12 may be the same or different and each represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. R a9 and R a10 , R a11 and R 12 may combine to form a divalent hydrocarbon group. R a9 or R a10 and R a11 or R a12 may be bonded to each other to form a ring. n is 0 or a positive integer. If n is 2 or more, R a5 ~R a8 may be the same or different in each repeating unit. However, if n is 0, R a1 ~R a4 and Ra9 ~R a12 At least one of the is not a hydrogen atom.

[0033] R a1 ~R a8 Specific examples of R include a hydrogen atom; a halogen atom such as fluorine, chlorine, and bromine; and an alkyl group having 1 to 20 carbon atoms. a1 ~R a8 R may all consist of different atoms or groups. a1 ~R a8 Some or all of these may be the same atom or group.

[0034] R a9 ~R a12 Specific examples of R include a hydrogen atom; halogen atoms such as fluorine, chlorine, and bromine; alkyl groups having 1 to 20 carbon atoms; cycloalkyl groups such as a cyclohexyl group; substituted or unsubstituted aromatic hydrocarbon groups such as a phenyl group, a tolyl group, an ethylphenyl group, an isopropylphenyl group, a naphthyl group, and an anthryl group; and aralkyl groups such as a benzyl group and a phenethyl group. a9 ~R a12 R may all consist of different atoms or groups. a9 ~R a12 Some or all of these may be the same atom or group.

[0035] R a9 and R a10 , or R a11 and R a12 Specific examples of divalent hydrocarbon groups that can be formed by combining the above groups include alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group.

[0036] R a9 or R a10 and R a11 or R a12When these bond to each other to form a ring, the ring formed may be a monocyclic or polycyclic ring. The ring formed may be a polycyclic ring having a bridge. The ring formed may have a double bond. The ring formed may have a substituent such as a methyl group.

[0037] Specific examples of the substituted norbornene represented by 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-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-hexyl-bicyclo[2.2.1]hept-2-ene, 5-methyl ... Bicyclic olefins such as cyclo[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, and 5-propenyl-bicyclo[2.2.1]hept-2-ene; Tricyclo[4.3.0.1 2,5 ]Deca-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 2,5 ]dec-3-ene; tricyclo[4.4.0.1 2,5 ]undeca-3,7-diene or tricyclo[4.4.0.1 2,5 ]undeca-3,8-diene or partially hydrogenated products thereof (or adducts of cyclopentadiene and cyclohexene), tricyclo[4.4.0.1 2,5 ]undec-3-ene; three-ring 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; 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 .17,10 ]dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene, 8-methylidenetetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene, 8-ethylidenetetracyclo[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 olefins 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 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); 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 .13,6 .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; and polycyclic olefins such as a tetramer of cyclopentadiene.

[0038] Among these, alkyl-substituted norbornenes such as bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups, and alkylidene-substituted norbornenes such as bicyclo[2.2.1]hept-2-ene substituted with one or more alkylidene groups are preferred. 5-Ethylidene-bicyclo[2.2.1]hept-2-ene (common name: 5-ethylidene-2-norbornene, or simply ethylidenenorbornene) is particularly preferred.

[0039] [α-Olefin] The α-olefin is an α-olefin having 3 to 20 carbon atoms. As such an α-olefin, not only unsubstituted α-olefins but also substituted α-olefins having a substituent such as a halogen atom can be used. The number of carbon atoms in the α-olefin is 3 to 20, preferably 4 to 12, and more preferably 6 to 10.

[0040] Specific examples of α-olefins having 3 to 12 carbon atoms 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 these, 1-hexene, 1-octene, and 1-decene are preferred.

[0041] [(A) Method for producing cyclic olefin copolymer] The method for producing the cyclic olefin copolymer (A) will be described below. (A) A method for producing a cyclic olefin copolymer includes addition polymerizing a cyclic olefin monomer and an α-olefin in the presence of a titanocene catalyst represented by the following formula (1) and a co-catalyst, wherein the co-catalyst includes a borate compound and a hindered phenol. In the above production method, the cyclic olefin monomer and the α-olefin are each added in two or more batches to the reaction system where addition polymerization is carried out. [ka] (In formula (1), R 1 ~R 3 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R 4 and R 5 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom; R 6 ~R 13 are each independently a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, an aryl group having from 6 to 12 carbon atoms, or a silyl group which may have, as a substituent, a monovalent hydrocarbon group having from 1 to 12 carbon atoms.

[0042] According to this method, it is possible to provide a cyclic olefin copolymer (A) that satisfies any one of the above-mentioned requirements (I) to (III). Hereinafter, this method will also be referred to as the "first production method."

[0043] The following production method is also preferred as a method for producing the cyclic olefin copolymer (A). This method can provide the cyclic olefin copolymer (A) that satisfies the constituent requirements described in (I) or (II) above. Specifically, this method involves addition polymerizing a cyclic olefin monomer and an α-olefin in the presence of a titanocene catalyst represented by formula (1) and a co-catalyst. The co-catalyst includes a borate compound and a hindered phenol. The addition polymerization is carried out at a temperature ranging from 10°C to 60°C. The titanocene catalyst represented by formula (1) is the same as the titanocene catalyst described above for the first production method. Hereinafter, this method will also be referred to as the "second manufacturing method."

[0044] (First manufacturing method) In the first production method, a monomer containing the above-mentioned cyclic olefin monomer and α-olefin is used. The types of cyclic olefin monomer, α-olefin, and copolymerization ratio thereof are the same as those described for (A) cyclic olefin copolymer.

[0045] In the first production method, the cyclic olefin monomer and the α-olefin are each added in two or more batches to a reaction system where addition polymerization is carried out. By adding the cyclic olefin monomer and the α-olefin in this way, it is easy to obtain a cyclic olefin copolymer (A) having good mechanical properties, and also, by adding the cyclic olefin monomer and the α-olefin in this way, it is easy to obtain a cyclic olefin copolymer (A) having a glass transition temperature in the range of less than 0°C.

[0046] When adding in portions, the number of portions is not particularly limited. For example, the number of portions is preferably 2 or more and 5 or less, more preferably 2 or 3, and even more preferably 2. When adding in portions, the amount of cyclic olefin monomer or α-olefin added per portion is preferably TA / N×0.5 or more and TA / N×1.5 or less, more preferably TA / N×0.7 or more and TA / N×1.3 or less, and even more preferably TA / N×0.9 or more and TA / N×1.1 or less, where TA is the mass of the total amount added and N is the number of portions added.

[0047] When the number of divisions is two, the amount of cyclic olefin monomer or α-olefin added per division is preferably 25% by mass or more and 75% by mass or less, more preferably 35% by mass or more and 65% by mass or more, and even more preferably 45% by mass or more and 55% by mass or less, based on the total mass of the addition amount.

[0048] When the divided addition is carried out, at least one of the cycloolefin monomer and the α-olefin is added to the reaction vessel at or before the start of the addition polymerization, and then, at any timing after the start of the addition polymerization, the second or subsequent addition of the cycloolefin monomer or the α-olefin is carried out. When adding the components in portions, the time between each addition is preferably 3 minutes or more and 20 minutes or less, more preferably 5 minutes or more and 15 minutes or less. When the divided additions are carried out, the timing of addition of the cyclic olefin monomer and the timing of addition of the α-olefin may be simultaneous or different. The number of times the cyclic olefin monomer is added may be different from the number of times the α-olefin is added.

[0049] As described above, when producing the cyclic olefin copolymer (A), a titanocene catalyst represented by the above formula (1) is used. In formula (1), R 1 ~R 3are each independently an alkyl group having from 1 to 6 carbon atoms or an aryl group having from 6 to 12 carbon atoms. Specific examples thereof include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclopentyl group, and a cyclohexyl group; and aryl groups such as a phenyl group, a biphenyl group, a phenyl group or a biphenyl group having the above alkyl group as a substituent, a naphthyl group, and a naphthyl group having the above alkyl group as a substituent.

[0050] R 4 and R 5 are each independently an alkyl group having from 1 to 12 carbon atoms, an aryl group having from 6 to 12 carbon atoms, or a halogen atom, and specific examples thereof include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, or any of these alkyl groups having the above-mentioned halogen atom as a substituent; a phenyl group, a biphenyl group, a naphthyl group, or any of these aryl groups having the above-mentioned halogen atom or alkyl group as a substituent.

[0051] R 6 ~R 13are each independently a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, an aryl group having from 6 to 12 carbon atoms, or a silyl group which may have a monovalent hydrocarbon group having from 1 to 12 carbon atoms as a substituent. Specific examples of alkyl groups having from 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, and cyclohexyl. Specific examples of aryl groups having from 6 to 12 carbon atoms include phenyl, biphenyl, naphthyl, and these aryl groups having the above alkyl groups as a substituent. Furthermore, specific examples of silyl groups having a monovalent hydrocarbon group having from 1 to 12 carbon atoms as a substituent include silyl groups having an alkyl group having from 1 to 12 carbon atoms as a substituent, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, or a cyclohexyl group.

[0052] Specific examples of the titanocene catalyst represented by general formula (1) include (isopropylamido)dimethyl-9-fluorenylsilanetitanium dimethyl, (isobutylamido)dimethyl-9-fluorenylsilanetitanium dimethyl, (t-butylamido)dimethyl-9-fluorenylsilanetitanium dimethyl, (isopropylamido)dimethyl-9-fluorenylsilanetitanium dichloride, (isobutylamido)dimethyl-9-(3,6-dimethylfluorenyl)silanetitanium dichloride, (t-butylamido)dimethyl-9-fluorenylsilanetitanium dichloride, ( (Isopropylamido)dimethyl-9-(3,6-dimethylfluorenyl)silanetitanium dichloride, (isobutylamido)dimethyl-9-(3,6-dimethylfluorenyl)silanetitanium dichloride, (t-butylamido)dimethyl-9-(3,6-dimethylfluorenyl)silanetitanium dimethyl, (isopropylamido)dimethyl-9-[3,6-di(i-propyl)fluorenyl]silanetitanium dichloride, (isobutylamido)dimethyl-9-[3,6-di(i-propyl)fluorenyl]silanetitanium dichloride, (t-butylamido)dimethyl methyl-9-[3,6-di(i-propyl)fluorenyl]silanetitanium dimethyl, (isopropylamido)dimethyl-9-[3,6-di(t-butyl)fluorenyl]silanetitanium dichloride, (isobutylamido)dimethyl-9-[3,6-di(t-butyl)fluorenyl]silanetitanium dichloride, (t-butylamido)dimethyl-9-[3,6-di(t-butyl)fluorenyl]silanetitanium dimethyl, (isopropylamido)dimethyl-9-[2,7-di(t-butyl)fluorenyl]silanetitanium dichloride, (isobutylamido)dimethyl

[0033] Examples of the silane titanium dichloride include (t-butylamido)dimethyl-9-[2,7-di(t-butyl)fluorenyl]silanetitanium dichloride, (t-butylamido)dimethyl-9-[2,7-di(t-butyl)fluorenyl]silanetitanium dimethyl, (isopropylamido)dimethyl-9-(2,3,6,7-tetramethylfluorenyl)silanetitanium dichloride, (isobutylamido)dimethyl-9-(2,3,6,7-tetramethylfluorenyl)silanetitanium dichloride, and (t-butylamido)dimethyl-9-(2,3,6,7-tetramethylfluorenyl)silanetitanium dimethyl.Preferred is (t-butylamido)dimethyl-9-fluorenylsilanetitanium dimethyl ((t-BuNSiMe2Flu)TiMe2). (t-BuNSiMe2Flu)TiMe2 is a titanium complex represented by the following formula (2), and can be easily synthesized, for example, based on the description in "Macromolecules, Vol. 31, p. 3184, 1998."

[0053] [ka] (In the formula, Me represents a methyl group, and t-Bu represents a tert-butyl group.)

[0054] The amount of the titanocene catalyst used is not particularly limited as long as the addition polymerization reaction proceeds smoothly. The amount of the titanocene catalyst used is preferably 0.001 parts by mass or more and 10 parts by mass or less, more preferably 0.01 parts by mass or more and 5 parts by mass or less, and even more preferably 0.1 parts by mass or more and 1 part by mass or less, relative to 100 parts by mass of the total amount of the cyclic olefin monomer and the α-olefin.

[0055] The addition polymerization of a cyclic olefin monomer and a monomer containing an α-olefin is carried out in the presence of the titanocene catalyst and a co-catalyst, which includes a borate compound and a hindered phenol. By carrying out addition polymerization in the presence of the titanocene catalyst and a cocatalyst so as to satisfy the above-mentioned predetermined conditions, a cyclic olefin copolymer (A) having both excellent breaking strain and excellent toughness can be obtained.

[0056] As the borate compound, any borate compound that has been conventionally used as a co-catalyst in the homopolymerization or copolymerization of cyclic olefin monomers can be used without any particular limitation. Specific preferred examples of the borate compound include triphenylmethylium tetrakis(pentafluorophenyl)borate, dimethylphenylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, and N-methyldin-normal-decylammonium tetrakis(pentafluorophenyl)borate.

[0057] As the hindered phenol, any hindered phenol that has been conventionally used as a co-catalyst in the homopolymerization or copolymerization of cyclic olefin monomers can be used without any particular limitation. Here, the hindered phenol is a phenol having a bulky substituent at at least one of the two adjacent positions to the phenolic hydroxyl group, such as an alkyl group other than a methyl group (e.g., isopropyl, isobutyl, sec-butyl, or tert-butyl group), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a substituted amino group, an alkylthio group, or an arylthio group.

[0058] Specific examples of hindered phenols include 2,6-di-tert-butyl-4-hydroxytoluene (BHT), 2,6-di-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-p-cresol, 3,3',5,5'-tetra-tert-butyl-4,4'-dihydroxybiphenyl, 3,3',5,5'-tetra-tert-butyl-2,2'-dihydroxybiphenyl, 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4',4"-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)2,4,6-trimethylbenzene. Among these, 2,6-di-tert-butyl-4-hydroxytoluene (BHT) and 2,6-di-tert-butylphenol are preferred because they have a small molecular weight and the desired effect of using a hindered phenol can be easily obtained by using a small amount.

[0059] Furthermore, the hindered phenol can increase the yield of the cyclic olefin copolymer (A) by reacting with the alkylaluminum compound in the polymerization system, and therefore it is preferred that the co-catalyst further contains an alkylaluminum compound. Specific examples of alkylaluminum compounds 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.

[0060] The amount of the borate compound used is not particularly limited as long as the addition polymerization reaction proceeds smoothly and a cyclic olefin copolymer (A) having the desired properties is obtained. The amount of the borate compound used is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total amount of the cyclic olefin monomer and the α-olefin.

[0061] The amount of the hindered phenol used is not particularly limited as long as the addition polymerization reaction proceeds smoothly and a cyclic olefin copolymer (A) having the desired properties is obtained. The amount of the hindered phenol used is preferably 0.001 to 100 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the total amount of the cyclic olefin monomer and the α-olefin.

[0062] The amount of the alkylaluminum compound used is not particularly limited as long as the addition polymerization reaction proceeds smoothly and a cyclic olefin copolymer (A) having the desired properties is obtained. The amount of the alkylaluminum compound used is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the total amount of the cyclic olefin monomer and the α-olefin.

[0063] The addition polymerization may be carried out in the presence of a solvent. The solvent is not particularly limited as long as it does not inhibit the polymerization reaction. Preferred solvents include, for example, hydrocarbon solvents and halogenated hydrocarbon solvents, with hydrocarbon solvents being preferred due to their ease of handling, thermal stability, and chemical stability. Specific examples of preferred solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), benzene, toluene, and xylene, and halogenated hydrocarbon solvents such as chloroform, methylene chloride, dichloromethane, dichloroethane, and chlorobenzene.

[0064] The solvent may be charged into the polymerization vessel alone, or may be charged into the polymerization vessel in the form of a monomer solution, a catalyst solution, or a cocatalyst solution.

[0065] When a solvent is used, the amount thereof is not particularly limited, and the amount of the solvent used is preferably 100 parts by mass or more and 100,000 parts by mass or less, more preferably 500 parts by mass or more and 10,000 parts by mass or less, and even more preferably 1,000 parts by mass or more and 5,000 parts by mass or less, relative to 100 parts by mass of the total amount of the cyclic olefin monomer and the α-olefin.

[0066] The temperature of the addition polymerization is not particularly limited and is, for example, preferably from -20°C to 200°C, more preferably from -10°C to 10°C, and even more preferably from -5°C to 5°C. When producing (A) cyclic olefin copolymers having glass transition temperatures in the range of less than 0°C, 0°C to 100°C, and 160°C to 300°C, respectively, the temperature of the addition polymerization is preferably -20°C or higher and lower than 10°C. The time for addition polymerization is not particularly limited and is, for example, preferably from 5 minutes to 30 minutes, more preferably from 8 minutes to 20 minutes, and even more preferably from 10 minutes to 15 minutes.

[0067] The atmosphere in which the addition polymerization reaction is carried out is not particularly limited, but an inert gas atmosphere is preferred, and examples of the inert gas that can be used include nitrogen gas and helium gas.

[0068] After the addition polymerization is carried out as described above to produce the cyclic olefin copolymer (A), the cyclic olefin copolymer is recovered from the reaction vessel in a conventional manner.

[0069] (Second manufacturing method) The second production method is similar to the first production method, except that the method for charging the cyclic olefin monomer and the α-olefin is not particularly limited, and the addition polymerization is carried out at a temperature in the range of 10°C or higher and 60°C or lower.

[0070] In the second production method, the method for charging the cyclic olefin monomer and the α-olefin may be the same as in the first production method. Because the charging operation is simple, the method for charging the cyclic olefin monomer and the α-olefin in the second production method is preferably a method in which the cyclic olefin monomer and the α-olefin are charged all at once into a reaction vessel at or before the start of the addition polymerization reaction.

[0071] <(B) Organic Solvent> The organic solvent (B) is not particularly limited as long as it can dissolve the cyclic olefin copolymer (A). Specific examples of the (B) organic solvent include aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, p-menthane, and decahydronaphthalene; aromatic hydrocarbon solvents such as toluene and xylene; and halogenated hydrocarbon solvents such as dichloromethane, chloroform, and carbon tetrachloride. Of these, cyclohexane, methylcyclohexane, dimethylcyclohexane, p-menthane, toluene, and xylene are preferred. The solvents can be used alone or in combination of two or more.

[0072] The amount of (B) organic solvent used in the solution composition is appropriately determined taking into consideration the intended use of the solution composition. Typically, the amount of (B) organic solvent used is such that the concentration of components other than (B) organic solvent in the solution composition is preferably 1.0 to 50.0 mass%, more preferably 5.0 to 40.0 mass%. When the concentrations of the components other than (B) the organic solvent in the solution composition are within the above ranges, the solution composition can be easily formed into a film with a desired thickness.

[0073] <Other additives> The solution composition may contain other additives in addition to (A) the cyclic olefin copolymer and (B) the organic solvent, as long as the desired effects are not impaired. Examples of other additives include (B) a resin other than the (A) cyclic olefin copolymer that is soluble in an organic solvent, a filler, a reinforcing agent, an antioxidant, an ultraviolet absorber, a flame retardant, a colorant, and an adhesion enhancer.

[0074] Preferred examples of the resin other than the (A) cyclic olefin copolymer include aliphatic polyimide resins, polyphenylene ether resins, and modified polyphenylene ether resins.

[0075] As the filler and reinforcing agent, in terms of film-forming properties of the solution composition, particulate fillers, scaly fillers, whiskers which are minute short fibers, etc. are preferred. Specific examples of the filler and reinforcing agent include silica, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, aluminum borate, potassium titanate, barium sulfate, boron nitride, forsterite, zinc oxide, magnesium oxide, and calcium carbonate. Furthermore, for the purpose of improving the dielectric properties in the high frequency band, hollow particles such as hollow silica, glass balloons, and various hollow resin particles can be used as a filler.

[0076] The filler and reinforcing agent may be surface-treated with a surface treatment agent having a polymerizable unsaturated bond, such as a vinyl group, an allyl group, a metallic group, a styryl group, an acryloyl group, a methacryloyl group, or a maleimido group. The surface treatment agent may be a silane coupling agent having a polymerizable unsaturated bond.

[0077] When the solution composition contains other additives, the ratio of the mass of the other additives to the total mass of the (A) cyclic olefin copolymer and the mass of the other additives can be adjusted appropriately depending on the effect to be obtained.

[0078] <Method of producing solution composition> The method for producing the solution composition is not particularly limited. Typically, the solution composition is obtained by uniformly dissolving or dispersing the desired types and amounts of each of the components of the solution composition. If the (A) cyclic olefin copolymer is difficult to dissolve in the (B) organic solvent, the (B) organic solvent containing the (A) cyclic olefin copolymer may be heated as necessary.

[0079] <Film> A film can be obtained from the above-mentioned solution composition. More specifically, the film is a so-called cast film formed using the above-mentioned solution composition.

[0080] The method for producing the cast film is not particularly limited. For example, the cast film can be produced by the following method. First, the solution composition is applied onto a support composed of a resin film, a metal foil, or the like. The application method is not particularly limited. Examples of the application method include known application methods such as dip coating, roll coating, curtain coating, die coating, and slit coating. The thickness of the cast film can be adjusted by adjusting the amount of the solution composition applied. Therefore, the amount of application is appropriately determined taking into consideration the intended use of the cast film, etc. The organic solvent (B) is then removed from the coating film on the support, which is made of the solution composition, to obtain a cast film. The organic solvent (B) can be removed by heating the coating film, placing the coating film in a reduced pressure atmosphere, or a combination of heating the coating film and placing the coating film in a reduced pressure atmosphere.

[0081] The film obtained in the above manner has both excellent breaking strain and excellent toughness, and is excellent in bending resistance.The film obtained in the above manner also has excellent bending resistance. Specifically, the film exhibits a folding endurance of 100 or more times as measured in accordance with JIS P815. Therefore, the above film is suitable for use in, for example, optical applications, medical applications, packaging applications, and electrical and electronic component applications. [Example]

[0082] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0083] [Examples 1 to 3] In Examples 1 to 3, 2-norbornene (Nb) and 1-octene (Oct) were used in the ratios shown in Table 1, with the total amount of 2-norbornene and 1-octene being 118.8 mmol. A 500 mL eggplant-shaped flask purged with nitrogen was charged with half of the 2-norbornene and 1-octene, 0.198 mmol of tri-n-octylaluminum, and 0.396 mmol of 2,6-di-tert-butyl-4-hydroxytoluene. The contents of the flask were then diluted with toluene to a volume of 258 mL. The contents of the flask were then cooled to 0°C. After cooling, a toluene solution containing a titanocene catalyst at a concentration of 0.04 mmol / L was added to the reaction mixture to adjust the titanocene catalyst amount to 0.22 mmol. The titanocene catalyst used was a compound represented by the aforementioned formula (2). Next, a toluene solution containing a borate compound at a concentration of 0.008 mmol / L was added to the reaction solution to adjust the amount of borate compound to 0.22 mmol. Triphenylmethylium tetrakis(pentafluorophenyl)borate was used as the borate compound. After adding the titanocene catalyst and the borate compound to initiate addition polymerization, the reaction solution was stirred with a magnetic stirrer at 0°C for 10 minutes. After the 10-minute reaction, the remaining half of the amounts of 2-norbornene and 1-octene, along with 0.022 mmol of tri-n-octylaluminum and 0.044 mmol of 2,6-di-tert-butyl-4-hydroxytoluene, were added to the eggplant-shaped flask. The addition polymerization reaction was then continued for 15 minutes. After a total of 25 minutes of reaction, a small amount of 2-propanol was added to the reaction solution to terminate the addition polymerization reaction. Hydrochloric acid was added to the reaction solution and stirred for 10 minutes, after which the organic layer was washed with ion-exchanged water. Repeated washing with ion-exchanged water was performed until the aqueous layer became neutral, and the washed organic layer was recovered. The recovered organic layer was added dropwise to a large amount of acetone to precipitate the resulting cyclic olefin copolymer. The precipitated copolymer was recovered by filtration, and then washed twice or more with methanol and acetone. The washed copolymer was dried under reduced pressure at 110°C for 16 hours or more to obtain a dried cyclic olefin copolymer.

[0084] For the resulting cyclic olefin copolymer, the ratio of the number of moles of structural units derived from α-olefin (1-octene) (α-olefin ratio) was determined by the following method. Approximately 50 mg of the obtained cyclic olefin copolymer was dissolved in 0.6 mL of chloroform-d, and subjected to 1000 total pulses at 300 K with a 90° pulse repetition time of 30 seconds using a BRUKER AVANCE III 400+ cryoprobe. 13 C-NMR spectrum was measured. From the obtained spectrum, the ratio of α-olefin was calculated based on the following formula in accordance with the method described in Macromolecules 2010, 43, 4527-4531. The results are shown in Table 1 as the Oct ratio in the resin. α-olefin ratio (mol%) = [integral value of carbon derived from α-olefin / (integral value of carbon derived from α-olefin + integral value of carbon derived from cyclic olefin monomer)] × 100

[0085] The resulting cyclic olefin copolymer was subjected to molecular weight measurement by gel permeation chromatography, glass transition temperature measurement by the method described above, and tensile testing by the same method. The results of these measurements are shown in Tables 1 and 2. The tensile test was performed in accordance with ISO 527-3 using a tensile tester (Tensilon Universal Testing Machine RTM-100, manufactured by A&D Co., Ltd.) at a temperature of 23°C, a chuck distance of 50 mm, and a tensile speed of 50 mm / min, using No. 2 dumbbell test pieces cut out from the film obtained by the method described below as measurement samples.

[0086] The films used as samples in the measurement of glass transition temperature and the tensile test were prepared by the following method. A mold with a depth of 50 μm was prepared using Kapton (registered trademark) film measuring 10 cm × 10 cm × 50 μm. The mold was filled with the obtained cyclic olefin copolymer, and then vacuum-pressed using a hot vacuum press under conditions of a pressure of 15 MPa, a temperature of 320 to 340°C, and a time of 15 minutes. After pressing, the pressed cyclic olefin copolymer was rapidly cooled by sandwiching it between metal plates at room temperature. After cooling, the metal plates were removed, yielding a cyclic olefin copolymer film with a thickness of approximately 50 μm.

[0087] 100 parts by mass of the obtained cyclic olefin copolymer was dissolved in 344 parts by mass of toluene to obtain a solution composition. The viscosity of the obtained solution composition at 23°C was measured using a viscometer (TV-22 type viscometer, manufactured by Toki Sangyo Co., Ltd.). The viscosity measurement results are shown in Table 2. Details of the viscometer are as follows. Viscous torque detection method: Torque balance servo type Jig: Corn plate

[0088] The resulting solution composition was applied to a PET film using a film applicator (Tester Sangyo Co., Ltd., SA202 doctor blade, gap thickness 310 μm). The coating on the PET film was dried at 90°C for 8 minutes and then further dried in a vacuum dryer at 150°C for 12 hours to obtain a film. The resulting film had a thickness of 50 μm. The obtained film was subjected to a folding endurance test (MIT test) in accordance with JIS P8115 using an MIT folding fatigue tester (manufactured by Toyo Seiki Seisakusho, Ltd.), and the number of folding cycles until the film broke due to folding was measured. The measurement results are shown in Table 2. Details of the MIT test conditions are as follows: Loading method: Spring load Load: 1kgf Bending angle: 135° Bending speed: 175 cpm

[0089] [Comparative Example 1] A cyclic olefin copolymer was obtained in the same manner as in Example 1, except that the norbornene and 1-octene were all charged at once before the start of the addition polymerization reaction, the reaction temperature was changed to 40°C, and the reaction time was changed to 4 hours. The charging ratio of norbornene and 1-octene is as shown in Table 1. The obtained cyclic olefin copolymer was subjected to measurement of the Oct ratio in the resin, measurement of the molecular weight by gel permeation chromatography, measurement of the glass transition temperature by the above-mentioned method, and tensile testing by the above-mentioned method in the same manner as in Example 1. The results of these measurements are shown in Tables 1 and 2.

[0090] Furthermore, a solution composition was obtained using the obtained cyclic olefin copolymer in the same manner as in Example 1. The viscosity of the obtained solution composition was measured in the same manner as in Example 1. A film was obtained using the obtained solution composition in the same manner as in Example 1. The obtained film was subjected to a folding endurance test (MIT test) in the same manner as in Example 1, and the number of folding times it could withstand was measured. The measurement results are shown in Table 2.

[0091] Comparative Example 2 A cyclic olefin copolymer was obtained in the same manner as in Example 1, except that 0.97 mmol of CC1 below and 0.68 mmol of CC2 below were used as cocatalysts, the reaction temperature was changed to 40°C, and the polymerization time was changed to 4 hours. The charging ratios and charging methods of norbornene and 1-octene are as shown in Table 1. The obtained cyclic olefin copolymer was subjected to measurement of the Oct ratio in the resin, measurement of the molecular weight by gel permeation chromatography, measurement of the glass transition temperature by the above-mentioned method, and tensile testing by the above-mentioned method in the same manner as in Example 1. The results of these measurements are shown in Tables 1 and 2. CC1: 6.5 mass% (as Al atom content) MMAO-3A toluene solution ([ (CH3) 0.7 (iso-C4H9) 0.3 AlO] n (Tosoh Finechem Co., Ltd., containing 6 mol% trimethylaluminum based on the total aluminum) CC2: 9.0 mass% (as Al atom content) TMAO-211 toluene solution (methylaluminoxane solution, manufactured by Tosoh Finechem Co., Ltd., containing 26 mol% trimethylaluminum based on the total Al)

[0092] Furthermore, a solution composition was obtained using the obtained cyclic olefin copolymer in the same manner as in Example 1. The viscosity of the obtained solution composition was measured in the same manner as in Example 1. A film was obtained using the obtained solution composition in the same manner as in Example 1. The obtained film was subjected to a folding endurance test (MIT test) in the same manner as in Example 1, and the number of folding times it could withstand was measured. The measurement results are shown in Table 2.

[0093] Comparative Example 3 A cyclic olefin copolymer was obtained in the same manner as in Comparative Example 1, except that only 0.22 mmol of triphenylmethylium tetrakis(pentafluorophenyl)borate was used as the co-catalyst, the reaction temperature was changed to 25°C, and the reaction time was changed to 2 hours. The charging ratios of norbornene and 1-octene are as shown in Table 1. The obtained cyclic olefin copolymer was subjected to measurement of the Oct ratio in the resin, measurement of the molecular weight by gel permeation chromatography, measurement of the glass transition temperature by the above-mentioned method, and tensile testing by the above-mentioned method in the same manner as in Example 1. The results of these measurements are shown in Tables 1 and 2.

[0094] Furthermore, a solution composition was obtained using the obtained cyclic olefin copolymer in the same manner as in Example 1. The viscosity of the obtained solution composition was measured in the same manner as in Example 1. A film was obtained using the obtained solution composition in the same manner as in Example 1. The obtained film was subjected to a folding endurance test (MIT test) in the same manner as in Example 1, and the number of folding times it could withstand was measured. The measurement results are shown in Table 2.

[0095] Comparative Example 4 Toluene (4 L) and a toluene solution (75 mL) of PMAO (manufactured by Tosoh Finechem Corporation) adjusted to a concentration of 2.2 mol / L were charged into a 5 L autoclave equipped with a heater, a stirrer, and a nitrogen injection device. Next, 2-norbornene (1650 g) was poured into the vessel, and the vessel was purged with nitrogen to reduce the pressure. Then, ethylene (Et) was injected from an ethylene cylinder to fill the vessel with a gauge pressure of 10 atm. Thereafter, the vessel was heated to 70°C and stirred for 5 minutes. A toluene solution (5 mL) of isopropylidene(9-fluorenyl)-(1-(3-methyl)cyclopentadienyl)zirconium dichloride adjusted to 1 μmol / mL in a glove box was added to the autoclave, and the reaction was allowed to proceed for 15 minutes. After the reaction, the contents were discharged, and 500 mL of distilled water and a filtering agent were added, followed by pressure filtration. The filtrate was poured into 10 L of acetone, stirred, filtered, and then washed with the same amount of acetone. The washed copolymer was dried under reduced pressure to obtain a dried cyclic olefin copolymer.

[0096] The obtained cyclic olefin copolymer was subjected to measurement of the Et ratio in the resin, measurement of the molecular weight by gel permeation chromatography, measurement of the glass transition temperature by the above-mentioned method, and tensile testing by the above-mentioned method in the same manner as in Example 1. The results of these measurements are shown in Tables 1 and 2.

[0097] Furthermore, a solution composition was obtained using the obtained cyclic olefin copolymer in the same manner as in Example 1. The viscosity of the obtained solution composition was measured in the same manner as in Example 1. A film was obtained using the obtained solution composition in the same manner as in Example 1. The obtained film was subjected to a folding endurance test (MIT test) in the same manner as in Example 1, and the number of folding times it could withstand was measured. The measurement results are shown in Table 2.

[0098] [Table 1]

[0099] [Table 2]

[0100] Tables 1 and 2 show that the (A) cyclic olefin copolymers prepared in Examples 1 to 3, in which the ratio of the number of moles of structural units derived from α-olefins to the number of moles of all structural units is 10 mol % or more and 40 mol % or less, and which have two or more glass transition temperatures determined by viscoelasticity measurement within the range of 0°C to 300°C, exhibit excellent tensile properties and combine excellent breaking strain with excellent toughness. Therefore, the films obtained using the solution compositions prepared in Examples 1 to 3 also have excellent breaking strain and excellent toughness. Furthermore, the films obtained using the solution compositions prepared in Examples 1 to 3 were excellent in bending resistance. On the other hand, the (A) cyclic olefin copolymers prepared in Comparative Examples 1 to 4, which had only one glass transition temperature within the range of 0°C to 300°C as determined by viscoelasticity measurement, were inferior in at least one of tensile strength, breaking strain, and tensile modulus. Furthermore, the films obtained using the solution compositions obtained in Comparative Examples 1 to 4 were poor in bending resistance.

Claims

1. A solution composition comprising (A) a cyclic olefin copolymer and (B) an organic solvent, The cyclic olefin copolymer (A) is an addition polymer of a cyclic olefin monomer and an α-olefin having 3 to 20 carbon atoms, the ratio of the number of moles of structural units derived from the α-olefin to the number of moles of all structural units of the cyclic olefin copolymer (A) is 10 mol % or more and 40 mol % or less, The solution composition, wherein the cyclic olefin copolymer (A) has at least one glass transition temperature measured by viscoelasticity measurement in the range below 0°C, in the range of 0°C to 100°C, and in the range of 160°C to 300°C.

2. A film obtained from the solution composition of claim 1.

3. 3. The film according to claim 2, which has a folding endurance of 100 or more times as measured in accordance with JIS P8115.

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