Optical components

Abstract

An optical component comprising a cyclic olefin-based copolymer (A), wherein the cyclic olefin-based copolymer (A) comprises a constituent unit (a) derived from at least one olefin represented by the following general formula (I), a constituent unit (b) derived from at least one cyclic olefin represented by the following general formula (II), and a constituent unit (c) derived from at least one cyclic olefin represented by the following general formula (III), wherein the content of the constituent unit (a) is 50 mol% or less, when the total content of the constituent units (a), (b), and (c) is 100 mol%.

Description

Technical Field

[0001] The present invention relates to optical components. Background Art

[0002] Cyclic olefin copolymers have excellent optical properties and are used, for example, as optical components such as optical lenses.

[0003] As a technology related to cyclic olefin copolymers used in optical components, for example, there is the technology described in Patent Document 1 (Japanese Patent Application Laid-Open No. 2015-199939).

[0004] Patent Document 1 discloses a cyclic olefin resin composition comprising a cyclic olefin copolymer and a diglycerol fatty acid ester. Patent Document 1 states that the use of such a cyclic olefin resin composition can provide a molded article having excellent optical properties and suppressing degradation of the optical properties under high-temperature and high-humidity conditions.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2015-199939 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] In recent years, demand for camera lenses for vehicles and portable devices (such as cell phones, smartphones, and tablets) has increased. These lenses are required to have high heat resistance. Cyclic olefin copolymers are widely used in optical components such as camera lenses due to their excellent optical and mechanical properties.

[0010] However, according to the research of the present inventors, it was found that when an optical component including a cyclic olefin-based copolymer is exposed to a high-temperature environment for a long period of time, the refractive index may change and the optical performance may deteriorate.

[0011] The present invention has been made in view of the above circumstances, and provides an optical component having a high refractive index and excellent long-term reliability of optical performance in a high-temperature environment.

[0012] Methods for solving problems

[0013] According to the present invention, the following optical components are provided. [1]

[0015] An optical component comprising a cyclic olefin copolymer (A).

[0016] The cyclic olefin copolymer (A) has:

[0017] The constituent unit (a) derived from at least one olefin represented by the following general formula (I)

[0018] The structural unit (b) derived from at least one cyclic olefin represented by the following general formula (II), and

[0019] The structural unit (c) derived from at least one cyclic olefin represented by the following general formula (III) is:

[0020] When the total content of the structural unit (a), the structural unit (b), and the structural unit (c) is 100 mol %, the content of the structural unit (a) is 50 mol % or less.

[0021] [Chemical Formula 1]

[0022]

[0023] (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.

[0024] [Chemical Formula 2]

[0025]

[0026] (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, R 5 ~R 8 can be combined with each other to form a monocyclic ring, and the monocyclic ring may have a double bond, and furthermore may be formed by R 5 With R 6 , or R 7 With R 8 to form an alkylene group.)

[0027] [Chemical Formula 3]

[0028]

[0029] (In the above general formula (III), n is 0 or 1, m is 0 or a positive integer, n+m is a positive integer, q is 0 or 1, R 1 ~R 18 and R a and R b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, R 15 ~R 18 may be combined with each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, and may be further represented by R 15 With R 16, or R 17 With R 18 to form an alkylene group.) [2]

[0031] The optical component according to the above [1], wherein the glass transition point (Tg) of the cyclic olefin copolymer (A) measured by DSC is 140° C. or higher. [3]

[0033] The optical component according to [1] or [2], wherein the ratio ((b) / (c)) of the content of the structural unit (b) to the content of the structural unit (c) in the cyclic olefin-based copolymer (A) is 2 or more. [4]

[0035] The optical component according to any one of [1] to [3], wherein the structural unit (b) in the cyclic olefin copolymer (A) comprises a repeating unit derived from bicyclo[2.2.1]-2-heptene, and the structural unit (c) in the cyclic olefin copolymer (A) comprises a repeating unit derived from tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene repeating unit. [5]

[0037] The optical component according to any one of [1] to [4], wherein the structural unit (a) in the cyclic olefin-based copolymer (A) comprises a repeating unit derived from ethylene. [6]

[0039] The optical component according to any one of [1] to [5] above, which is an fθ lens, an imaging lens, a sensor lens, a prism, or a light guide plate. [7]

[0041] The optical component according to any one of [1] to [6] above, which is a vehicle-mounted camera lens or a camera lens for a portable device.

[0042] Effects of the Invention

[0043] According to the present invention, it is possible to provide an optical component having a high refractive index and excellent long-term reliability of optical performance in a high-temperature environment. DETAILED DESCRIPTION

[0044] Hereinafter, the present invention will be described based on the embodiment. In the present embodiment, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified.

[0045] [Optical components]

[0046] First, an optical component according to an embodiment of the present invention will be described.

[0047] The optical component involved in this embodiment is an optical component containing a cyclic olefin-based copolymer (A), which has: a structural unit (a) derived from at least one olefin represented by the following general formula (I), a structural unit (b) derived from at least one cyclic olefin represented by the following general formula (II), and a structural unit (c) derived from at least one cyclic olefin represented by the following general formula (III), and when the total content of the above-mentioned structural units (a), (b) and (c) is set to 100 mol%, the content of the above-mentioned structural unit (a) is 50 mol% or less.

[0048] [Chemical Formula 4]

[0049]

[0050] (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.

[0051] [Chemical Formula 5]

[0052]

[0053] (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, R 5 ~R 8 can be combined with each other to form a monocyclic ring, and the monocyclic ring may have a double bond, and furthermore may be formed by R 5 With R 6 , or R 7 With R 8 to form an alkylene group.)

[0054] [Chemical Formula 6]

[0055]

[0056] (In the above general formula (III), n is 0 or 1, m is 0 or a positive integer, n+m is a positive integer, q is 0 or 1, R 1 ~R 18 and R a and R b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, R 15 ~R 18 may be combined with each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, and may be further represented by R 15 With R 16 , or R17 With R 18 to form an alkylene group.)

[0057] According to the research conducted by the present inventors, it has been found that when an optical component including a cyclic olefin-based copolymer is exposed to a high-temperature environment for a long period of time, the refractive index changes and the optical performance deteriorates.

[0058] The present inventors conducted intensive research to address the above-mentioned issues. As a result, they discovered that an optical component using a cyclic olefin-based copolymer (A) comprising structural units (a) derived from at least one olefin represented by the general formula (I), structural units (b) derived from at least one cyclic olefin represented by the general formula (II), and structural units (c) derived from at least one cyclic olefin represented by the general formula (III), wherein the content of structural units (a) is 50 mol% or less, exhibits a high refractive index and is less likely to decrease in refractive index even after prolonged exposure to high-temperature environments, resulting in excellent long-term reliability of optical performance.

[0059] That is, according to this embodiment, it is possible to realize an optical component that has a high refractive index and is excellent in long-term reliability of optical performance in a high-temperature environment.

[0060] The lower limit of the content of the cyclic olefin copolymer (A) in the optical component according to the present embodiment is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, further more preferably 90% by mass or more, and particularly preferably 95% by mass or more, when the overall optical component is 100% by mass. When the content of the cyclic olefin copolymer (A) in the optical component according to the present embodiment is above the lower limit, the optical performance can be improved.

[0061] The upper limit of the content of the cyclic olefin-based copolymer (A) in the optical component according to the present embodiment is not particularly limited, but is, for example, 100% by mass or less.

[0062] The optical component involved in this embodiment has excellent optical performance because it contains a cyclic olefin copolymer (A). Therefore, it can be suitably used as an optical component in an optical system that needs to recognize images with high precision. The so-called optical component is a component used in optical system equipment, etc. Specifically, a sensor lens, a pickup lens, a projection lens, a prism, an fθ lens, a camera lens, a light guide plate, etc. used as a lens for various sensors can be cited. From the perspective of the effect involved in this embodiment, it can be suitably used for an fθ lens, a camera lens, a sensor lens, a prism or a light guide plate.

[0063] In particular, an optical component containing a cyclic olefin-based copolymer (A) having a glass transition point in the range of 140° C. or higher has high heat resistance and satisfies moist heat resistance.

[0064] Therefore, optical components comprising a cyclic olefin-based copolymer (A) having a glass transition point in the range of 140°C or higher can be particularly suited for use in optical components requiring heat resistance, such as vehicle-mounted camera lenses and camera lenses for portable devices (such as mobile phones, smartphones, and tablet computers). Examples of vehicle-mounted camera lenses and camera lenses for portable devices include large-format view camera lenses, sensor camera lenses, and light-converging and light-diffusing lenses for head-up displays.

[0065] The optical component according to this embodiment may be combined with a second optical component different from the above-mentioned optical component.

[0066] The second optical component is not particularly limited, and for example, an optical component made of at least one resin selected from polycarbonate resin and polyester resin can be used.

[0067] Hereinafter, each component will be described in detail.

[0068] (Cyclic olefin copolymer (A))

[0069] The cyclic olefin-based copolymer (A) comprises a structural unit (a) derived from at least one olefin represented by the above general formula (I), a structural unit (b) derived from at least one cyclic olefin represented by the above general formula (II), and a structural unit (c) derived from at least one cyclic olefin represented by the above general formula (III).

[0070] <Constitutional unit (a)>

[0071] 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. As the olefin monomer for forming the constituent unit (a), for example, 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, 1-eicosene, etc. From the viewpoint of obtaining an optical component with more excellent heat resistance, mechanical properties and optical properties, among these, ethylene or propylene is preferred, and ethylene is particularly preferred. The olefin monomer for forming the constituent unit (a) may be used alone or in combination of two or more.

[0072] In the cyclic olefin-based copolymer (A) involved in this embodiment, when the total content of the constituent units (a), (b) and (c) is 100 mol%, from the viewpoint of improving the heat resistance of the optical component, the content of the constituent units (a) is 50 mol% or less, preferably 49 mol% or less, more preferably 48 mol% or less, and preferably 35 mol% or more, more preferably 40 mol% or more.

[0073] In addition, the content of the structural unit (a) can be adjusted by 13 C-NMR determination.

[0074] <Constitutional unit (b)>

[0075] In the above general formula (II), R 1 ~R 8 Each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having a carbon number of not more than 4. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0076] Examples of the hydrocarbon group having 4 or less carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and cycloalkyl groups such as cyclopropyl.

[0077] In addition, R 5 ~R 8 can be combined with each other to form a monocyclic ring, and the monocyclic ring may have a double bond, and furthermore may be formed by R 5 With R 6 , or R 7 With R 8 to form an alkylene group.

[0078] The monocyclic ring formed here is exemplified below.

[0079] [Chemical Formula 7]

[0080]

[0081] In the above monocyclic ring, the carbon atoms numbered 1 or 2 are in the general formula (II), forming R 5 (R 6 ) or R 7 (R 8 ) is bound to the carbon atom of the alicyclic structure.

[0082] Moreover, specific examples of the alkylene group include an ethylene group, a propylene group, and an isopropylene group.

[0083] Examples of the cyclic olefin monomer for forming the structural unit (b) include bicyclo[2.2.1]-2-heptene (also called norbornene), bicyclo[2.2.1]hept-2-ene derivatives having 11 or less carbon atoms, tricyclo[4.3.0.12,5 ]-3-decene derivatives, tricyclo[4.4.0.1 2,5 Among these, bicyclo[2.2.1]-2-heptene is preferred.

[0084] The cyclic olefin monomer for forming the structural unit (b) may be used alone or in combination of two or more.

[0085] In the cyclic olefin-based copolymer (A) involved in this embodiment, when the total content of the constituent units (a), (b) and (c) is set to 100 mol%, from the viewpoint of improving the long-term reliability of optical performance in a high-temperature environment, and the balance between the refractive index and heat resistance, the content of the constituent units (b) is preferably from 25 mol% to 64 mol%, more preferably from 30 mol% to 60 mol%, further preferably from 35 mol% to 55 mol%, and particularly preferably from 40 mol% to 55 mol%.

[0086] In addition, the content of the structural unit (b) can be adjusted by 13 C-NMR determination.

[0087] <Constitutional unit (c)>

[0088] In the above general formula (III), n is 0 or 1, m is 0 or a positive integer, n+m is a positive integer, and q is 0 or 1. In addition, when q is 1, R a and R b Each independently represents the following atom or hydrocarbon group, and when q is 0, each bond is bonded to form a 5-membered ring.

[0089] In addition, in the above general formula (III), R 1 ~R 18 and R a and R b Each is independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is the same as the halogen atom in the above general formula (II).

[0090] Examples of the hydrocarbon group include, independently of one another, alkyl groups having 1 to 20 carbon atoms and cycloalkyl groups having 3 to 15 carbon atoms. More specifically, examples of the alkyl group include methyl, ethyl, propyl, isopropyl, pentyl, hexyl, octyl, decyl, dodecyl, and octadecyl, and examples of the cycloalkyl group include cyclohexyl. These groups may be substituted with halogen atoms.

[0091] Furthermore, in the above general formula (III), R 15 With R 16 、R 17 With R 18 、R 15 With R17 、R 16 With R 18 、R 15 With R 18 , or R 16 With R 17 They are respectively combined (jointly with each other) to form a monocyclic ring or polycyclic rings, and the monocyclic ring or polycyclic ring thus formed may have a double bond.

[0092] The monocyclic or polycyclic rings formed here are exemplified below.

[0093] [Chemical Formula 8]

[0094]

[0095] In the above examples, the carbon atoms numbered 1 or 2 are carbon atoms that form R 15 (R 16 ) or R 17 (R 18 ) is bound to the carbon atom of the alicyclic structure.

[0096] In addition, R 15 With R 16 , or R 17 With R 18 Examples of such an alkylene group generally include an alkylene group having 2 to 20 carbon atoms, and specific examples include an ethylene group, a propylene group, and an isopropylene group.

[0097] Examples of the cyclic olefin monomer for forming the structural unit (c) include tetracyclo[4.4.0.1 2,5 .1 7 ,10 ]-3-dodecene (also called tetracyclododecene), tricyclic [4.3.0.1 2,5 ]-3-decene derivatives, tricyclo[4.3.0.1 2,5 ]-3-undecene derivatives, tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene derivatives, pentacyclic [6.6.1.1 3,6 .0 2,7 .0 9,14 ]-4-hexadecene derivatives, pentacyclic [8.4.0.1 2,3 .1 9,12 .0 8,13 ]-3-hexadecene derivatives, pentacyclic [6.5.1.1 3,6 .0 2,7 .0 9,13 ]-4-pentadecenyl derivatives, pentacyclic [7.4.0.12,5 .1 9,12 .0 8,13 ]-3-pentadecaene derivatives, pentacyclopentadecadiene derivatives, hexacyclo[6.6.1.1 3,6 .1 10,13 .0 2,7 .0 9,14 ]-4-heptadecene derivatives, heptacyclic [8.7.0.1.3.6.1 10,17 .1 12,15 .0 2,7 .0 11,16 ]-4-eicosene derivatives, heptacyclic-5-eicosene derivatives, heptacyclic [8.8.0.1 4,7 .1 11,18 .1 13,16 .0 3,8 .0 12,17 ]-5-heneicosene derivatives, octacyclic [8.8.0.1 2, 9 .1 4,7 .1 11,18 .1 13,16 .0 3,8 .0 12,17 ]-5-docosahexaene derivatives, nonacyclic [10.9.1.1 4,7 .1 13,20 .1 15,18 .0 3, 8 .0 2,10 .0 12,21 .0 14,19 ]-5-pentacosene derivatives, nine rings [10.10.1.1 5,8 .1 14,21 .1 16,19 .0 2,11 .0 4,9 .0 13 ,22 .0 15,20 ]-5-hexacosene derivatives, etc.

[0098] Among these, tetracyclic [4.4.0.1 2,5 .1 7,10 ]-3-dodecene.

[0099] The cyclic olefin monomer for forming the structural unit (c) may be used alone or in combination of two or more.

[0100] In the cyclic olefin-based copolymer (A) involved in this embodiment, when the total content of the structural units (a), the structural units (b) and the structural units (c) is set to 100 mol%, from the viewpoint of facilitating the maintenance of a high refractive index of the optical component, the content of the structural unit (c) is preferably from 1 mol% to 25 mol%, and more preferably from 3 mol% to 20 mol%.

[0101] In addition, the content of the structural unit (c) can be adjusted by 13 C-NMR determination.

[0102] In the cyclic olefin copolymer (A) according to this embodiment, the ratio of the content of the constituent unit (b) to the content of the constituent unit (c) ((b) / (c)) is preferably 2 or more, more preferably 3 or more. If (b) / (c) is at least the above lower limit, an optical component having a higher refractive index and excellent long-term reliability of optical performance in high-temperature environments can be obtained. The upper limit of (b) / (c) is not particularly limited, but is preferably 13 or less, for example.

[0103] The cyclic olefin monomer for forming the structural unit (b) and the cyclic olefin monomer for forming the structural unit (c) can be produced by, for example, subjecting cyclopentadiene to a Diels-Alder reaction with olefins having corresponding structures.

[0104] Furthermore, the cyclic olefin-based copolymer (A) according to the present embodiment may contain, as necessary, constituent units derived from other copolymerizable monomers within a range not impairing the purpose of the present invention.

[0105] Examples of such other monomers include cyclic olefins other than the cyclic olefin monomers for forming the structural unit (b) and the cyclic olefin monomers for forming the structural unit (c), and examples thereof include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclohexene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, and 3a,5,6,7a-tetrahydro-4,7-methylene-1H-indene.

[0106] These can be used alone or in combination. Other olefins such as styrene and α-methylstyrene can also be mentioned.

[0107] The cyclic olefin-based copolymer (A) according to this embodiment preferably contains substantially no gel-like crosslinked polymer and has a substantially linear structure that may have a branched structure. The substantially linear structure can be confirmed by the copolymer being soluble in an organic solvent without containing any insoluble matter. For example, when measuring the intrinsic viscosity [η] as described below, this can be confirmed by the copolymer being completely soluble in decalin at 135°C.

[0108] Furthermore, the cyclic olefin-based copolymer (A) according to this embodiment preferably has an intrinsic viscosity ([η]) of 0.1 to 2.0 dl / g, more preferably 0.15 to 1.7 dl / g, as measured in decalin at 135°C. Such an intrinsic viscosity ([η]) provides excellent moldability without compromising mechanical strength, and minimizes the effect on melt flowability associated with an increase in molecular weight.

[0109] The copolymerization type of the cyclic olefin copolymer (A) involved in the present embodiment is not particularly limited, and for example, random copolymers, block copolymers, etc. can be mentioned. In the present embodiment, from the viewpoint of being able to obtain optical components with excellent optical properties such as transparency, refractive index, and birefringence, and high precision, it is preferred to use a random copolymer as the cyclic olefin copolymer (A) involved in the present embodiment.

[0110] It is preferred that the structural unit (b) in the cyclic olefin copolymer (A) according to this embodiment includes a repeating unit derived from bicyclo[2.2.1]-2-heptene, and the structural unit (c) in the cyclic olefin copolymer (A) includes a repeating unit derived from tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene repeating unit.

[0111] The cyclic olefin copolymer (A) according to the present embodiment is preferably a copolymer of ethylene, bicyclo[2.2.1]-2-heptene, and tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene random copolymer.

[0112] In the present embodiment, the cyclic olefin-based copolymer (A) may be used alone or in combination of two or more.

[0113] The cyclic olefin-based copolymer (A) according to the present embodiment can be produced by selecting appropriate conditions according to the methods of, for example, Japanese Patent Application Laid-Open No. 60-168708, Japanese Patent Application Laid-Open No. 61-120816, Japanese Patent Application Laid-Open No. 61-115912, Japanese Patent Application Laid-Open No. 61-115916, Japanese Patent Application Laid-Open No. 61-271308, Japanese Patent Application Laid-Open No. 61-272216, Japanese Patent Application Laid-Open No. 62-252406, and Japanese Patent Application Laid-Open No. 62-252407.

[0114] The glass transition point (Tg) of the cyclic olefin copolymer (A) according to this embodiment is preferably 140°C or higher, more preferably 143°C or higher, even more preferably 145°C or higher, and even more preferably 150°C or higher. When the glass transition point (Tg) of the cyclic olefin copolymer (A) is within the above range, better heat resistance can be achieved when used in optical components requiring heat resistance, such as vehicle-mounted camera lenses and portable device camera lenses. The upper limit of the glass transition point (Tg) of the cyclic olefin copolymer (A) according to this embodiment is not particularly limited, but from the perspective of moldability, it is preferably 180°C or lower, and more preferably 170°C or lower.

[0115] The glass transition point (Tg) of the cyclic olefin-based copolymer (A) according to the present embodiment can be measured using a differential scanning calorimeter (DSC).

[0116] (Other ingredients)

[0117] The optical component according to the present embodiment may contain, in addition to the cyclic olefin-based copolymer (A), known additives as optional components within a range that does not impair the excellent physical properties of the optical component according to the present embodiment.

[0118] Examples of the additives include hydrophilic stabilizers, hydrophilic agents, antioxidants, secondary antioxidants, lubricants, mold release agents, anti-fogging agents, weathering stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, metal deactivators, phenolic stabilizers, higher fatty acid metal salts, hindered amine light stabilizers, hydrochloric acid absorbers, lubricants, nucleating agents, plasticizers, flame retardants, and phosphorus stabilizers.

[0119] If a hydrophilic stabilizer is contained, degradation of optical performance under high temperature and high humidity conditions can be suppressed, which is more preferable.

[0120] The hydrophilic stabilizer is preferably a fatty acid ester of a fatty acid and a polyol, and more preferably a fatty acid ester of a fatty acid and a polyol having one or more ether groups.

[0121] [Method for manufacturing optical components]

[0122] The optical component according to the present embodiment can be produced by molding a cyclic olefin-based resin composition containing the cyclic olefin-based copolymer (A) into a predetermined shape.

[0123] As a method for molding a cyclic olefin resin composition to obtain an optical component, there is no particular limitation and known methods can be used. Depending on its use and shape, for example, extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, compression molding, vacuum molding, powder slush molding, calendering molding, foam molding, etc. can be applied. Among these, from the viewpoint of moldability and productivity, injection molding is preferably used. In addition, molding conditions are appropriately selected according to the purpose of use or molding method. For example, the resin temperature during injection molding is usually 150°C to 400°C, preferably 200°C to 350°C, and more preferably appropriately selected within the range of 230°C to 330°C.

[0124] The cyclic olefin resin composition involved in this embodiment can be obtained by, for example, the following methods: a method of melt-kneading the cyclic olefin copolymer (A) and other components added as needed using a well-known kneading device such as an extruder and a Banbury mixer; a method of dissolving the cyclic olefin copolymer (A) and other components added as needed in a common solvent and then evaporating the solvent; a method of adding a solution of the cyclic olefin copolymer (A) and other components added as needed to a poor solvent to cause precipitation, etc.

[0125] While the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be employed.

[0126] In addition, the present invention is not limited to the above-described embodiment, and modifications and improvements within the scope that can achieve the object of the present invention are included in the present invention.

[0127] Example

[0128] Hereinafter, the present invention will be further described in detail with reference to examples, but the present invention is not limited thereto.

[0129] <Production of Cyclic Olefin Copolymer>

[0130] [Production Example 1]

[0131] In a 500 ml glass reaction container equipped with a stirring device, nitrogen as an inert gas was flowed at a flow rate of 100 Nl / hr for 30 minutes, and then cyclohexane, tetracyclo[4.4.0.1 2,5 .1 7,10]-3-dodecene (10 mmol, hereinafter also referred to as tetracyclododecene (indicated as TD in Table 1).) and 2-norbornene (45 mmol, in Table 1, indicated as NB). The polymerization solvent was then stirred at a rotation speed of 600 rpm while the solvent temperature was raised to 50°C. After the solvent temperature reached a predetermined temperature, the circulating gas was switched from nitrogen to ethylene, and ethylene was circulated in the reaction vessel at a supply rate of 50 Nl / hr and hydrogen at a supply rate of 0.2 Nl / hr. After 10 minutes, methylaluminoxane (MMAO) (0.9 mmol) and a catalyst (0.003 mmol) in which titanium in the transition metal compound (1) described in paragraphs 0158 and 0159 of WO2017 / 150218 was changed to zirconium were added to a glass reaction vessel to start polymerization. The above-mentioned catalyst was synthesized by the method described in Japanese Patent Publication No. 2004-331965.

[0132] After 30 minutes, 5 ml of isobutanol was added to stop the polymerization, obtaining a polymerization solution containing a copolymer of ethylene, tetracyclododecene, and norbornene. The polymerization solution was then transferred to a separately prepared 2 L beaker, and 5 ml of concentrated hydrochloric acid and a stirrer were further added. The mixture was allowed to stand for 2 hours under vigorous stirring for deashing. The deashed polymerization solution was added to a beaker containing approximately 4 times the volume of acetone relative to the polymerization solution under stirring, and the copolymer was precipitated. The precipitated copolymer was then separated from the filtrate by filtration. The resulting solvent-containing polymer was dried under reduced pressure at 130° C. for 10 hours, yielding 2.72 g of a white powdery ethylene-tetracyclododecene-norbornene copolymer.

[0133] As described above, a cyclic olefin-based copolymer (P-1) was obtained.

[0134] [Production Examples 2 to 8]

[0135] Cyclic olefin copolymers (P-2) to (P-8) described in Table 1 were obtained in the same manner as in Production Example 1 except that the contents of the constituent units constituting the cyclic olefin copolymer were adjusted to the values ​​described in Table 1.

[0136] [Method for measuring the content of each structural unit constituting the cyclic olefin copolymer]

[0137] The contents of the structural unit (a) derived from ethylene, the structural unit (b) derived from norbornene, and the structural unit (c) derived from tetracyclododecene were measured using an "ECA500" nuclear magnetic resonance apparatus manufactured by JEOL Ltd. under the following conditions.

[0138] Solvent: Deuterated tetrachloroethane

[0139] Sample concentration: 50-100g / l-solvent

[0140] Pulse repetition time: 5.5 seconds

[0141] Cumulative times: 6000 to 16000 times

[0142] Measurement temperature: 120°C

[0143] By measuring under the above conditions 13 The contents of the constituent units (a) derived from ethylene, (b) derived from norbornene, and (c) derived from tetracyclododecene, constituting the cyclic olefin copolymer, were quantified by C-NMR spectroscopy.

[0144] [Glass transition point (Tg)]

[0145] The glass transition point (Tg) of the cyclic olefin copolymer was measured using a DSC-6220 manufactured by Shimadzu Science Corporation under an N2 (nitrogen) atmosphere. The cyclic olefin copolymer was heated from room temperature to 200°C at a heating rate of 10°C / min, held for 5 minutes, then cooled to -20°C at a cooling rate of 10°C / min, and held for 5 minutes. The glass transition point (Tg) of the cyclic olefin copolymer was then determined from the endothermic curve obtained when the temperature was increased to 200°C at a heating rate of 10°C / min.

[0146] [Intrinsic viscosity [η]]

[0147] Using a dynamic viscometer (manufactured by Lihe Co., Ltd., Model VNR053U), 0.25-0.30 g of the cyclic olefin copolymer was dissolved in 25 ml of decalin as a sample. The specific viscosity of the cyclic olefin copolymer was measured at 135°C according to ASTM J1601, and the intrinsic viscosity (η) of the cyclic olefin copolymer was calculated by extrapolating the specific viscosity to a concentration of 0.

[0148] [Example 1]

[0149] The cyclic olefin resin (P-1) was injection molded using an injection molding machine (ROBOSHOTα-S30iA manufactured by FANUC) at a cylinder temperature of 275°C and a mold temperature of 125°C to produce an injection-molded sheet of 65 mm × 35 mm × 3 mm thick.

[0150] The following evaluations were performed on the obtained injection-molded sheets. The obtained results are shown in Table 1.

[0151] (1) Refractive index

[0152] The refractive index (nd) at a wavelength of 589 nm was measured using a refractometer (KPR200, manufactured by Shimadzu Scientific Corporation) in accordance with ASTM D542 on a 30 mm × 30 mm × 2.0 mm thick injection-molded sheet formed using a microcompounder. The refractive index (nd) at a wavelength of 589 nm of the injection-molded sheet was measured before and after the heat resistance test described below.

[0153] (2) Heat resistance test

[0154] The obtained injection-molded sheet was left to stand in air at 139° C. for 168 hours and then taken out 3 hours later. The refractive index (nd) at a wavelength of 589 nm was measured to determine the change in refractive index before and after the heat resistance test.

[0155] (3) Internal haze

[0156] The internal haze of the obtained injection-molded sheet was measured using benzyl alcohol in accordance with JIS K-7136 (HAZE) using HazeMeter RHM-150 manufactured by Murakami Color Research Laboratory Co., Ltd. The internal haze was then evaluated using the following criteria.

[0157] ○: less than 5%

[0158] ×: 5% or more

[0159] [Examples 2 to 8 and Comparative Examples 1 to 4]

[0160] Injection-molded sheets were produced in the same manner as in Example 1, except that the type of cyclic olefin copolymer was changed to the polymers shown in Table 1. Furthermore, the same evaluations as in Example 1 were performed, except that the heat resistance test temperature in the heat resistance test was set to the temperature shown in Table 1. The obtained results are shown in Table 1.

[0161] [Table 1]

[0162]

[0163] This application claims the benefit of priority based on Japanese patent application No. 2020-008687, filed on January 22, 2020, the disclosure of which is incorporated herein in its entirety.

Claims

1. An optical component comprising a cyclic olefin copolymer (A), The cyclic olefin copolymer (A) has: The constituent unit (a) derived from at least one olefin represented by the following general formula (I) Derived from a compound selected from the group consisting of bicyclo[2.2.1]-2-heptene, bicyclo[2.2.1]hept-2-ene derivatives, tricyclo[4.3.0.1 2,5 ]-3-decene derivatives and tricyclic [4.4.0.1 2,5 ]-3-undecene, and The structural unit (c) derived from at least one cyclic olefin represented by the following general formula (III) is: When the total content of the structural unit (a), the structural unit (b) and the structural unit (c) is 100 mol%, the content of the structural unit (a) is 50 mol% or less, In the general formula (I), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms, In the general formula (III), n is 0 or 1, m is 0 or a positive integer, n+m is a positive integer, q is 0 or 1, R 1 ~R 18 and R a and R b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, R 15 ~R 18 may be combined with each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, and may be further represented by R 15 With R 16 , or R 17 With R 18 to form an alkylene group. 2 . The optical component according to claim 1 , wherein the glass transition point (Tg) of the cyclic olefin-based copolymer (A) measured by DSC is 140° C. or higher. 3 . The optical component according to claim 1 , wherein the ratio of the content of the structural unit (b) to the content of the structural unit (c) in the cyclic olefin-based copolymer (A), that is, (b) / (c), is 2 or more.

4. The optical component according to claim 1 or 2, wherein the structural unit (b) in the cyclic olefin copolymer (A) comprises a repeating unit derived from bicyclo[2.2.1]-2-heptene, and the structural unit (c) in the cyclic olefin copolymer (A) comprises a repeating unit derived from tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene repeating unit. The optical component according to claim 1 or 2, wherein the structural unit (a) in the cyclic olefin-based copolymer (A) comprises a repeating unit derived from ethylene. The optical component according to claim 1 or 2, 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 1 , which is a vehicle-mounted camera lens or a camera lens for portable devices.

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