Cyclic olefin-based polymer, molded article, and high-frequency communication device

Abstract

To provide a cyclic olefin-based polymer having excellent chemical resistance and heat resistance, exhibiting low transmission loss, and being resistant to variation in dielectric loss tangent due to applied frequency, a molded article, and a high-frequency communication device including the molded article.SOLUTION: A cyclic olefin-based polymer is insoluble in decalin at 135°C, has a glass transition temperature of 110.0°C or higher, and has a degree of crystallinity of 1% or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a cyclic olefin polymer, a molded article containing the polymer, and a high-frequency communication device including the molded article. [Background technology]

[0002] Cyclic olefin polymers have excellent transparency and a high refractive index, and therefore have been widely used in lenses and optical members. Cyclic olefin polymers are also known to have excellent electrical properties, and for this reason, attempts have been made to use cyclic olefin polymers in electrical insulation applications.

[0003] As an example of such a cyclic olefin polymer and its applications, Patent Document 1 discloses that a cycloolefin copolymer having predetermined physical properties and structure can be used for an electrical insulating film. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 6-298956 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, with the increase in communication speeds, the frequency bands used in communication devices have been shifting toward higher frequencies. In particular, for devices that communicate in frequency bands including frequencies above 10 GHz, the requirements for the heat resistance of the materials used in such devices as well as electrical properties such as dielectric constant and dielectric loss tangent are becoming stricter. At the same time, as the requirements for the cost of communication devices are also stricter, there is also a demand for communication devices to be manufactured using fewer parts and materials. However, at present, although there are materials that exhibit excellent electrical properties in the high-frequency band but have room for improvement in electrical properties in other frequency bands, and materials that are excellent in frequency bands other than the high-frequency band but have room for improvement in electrical properties in the high-frequency band, by combining these materials, the requirements for electrical properties have been met. There was no material for communication equipment that had excellent electrical properties regardless of the applied frequency and sufficient heat resistance. In addition, since such communication equipment may be used in an environment exposed to chemicals such as organic solvents, there has been a demand to improve the chemical resistance of the materials used in communication equipment. However, through the research of the present inventors, it has been found that the films described in Patent Document 1 and the cycloolefin copolymers contained therein have room for improvement in chemical resistance.

[0006] The present invention provides a cyclic olefin-based polymer, a molded body, and a high-frequency communication device including the molded body, which have excellent chemical resistance and heat resistance, low transmission loss, and a dielectric tangent that is difficult to change depending on the applied frequency.

Means for Solving the Problems

[0007] According to the present invention, the following cyclic olefin-based polymer, molded body, and high-frequency communication device are provided.

[0008] [1] A cyclic olefin-based polymer, where the cyclic olefin-based polymer is insoluble in decalin at 135°C, the glass transition temperature of the cyclic olefin-based polymer is 110.0°C or higher, A cyclic olefin-based polymer having a crystallinity of 1% or more of the cyclic olefin-based polymer determined by the following <X-ray Diffraction Measurement Conditions>. <X-ray Diffraction Measurement Conditions> Perform wide-angle X-ray diffraction measurement on the powdery cyclic olefin-based polymer, and calculate using the following formula from the crystal-derived peak area, which is the area of the peak derived from the crystal, and the amorphous halo-derived area, which is the area of the halo derived from the amorphous. Crystallinity (%) = crystalline peak area / (crystalline peak area + amorphous halo area) × 100 [2] The cyclic olefin polymer is One or more olefin-derived structural units (A) represented by the following general formula (I), A structural unit (B) derived from a cyclic olefin monomer represented by the following general formula (II), The cyclic olefin polymer according to [1] above, having [ka] (In the above general formula (I), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. [ka] (In the above general formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R 61 ~R 78 and R a1 and R b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring. [3] When the total amount of structural units in the cyclic olefin polymer is taken as 100 mol%, The content of the structural unit (A) is 35 mol% or more and 65 mol% or less, The cyclic olefin polymer according to [2] above, wherein the content of the structural unit (B) is 35 mol % or more and 65 mol % or less. [4] The cyclic olefin polymer according to any one of the above [1] to [3], wherein the melting point of the cyclic olefin polymer is 150.0°C or higher and 450.0°C or lower. [5] A molded article comprising the cyclic olefin polymer according to any one of [1] to [4] above. [6] The molded article according to [5] above, which can be used as an insulator. [7] The molded article according to [5] or [6] above, which can be used in high-frequency communication equipment. [8] A high-frequency communication device comprising the molded article according to any one of [5] to [7] above. [Advantages of the Invention]

[0009] According to the present invention, it is possible to provide a cyclic olefin polymer, a molded article, and a high-frequency communication device including the molded article, which have excellent chemical resistance and heat resistance, low transmission loss, and a dielectric tangent that hardly changes depending on the applied frequency. [Embodiments for Carrying Out the Invention]

[0010] Hereinafter, the present invention will be described based on embodiments. In this embodiment, "A to B" indicating a numerical range represents A or more and B or less unless otherwise specified. Also, when numerical ranges are described stepwise, the upper and lower limits of each numerical range can be arbitrarily combined. In the present invention, "high frequency" and "high frequency" refer to a frequency of 10 GHz or more, and "high-frequency communication" and "high-frequency communication device" refer to communication using a frequency band including a frequency of 10 GHz or more and a device used for such communication. Furthermore, various monomers in the present invention may be derived from fossil raw materials, may be derived from organisms such as biomass, or may be mixtures thereof.

[0011] [Cyclic Olefin Polymer] The cyclic olefin polymer of this embodiment is insoluble in decalin at 135°C, has a glass transition temperature of 110.0°C or more, and the crystallinity of the cyclic olefin polymer determined by the following <X-ray diffraction measurement conditions> is 1% or more. <X-ray Diffraction Measurement Conditions> Perform wide-angle X-ray diffraction measurement on the powdery cyclic olefin-based polymer, and calculate using the following formula from the crystal-derived peak area, which is the area of the peak derived from the crystal, and the amorphous halo-derived area, which is the area of the halo derived from the amorphous. Crystallinity (%) = Crystal-derived peak area / (Crystal-derived peak area + Amorphous halo-derived area) × 100

[0012] Here, the peak and the halo will be explained. When the cyclic olefin-based polymer contains crystals, a sharp peak derived from the crystal appears. On the other hand, when the cyclic olefin-based polymer contains amorphous, a very broad pattern derived from the amorphous, so-called halo, appears. In this embodiment, the crystallinity is calculated from the areas of the peak and the halo using the above formula.

[0013] Although the mechanism by which the above problems are solved by the cyclic olefin-based polymer of this embodiment is not clear, when the crystallinity of the cyclic olefin-based polymer having a specific chemical structure is a certain level or more, the molecules of the cyclic olefin-based polymer are properly arranged, and in addition to being able to resist erosion by chemicals, it is speculated that there is a mechanism in which the transmission loss is small and the dielectric tangent hardly changes depending on the applied frequency.

[0014] The crystallinity of the cyclic olefin-based polymer determined by X-ray diffraction measurement is preferably 5% or more, more preferably 10% or more, still more preferably 15% or more, still more preferably 16% or more, still more preferably 17% or more, still more preferably 18% or more, still more preferably 19% or more, still more preferably 20% or more, still more preferably 21% or more, still more preferably 22% or more, still more preferably 23% or more, still more preferably 24% or more, still more preferably 25% or more, still more preferably 26% or more, still more preferably 27% or more. The upper limit of the crystallinity is not particularly limited, and for example, it may be 80% or less, 70% or less, 60% or less, or 50% or less. When the crystallinity is within this range, the balance between the electrical properties and heat resistance of the cyclic olefin polymer is good. The crystallinity can be controlled by the type and amount of cyclic olefin monomer used in the cyclic olefin polymer, the type of catalyst used in polymerization, the polymerization temperature, etc. When the cyclic olefin polymer is a cyclic olefin copolymer described below, it can also be controlled by the type and proportion of acyclic olefin monomer. It can also be controlled by the molding conditions of the polymer and the composition containing the polymer, whether or not the molded product is subjected to the annealing treatment described below, and the annealing conditions. The specific method for X-ray diffraction measurement will be described later.

[0015] The cyclic olefin polymer of this embodiment is insoluble in decalin at 135° C. When the cyclic olefin polymer is insoluble in decalin at 135° C., the chemical resistance of the cyclic olefin polymer and a molded article containing the cyclic olefin polymer is improved. In this specification, the phrase "a cyclic olefin polymer is insoluble in decalin at 135°C" refers to a case where 0.02 g of the cyclic olefin polymer is dissolved in 20 mL of decalin and stirred at 135°C for 1 hour in accordance with ASTM J1601, and still undissolved matter is observed.

[0016] The glass transition temperature (Tg) of the cyclic olefin polymer of this embodiment is 110.0° C. or higher, preferably 115.0° C. or higher, more preferably 120.0° C. or higher, and even more preferably 125.0° C. or higher. There is no particular upper limit to Tg, and it may be, for example, 400.0° C. or lower, 300.0° C. or lower, 250° C. or lower, 200° C. or lower, 150° C. or lower, 140° C. or lower, or 130° C. or lower. When the glass transition temperature is equal to or higher than the lower limit, a good balance of electrical properties and heat resistance is achieved. Tg can be controlled by the type and amount of cyclic olefin monomer used in the cyclic olefin polymer, the type of catalyst used in polymerization, the polymerization temperature, etc. When the cyclic olefin polymer is a cyclic olefin copolymer described below, Tg can also be controlled by the type and proportion of acyclic olefin monomer.

[0017] From the viewpoint of further improving the heat resistance and improving the moldability while maintaining a good balance between the transparency and refractive index of the resulting molded article, the cyclic olefin polymer of the present embodiment is preferably a cyclic olefin copolymer having the following characteristics: One or more olefin-derived structural units (A) represented by the following general formula (I), A structural unit (B) derived from a cyclic olefin monomer represented by the following general formula (II), It has. [ka] In the above general formula (I), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. [ka] In the above general formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R 61 ~R 78 and R a1 and R b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring.

[0018] Specific examples of the one or more olefins represented by general formula (I) in the cyclic olefin copolymer of this embodiment include olefin monomers represented by the following general formula (Ia) corresponding to the above general formula (I):

[0019] [ka] In the above general formula (Ia), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. Examples of olefin monomers represented by the general formula (Ia) include ethylene, 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, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Among these, ethylene and propylene are preferred, with ethylene being particularly preferred, from the viewpoint of obtaining molded articles having superior heat resistance, mechanical properties, and optical properties. Two or more types of olefin monomers represented by the general formula (Ia) may be used.

[0020] A specific example of the cyclic olefin monomer represented by general formula (II) in the cyclic olefin copolymer of this embodiment is a cyclic olefin monomer represented by general formula (IIa) corresponding to the above general formula (II).

[0021] [ka] In the above general formula (IIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, and R 61 ~R 78 and R a1 and R b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R 75 ~R 78may be bonded to each other to form a monocyclic or polycyclic ring.

[0022] By using the olefin monomer represented by the general formula (Ia) and the cyclic olefin monomer represented by the general formula (IIa) as copolymerization components, the solubility of the cyclic olefin copolymer in a solvent is further improved, resulting in good moldability and improved product yield.

[0023] Examples of the cyclic olefin monomer represented by the general formula (IIa) include bicyclo[2.2.1]-2-heptene (also called norbornene), tetracyclo[4.4.0.1 2,5 .1 7,10 It is preferable to use cyclo[2.2.1]-3-dodecene (also called tetracyclododecene), and it is more preferable to use bicyclo[2.2.1]-2-heptene (norbornene). These cyclic olefins have a rigid ring structure, which has the advantage that the elastic modulus of the copolymer and molded article is easily maintained.

[0024] The copolymerization type of the cyclic olefin copolymer of this embodiment is not particularly limited, and examples thereof include random copolymers, block copolymers, etc. In this embodiment, a random copolymer is preferred from the viewpoint of being excellent in optical properties such as transparency, refractive index, and birefringence, and being able to obtain high-precision optical components.

[0025] The cyclic olefin copolymer of this embodiment is a copolymer of ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10

[0039] It is preferable that the copolymer is at least one selected from the group consisting of a random copolymer of ethylene and bicyclo[2.2.1]-3-dodecene and a random copolymer of ethylene and bicyclo[2.2.1]-2-heptene, and a random copolymer of ethylene and bicyclo[2.2.1]-2-heptene is more preferable.

[0026] When the cyclic olefin polymer of the present embodiment is the above-mentioned copolymer, from the viewpoint of obtaining a molded article that has excellent chemical resistance and heat resistance, small transmission loss, and a dielectric loss tangent that is not easily changed even at applied frequencies, the content of the structural unit (A) is preferably 35 mol% or more, more preferably 40 mol% or more, even more preferably 45 mol% or more, and even more preferably 50 mol% or more, when the total amount of structural units in the cyclic olefin polymer is 100 mol%, and is preferably 65 mol% or less, more preferably 60 mol% or less, and even more preferably 55 mol% or less. That is, when the cyclic olefin polymer of the present embodiment is the above-mentioned copolymer, from the viewpoint of obtaining a molded article that has excellent chemical resistance and heat resistance, small transmission loss, and a dielectric loss tangent that is unlikely to change depending on the applied frequency, the content of the structural unit (A) is preferably 35 mol% or more and 65 mol or less, more preferably 40 mol% or more and 65 mol or less, even more preferably 45 mol% or more and 60 mol or less, and still more preferably 50 mol% or more and 55 mol or less, when the total amount of structural units in the cyclic olefin polymer is taken as 100 mol%.

[0027] When the cyclic olefin polymer of the present embodiment is the above-mentioned copolymer, from the viewpoint of obtaining a molded article that has excellent chemical resistance and heat resistance, small transmission loss, and a dielectric loss tangent that is not easily changed even at applied frequencies, the content of the structural unit (B) is preferably 35 mol% or more, more preferably 40 mol% or more, even more preferably 45 mol% or more, and is preferably 65 mol% or less, more preferably 60 mol% or less, even more preferably 55 mol% or less, even more preferably 50 mol% or less, when the total amount of structural units in the cyclic olefin polymer is taken as 100 mol%. That is, when the cyclic olefin polymer of the present embodiment is the above-mentioned copolymer, from the viewpoint of obtaining a molded article that has excellent chemical resistance and heat resistance, small transmission loss, and a dielectric loss tangent that is unlikely to change depending on the applied frequency, the content of the structural unit (B) is preferably 35 mol% or more and 65 mol% or less, more preferably 40 mol% or more and 65 mol% or less, even more preferably 45 mol% or more and 60 mol% or less, and even more preferably 45 mol% or more and 50 mol% or less, when the total amount of structural units in the cyclic olefin polymer is taken as 100 mol%.

[0028] When the cyclic olefin polymer of this embodiment is the copolymer, the cyclic olefin copolymer may have other structural units (C) derived from one or more olefins represented by general formula (I) and other monomers other than the cyclic olefin monomer represented by general formula (II), within the range that does not impair the effects of this embodiment. Examples of other monomers include acrylic monomers such as acrylic acid and methacrylic acid, vinyl monomers such as vinyl chloride monomers, and styrene monomers. When the cyclic olefin polymer of the present embodiment is the above copolymer, the content of the structural unit (C) is preferably 5 mol % or less, more preferably 2 mol % or less, and even more preferably 0 mol %. The total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer is 100 mol %.

[0029] The types and contents of the structural unit (A), the structural unit (B), and, if necessary, the structural unit (C) are, for example, 13 It can be measured by C-NMR.

[0030] The cyclic olefin polymer of the present embodiment may be a ring-opening polymer of a cyclic olefin. Examples of the ring-opening polymer of a cyclic olefin include a ring-opening polymer of a norbornene-based monomer, a ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with the norbornene-based monomer, and hydrogenated products thereof.

[0031] Examples of norbornene-based monomers used in the polymerization of ring-opening polymers include bicyclo[2.2.1]hept-2-ene (common name: norbornene) and its derivatives (those having a substituent on the ring), tricyclo[4.3.0]hept-2-ene, and the like. 1,6 .1 2,5 ]deca-3,7-diene (commonly known as dicyclopentadiene) and its derivatives, 7,8-benzotricyclo[4.3.0.1 2,5 ]dec-3-ene (commonly known as methanotetrahydrofluorene: 1,4-methano-1,4,4a,9a-tetrahydrofluorene) and its derivatives, tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene (common name: tetracyclododecene) and its derivatives, etc. The substituents substituted on the ring of these derivatives include alkyl groups, alkylene groups, vinyl groups, alkoxycarbonyl groups, alkylidene groups, etc. The substituents may be one or more. Examples of derivatives having a substituent on the ring include 8-methoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene, 8-ethylidene-tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene and the like. These norbornene-based monomers may be used alone or in combination of two or more.

[0032] A ring-opening polymer of a norbornene-based monomer, or a ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization therewith, can be obtained by polymerizing the monomer components in the presence of a known ring-opening polymerization catalyst. Examples of the ring-opening polymerization catalyst that can be used include catalysts composed of a halide of a metal such as ruthenium or osmium, a nitrate or an acetylacetone compound, and a reducing agent; and catalysts composed of a halide or an acetylacetone compound of a metal such as titanium, zirconium, tungsten, or molybdenum, and an organoaluminum compound. Examples of other monomers capable of undergoing ring-opening copolymerization with norbornene-based monomers include monocyclic olefin-based monomers such as cyclohexene, cycloheptene, and cyclooctene.

[0033] A hydrogenated ring-opening polymer of a norbornene-based monomer or a hydrogenated ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with the norbornene-based monomer can usually be obtained by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium to a polymerization solution of the ring-opening polymer and hydrogenating the carbon-carbon unsaturated bonds.

[0034] From the viewpoint of improving the balance between heat resistance and processability, the melting point (Tm) of the cyclic olefin polymer of the present embodiment is preferably 150.0°C or more and 450.0°C or less, more preferably 200.0°C or more and 450.0°C or less, even more preferably 250.0°C or more and 450.0°C or less, and still more preferably 260.0°C or more and 450.0°C or less.

[0035] [Molded body] The molded article of the present embodiment contains the cyclic olefin polymer, which allows the production of a molded article that has excellent chemical resistance and heat resistance, low transmission loss, and a dielectric loss tangent that is resistant to change depending on the applied frequency.

[0036] The shape of the molded article of this embodiment is not particularly limited, and may be a film, sheet, lens, container, or the like, but from the viewpoint of application to the uses described below, a film or sheet is preferred.

[0037] From the viewpoint of improving the performance balance of chemical resistance, heat resistance, transmission loss, and processability, the thickness of the molded body of this embodiment is preferably 0.1 μm or more and 5.0 mm or less, more preferably 1.0 μm or more and 1.0 mm or less, even more preferably 10.0 μm or more and 0.9 mm or less, even more preferably 50.0 μm or more and 0.8 mm or less, even more preferably 100 μm or more and 0.7 mm or less, and even more preferably 300 μm or more and 0.6 mm or less.

[0038] The molded article of the present embodiment can be produced by molding the cyclic olefin polymer of the present embodiment or a composition containing the same by a well-known resin molding method, such as injection molding, extrusion molding, cast molding, inflation molding, blow molding, vacuum molding, press molding, compression molding, rotational molding, calendar molding, roll molding, or cutting molding. From the viewpoint of improving the balance of production efficiency, heat resistance, chemical resistance, and mechanical strength, the molded article is preferably molded by press molding.

[0039] The molding temperature in the press molding method is preferably (Tm)°C or higher and (Tm+100)°C or lower, more preferably (Tm+10)°C or higher and (Tm+100)°C or lower, even more preferably (Tm+20)°C or higher and (Tm+80)°C or lower, and even more preferably (Tm+20)°C or higher and (Tm+50)°C or lower, relative to the melting point (Tm) measured by DSC. The molding time by the press molding method is not particularly limited as long as it is possible to form a molded body, but from the viewpoint of improving the performance balance of heat resistance, chemical resistance, and mechanical strength, it is preferably less than 15 minutes, more preferably 10 minutes or less, and even more preferably 5 minutes or less.

[0040] From the viewpoint of increasing the degree of crystallinity, the molded body of this embodiment is preferably subjected to an annealing treatment in which the molded body is held at a predetermined temperature for a predetermined time after being molded. The temperature during the annealing treatment is preferably 150 to 250° C., more preferably 170 to 230° C., from the viewpoint of improving the balance of production efficiency, heat resistance, chemical resistance, and mechanical strength. The holding time during the annealing treatment is preferably 1 to 20 minutes, more preferably 5 to 15 minutes, from the viewpoint of improving the balance of production efficiency, heat resistance, chemical resistance, and mechanical strength.

[0041] [Uses of molded products] The molded article of the present embodiment preferably functions as an insulator, that is, the molded article of the present embodiment can be preferably used as an insulator. Furthermore, since it has excellent electrical properties regardless of the frequency to which it is applied, it can be suitably used in devices used for communications using frequency bands including frequencies of 10 GHz or higher, i.e., high-frequency communication devices.

[0042] When the molded article of this embodiment is used in a high-frequency communication device, it can be preferably used as an insulating layer of an internal circuit board. The method for producing the circuit board is not particularly limited and may be a generally known method, but for example, the circuit board can be produced by the following method. The molded article of this embodiment is heat-cured by a lamination press or the like to form an electrical insulating layer. Next, a conductor layer is laminated on the obtained electrical insulating layer by a known method to produce a laminate. Thereafter, the conductor layer in the laminate is subjected to circuit processing or the like to obtain a circuit board.

[0043] Metals that can be used for the conductor layer include copper, aluminum, nickel, gold, silver, stainless steel, etc. Methods for forming the conductor layer include, for example, a method in which the metal is made into a foil or the like and heat-fused onto the electrical insulating layer, a method in which the metal is made into a foil or the like and attached to the electrical insulating layer using an adhesive, or a method in which a conductor layer made of the metal is formed on the electrical insulating layer by a method such as sputtering, vapor deposition, or plating. The circuit board may be either a single-sided board or a double-sided board.

[0044] [Method of producing cyclic olefin copolymer] When the cyclic olefin polymer of the present embodiment is a cyclic olefin copolymer, the cyclic olefin copolymer can be produced by the following production method. The method for producing the cyclic olefin copolymer of this embodiment will be described in detail below.

[0045] The method for producing a cyclic olefin copolymer of this embodiment is the method for producing a cyclic olefin copolymer described above, and preferably includes a step (hereinafter also referred to as a polymerization step) of copolymerizing one or more olefin monomers represented by the general formula (Ia) above with a cyclic olefin monomer represented by the general formula (IIa) above in the presence of a catalyst containing a transition metal compound (X) represented by the general formula (1) described below.

[0046] According to the method for producing a cyclic olefin copolymer of this embodiment, a cyclic olefin copolymer having an excellent balance of chemical resistance, electrical properties, and heat resistance can be produced. Although the detailed mechanism by which a cyclic olefin copolymer having an excellent balance of chemical resistance, electrical properties, and heat resistance can be produced is unknown, a catalyst containing a transition metal compound (X) represented by the general formula (1) described later is believed to be capable of producing a cyclic olefin copolymer having an excellent balance of chemical resistance, electrical properties, and heat resistance. 1 ~R 14 One or more of the substituents is a group having a certain degree of bulkiness, such as a heteroatom-containing group such as a halogen-containing group or an oxygen-containing group, or a hydrocarbon group having one or more carbon atoms such as a methyl group or a t-butyl group. It is presumed that the presence of such bulky substituents has some effect on the crystallinity of the cyclic olefin copolymer, thereby improving the balance of chemical resistance, electrical properties, and heat resistance. This effect is more pronounced when multiple bulky substituents are present.

[0047] Specific examples of the transition metal compound (X) represented by general formula (1) are not particularly limited, but include, for example, dimethylmethylene(3-tert-butyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconium dichloride, dimethylmethylene(3-methyl-cyclopentadienyl)(fluorenyl)zirconium dichloride, and the like.

[0048] The temperature of the polymerization step in the method for producing a cyclic olefin copolymer of the present embodiment is preferably 10°C or higher, more preferably 20°C or higher, and even more preferably 25°C or higher, from the viewpoint of improving reaction efficiency, and is preferably 35°C or lower, from the viewpoint of suppressing catalyst deactivation and side reactions, and from the viewpoint of increasing the crystallinity of the resulting polymer to improve the balance of electrical properties and heat resistance.

[0049] The duration of the polymerization step in the method for producing a cyclic olefin copolymer of the present embodiment is preferably 30 minutes or more, more preferably 45 minutes or more, from the viewpoints of improving reaction efficiency, suppressing catalyst deactivation and side reactions, and increasing the crystallinity of the resulting polymer to improve the balance of electrical properties and heat resistance. The pressure in the polymerization step in the method for producing a cyclic olefin copolymer of the present embodiment is preferably 0.10 MPa or more, more preferably 0.15 MPa or more, from the viewpoints of improving the reaction efficiency, suppressing catalyst deactivation and side reactions, and increasing the crystallinity of the resulting polymer to improve the balance of electrical properties and heat resistance.

[0050] The polymerization step of the method for producing a cyclic olefin copolymer of this embodiment may be carried out in a solvent or without a solvent. The solvent used in the polymerization step of the method for producing a cyclic olefin copolymer of this embodiment includes, for example, one or more solvents selected from the group consisting of tetrahydrofuran, toluene, cyclohexane, cyclohexanone, MEK, MIBK, PGMEA, PGME, ethyl acetate, and methyl acetate, and preferably includes toluene.

[0051] In the polymerization step of the method for producing a cyclic olefin copolymer of the present embodiment, any component other than the catalyst containing the transition metal compound (X) represented by the general formula (1) may be used. For example, an organoaluminum oxy compound described below may be used as a co-catalyst.

[0052] <Transition metal compound (X)> In the polymerization step of the method for producing a cyclic olefin copolymer of this embodiment, the polymerization reaction is carried out in the presence of a transition metal compound (X) represented by the following general formula (1).

[0053] [ka]

[0054] In the above general formula (1), M 1 indicates a transition metal atom in Group 4 of the periodic table, X 1 each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and substitution products thereof; n 1 represents an integer from 1 to 4, Y 1 represents a carbon atom or a silicon atom, R 1 ~R 14 each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and substitution products thereof; R 1 ~R 14 adjacent ones of these may be bonded to each other to form a ring, and the ring formed may have aromaticity containing a conjugated double bond, R 1 ~R 14At least one of the groups is a group selected from the group consisting of hydrocarbon groups having one or more carbon atoms, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, and aluminum-containing groups, and substitution products thereof.

[0055] In the above general formula (1), M 1 indicates a transition metal atom in Group 4 of the periodic table. M 1 Examples of the atom include a titanium atom, a zirconium atom, and a hafnium atom.

[0056] M 1 is preferably a titanium atom or a zirconium atom, and more preferably a zirconium atom.

[0057] In the above general formula (1), X 1 each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and substitution products thereof.

[0058] X 1 Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, and a bromine atom.

[0059] In the above general formula (1), X 1Examples of the hydrocarbon group represented by the formula (I) include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, hexyl, octyl, 2-ethylhexyl, and decyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, cyclooctyl, norbornyl, bicyclononyl, and tricyclodecane; aryl groups such as phenyl, tolyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl; aralkyl groups such as benzyl and phenylethyl; and divalent diene derivative groups such as 1,3-butadienyl, isoprenyl(2-methyl-1,3-butadienyl), piperylenyl(1,3-pentadienyl), 2,4-hexadienyl, 1,4-diphenyl-1,3-pentadienyl, and cyclopentadienyl.

[0060] In the above general formula (1), X 1 Examples of the halogen-containing group represented by the formula (I) include halogen-containing hydrocarbon groups such as trifluoromethyl, pentafluoroethyl, 1,1,1,3,3,3-hexafluoro-2-propyl, and nonafluoro-t-butyl; halogen-containing aryl groups such as pentafluorophenyl and pentachlorophenyl; and the like.

[0061] In the above general formula (1), X 1 Examples of the oxygen-containing group represented by the formula (I) include alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, or a t-butoxy group; aryloxy groups such as a phenoxy group, a 2,6-dimethylphenoxy group, or a 2,4,6-trimethylphenoxy group; ester groups such as an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, or a p-chlorophenoxycarbonyl group; an ether group; acyl groups such as a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, or a p-methoxybenzoyl group; a carboxyl group; a carbonate group; a hydroxy group; a peroxy group; a carboxylic anhydride group; a furyl group; and the like.

[0062] In the above general formula (1), X1 Examples of the sulfur-containing group represented by the formula (I) include a mercapto group; a thioester group such as an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, or a phenylthiocarbonyl group; a dithioester group; an alkylthio group such as a methylthio group or an ethylthio group; an arylthio group such as a phenylthio group, a methylphenylthio group, or a naphthylthio group; a thioacyl group; a thioether group; a thiocyanate ester group; an isothiocyanate ester group; a sulfonate ester group such as a methyl sulfonate group, an ethyl sulfonate group, or a phenyl sulfonate group; a sulfonamide group such as a phenylsulfonamide group, an N-methylsulfonamide group, or an N-methyl-p-toluenesulfonamide group; a thiocarboxyl group; a dithiocarboxyl group; a sulfo group; a sulfonyl group; a sulfinyl group; a sulfenyl group; and the like.

[0063] In the above general formula (1), X 1 Examples of the nitrogen-containing group represented by the formula (I) include an amino group; an alkylamino group such as a dimethylamino group or an ethylmethylamino group; an arylamino group such as a diphenylamino group; an imino group; an alkylimino group such as a methylimino group, an ethylimino group, a propylimino group, or a butylimino group; an arylimino group such as a phenylimino group; an amido group; an alkylamido group such as an acetamido group or an N-methylacetamido group; an arylamido group such as an N-methylbenzamido group; an imido group; an alkylimido group such as an acetimido group; an arylimido group such as a benzimido group; a pyrrolidino group; a hydrazino group; a hydrazono group; a nitro group; a nitroso group; a cyano group; an isocyano group; a cyanate ester group; an amidino group; a diazo group; and an amino group in the form of an ammonium salt. Also, X 1 Examples of the nitrogen-containing group substituent represented by the formula include a silylamide group and a phosphinoamide group.

[0064] In the above general formula (1), X 1 Examples of the phosphorus-containing group represented by the formula (I) include a phosphido group, a phosphoryl group, a thiophosphoryl group, and a phosphate group.

[0065] In the above general formula (1), X 1 Examples of the silicon-containing group represented by the formula (I) include alkylsilyl groups such as a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group, a dimethylphenylsilyl group, and a dimethyl-t-butylsilyl group.

[0066] In the above general formula (1), X 1 Examples of the boron-containing group represented by the formula include a boranediyl group, a boranetriyl group, a diboranyl group, and the like. In the above general formula (1), X 1 Examples of the boron-containing group substituents represented by the formula (I) include alkyl group-substituted boron represented by (Et)B-, (iPr)B-, (iBu)B-, (Et)B, (iPr)B, or (iBu)B, etc.; aryl group-substituted boron represented by (CH)B-, (CH)B, (CF)B, or (3,5-(CF)CH)B, etc.; boron halides represented by BCl- or BCl; alkyl group-substituted boron halides represented by (Et)BCl-, (iBu)BCl-, or (CH)BCl, etc. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

[0067] In the above general formula (1), X 1 Examples of the aluminum-containing group represented by the formula include AlR4 (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.). In the above general formula (1), X 1 Examples of the aluminum-containing group substituents represented by the formula (I) include alkyl group-substituted aluminum represented by (Et)Al-, (iPr)Al-, (iBu)Al-, (Et)Al, (iPr)Al, (iBu)Al, or the like; aryl group-substituted aluminum represented by (C6H5)Al-, or the like; aluminum halides represented by AlCl-, AlCl, or the like; and alkyl group-substituted aluminum halides represented by (Et)AlCl-, (iBu)AlCl-, or the like. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

[0068] In the above general formula (1), X 1 is a group selected from the group consisting of hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, aluminum-containing groups, and substituted groups thereof, X 1 Each of these independently preferably has 1 to 20 carbon atoms.

[0069] In the above general formula (1), X 1 are each independently preferably a halogen atom or a hydrocarbon group, more preferably a halogen atom.

[0070] In the above general formula (1), X 1 is a halogen atom, X 1 are each independently a chlorine atom.

[0071] In the above general formula (1), n 1 represents an integer of 1 to 4. 1 is M 1 Valence and X 1 Depending on the type of the transition metal compound (X) represented by the general formula (1) above, the transition metal compound (X) is selected so that the entire transition metal compound (X) is electrically neutral.

[0072] In the above general formula (1), n 1 is preferably 2 or 3, and more preferably 2.

[0073] In the above general formula (1), Y 1 represents a carbon atom or a silicon atom.

[0074] In the above general formula (1), Y 1 is preferably a carbon atom.

[0075] In the above general formula (1), R1 ~R 14 each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and substitution products thereof.

[0076] In the above general formula (1), R 1 ~R 14 Examples of the halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups represented by X include, but are not limited to, X 1 Examples of the halogen atom include a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, as well as those exemplified as substitution products thereof.

[0077] In the above general formula (1), R 1 ~R 14 Adjacent ones of these may be bonded to each other to form a ring, and the ring formed may have aromaticity containing a conjugated double bond.

[0078] In the above general formula (1), R 1 ~R 14 It is preferred that adjacent ones of the groups be bonded to each other to form a ring, and that the ring thus formed be bonded to a cyclopentadienyl group. The structure in which the ring thus formed is bonded to a cyclopentadienyl group is, for example, the structure shown below, and preferably a fluorenyl ring structure.

[0079] [ka]

[0080] In the above general formula (1), R 1 ~R 14At least one of the groups is a group selected from the group consisting of halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, aluminum-containing groups, and hydrocarbon groups having one or more carbon atoms, and substitution products thereof.

[0081] In the above general formula (1), R 1 ~R 14 It is preferable that at least one of R is a hydrocarbon group having one or more carbon atoms. 1 ~R 14 It is more preferable that at least one of R is a hydrocarbon group having 4 or more carbon atoms. 1 ~R 14 More preferably, one or more of R 1 ~R 14 More preferably, two or more of R 1 ~R 14 It is more preferable that three or more of the groups be t-butyl groups, which further improves the chemical resistance of the resulting cyclic olefin copolymer. R 1 ~R 14 Although the detailed mechanism by which the chemical resistance of the resulting cyclic olefin copolymer is improved by having one or more of these groups is unknown, it is speculated that the presence of bulky groups such as methyl groups or t-butyl groups in the catalyst has some effect on the crystallinity of the cyclic olefin copolymer, thereby improving its chemical resistance. This effect is more pronounced when there are multiple bulky substituents.

[0082] <Organoaluminum oxy compounds> In the polymerization step of the method for producing a cyclic olefin copolymer of this embodiment, an organoaluminum oxy compound can be used as a co-catalyst.

[0083] As the organoaluminum oxy-compound, any of the conventionally known organoaluminum oxy-compounds can be used. Specific examples include compounds represented by the following formulas [B2-1], [B2-2], [B2-3] and [B2-4], benzene-insoluble organoaluminum oxy compounds described in JP-A-2-78687 and JP-A-2-167305, and aluminoxanes having two or more types of alkyl groups described in JP-A-3-103407.

[0084] [ka]

[0085] In formula [B2-1], R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.

[0086] [ka]

[0087] In formula [B2-2], R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.

[0088] [ka]

[0089] In formula [B2-3], R represents a hydrocarbon group having 1 to 10 carbon atoms, Me represents a methyl group, and m and n each independently represent an integer of 2 or greater.

[0090] The compound represented by formula [B2-3] is called modified methylaluminoxane and is prepared using trimethylaluminum and alkylaluminums other than trimethylaluminum. Such compounds are generally called MMAO. Such MMAO can be prepared by the methods described in U.S. Patent Nos. 4,960,878 and 5,041,584.

[0091] [ka]

[0092] In formula [B2-4], R c represents a hydrocarbon group having 1 to 10 carbon atoms. d may be the same or different and represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0093] As the organoaluminum oxy compound, methylaluminoxane, which is a commercially available product and therefore easily available, and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferred.

[0094] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted. Furthermore, the present invention is not limited to the above-described embodiment, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention. [Example]

[0095] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0096] [Method for measuring the content of each structural unit] The obtained cyclic olefin copolymer 13 The C-NMR spectrum was measured using a Bruker Biospin AVANCE III cryo-500 nuclear magnetic resonance spectrometer under the following conditions to determine the contents of structural units (A) and (B). The results are shown in Table 1. Solvent: deuterated orthodichlorobenzene Sample concentration: 50~100g / L-solvent Pulse repetition time: 5.5 seconds Accumulation times: 6000 to 16000 times Measurement temperature: 120℃

[0097] [Method for measuring glass transition temperature (Tg) and melting point (Tm)] The resulting cyclic olefin copolymer was subjected to thermal analysis according to the following procedure. (1) Using a differential scanning calorimeter (TA Instrument, Discovery DSC2500), the cyclic olefin copolymer was heated from room temperature to 400°C at a heating rate of 10°C / min under a nitrogen atmosphere. (2) The temperature was held at 400°C for 5 minutes. (3) The temperature was lowered to -20°C at a rate of 10°C / min. (4) The mixture was kept at -20°C for 5 minutes. (5) The temperature was increased to 400°C at a rate of 10°C / min.

[0098] The endothermic peak observed in the DSC curve obtained in the second heating step of the thermal analysis performed according to the above procedure was taken as the melting peak. The temperature at the apex of the melting peak was taken as the melting point. The results are shown in Table 1.

[0099] In the second heating step of the thermal analysis performed according to the above procedure, the Tg was determined as the temperature at which the curve representing the stepwise change in the glass transition intersected with a line equidistant along the vertical axis from the line extending from the low-temperature baseline and the line extending from the high-temperature baseline of the DSC curve. The results are shown in Table 1.

[0100] [Method for measuring crystallinity] The powdered cyclic olefin copolymers obtained by the methods described in each Example and Comparative Example were subjected to wide-angle X-ray diffraction measurement, and the crystal-derived peak area, which is the area of the peak derived from the crystal, and the amorphous halo area, which is the area of the halo derived from the amorphous, were calculated using the following formula. When multiple crystal-derived peaks appeared, the crystal-derived peak area was calculated as the sum of the areas of the multiple peaks. The X-ray diffraction patterns were analyzed using a profile fitting technique. For the profile fitting, analysis software (manufactured by Spectris Inc., product name: High Score) attached to the X-ray diffractometer was used. The results obtained are shown in Table 1. Crystallinity (%) = crystalline peak area / (crystalline peak area + amorphous halo area) × 100 Equipment: EMPYREAN, manufactured by Spectris X-ray source: CuKα ray Output: 45kV 40mA Measurement range: 3°~35° Scan speed: 1° / min Step width: 0.026° Detector: PIXcel 3D

[0101] [Measuring method for relative permittivity (Dk) and dielectric loss tangent (Df)] The dielectric constant (Dk) and dielectric loss tangent (Df) of the test press sheets of the cyclic olefin copolymers obtained by the methods described in each Example and Comparative Example, which will be described later, were measured using the automatic balancing bridge method in accordance with ASTM D150 or the cylindrical cavity resonator method (TE011 method) in accordance with JIS R1641. The results are shown in Table 1. Specifically, Dk and Df at a measurement frequency of 1 MHz were measured by the automatic balancing bridge method using an LCR meter (product name: "4284A", manufactured by Agilent Technologies) in accordance with ASTM D150. Dk and Df at measurement frequencies of 10 GHz and 24 GHz were measured by the cylindrical cavity resonator method using a resonator (material: copper, internal mirror finish), a synthesized sweeper (product name: "8340B", manufactured by YHP), and a network analyzer (product name: "8510B", manufactured by YHP) in accordance with JIS R1641.

[0102] [Example 1] A 1.0 L stainless steel autoclave that had been thoroughly purged with nitrogen was charged with 500 mL of an 87% by mass toluene solution of norbornene (380.4 g of norbornene) and 14.0 mmol of methylaluminoxane. The autoclave was sealed and stirred at 300 rpm while maintaining the temperature at 30°C. Ethylene gas was then blown in at 0.19 MPa for 10 minutes to saturate the solution with ethylene gas. Next, 0.01 mmol of catalyst 1 (dimethylmethylene(3-methyl-cyclopentadienyl)(fluorenyl)zirconium dichloride) was added to initiate polymerization. Ethylene gas was continuously fed while maintaining a pressure of 0.19 MPa. After polymerization at 30°C for 60 minutes, an excess amount of methanol was added to terminate the polymerization, yielding a polymer solution. The resulting polymer solution was added to an excess amount of a methanol / acetone mixed solution (mixing ratio 1 / 3 (volume ratio)) containing a small amount of hydrochloric acid to precipitate the polymer. The precipitated polymer was removed and dried under reduced pressure at 130°C overnight, yielding 18.09 g of an ethylene / norbornene copolymer. The polymerization activity was 1.81 kg / mmol·hr, and the composition of the obtained ethylene-norbornene copolymer was 13 C-NMR analysis revealed that the structural unit (A) was 51 mol% ethylene and the structural unit (B) was 49 mol% norbornene. DSC analysis revealed that the polymer had a glass transition temperature of 126.8°C and a melting point of 277.7°C. XRD analysis revealed that the polymer had a crystallinity of 30%.

[0103] Catalyst 1 (dimethylmethylene(3-methyl-cyclopentadienyl)(fluorenyl)zirconium dichloride) used in Example 1 is a catalyst having a structure represented by the following general formula (1). When the structure of catalyst 1 is applied to the following general formula (1), M 1 is a zirconium atom, and X 1 is a chlorine atom, and n 1 is 2 and Y 1 is a carbon atom and R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 is a hydrogen atom, and R 3 , R 13 and R 14 is a methyl group.

[0104] [ka]

[0105] [Example 2] A 500 mL glass autoclave that had been thoroughly purged with nitrogen was charged with 300 mL of toluene and 142.8 g of norbornene, and ethylene gas was passed through at a flow rate of 96 L / hour. The mixture was heated to 80°C while stirring at 600 rpm, and then maintained at that temperature for 10 minutes. 14.0 mmol of methylaluminoxane was added, followed by 0.01 mmol of catalyst 3 (dimethylmethylene(3-tert-butylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride) to initiate polymerization. Polymerization was carried out at 80°C for 10 minutes under atmospheric pressure, followed by the addition of an excess amount of isopropanol to terminate the polymerization and obtain a polymer solution. The resulting polymer solution was added to an excess amount of a methanol / acetone mixed solution (mixing ratio 1 / 3 (volume ratio)) containing a small amount of hydrochloric acid to precipitate the polymer. The precipitated polymer was removed and dried under reduced pressure at 130°C overnight to obtain 1.65 g of an ethylene / norbornene copolymer. The polymerization activity was 0.99 kg / mmol·hr, and the composition of the obtained ethylene-norbornene copolymer was 13 C-NMR analysis revealed that the structural unit (A) was 53 mol% ethylene and the structural unit (B) was 47 mol% norbornene. DSC analysis revealed that the polymer had a glass transition temperature of 121.7°C and a melting point of 297.6°C. XRD analysis revealed that the polymer had a crystallinity of 37%.

[0106] Catalyst 3 (dimethylmethylene(3-tert-butyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconium dichloride) used in Example 2 is a catalyst having a structure represented by the above general formula (1). When the structure of catalyst 3 is applied to the above general formula (1), M 1 is a zirconium atom, and X 1 is a chlorine atom, and n 1 is 2 and Y 1 is a carbon atom and R 1 , R 2 , R4 , R 5 , R 6 , R 8 , R 9 , R 11 and R 12 is a hydrogen atom, and R 3 , R 7 and R 10 is a t-butyl group, and R 13 and R 14 is a methyl group.

[0107] [Comparative Example 1] A 500 mL glass autoclave that had been thoroughly purged with nitrogen was charged with 300 mL of a mixed solvent of cyclohexane and hexane in a 9:1 ratio and 24.6 g of norbornene, and ethylene gas and nitrogen gas were passed through at flow rates of 84 L / hour and 12 L / hour, respectively. The mixture was heated to 50°C while stirring at 600 rpm, and then maintained at this temperature for 10 minutes. 0.5 mmol of TIBAL (triisobutylaluminum) was added, followed by 0.001 mmol of catalyst 2 (dimethylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride) and 0.004 mmol of TrB (triphenylcarbenium tetrakis(pentafluorophenyl)borate) to initiate polymerization. Polymerization was carried out at 50°C for 10 minutes under atmospheric pressure, followed by the addition of an excess amount of isopropanol to terminate the polymerization and obtain a polymer solution. The resulting polymer solution was added to an excess amount of a methanol / acetone mixture (mixture ratio 1 / 3 (volume ratio)) containing a small amount of hydrochloric acid to precipitate the polymer. The precipitated polymer was removed and dried under reduced pressure at 130°C overnight to obtain 8.14 g of ethylene / norbornene copolymer. The polymerization activity was 48.81 kg / mmol·hr, and the composition of the obtained ethylene-norbornene copolymer was 13 C-NMR measurement revealed that the structural unit (A) was 48 mol% ethylene and the structural unit (B) was 52 mol% norbornene. DSC measurement revealed that the glass transition temperature was 135.6°C. Since no melting peak was detected, crystallinity measurement by XRD was not performed.

[0108] Comparative Example 2 A commercially available cyclic olefin polymer (TOPAS 6013S-04, manufactured by Polyplastics Co., Ltd.) was used. The composition was 13 C-NMR measurement revealed that the structural unit (A) was 47 mol% ethylene and the structural unit (B) was 53 mol% norbornene. DSC measurement revealed that the glass transition temperature was 138.0°C. Since no melting peak was detected, crystallinity measurement by XRD was not performed.

[0109] [Chemical resistance to decalin at 135°C] Using a migration viscometer (Rigo Co., Ltd., Model VNR053U), 0.02 g of each of the cyclic olefin polymers of Examples 1 and 2 and Comparative Examples 1 and 2 was dissolved in 20 mL of decalin to prepare samples. When the samples were stirred at 135°C for 1 hour in accordance with ASTM J1601, if undissolved matter was observed, the chemical resistance was judged to be good (rating A), and if no undissolved matter was observed, the chemical resistance was judged to be poor (rating B). The results are shown in Table 1. It was determined that if undissolved matter was found in decalin at 135°C, it was not possible to determine the intrinsic viscosity.

[0110] [Preparation of test press sheet] 1.5 g of the cyclic olefin polymers of Examples 1 and 2 and Comparative Examples 1 and 2 were sandwiched between films of Upilex (trade name, manufactured by Ube Industries, Ltd.) and subjected to heat press molding under a load of 5 ton using a 50 mm x 50 mm x 0.5 mm spacer. Examples 1 and 2 were pressed at 300 °C, and Comparative Examples 1 and 2 were pressed at 250 °C for 4 minutes, and then slowly cooled by being sandwiched between two presses at room temperature (23 °C) for 4 minutes. This resulted in test press sheets measuring 50 mm x 50 mm and 0.5 mm thick. After heat pressing, the test press sheets were held at 200 °C for 10 minutes to promote crystallization. In general, it is believed that the higher the molding temperature, the higher the relative permittivity and dielectric loss tangent may be due to the effect of resin oxidation. The cyclic olefin polymers of Examples 1 and 2 of the present application were molded at 300°C, which is a stricter condition from the viewpoint of electrical properties. On the other hand, the cyclic olefin polymers of Comparative Examples 1 and 2 could not be molded at 300°C, so they were forced to be molded at 250°C. In other words, Examples 1 and 2 of the present application were tested under conditions that made the electrical properties more likely to deteriorate than Comparative Examples 1 and 2.

[0111] In Table 2, √Dk×Df is a calculated value that indicates the magnitude of transmission loss due to the dielectric. The smaller the value, the smaller the transmission loss, which is considered to be preferable. Evaluation was based on the following evaluation criteria. A:5.00×10 -4 below B:5.00×10 -4 Exceeding 8.00 x 10 -4 below C:8.00×10 -4 exceed

[0112] Also, ΔDf in Table 2 10GHz and ΔDf 24GHz is the value calculated using the following formula: ΔDf 10GHz = (Df at 10GHz - Df at 1MHz) / Df at 1MHz ΔDf 24GHz = (Df at 24 GHz - Df at 1 MHz) / Df at 1 MHz The smaller the value, the smaller the frequency dependency of the dielectric loss tangent, and the more preferable it was. Evaluation was made based on the following evaluation criteria. A: 1.00 or less B: Over 1.00 and 5.00 or less C: Over 5.00

[0113] [Table 1]

[0114] [Table 2]

[0115] As can be seen from Table 2, the molded articles (press sheets) using the cyclic olefin polymers of Examples 1 and 2 had small transmission losses at both 10 GHz and 24 GHz, and the rate of change between the dielectric loss tangent at 1 MHz and the dielectric loss tangent at 10 GHz, and the rate of change between the dielectric loss tangent at 1 MHz and the dielectric loss tangent at 24 GHz were all small. These findings demonstrate that the cyclic olefin polymers of Examples 1 and 2 are polymers with small frequency dependence and stable dielectric loss tangents. Furthermore, in the present invention, although Examples 1 and 2 were molded under stricter conditions in terms of electrical properties than Comparative Examples 1 and 2, the dielectric properties were low and good. On the other hand, the molded articles (press sheets) using the cyclic olefin polymers of Comparative Examples 1 and 2 showed good dielectric properties at 1 MHz, but the transmission loss increased in a high-frequency environment. Furthermore, the molded articles (press sheets) of Comparative Examples 1 and 2 showed a high rate of change in the dielectric loss tangent at each frequency relative to 1 MHz, indicating that the stability of the dielectric loss tangent was reduced.

Claims

1. A cyclic olefin polymer, the cyclic olefin polymer is insoluble in decalin at 135°C, the glass transition temperature of the cyclic olefin polymer is 110.0°C or higher, The cyclic olefin polymer has a crystallinity of 1% or more as determined by the following <X-ray diffraction measurement conditions>. <X-ray diffraction measurement conditions> A powdered cyclic olefin polymer is subjected to wide-angle X-ray diffraction measurement, and the crystalline peak area, which is the area of the peak derived from the crystal, and the amorphous halo area, which is the area of the halo derived from the amorphous, are used to calculate the crystalline peak area using the following formula. Crystallinity (%) = crystalline peak area / (crystalline peak area + amorphous halo area) × 100

2. The cyclic olefin polymer is one or more olefin-derived structural units (A) represented by the following general formula (I); a structural unit (B) derived from a cyclic olefin monomer represented by the following general formula (II), The cyclic olefin polymer according to claim 1, having the formula: 【Chemical 1】 (In the general formula (I), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. 【Chemistry 2】 (In the general formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ６１ ~R ７８ and R ａ１ and R ｂ１ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R ７５ ~R ７８ may be bonded to each other to form a monocyclic or polycyclic ring.

3. When the total amount of structural units in the cyclic olefin polymer is taken as 100 mol %, The content of the structural unit (A) is 35 mol% or more and 65 mol% or less, The cyclic olefin polymer according to claim 2, wherein the content of the structural unit (B) is 35 mol % or more and 65 mol % or less.

4. 3. The cyclic olefin polymer according to claim 1, wherein the melting point of the cyclic olefin polymer is 150.0°C or higher and 450.0°C or lower.

5. A molded article comprising the cyclic olefin polymer according to claim 1 or 2.

6. The molded article according to claim 5, which can be used as an insulator.

7. The molded article according to claim 5, which can be used in high-frequency communication devices.

8. A high-frequency communication device comprising the molded article according to claim 5.

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