Cyclic olefin-based copolymer and optical component

Abstract

To provide a cyclic olefin-based copolymer which can yield an optical component with improved performance balance between heat resistance and long-term reliability of optical performance under a high temperature environment.SOLUTION: A cyclic olefin-based copolymer comprises a structural unit (a) derived from at least one olefin and a structural unit (b) derived from at least one cyclic olefin represented by formula (II), where the cyclic olefin-based copolymer has a Tg, as measured by DSC, of 135°C or more and, in a sequence of (a)-(b)-(b)-(a), the abundance ratio of a racemic structure and a meso structure, as measured by 13C-NMR, is 0 / 100 to 5.0 / 95.0.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a cyclic olefin copolymer and an optical component. [Background technology]

[0002] Cyclic olefin copolymers have excellent optical performance and are therefore used as optical components such as optical lenses. In recent years, there has been increasing demand for in-vehicle camera lenses and camera lenses for mobile devices (mobile phones, smartphones, tablets, etc.). High heat resistance is required for in-vehicle camera lenses and camera lenses for mobile devices. Cyclic olefin copolymers are widely used in optical components such as camera lenses due to their excellent optical and mechanical properties. Examples of techniques relating to cyclic olefin copolymers used in optical components include those described in Patent Documents 1 and 2.

[0003] Patent Document 1 discloses a resin composition containing a polymer containing an alicyclic structure in at least a portion of the repeating structural units and a fatty acid ester of a fatty acid and a polyhydric alcohol having one or more ether groups, and describes that the resin composition can provide a molded article that has excellent optical performance and that is furthermore inhibited from deteriorating under high-temperature and high-humidity conditions, and that the resin composition can provide optical components such as lens components for in-vehicle cameras that have excellent optical performance, heat resistance, and moist heat resistance.

[0004] Patent Document 2 discloses an optical component comprising a cyclic olefin copolymer (A), wherein the cyclic olefin copolymer (A) has at least one olefin-derived structural unit (a) represented by general formula (I), at least one cyclic olefin-derived structural unit (b) represented by general formula (II), and at least one cyclic olefin-derived structural unit (c) represented by general formula (III), and the content of the structural unit (a) is 50 mol % or less when the total content of the structural units (a), (b), and (c) is taken as 100 mol %, and it describes that an optical component having a high refractive index and excellent long-term reliability of optical performance even in high-temperature environments can be provided. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-199939 [Patent Document 2] International Publication No. 2021 / 149400 Summary of the Invention [Problem to be solved by the invention]

[0006] The optical component described in Patent Document 2 has a high refractive index and is excellent in long-term reliability of optical performance in high-temperature environments, but there is an increasing demand for long-term reliability of optical performance in high-temperature environments, and further improvements are being sought. The present invention provides a cyclic olefin copolymer that can provide optical components having an improved balance of heat resistance and long-term reliability of optical performance under high-temperature environments. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to solve the above-mentioned problems. As a result, they have discovered that in a cyclic olefin copolymer having an olefin-derived structural unit (a) and a cyclic olefin-derived structural unit (b), by setting the glass transition temperature (Tg) to a predetermined value or higher and setting the ratio of racemostructure to mesostructure in the structural unit (a)-structural unit (b)-structural unit (b)-structural unit (a) sequence (racemostructure / mesostructure) within a specific range, the performance balance between heat resistance and long-term reliability of optical performance in high-temperature environments can be improved, leading to the completion of the present invention. That is, according to the present invention, the following cyclic olefin copolymers and optical components are provided.

[0008] [1] At least one olefin-derived structural unit (a) represented by the following general formula (I), and at least one cyclic olefin-derived structural unit (b) represented by the following general formula (II), the glass transition temperature (Tg) of the cyclic olefin copolymer measured by a differential scanning calorimeter (DSC) is 135°C or higher; 13 A cyclic olefin copolymer, wherein the ratio of racemostructures to mesostructures (racemostructures / mesostructures) in the structural unit (a)-structural unit (b)-structural unit (b)-structural unit (a) chain, as measured by C-NMR, is 0 / 100 or more and 5.0 / 95.0 or less. [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), R 1 ~R 8 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 4 or less carbon atoms, and R 5 ~R 8may be bonded to each other to form a monocyclic ring, and the monocyclic ring may have a double bond, and R 5 and R 6 and, or R 7 and R 8 and may form an alkylidene group.) [2] the content of the structural unit (a) in the cyclic olefin copolymer is 30.0 mol% or more and less than 50.0 mol%, the content of the structural unit (b) in the cyclic olefin copolymer is more than 50.0 mol% and not more than 70.0 mol%, The cyclic olefin copolymer according to [1], wherein the total content of the structural unit (a) and the structural unit (b) in the cyclic olefin copolymer is more than 96.0 mol % and 100.0 mol % or less. [3] 13 The cyclic olefin copolymer according to [1] or [2], wherein the proportion of the structural unit (b)-structural unit (b) chains in all structural units constituting the cyclic olefin copolymer measured by C-NMR is 10.0 mol % or more and 30.0 mol % or less. [4] 13 The cyclic olefin copolymer according to any one of [1] to [3], wherein the proportion of the chain of the structural unit (b) - the structural unit (a) in all structural units constituting the copolymer, as measured by C-NMR, is 60.0 mol % or more and 80.0 mol % or less. [5] An optical component comprising the cyclic olefin copolymer according to any one of [1] to [4]. [6] The optical component according to [5], which is an fθ lens, an imaging lens, a sensor lens, a prism, or a light guide plate. [7] The optical component according to [5], which is an in-vehicle camera lens or a camera lens for a mobile device. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a cyclic olefin copolymer that can provide optical components having an improved balance of heat resistance and long-term reliability of optical performance in high-temperature environments. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, the present invention will be described based on the embodiments. In the present embodiments, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified. When numerical ranges are stated in stages, the upper and lower limits of each numerical range can be combined in any way. Each of the monomers constituting the cyclic olefin copolymer of the present embodiment may be a monomer obtained from a fossil raw material, or may be a monomer obtained from an animal or plant raw material.

[0011] <Cyclic olefin copolymer> The cyclic olefin copolymer of the present embodiment comprises at least one olefin-derived structural unit (a) represented by the following general formula (I) and at least one cyclic olefin-derived structural unit (b) represented by the following general formula (II), and the glass transition temperature (Tg) of the cyclic olefin copolymer measured by a differential scanning calorimeter (DSC) is 135°C or higher, 13 The ratio of racemostructure to mesostructure (racemostructure / mesostructure) in the sequence of structural unit (a)-structural unit (b)-structural unit (b)-structural unit (a) measured by C-NMR is 0 / 100 or more and 5.0 / 95.0 or less.

[0012] [ka]

[0013] 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.

[0014] [ka]

[0015] In the above general formula (II), R 1 ~R 8 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 4 or less carbon atoms, and R 5 ~R 8 may be bonded to each other to form a monocyclic ring, and the monocyclic ring may have a double bond, and R 5 and R 6 and, or R 7 and R 8 may form an alkylidene group.

[0016] The total content of the structural unit (a) and the structural unit (b) in the cyclic olefin copolymer is preferably more than 96.0 mol% and not more than 100.0 mol%, more preferably 98.0 mol% or more and not more than 100.0 mol%, from the viewpoint of further improving the performance balance of heat resistance, mechanical properties, and optical properties.

[0017] [Constituent unit (a)] In the above general formula (I), R 300represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. The olefin monomer for forming the structural unit (a) preferably includes one or more monomers selected from the group consisting of 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. From the viewpoint of improving the balance of heat resistance, mechanical properties, and optical properties, the olefin monomer for forming the structural unit (a) preferably contains ethylene or propylene, and more preferably contains ethylene. The olefin monomer for forming the structural unit (a) may be used alone or in combination of two or more.

[0018] From the viewpoint of further improving the heat resistance of optical components, the content of the structural unit (a) in the cyclic olefin copolymer is preferably 30.0 mol% or more and less than 50.0 mol%, more preferably 40.0 mol% or more and 49.0 mol% or less, even more preferably 43.0 mol% or more and 48.5 mol% or less, and even more preferably 45.0 mol% or more and 48.0 mol% or less. The content of the structural unit (a) is 13 It can be measured by C-NMR.

[0019] [Constituent unit (b)] In the above general formula (II), R 1 ~R 8 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 4 or less carbon atoms. Here, the halogen atom is one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The hydrocarbon group having 4 or less carbon atoms may be one selected from the group consisting of alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups, and cycloalkyl groups such as cyclopropyl groups. Also R 5 ~R 8 may be bonded to each other to form a monocyclic ring, and the monocyclic ring may have a double bond, and R 5 and R 6 and, or R 7 and R 8 may form an alkylidene group. where R 5 ~R 8 Examples of monocyclic rings formed by bonding together are shown below.

[0020] [ka]

[0021] In the above monocyclic ring, the carbon atom numbered 1 or 2 corresponds to the carbon atom in general formula (II) R 5 (R 6 ) or R 7 (R 8 ) is a carbon atom forming an alicyclic structure to which is bonded. Specific examples of the alkylidene group include one or more groups selected from the group consisting of an ethylidene group, a propylidene group, and an isopropylidene group.

[0022] From the viewpoint of improving the balance of heat resistance, mechanical properties, and optical properties, the cyclic olefin monomer for forming the structural unit (b) is preferably bicyclo[2.2.1]-2-heptene (also called norbornene), a bicyclo[2.2.1]hept-2-ene derivative having 11 or less carbon atoms, or a tricyclo[4.3.0.1 2,5 ]-3-decene derivatives and tricyclo[4.4.0.1 2,5

[0047] Among these, the cyclic olefin monomer for forming the structural unit (b) more preferably includes bicyclo[2.2.1]-2-heptene. The cyclic olefin monomer for forming the structural unit (b) may be used alone or in combination of two or more types.

[0023] From the viewpoint of further improving the long-term reliability of optical performance in high-temperature environments and the balance of refractive index and heat resistance, the content of structural unit (b) in the cyclic olefin copolymer is preferably more than 50.0 mol% and not more than 70.0 mol%, more preferably 51.0 mol% or more and 60.0 mol% or less, even more preferably 51.5 mol% or more and 57.0 mol% or less, and even more preferably 52.0 mol% or more and 55.0 mol% or less. The content of the structural unit (b) is 13 It can be measured by C-NMR.

[0024] The cyclic olefin copolymer may contain, as necessary, structural units derived from other copolymerizable monomers other than the monomers for forming the structural units (a) and (b), as long as the object of the present invention is not impaired. Such other monomers include cyclic olefins other than the cyclic olefin monomers for forming the above-mentioned structural unit (b), such as cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclohexene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene, etc. Other olefins such as styrene and α-methylstyrene are also included. These may be used alone or in combination of two or more.

[0025] The cyclic olefin copolymer of the present embodiment may be used alone or in combination of two or more kinds.

[0026] The cyclic olefin copolymer of the present embodiment can be produced by appropriately selecting conditions according to the methods described in, for example, JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, JP-A-61-115916, JP-A-61-271308, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407, or the like.

[0027] [Glass transition temperature (Tg)] The cyclic olefin copolymer of this embodiment has a glass transition point (Tg) of 135° C. or higher. The glass transition point (Tg) of the cyclic olefin copolymer is preferably 136° C. or higher, more preferably 137° C. or higher, even more preferably 138° C. or higher, even more preferably 139° C. or higher, and even more preferably 140° C. or higher. There are no particular limitations on the upper limit of the glass transition point (Tg) of the cyclic olefin copolymer, but from the viewpoint of further improving moldability, it is preferably 180° C. or lower, more preferably 170° C. or lower, and even more preferably 160° C. or lower. The glass transition point (Tg) of the cyclic olefin copolymer is 135°C or higher, preferably 136°C or higher and 180°C or lower, more preferably 138°C or higher and 170°C or lower, and even more preferably 140°C or higher and 160°C or lower. When the glass transition temperature (Tg) of the cyclic olefin copolymer is within the above range, the heat resistance can be improved.

[0028] The glass transition point (Tg) of the cyclic olefin copolymer of the present embodiment can be determined using a differential scanning calorimeter (DSC) from the endothermic curve obtained by increasing the temperature from room temperature to 250°C at a rate of 10°C / min, holding the temperature for 5 minutes, then decreasing the temperature to -20°C at a rate of 10°C / min, holding the temperature for 5 minutes, and then increasing the temperature to 300°C at a rate of 10°C / min.

[0029] [stereoregularity] The cyclic olefin copolymer of the present embodiment is 13The ratio of racemostructure to mesostructure (racemostructure / mesostructure) in the sequence of structural unit (a)-structural unit (b)-structural unit (b)-structural unit (a) measured by C-NMR is 0 / 100 or more and 5.0 / 95.0 or less.

[0030] If the ratio of racemostructures to mesostructures in the structural unit (a)-structural unit (b)-structural unit (b)-structural unit (a) chain is within the above range, the cyclic olefin copolymer will have a specific stereoregularity, thereby improving the long-term reliability of optical performance in high-temperature environments. The mechanism by which this long-term reliability is improved is presumed to be as follows. If the stereoregularity of the cyclic olefin copolymer is high and the mesostructure is dominant, the polymers can be regularly aligned when the resin (i.e., the cyclic olefin copolymer) is solidified, which is thought to reduce the gaps between the polymers in the cyclic olefin copolymer. The polymer mobility of the solidified resin is reduced even in high-temperature environments, which is thought to result in reduced thermal shrinkage. On the other hand, if the stereoregularity of the cyclic olefin copolymer is low, the polymers cannot be regularly aligned when the resin is solidified, and the gaps between the polymers in the cyclic olefin copolymer are thought to become large.The mobility of the polymers in the solidified resin increases in a high-temperature environment, resulting in large thermal shrinkage. Furthermore, even if the stereoregularity is high, when the racemostructure predominates, the gaps between the polymers in the cyclic olefin copolymer are larger than when the mesostructure predominates, and therefore the mobility of the polymers is higher even in high-temperature environments than when the mesostructure predominates, which is thought to result in greater thermal shrinkage. The reduced thermal shrinkage of the resin reduces the change in refractive index in high temperature environments, improving the long-term reliability of optical performance.

[0031] First, the specific stereoregularity of the cyclic olefin copolymer according to this embodiment will be described. For example, a polymer having a structure represented by the following general formula (X) will be described, taking ethylene as the olefin forming the structural unit (a) and norbornene as the cyclic olefin forming the structural unit (b).

[0032] [ka]

[0033] In the above general formula (X), m and n represent repeating units. Here, if the norbornene-derived structure is NB and the ethylene-derived structure is E, then in the example of the above general formula (X), the structure is linked as follows: -NB-E-NB-E-NB-E-... The same applies when the olefin forming the structural unit (a) is a monomer other than ethylene, or when the cyclic olefin forming the structural unit (b) is a monomer other than norbornene. The mesostructure and racemostructure are 13 This is measured by C-NMR. An example of this bonding mode is shown below.

[0034] [ka]

[0035] In the cyclic olefin copolymer of this embodiment, the ratio of the racemic structure to the meso structure in the structural unit (a)-structural unit (b)-structural unit (b)-structural unit (a) chain, i.e., the ratio of the racemic structure to the meso structure [racemic structure / meso structure], which represents the stereoregularity, is 0 / 100 to 5.0 / 95.0 (i.e., racemic:meso=0:100 to 5.0:95.0), preferably 0 / 100 to 2.5 / 97.5, more preferably 0 / 100 to 1.5 / 98.5, even more preferably 0 / 100 to 1.0 / 99.0, and even more preferably 0 / 100 (i.e., all meso structure). By having the racemic structure / meso structure ratio in the above range, the long-term reliability of optical performance in high-temperature environments is improved. The stereoregularity can be appropriately adjusted by selecting a catalyst and a co-catalyst during polymerization of the cyclic olefin copolymer, which will be described later.

[0036] The stereoregularity of the cyclic olefin copolymer according to this embodiment is 13 It is measured by C-NMR. The specific measurement conditions will be described later. Here, we show the mesostructure and racemostructure. 13 The C-NMR signal positions vary depending on the cyclic olefin copolymer. Below, we take the cyclic olefin copolymer of ethylene and NB as an example. 13 This section explains the signal positions and signal measurement methods of C-NMR.

[0037] 13 In the C-NMR spectrum, The sum of the integrals of the signals in the range of 31.3 to 32.0 ppm (X B ) The sum of the integrals of the signals in the range of 25.4 to 26.6 ppm (Y B ) In the formula, the stereoregularity (racemo structure / meso structure in the sequence of structural unit (a)-structural unit (b)-structural unit (b)-structural unit (a)) is X B / Y BThis ratio is defined as 0 / 100 or more and 5.0 / 95.0 or less (i.e., racemo:meso=0:100 to 5.0:95.0), preferably 0 / 100 or more and 2.5 / 97.5 or less, more preferably 0 / 100 or more and 1.5 / 98.5 or less, even more preferably 0 / 100 or more and 1.0 / 99.0 or less, and even more preferably 0 / 100 (i.e., all mesostructures). In the case of a polymer of ethylene and NB, multiple peaks appear within the range, so the sum of the integrated values ​​of the signals is used.

[0038] The cyclic olefin copolymer of the present embodiment is 13 The proportion of the structural unit (b)-structural unit (b) chain, as measured by C-NMR, in all structural units constituting the cyclic olefin copolymer is preferably 10.0 mol % or more and 30.0 mol % or less. 13 The proportion of the structural unit (b)-structural unit (b) chain to all structural units constituting the cyclic olefin copolymer measured by C-NMR is: 13 C-NMR spectrum Sum of integrals of signals in the range of 32.0 to 35.7 ppm (P) Sum of integrals of signals in the range of 31.3 to 32.0 ppm (Q) Sum of integrals of signals in the range of 25.4 to 26.6 ppm (R) It can be calculated by measuring (P), (Q), and (R) and dividing the sum by two. At this time, 13The proportion of the structural unit (b)-structural unit (b) chains in all structural units constituting the cyclic olefin copolymer, as measured by C-NMR, is preferably 10.0 mol% or more and 30.0 mol% or less, more preferably 11.0 mol% or more and 20.0 mol% or less. The proportion of the structural unit (b)-structural unit (b) chains in all structural units constituting the cyclic olefin copolymer represents the content of chains of cyclic olefin compounds having a norbornene skeleton, for example, NB and NB. When the proportion of the structural unit (b)-structural unit (b) chains in all structural units constituting the cyclic olefin copolymer is within the above range, the long-term reliability of optical performance in high-temperature environments is further improved.

[0039] In the cyclic olefin copolymer of this embodiment, the ratio of the racemo-structured structure to the meso-structured structure in the structural unit (b)-structural unit (b) chain, i.e., the ratio of the racemo-structured structure to the meso-structured structure [racemo-structure / meso-structure], which represents the stereoregularity, is preferably 0 / 100 to 5.0 / 95.0 (i.e., racemo:meso=0:100 to 5.0:95.0), more preferably 0 / 100 to 2.5 / 97.5, even more preferably 0 / 100 to 1.5 / 98.5, even more preferably 0 / 100 to 1.0 / 99.0, and even more preferably 0 / 100 (i.e., all meso-structured). By having the racemo-structure / meso-structure ratio in the above range, the long-term reliability of optical performance in high-temperature environments is further improved.

[0040] The cyclic olefin copolymer according to this embodiment is 13 The proportion of the chain of structural unit (b)-said structural unit (a) in all structural units constituting the cyclic olefin copolymer, as measured by C-NMR, is preferably 60.0 mol % or more and 80.0 mol % or less. Here, we show the mesostructure and racemostructure. 13 The C-NMR signal positions vary depending on the cyclic olefin copolymer. Below, we take the cyclic olefin copolymer of ethylene and NB as an example. 13This section explains the signal positions and signal measurement methods of C-NMR. 13 In the C-NMR spectrum, Sum of integrals of signals in the range of 30.6 to 35.7 ppm (S) Sum of integrals of signals in the range of 31.3 to 32.0 ppm (T) The ratio of structural unit (b) - structural unit (a) linkages can be calculated from the value (ST) obtained by subtracting (T) from (S) and multiplying the result by 2 (ST) × 2. At this time, 13 The proportion of the structural unit (b)-structural unit (a) chain to all structural units constituting the cyclic olefin copolymer, as measured by C-NMR, is preferably 60.0 mol% to 80.0 mol%, more preferably 70.0 mol% to 78.0 mol%. The proportion of the structural unit (b)-structural unit (a) chain to all structural units constituting the cyclic olefin copolymer represents the content of chains of cyclic olefin compounds having a norbornene skeleton, such as chains of ethylene and NB. When the proportion of the structural unit (b)-structural unit (a) chain to all structural units constituting the cyclic olefin copolymer is within the above range, the long-term reliability of optical performance in high-temperature environments is further improved.

[0041] <Optical components> The optical component according to this embodiment contains the cyclic olefin-based copolymer according to this embodiment, and therefore has excellent optical performance. Therefore, it can be suitably used as an optical component in an optical system that requires highly accurate image identification. Optical components are components used in optical equipment, etc., and specific examples include sensor lenses, which are lenses used in various sensors, pickup lenses, projector lenses, prisms, fθ lenses, imaging lenses, and light guide plates. From the viewpoint of the effects according to this embodiment, it can be suitably used in fθ lenses, imaging lenses, sensor lenses, prisms, or light guide plates. Therefore, optical components containing the cyclic olefin-based copolymer according to this embodiment can be particularly suitably used for optical components that require heat resistance, such as in-vehicle camera lenses and camera lenses for mobile devices (mobile phones, smartphones, tablets, etc.). Examples of in-vehicle camera lenses and camera lenses for mobile devices include view camera lenses, sensing camera lenses, light converging lenses for head-up displays, and light diffusing lenses for head-up displays.

[0042] The optical component according to this embodiment may be combined with a second optical component different from the optical component described above. The second optical component is not particularly limited, but for example, an optical component made of at least one type of resin selected from polycarbonate resin and polyester resin can be used.

[0043] (Other ingredients) In addition to the cyclic olefin-based copolymer of the present embodiment, the optical component according to the present embodiment may contain known additives as optional components within a range that does not impair the favorable physical properties of the optical component according to the present embodiment. Examples of additives include hydrophilic stabilizers, hydrophilic agents, antioxidants, secondary antioxidants, lubricants, release agents, antifogging agents, weathering stabilizers, light resistance stabilizers, ultraviolet absorbers, antistatic agents, metal deactivators, phenolic stabilizers, higher fatty acid metal salts, hindered amine light stabilizers, hydrochloric acid absorbers, slip agents, nucleating agents, plasticizers, flame retardants, and phosphorus-based stabilizers.

[0044] <Manufacturing methods for optical components> The optical component according to this embodiment can be produced by molding a cyclic olefin resin composition containing a cyclic olefin copolymer into a predetermined shape. The method for molding a cyclic olefin resin composition to obtain an optical component is not particularly limited, and known methods can be used. Depending on the application and shape, for example, extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, foam molding, etc. can be applied. Among these, injection molding is preferred from the viewpoints of moldability and productivity. Furthermore, molding conditions are appropriately selected depending on the intended use or molding method. For example, the resin temperature in injection molding is appropriately selected from the range of usually 150°C to 400°C, preferably 200°C to 350°C, and more preferably 230°C to 330°C.

[0045] The cyclic olefin resin composition according to the present embodiment can be obtained by, for example, a method of melt-kneading the cyclic olefin copolymer and other components added as needed using a known kneading device such as an extruder or a Banbury mixer; a method of dissolving the cyclic olefin copolymer and other components added as needed in a common solvent and then evaporating the solvent; or a method of adding a solution of the cyclic olefin copolymer and other components added as needed to a poor solvent to cause precipitation. [Example]

[0046] The present embodiment will be described in detail below with reference to examples, etc. However, the present embodiment is not limited to the descriptions of these examples. First, the measurement methods used in the examples will be described.

[0047] [ 13 C-NMR measurement] The contents of the structural units (a) and (b) constituting the cyclic olefin copolymer of each example were measured using a Bruker Biospin AVANCE111cryo-500 nuclear magnetic resonance spectrometer under the following conditions. Measurement nuclei: 13 C Frequency: 125MHz Measurement mode: Single pulse proton inverse gated decoupling Pulse width: 45 degrees Number of points: 64k Measurement range: -55 to 195 ppm (total 250 ppm) Solvent: 1,1,2,2-tetrachloroethane-d2 Sample concentration: 40-60mg / 0.6mL Pulse repetition time: 10 seconds Number of times accumulated: 1024 Measurement temperature: 120℃ Chemical shift reference: 1,1,2,2-tetrachloroethane-d2 was used as the reference.

[0048] Measured under the above conditions 13 The contents of the structural unit (a) and the structural unit (b) constituting the cyclic olefin copolymer were each quantified by C-NMR spectroscopy. In addition, the proportion of [CO]-[CO] chains, the proportion of [CO]-[E] chains, and the proportion of [E]-[E] chains in the cyclic olefin copolymer (the sum of [CO]-[CO] chains, [CO]-[E] chains, and [E]-[E] chains was set to 100 mol%), the abundance ratio of racemostructures and mesostructures in [CO]-[CO] chains, and the abundance ratio of racemostructures and mesostructures in [E]-[CO]-[CO]-[E] chains were determined. Here, [CO] means the structural unit (b), and [E] means the structural unit (a).

[0049] [Ratio of structural unit (b)-structural unit (b) chains] Sum of integrals of signals in the range of 32.0 to 35.7 ppm (P) Sum of integrals of signals in the range of 31.3 to 32.0 ppm (Q) Sum of integrals of signals in the range of 25.4 to 26.6 ppm (R) The ratio of the linkage of building block (b)-building block (b) was calculated by measuring the ratio of the linkage of building block (b)-building block (b) and dividing the sum of (P), (Q), and (R) by two.

[0050] [Ratio of structural unit (b)-structural unit (a) chain] Also,13 In the C-NMR spectrum, Sum of integrals of signals in the range of 30.6 to 35.7 ppm (S) Sum of integrals of signals in the range of 31.3 to 32.0 ppm (T) The ratio of the linkage of the structural unit (b) - structural unit (a) was calculated from the value (ST) obtained by subtracting (T) from (S) and multiplying the result by 2 (ST) × 2).

[0051] [Ratio of structural unit (a)-structural unit (a) chains] Also, 13 In the C-NMR spectrum, Sum of integrals of signals in the range of 25.4 to 30.6 ppm (V) In this step, the value obtained by multiplying (S) by 2 was subtracted from (V), and the value obtained by subtracting (ST) x 2 from this value (VS x 2) was divided by 2 to calculate the proportion of structural unit (a)-structural unit (a) linkages (((VS x 2) - (ST) x 2) / 2).

[0052] [Structural unit (a)-structural unit (b)-structural unit (b)-structural unit (a) racemostructure / mesostructure] Also, 13 In the C-NMR spectrum, The sum of the integrals of the signals in the range of 31.3 to 32.0 ppm (X B ) The sum of the integrals of the signals in the range of 25.4 to 26.6 ppm (Y B ) In X B Y B The ratio of the racemo structure to the meso structure in the structural unit (a)-structural unit (b)-structural unit (b)-structural unit (a) sequence was calculated by dividing by .

[0053] [Glass transition temperature Tg (℃)] The glass transition temperature (Tg) of each cyclic olefin copolymer was measured under a nitrogen atmosphere using a differential scanning calorimeter (DSC-7020, manufactured by Hitachi High-Tech Science Corporation). Each cyclic olefin copolymer was heated from room temperature to 250°C at a heating rate of 10°C / min and then held for 5 minutes. The temperature was then lowered to -20°C at a heating rate of 10°C / min and then held for 5 minutes. The glass transition temperature (Tg) of the cyclic olefin copolymer was then determined from the endothermic curve when the temperature was raised to 300°C at a heating rate of 10°C / min.

[0054] [Press sheet production] The cyclic olefin copolymer obtained in each example was sandwiched between ultra-heat-resistant polyimide films (UPILEX, manufactured by UBE Corporation) and vacuum-pressed using a spacer measuring 30 mm x 30 mm x 1 mm at 260 °C, 10 MPa, and 2 minutes. This resulted in a pressed sheet with a thickness of 1 mm. The resulting pressed sheets were evaluated as follows.

[0055] [Refractive Index] The refractive index (nd) of each press sheet at a wavelength of 589 nm was measured using a refractometer (Shimadzu Science Corporation, KPR200) ​​in accordance with ASTM D542. Here, the refractive index (nd) of the press sheet at a wavelength of 589 nm was measured before and after the heat resistance test described below.

[0056] [Heat resistance test] The pressed sheet of each example was left at a temperature of Tg-20°C in the air for 168 hours, and then the refractive index (nd) at a wavelength of 589 nm was measured after 3 hours, and the change in refractive index (Δnd) before and after the heat resistance test was determined.

[0057] [Example 1] A 500 mL glass reactor, thoroughly purged with nitrogen, was charged with 250 mL of a 9:1 cyclohexane / hexane mixed solution and 0.75 g of 2-norbornene (referred to as NB in ​​Table 1). The liquid and gas phases were saturated with ethylene at 51 L / hr and hydrogen at 0.24 L / hr. Methylaluminoxane (MMAO) (0.9 mmol) and a catalyst (0.003 mmol) in which the titanium in the transition metal compound (1) described in paragraphs 0158 and 0159 of WO 2017 / 150218 was replaced with zirconium were added to the glass reactor to initiate the polymerization reaction. Ethylene was continuously supplied at 51 liters / hour and hydrogen at 0.24 liters / hour, and polymerization was carried out at 50°C under atmospheric pressure for 3 minutes, after which the polymerization was terminated by adding a small amount of isobutyl alcohol. After polymerization was completed, the reactants were added to an excess amount of a methanol / acetone mixed solution (mixture ratio 1 / 3 (volume ratio)) containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the polymer was dried under reduced pressure overnight at 130°C, yielding 0.336 g of ethylene / norbornene copolymer. The polymerization activity was 2.24 kg / mmol·hr. The composition, Tg, and 13 The sequence distribution, stereoregularity and Δnd measured by C-NMR are listed in Table 1.

[0058] [Comparative Example 1] A commercially available cyclic olefin copolymer (TOPAS 5013L-10, manufactured by Polyplastics Co., Ltd.) was used and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0059] Comparative Example 2 A 500 mL glass reactor, thoroughly purged with nitrogen, was charged with 300 mL of a 9 / 1 cyclohexane / hexane mixed solution and 6.34 g of 2-norbornene. The liquid and gas phases were saturated with 90 L / hr of ethylene and 0.24 L / hr of hydrogen. Methylaluminoxane (MMAO) (0.3 mmol) was added to the glass reactor. Next, 0.0005 mmol of the titanium compound (3) catalyst described in paragraph 0157 of JP 2021-73223 A was added, followed by 0.004 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate (hereinafter referred to as borate compound (1)). Synthesized with reference to JP 2018-105273 A) to initiate the polymerization reaction. Ethylene was continuously supplied at 90 liters / hour and hydrogen at 0.24 liters / hour. Polymerization was carried out at 50°C under atmospheric pressure for 3 minutes, after which the polymerization was terminated by adding a small amount of isobutyl alcohol. After polymerization was completed, the reactants were added to an excess amount of a methanol / acetone mixed solution (mixture ratio 1 / 3 (volume ratio)) containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the polymer was dried under reduced pressure overnight at 130°C, yielding 3.139 g of ethylene / norbornene copolymer. The polymerization activity was 125.56 kg / mmol·hr. The resulting cyclic olefin copolymer was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0060] Comparative Example 3 A 2000 mL glass reactor, thoroughly purged with nitrogen, was charged with 1000 mL of a 9:1 cyclohexane / hexane mixture and 13.18 g of 2-norbornene. The liquid and gas phases were saturated with ethylene at 30 L / hr and hydrogen at 0.5 L / hr. TIBAL (triisobutylaluminum) (4.0 mmol) was added to the glass reactor. Next, 0.01 mmol of the transition metal compound (A-5) catalyst described in paragraph 0159 of P2020-117711A was added, followed by 0.04 mmol of the borate compound (1), to initiate the polymerization reaction. Ethylene was continuously supplied at 30 liters / hour and hydrogen at 0.5 liters / hour, and polymerization was carried out at 50°C under atmospheric pressure for 10 minutes, after which the polymerization was terminated by adding a small amount of isobutyl alcohol. After polymerization was completed, the reactants were added to an excess amount of a methanol / acetone mixed solution (mixture ratio 1 / 3 (volume ratio)) containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the polymer was dried under reduced pressure overnight at 130°C, yielding 5.542 g of ethylene / norbornene copolymer. The polymerization activity was 10.55 kg / mmol·hr. The resulting cyclic olefin copolymer was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0061] Comparative Example 4 A 500 mL glass reactor, thoroughly purged with nitrogen, was charged with 200 mL of a 9:1 cyclohexane / hexane mixed solution and 9.42 g of 2-norbornene, and the liquid and gas phases were saturated with ethylene at 51 L / hr. Methylaluminoxane (MMAO) (0.9 mmol) and a catalyst (0.003 mmol) of the transition metal compound (1) described in paragraphs 0158 and 0159 of WO 2017 / 150218 were added to the glass reactor to initiate the polymerization reaction. Ethylene was continuously supplied at a rate of 51 liters / hr, and polymerization was carried out at 50°C under atmospheric pressure for 30 minutes, after which the polymerization was terminated by adding a small amount of isobutyl alcohol. After polymerization was completed, the reactants were added to an excess amount of a methanol / acetone mixed solution (mixture ratio 1 / 3 (volume ratio)) containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the polymer was dried under reduced pressure at 130°C overnight, yielding 1.024 g of ethylene / norbornene copolymer. The polymerization activity was 0.68 kg / mmol·hr. The resulting cyclic olefin copolymer was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0062] [Table 1]

[0063] It was found that the ethylene-norbornene copolymer of Example 1, in which the ratio of racemostructure to mesostructure in the structural unit (a)-structural unit (b)-structural unit (b)-structural unit (a) sequence (racemostructure / mesostructure) was within the range of 0 / 100 or more and 5 / 95 or less, showed a small change in refractive index before and after the heat resistance test. On the other hand, in Comparative Examples 1 to 4, the ratio of racemostructure to mesostructure was outside the range of 0 / 100 or more and 5 / 95 or less, and showed a large change in refractive index before and after the heat resistance test.

Claims

1. At least one olefin-derived structural unit (a) represented by the following general formula (I), and at least one cyclic olefin-derived structural unit (b) represented by the following general formula (II), the glass transition point (Tg) of the cyclic olefin copolymer measured by a differential scanning calorimeter (DSC) is 135°C or higher; １３ a ratio of the racemo structure to the meso structure (racemo structure / meso structure) in the structural unit (a)-structural unit (b)-structural unit (b)-structural unit (a) chain, as measured by C-NMR, of 0 / 100 or more and 5.0 / 95.0 or less. 【Chemical 1】 (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. 【Chemistry 2】 (In the above general formula (II), R １ ~R ８ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 4 or less carbon atoms, and R ５ ~R ８ may be bonded to each other to form a monocyclic ring, and the monocyclic ring may have a double bond, and R ５ and R ６ With or R ７ and R ８ and may form an alkylidene group.)

2. the content of the structural unit (a) in the cyclic olefin copolymer is 30.0 mol% or more and less than 50.0 mol%, the content of the structural unit (b) in the cyclic olefin copolymer is more than 50.0 mol% and not more than 70.0 mol%, 2. The cyclic olefin copolymer according to claim 1, wherein the total content of the structural unit (a) and the structural unit (b) in the cyclic olefin copolymer is more than 96.0 mol% and not more than 100.0 mol%.

3. １３ 3. The cyclic olefin copolymer according to claim 1, wherein the proportion of the structural unit (b)-structural unit (b) chains in all structural units constituting the cyclic olefin copolymer, as measured by C-NMR, is 10.0 mol % or more and 30.0 mol % or less.

4. １３ 3. The cyclic olefin copolymer according to claim 1, wherein the proportion of the structural unit (b) - structural unit (a) chains in all structural units constituting the copolymer, as measured by C-NMR, is 60.0 mol % or more and 80.0 mol % or less.

5. An optical component comprising the cyclic olefin copolymer according to claim 1 or 2.

6. The optical component according to claim 5 , which is an fθ lens, an imaging lens, a sensor lens, a prism, or a light guide plate.

7. The optical component according to claim 5, which is an in-vehicle camera lens or a camera lens for a mobile device.

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