Invention name: Optical lens
Technical field
[0001]
　The present invention relates to an optical lens.
Background technology
[0002]
　Cyclic olefin polymers are used in optical lenses such as imaging lenses, fθ lenses, and pickup lenses. Cyclic olefin-based polymers used in molded articles such as optical lenses are required to have characteristics such as high transparency, excellent dimensional stability, and excellent heat resistance.
　Further, for example, an imaging lens used in a smartphone, a digital camera, or the like is required to further improve the refractive index while keeping the birefringence value low in order to reduce the size and thickness.
[0003]
　Examples of techniques relating to cyclic olefin-based polymers used in such optical lenses are those described in Patent Document 1 (Japanese Patent Laid-Open No. 10-287713) and Patent Document 2 (Japanese Patent Laid-Open No. 2010-235719). Can be mentioned.
[0004]
　Patent Document 1 describes (A) a linear or branched α-olefin having 2 to 20 carbon atoms, (B) a cyclic olefin represented by a predetermined chemical formula, and (C) an aromatic vinyl compound. The ultimate viscosity [η] is in the range of 0.1 to 10 dl / g, and is derived from the content ratio of the structural unit derived from the above (B) cyclic olefin and the above (C) aromatic vinyl compound. Cyclic olefin-based copolymers in which the content ratio of the structural unit satisfies a specific relationship are described.
[0005]
　Patent Document 2 describes a structural unit (A) derived from ethylene or an α-olefin having 3 to 20 carbon atoms in an amount of 30 to 70 mol%, and a structural unit (B) derived from a cyclic olefin represented by a predetermined chemical formula. ) Is 20 to 50 mol%, the structural unit (C) derived from the aromatic vinyl compound is 0.1 to 20 mol%, and the ultimate viscosity [η], 1 H-NMR and the glass transition temperature satisfy the predetermined requirements. Cyclic olefin-based polymers characterized by this are described.
Prior art literature
Patent documents
[0006]
Patent Document 1: Japanese Patent Application Laid-Open No. 10-287713
Patent Document 2: Japanese Patent Application Laid-Open No. 2010-235719
Outline of the invention
Problems to be solved by the invention
[0007]
　According to the study by the present inventors, in applications such as optical lenses, a resin material adjusted to have a lower Abbe number than a conventional resin material for the purpose of improving image quality and improving the degree of freedom in designing an optical lens. It became clear that it was required.
　The present invention has been made in view of the above circumstances, and provides an optical lens which has a high refractive index and can be adjusted to have a lower Abbe number than a conventional resin material.
Means to solve problems
[0008]
　The present inventors have diligently studied to solve the above problems. As a result, the structural unit (A) derived from the α-olefin having 2 to 20 carbon atoms, the structural unit (B) derived from the cyclic olefin, and the aromatic vinyl represented by the general formula (C-1). By using a cyclic olefin-based copolymer having a structural unit (C) derived from a compound, the Abbe number of an optical lens obtained can be adjusted to be lower than that of a conventional resin material while having a high refractive index. The present invention was completed.
[Chemical formula 1]

[Chemical

formula 2] (In the above formula (C-1), any one of all R represented by R 1 to R 10 is a vinyl group represented by the above formula (D-1). In the above formula (D-1), * indicates a bond. In the
　above formulas (C-1) and (D-1), m, n and q are all 0 or positive. However, when m and n are both 0, q is a positive integer, and when
　m is 2 or more, a plurality of R 1 and R 4 may be the same or different, and n is 2. In the above case, the plurality of R 6 and R 9 may be the same or different, and
　R 1 to R other than the hydrocarbon group having a vinyl group represented by the above formula (D-1). 10 , and R 21 and R 22 are each independently substituted hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom. in
　and, R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 form a bond together with each other mono- The monocyclic ring may have a double bond. )
[0009]
　That is, according to the present invention, the following optical lenses are provided.
[0010]
[1]
　A structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms,
　a structural unit (B) derived from a cyclic olefin , and
　an aromatic vinyl represented by the general formula (C-1).
　An optical lens composed of a molded product containing a cyclic olefin copolymer having a structural unit (C) derived from a compound .
[Chemical formula 3]

[Chemical

formula 4] (In the above formula (C-1), any one of all R represented by R 1 to R 10 is a vinyl group represented by the above formula (D-1). In the above formula (D-1), * indicates a bond. In the
　above formulas (C-1) and (D-1), m, n and q are all 0 or positive. However, when m and n are both 0, q is a positive integer, and when
　m is 2 or more, a plurality of R 1 and R 4 may be the same or different, and n is 2. In the above case, the plurality of R 6 and R 9 may be the same or different, and
　R 1 to R other than the hydrocarbon group having a vinyl group represented by the above formula (D-1). 10 , and R 21 and R 22 are each independently substituted hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom. in
　and, R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 form a bond together with each other mono- The monocyclic ring may have a double bond.
(2 ) In
　the optical lens according to the above [1], an optical lens
　having an Abbe number (ν) of 30 or more and 55 or less.
[3] In
　the optical lens according to the above [1] or [2],
　When 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%, the cyclic olefin copolymer An optical lens in which the content of the structural unit (A) is 10 mol% or more and 80 mol% or less.
[4] In
　the optical lens according to any one of the above [1] to [3],
　the total content of the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer is determined. An optical lens in which the content of the structural unit (C) in the cyclic olefin copolymer is 1 mol% or more and 95 mol% or less when the content is 100 mol%.
[5] In
the optical lens according to any one of the above [1] to [4], the optical lens in which the
　cyclic olefin contains a compound represented by the following formula (B-1).
[Chemical

formula 5] (In the above formula [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R 1 to R 18 and R a and R. b is a hydrocarbon group which may be independently substituted with a hydrogen atom, a halogen atom or a halogen atom, and R 15 to R 18 respectively.May be bonded to each other to form a monocyclic or polycyclic, and the monocyclic or polycyclic may have a double bond, with R 15 and R 16 or with R 17 And R 18 may form an alkylidene group. )
[6]
　The optical lens according to [5], in the formula (B-1), m is a positive integer, the optical lens.
[7] In
　the optical lens according to any one of the above [1] to [6], m, n and q are 0, 1 in the general formulas (C-1) and (D-1). Alternatively, the optical lens is 2, where q is 1 or 2 when both m and n are 0.
[8] In
　the optical lens according to any one of the above [1] to [7],
　the glass transition temperature (Tg) of the cyclic olefin copolymer measured by a differential scanning calorimeter (DSC) is determined. An optical lens having a temperature of 100 ° C. or higher and 180 ° C. or lower.
[9] In
　the optical lens according to any one of the above [1] to [8],
　the ultimate viscosity [η] of the cyclic olefin copolymer measured in decalin at 135 ° C. is 0.05 dl / g. An optical lens having a value of 5.00 dl / g or less.
[10]
　The optical lens according to any one of [1] to [9] above, wherein the
　birefringence is 1 nm or more and 200 nm or less.
[11] In
　the optical lens according to any one of the above [1] to [10], the
　aromatic vinyl compound is selected from allylbenzene, 1-vinylnaphthalene, 2-vinylnaphthalene and 9-vinylanthracene. An optical lens containing at least one type of lens.
[12] In
　the optical lens according to any one of the above [1] to [11], the optical lens in which
　q is 0 in the above formula (D-1).
Effect of the invention
[0011]
　According to the present invention, it is possible to provide an optical lens composed of a molded product containing a cyclic olefin copolymer which has a high refractive index and can be adjusted to have a lower Abbe number than a conventional resin material. ..
Mode for carrying out the invention
[0012]
　Hereinafter, the present invention will be described based on the embodiments. In the present embodiment, "A to B" indicating a numerical range represent A or more and B or less unless otherwise specified.
[0013]
[Cyclic olefin copolymer]
　First, the cyclic olefin copolymer (P) according to the present embodiment will be described.
　The cyclic olefin copolymer (P) according to the present embodiment has a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms, a structural unit (B) derived from the cyclic olefin, and the following. It has a structural unit (C) derived from an aromatic vinyl compound represented by the formula (C-1).
[Chemical formula 6]

[Chemical

formula 7] (In the above formula (C-1), any one of all R represented by R 1 to R 10 is a vinyl group represented by the above formula (D-1). In the above formula (D-1), * indicates a bond. In the
　above formulas (C-1) and (D-1), m, n and q are all 0 or positive. However, when m and n are both 0, q is a positive integer, and when
　m is 2 or more, a plurality of R 1 and R 4 may be the same or different, and n is 2. In the above case, the plurality of R 6 and R 9 may be the same or different, and
　R 1 to R other than the hydrocarbon group having a vinyl group represented by the above formula (D-1). 10 , and R 21 and R 22 are each independently substituted hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom. in
　and, R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 form a bond together with each other mono- The monocyclic ring may have a double bond. )
[0014]
　The cyclic olefin-based copolymer (P) according to the present embodiment includes a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms, a structural unit (B) derived from the cyclic olefin, and the above (C). By including the structural unit (C) derived from the aromatic vinyl compound represented by -1), the Abbe number can be adjusted to be low while satisfying the high refractive index required for an optical lens or the like.
　From the above, according to the cyclic olefin copolymer (P) according to the present embodiment, it is possible to obtain a molded product having a high refractive index and a lower Abbe number than the conventional resin material.
[0015]
(Constituent Unit (A) Derived from α-olefin) The structural unit (A) according to the
　present embodiment is a structural unit derived from α-olefin having 2 to 20 carbon atoms.
　Here, the α-olefin having 2 to 20 carbon atoms may be linear or branched, and may be ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, etc. Linear α-olefins with 2 to 20 carbon atoms such as 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; 3-methyl-1-butene, 3-methyl-1- Penten, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl- Examples thereof include branched α-olefins having 4 to 20 carbon atoms such as 1-hexene and 3-ethyl-1-hexene. Among these, a linear α-olefin having 2 to 4 carbon atoms is preferable, and ethylene is particularly preferable. Such linear or branched α-olefins can be used alone or in combination of two or more.
[0016]
　When the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (P) according to the present embodiment is 100 mol%, the present embodiment The content of the structural unit (A) in the cyclic olefin copolymer (P) according to the form is preferably 10 mol% or more and 80 mol% or less, more preferably 30 mol% or more and 75 mol% or less, still more preferably. Is 40 mol% or more and 70 mol% or less, particularly preferably 50 mol% or more and 70 mol% or less.
　When the content of the structural unit (A) is at least the above lower limit value, the heat resistance and dimensional stability of the obtained molded product can be improved. Further, when the content of the structural unit (A) is not more than the upper limit value, the transparency of the obtained molded product can be improved.
　In this embodiment, the content of the structural unit (A) can be measured by , for example, 1 1 H-NMR or 13 C-NMR.
[0017]
(Constituent Unit (B) Derived from Cyclic Olefin) The structural unit (B) according to the
　present embodiment is a structural unit derived from cyclic olefin. The structural unit (B) according to the present embodiment preferably includes a structural unit derived from a compound represented by the following formula (B-1) from the viewpoint of further improving the refractive index of the obtained molded product.
[Chemical

formula 8] (In the above formula [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R 1 to R 18 and R a and R. b is a hydrocarbon group which may be independently substituted with a hydrogen atom, a halogen atom or a halogen atom, and R 15 to R 18 may be bonded to each other to form a monocyclic or polycyclic ring. And, the monocyclic or polycyclic ring may have a double bond, and R 15 and R 16 may form an alkylidene group , or R 17 and R 18 may form an alkylidene group.)
　R 1 to R 18 and R It is preferable that a and R b are hydrocarbon groups having 1 to 20 carbon atoms.
　Further, from the viewpoint of optimally adjusting the glass transition temperature (Tg) of the obtained cyclic olefin copolymer, m is preferably a positive integer in the above formula (B-1).
　Among these, the structural unit (B) according to the present embodiment is a structural unit derived from bicyclo [2.2.1] -2-heptene, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene constitutional unit derived from and hexacyclo [6,6,1,1 3,6 , 1 10,13 , 0 2,7 , 0 9,14 ] heptadecene -4 constituent units derived from such It preferably contains at least one structural unit selected from, vicyclo [2.2.1] -2-heptene-derived structural units and tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3 more preferably containing at least one structural unit dodecene selected from constituent unit derived from tetracyclo [4.4.0.1 2, 5 . 1 7,10 It is particularly preferred to include a] -3-dodecene constitutional unit derived.
[0018]
(Constituent Unit (C) Derived from Aromatic Vinyl Compound) The structural unit (C) according to the
　present embodiment is a structural unit derived from an aromatic vinyl compound represented by the above general formula (C-1).
　The compound according to the present embodiment may be used alone or in combination of two or more.
[0019]
　The above formula (C-1) is a hydrocarbon group in which any one of all R represented by R 1 to R 10 has a vinyl group represented by the above formula (D-1). In formula (D-1), * indicates a bond.
　In the above equations (C-1) and (D-1), m, n and q are all 0 or positive atoms, but when m and n are both 0, q is a positive integer and
　m. for but 2 or more, R the plurality of 1 , R 4 each may be the same or different, when n is 2 or more, a plurality of R 6 , R 9 or different in each identical,
　the formula ( D-1 R other than a hydrocarbon group having a vinyl group represented by) 1 ~ R 10 , and, R 21 , and R 22 each independently represent a hydrogen atom, a halogen atom except fluorine atom or a fluorine atom, It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding the above, and
　R 1 , R 2 , and R. 2 and R 3 , R 3 and R 4 , R 6 and R 7 , R 7 and R 8 , and R 8 and R 9 may be bonded to each other to form a single ring, and the single ring may be double bonded. May have.
[0020]
　Further, in the above formulas (C-1) and (D-1), preferably, m, n and q are all 0, 1 or 2, but when m and n are all 0, q is 1. Or 2, more preferably, both m and n are 0 and q is 1, or m is 0 and n is 1 or 2, and q is 0 or 1. m is preferably 0 or 1. n is preferably 1 or 2. q is preferably 0.
　The formula (C-1) R in 1 ~ R 10 R other than a hydrocarbon group having a vinyl group represented by the formula (D-1) of R represented by 1 ~ R 10 , and, the R 21 and R 22 in the formula (D-1) are preferably hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms , and more preferably hydrogen atoms.
[0021]
　Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. Be done. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group, and the cycloalkyl group includes cyclohexyl. Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a trill group, a naphthyl group, a benzyl group and a phenylethyl group, or an aralkyl group. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.
[0022]
　Among these, as the structure represented by (C-1) according to the present embodiment, for example, at least one selected from allylbenzene, 1-vinylnaphthalene, 2-vinylnaphthalene and 9-vinylanthracene is preferable. It is particularly preferred that it be at least one selected from 1-vinylnaphthalene, 2-vinylnaphthalene and 9-vinylanthracene. When these particularly preferable aromatic vinyl compounds are used, the obtained cyclic olefin-based copolymer is excellent in copolymerizability with the α-olefin leading to the structural unit (A) and the cyclic olefin leading to the structural unit (B). Since many aromatic rings can be introduced efficiently, it is considered that a particularly high refractive index and a low copolymer number can be adjusted.
　The aromatic vinyl compound represented by the above general formula (C-1) according to the present embodiment does not contain styrene. When styrene is used as the aromatic vinyl compound, it becomes difficult to adjust the Abbe number to an optimum range of, for example, 30 or more and 50 or less.
[0023]
　When the total content of the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer (P) according to the present embodiment is 100 mol%, the cyclic olefin copolymer according to the present embodiment is used. The content of the structural unit (C) in the polymer (P) is preferably 1 mol% or more and 95 mol% or less, more preferably 2 mol% or more and 60 mol% or less, and further preferably 3 mol% or more and 40 mol% or less. It is as follows.
　When the content of the structural unit (C) is at least the above lower limit value, the Abbe number can be further reduced while maintaining a high refractive index in the obtained molded product. Further, when the content of the structural unit (C) is not more than the upper limit value, the balance between the refractive index and the Abbe number of the obtained molded product can be improved.
　In this embodiment, the content of the structural unit (B) and the structural unit (C) can be measured by , for example, 1 1 H-NMR or 13 C-NMR.
[0024]
　The copolymerization type of the cyclic olefin-based copolymer (P) according to the present embodiment is not particularly limited, and examples thereof include random copolymers and block copolymers. In the present embodiment, the cyclic olefin copolymer (P) according to the present embodiment is selected from the viewpoint of obtaining a molded product having excellent optical properties such as transparency, Abbe number, refractive index and birefringence. It is preferably a random copolymer.
[0025]
　The cyclic olefin copolymer (P) according to the present embodiment is, for example, JP-A-60-168708, JP-A-61-12816, JP-A-61-115912, JP-A-61- 115916, Japanese Patent Application Laid-Open No. 61-272118, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407, JP-A-2007-314806, JP-A. It can be produced by appropriately selecting conditions according to a method such as those published in 2010-241932.
[0026]
　In the cyclic olefin copolymer (P) according to the present embodiment, when an injection-molded sheet having a thickness of 1.0 mm made of the cyclic olefin copolymer (P) is produced, it is measured according to ASTM D542. The refractive index (nd) of the injection-molded sheet at a wavelength of 589 nm is preferably 1.545 or more, preferably 1.550 or more, and more preferably 1.555 or more. The upper limit of the refractive index (nd) is not particularly limited, but is, for example, 1.580 or less.
　When the refractive index is within the above range, the thickness can be made thinner while maintaining good optical properties of the molded product obtained by using the cyclic olefin copolymer (P) according to the present embodiment.
　The optical lens according to this embodiment has a refractive index (nd) at a wavelength of 589 nm measured according to ASTM D542, which is preferably 1.545 or more, preferably 1.550 or more, and more preferably 1.555 or more. The upper limit of the refractive index (nd) is not particularly limited, but is, for example, 1.580 or less.
[0027]
　Further, in the cyclic olefin copolymer (P) according to the present embodiment, from the viewpoint of further improving the transparency of the obtained molded product, injection of the cyclic olefin copolymer (P) having a thickness of 1.0 mm When the molded sheet is produced, the haze of the injection-molded sheet measured in accordance with JIS K7136 is preferably less than 5%.
　The optical lens according to this embodiment has a haze of preferably less than 5% at a thickness of 1.0 mm measured in accordance with JIS K7136.
[0028]
　Further, in the cyclic olefin copolymer (P) according to the present embodiment, the cyclic olefin copolymer (P) is composed of the cyclic olefin copolymer (P) from the viewpoint of adjusting the Abbe number (ν) of the obtained molded product to a more suitable range. When an injection-molded sheet having a thickness of 1.0 mm is produced, the Abbe number (ν) of the injection-molded sheet is preferably 30 or more and 55 or less, more preferably 35 or more and 50 or less, and further preferably 40 or more and 47 or less. ..
　The Abbe number (ν) of the injection-molded sheet can be calculated from the refractive indexes of the injection-molded sheet at wavelengths of 486 nm, 589 nm and 656 nm at 23 ° C. using the following formula.
　ν = (nD-1) / (nF-nC)
　nD: Refractive index at wavelength 589 nm
　nC: Refractive index at wavelength 656
　nm nF: Refractive index at wavelength 486 nm The
　optical lens according to this embodiment has an Abbe number (ν). ) Is preferably 30 or more and 55 or less, more preferably 35 or more and 50 or less, and further preferably 40 or more and 47 or less.
[0029]
　Further, in the cyclic olefin copolymer (P) according to the present embodiment, from the viewpoint of adjusting the birefringence of the obtained molded product to a more suitable range, the thickness 1 made of the cyclic olefin copolymer (P) is 1. When a 0.0 mm injection-molded sheet is produced, the birefringence of the injection-molded sheet is preferably 1 nm or more and 200 nm or less, more preferably less than 40 nm, and further preferably less than 30 nm.
　In the present embodiment, the birefringence of the injection-molded sheet is an average value of the phase difference of 20 to 35 mm from the gate direction measured at a measurement wavelength of 650 nm using a KOBRA CCD manufactured by Oji Measuring Instruments Co., Ltd.
　In the optical lens according to the present embodiment, the birefringence is preferably 1 nm or more and 200 nm or less, more preferably less than 40 nm, and further preferably less than 30 nm.
[0030]
　The glass transition temperature (Tg) of the cyclic olefin copolymer (P) according to the present embodiment, as measured by a differential scanning calorimeter (DSC), is the transparency, Abbe number, birefringence and refraction of the obtained molded product. From the viewpoint of further improving the heat resistance while maintaining a good rate and the like, the temperature is preferably 100 ° C. or higher and 180 ° C. or lower, more preferably 120 ° C. or higher and 170 ° C. or lower, and further preferably 130 ° C. or higher and 160 ° C. or lower.
[0031]
　The intrinsic viscosity [η] (in 135 ° C. decalin) of the cyclic olefin copolymer (P) according to the present embodiment is, for example, 0.05 to 5.00 dl / g, preferably 0.20 to 4.00 dl. It is / g, more preferably 0.30 to 2.00 dl / g, and particularly preferably 0.40 to 1.00 dl / g.
[0032]
[Molded product]
　The molded product according to the present embodiment is a molded product containing the cyclic olefin copolymer (P) according to the present embodiment.
　Since the molded product according to the present embodiment contains the cyclic olefin copolymer (P) according to the present embodiment, it has an excellent balance of heat resistance, transparency, birefringence, chemical resistance, low moisture absorption, etc. It has a higher refractive index and a lower Abbe number than conventional resin materials. Therefore, it is suitable for applications of optical lenses.
[0033]
　Since the molded body according to the present embodiment has excellent optical characteristics, it can be suitably used as an optical lens for, for example, a spectacle lens, an fθ lens, a pickup lens, an imaging lens, a sensor lens, a prism, a light guide plate, an in-vehicle camera lens, or the like. It can be used particularly preferably as an imaging lens because it has a high refractive index and a lower Abbe number than conventional resin materials.
[0034]
　Further, the content of the cyclic olefin-based copolymer (P) in the molded product according to the present embodiment is determined from the viewpoint of further improving the performance balance of transparency, double refraction, Abbe number and refractive index of the molded product. When the whole is 100% by mass, it is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, and further preferably 80% by mass or more and 100% by mass or less. Particularly preferably, it is 90% by mass or more and 100% by mass or less.
[0035]
　The molded product according to the present embodiment can be obtained by molding a resin composition containing the cyclic olefin copolymer (P) into a predetermined shape. The method for obtaining a molded product by molding the resin composition containing the cyclic olefin copolymer (P) is not particularly limited, and a known method can be used. Extrusion molding, injection molding, compression molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, foam molding, etc., depending on the application and shape. Is applicable. Among these, the injection molding method is preferable from the viewpoint of moldability and productivity. The molding conditions are appropriately selected depending on the purpose of use or the molding method. For example, the resin temperature in injection molding is usually 150 ° C. to 400 ° C., preferably 200 ° C. to 350 ° C., more preferably 230 ° C. to 330 ° C. It is appropriately selected in the range.
[0036]
　The molded product according to the present embodiment can be used in various forms such as a lens shape, a spherical shape, a rod shape, a plate shape, a columnar shape, a tubular shape, a tube shape, a fibrous shape, a film or a sheet shape.
[0037]
　If necessary, the molded product according to the present embodiment may contain a known additive as an optional component within a range that does not impair the good physical properties of the molded product according to the present embodiment. Additives include, for example, phenolic stabilizers, higher fatty acid metal salts, antioxidants, UV absorbers, hindered amine light stabilizers, hydrochloric acid absorbers, metal deactivators, antistatic agents, antifogging agents, lubricants. , Slip agents, nuclear agents, plasticizers, flame retardants, phosphorus-based stabilizers and the like can be blended to the extent that the object of the present invention is not impaired, and the blending ratio thereof is an appropriate amount.
[0038]
　The optical lens according to the present embodiment is composed of the molded body according to the present embodiment. The optical lens according to the present embodiment may be combined with an optical lens different from the above optical lens to form an optical lens system.
　That is, the optical lens system according to the present embodiment is different from the first optical lens composed of the molded body containing the cyclic olefin copolymer (P) according to the present embodiment and the first optical lens. It is provided with a second optical lens.
[0039]
　The second optical lens is not particularly limited, and for example, an optical lens composed of at least one resin selected from a polycarbonate resin and a polyester resin can be used.
[0040]
　Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.
　Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the range in which the object of the present invention can be achieved are included in the present invention.
Example
[0041]
　Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
[0042]

[Production Example 1] The
　polymerization, decalcification, precipitation, and filtration steps were carried out according to the methods described in paragraphs 0107 and 0108 of JP2010-235719A. As a cyclic olefin, instead of norbornene, tetracyclo [4.4.0.1 2,5 . 1 7, 10 ] -3-dodecene was used, and isopropylidenebis indenyl zirconium dichloride was used instead of (η 5- C 5 Me 4 SiMe 3 ) Sc (CH 2 C 6 H 4 NMe 2- o) 2 . .. 1-Vinylnaphthalene was used instead of styrene.
　A white powdery ethylene / tetracyclododecene / 1-vinylnaphthalene copolymer was obtained.
　From the above, a cyclic olefin copolymer (P-1) was obtained.
[0043]
[Production Examples 2 to 6, 8 and 10 to 12]
　The values ​​of the content of each structural unit constituting the cyclic olefin copolymer are adjusted so as to be the values ​​shown in Table 1, and the cyclic olefin and aromatic ring vinyl are adjusted. The same procedure as in Production Example 1 was carried out except that the cyclic olefins and aromatic cyclic vinyl compounds shown in Table 1 were used as the compounds, and the cyclic olefin copolymers (P-2) to (P-) shown in Table 1 were used. 6), (P-8) and (P-10) to (P-12) were obtained, respectively.
　Here, 1-VN in Table 1 means 1-vinylnaphthalene represented by the following formula (2), and 2-VN means 2-vinylnaphthalene represented by the following formula (3). 9-VA means 9-vinylanthracene represented by the following formula (4), and AB means allylbenzene represented by the following formula (5). TD is tetracyclo [4.4.0.1 2,5 . 1 7,10 means] -3-dodecene, CPDTD the hexacyclo [6,6,1,1 3,6 , 1 10,13 , 0 2,7 , 0 9,14 means] heptadecene -4.
[0044]
[Chemical 9]

[0045]
[Chemical 10]

[0046]
[Chemical 11]

[0047]
[Chemical 12]

[0048]
　NB means bicyclo [2.2.1] hept-2-ene (trivial name: norbornene) represented by the following formula.
[0049]
[Chemical 13]

[0050]
[table 1]

[0051]
In
　each Example and Comparative Example, various physical properties were measured or evaluated by the following methods, and the obtained results are shown in Table 1.
[0052]
[Method for measuring the content of each structural unit constituting the cyclic olefin copolymer]
　Ethylene, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, hexacyclo [6,6,1,1 3,6 , 1 10,13 , 0 2,7 , 0 9,14 ] heptadecene-4 or, bicyclo [2.2. 1] The contents of hept-2-ene and aromatic vinyl compound were measured by using an "ECA500 type" nuclear magnetic resonance apparatus manufactured by JEOL Ltd. under the following conditions.
　Solvent: Heavy tetrachloroethane
　Sample concentration: 50 to 100 g / l-solvent
　Pulse repetition time: 5.5 seconds
　Cumulative number: 6000 to 16000 times
　Measurement temperature: 120 ° C. According
　to 13 C-NMR spectrum measured under the above conditions . Ethylene, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, hexacyclo [6,6,1,1 3,6 , 1 10 and 13 , 0 2,7 , 0 9,14 ] heptadecene-4 or, bicyclo [2.2.1] hept-2-ene, and the composition of the aromatic vinyl compound and quantified, respectively.
[0053]
[Glass transition temperature Tg (° C.)] The glass transition temperature Tg of the cyclic olefin copolymer was measured under
　an N 2 (nitrogen) atmosphere using DSC-6220 manufactured by Shimadzu Science Co., Ltd. The cyclic olefin copolymer was heated from room temperature to 200 ° C. at a heating rate of 10 ° C./min and then held for 5 minutes, and then cooled to −20 ° C. at a temperature lowering rate of 10 ° C./min and then held for 5 minutes. .. Then, the glass transition point (Tg) of the cyclic olefin copolymer was determined from the endothermic curve when the temperature was raised to 200 ° C. at a heating rate of 10 ° C./min.
[0054]
[Ultimate Viscosity [η]] Using a
　mobile viscometer (manufactured by Rigo Co., Ltd., type VNR053U type), 0.25 to 0.30 g of a cyclic olefin copolymer was dissolved in 25 ml of decalin as a sample. The specific viscosity of the cyclic olefin-based copolymer was measured at 135 ° C. according to ASTM J1601, and the ratio of this to the concentration was extrapolated to a concentration of 0 to determine the ultimate viscosity [η] of the cyclic olefin-based copolymer.
[0055]
[Microcompounder molding] The
　cyclic olefin copolymers synthesized in Production Examples 1 to 6, 8 and 10 to 12 are kneaded at a kneading temperature of 280 ° C. and 50 rpm for 5 minutes using a small kneader manufactured by Xprore Instruments. After kneading, injection molding is performed using an injection molding machine manufactured by Xprore Instruments under the conditions of cylinder temperature = 280 ° C., injection pressure = 12 to 15 bar, and mold temperature 135 ° C. to obtain an injection molding sheet having a thickness of 1.0 mm. Each was prepared.
[0056]
[Birefringence]
　For an injection-molded sheet of 30 mm x 30 mm x 1.0 mm thickness molded with a microcompounder, a phase difference of 20 to 35 mm from the gate direction at a measurement wavelength of 650 nm using a KOBRA CCD manufactured by Oji Measuring Instruments Co., Ltd. The average value of was calculated.
　Next, the birefringence was evaluated according to the following criteria.
⊚: Mean value of phase difference is less than 30 nm
◯: Mean value of phase difference is 30 nm or more and less than 40 nm
×: Mean value of phase difference is 40 nm or more
[0057]
[Refractive index]
　Refractive index (nd) of an injection-molded sheet of 30 mm × 30 mm × thickness 1.0 mm molded with a microcompound according to ASTM D542 using a refractive index meter (KPR200 manufactured by Shimadzu Science Co., Ltd.) at a wavelength of 589 nm. ) Was measured respectively.
[0058]
[Abbe number (ν)] The
　refractive indexes of 30 mm × 30 mm × 1.0 mm thick injection-molded sheets molded with a microcompound were measured at wavelengths of 486 nm, 589 nm and 656 nm at 23 ° C. using an Abbe refractometer. Furthermore, the Abbe number (ν) was calculated using the following formula.
ν = (nD-1) / (nF-nC)
nD: Refractive index at wavelength 589 nm
nC: Refractive index at
wavelength 656 nm nF: Refractive index at wavelength 486 nm
[0059]
　As described above, the optical lens obtained in the example had a high refractive index, but had a lower Abbe number than the optical lens obtained in the comparative example. That is, the optical lens obtained in the examples exhibited a high refractive index and a low Abbe number while satisfying various characteristics required for the optical lens. Further, in Examples 1 to 7 in which TD and CPDTD in which m is a positive integer in the formula (B-1) are used as the cyclic olefin for deriving the structural unit (B), the cyclic olefins for deriving the structural unit (B) are used. As a result, in the formula (B-1), Tg was higher than in Examples 8 and 9 using NB in ​​which m was 0. On the other hand, the optical lens of the comparative example using the cyclic olefin-based copolymer not containing the structural unit (C) derived from the aromatic vinyl compound had a high Abbe number, and the desired optical lens could not be obtained.
[0060]
　This application claims priority on the basis of Japanese application Japanese Patent Application No. 2018-066628 filed on March 30, 2018, and incorporates all of its disclosures herein.
　The present invention also includes the following aspects.
1. 1. Derived from a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms,
　a structural unit (B) derived from a cyclic olefin , and
　an aromatic vinyl compound represented by the general formula (C-1).
A cyclic olefin-based copolymer having a structural unit (C) to be obtained .
[Chemical formula 14]

[Chemical

formula 15] (In the above formula (C-1), any one of all R represented by R 1 to R 10 is a vinyl group represented by the above formula (D-1). In the above formula (D-1), * indicates a bond. In the
　above formulas (C-1) and (D-1), m, n and q are all 0 or positive. However, when m and n are both 0, q is a positive integer, and when
　m is 2 or more, a plurality of R 1 and R 4 may be the same or different, and n is 2. In the above case, the plurality of R 6 and R 9 may be the same or different.
　The formula (D-1) R other than a hydrocarbon group having a vinyl group represented by 1 ~ R 10 , and, R 21 , and R 22 each independently represent a hydrogen atom, a halogen atom excluding a fluorine atom, Alternatively, it is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and is
　R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 6 and R 7. , R 7 and R 8 , and R 8 and R 9 may be bonded to each other to form a monocycle, and the monocycle may have a double bond. )
2. 1. 1. In the cyclic olefin-based copolymer described in
　When the total content of the structural unit (A), the structural unit (B) and the structural unit (C) in the cyclic olefin-based copolymer is 100 mol%, the cyclic olefin-based copolymer A cyclic olefin copolymer having a content of the structural unit (A) of 10 mol% or more and 80 mol% or less.
3. 3. 1. 1. Or 2. In the cyclic olefin-based copolymer described in the
　above , when the total content of the structural unit (B) and the structural unit (C) in the cyclic olefin-based copolymer is 100 mol%, the cyclic olefin-based copolymer is used. A cyclic olefin-based copolymer in which the content of the structural unit (C) in the polymer is 1 mol% or more and 95 mol% or less.
4. 1. 1. To 3. The cyclic olefin-based copolymer according to any one of the above,
　wherein the cyclic olefin contains a compound represented by the following formula (B-1).
[Chemical

formula 16] (In the above equation [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R 1 to R 18 and R a and R. b is a hydrocarbon group which may be independently substituted with a hydrogen atom, a halogen atom or a halogen atom, and R 15 to R 18 respectively.May be bonded to each other to form a monocyclic or polycyclic, and the monocyclic or polycyclic may have a double bond, with R 15 and R 16 or with R 17 And R 18 may form an alkylidene group. )
5. 1. 1. To 4. In the cyclic olefin copolymer according to any one of the above, in the general formulas (C-1) and (D-1), m, n and q are all 0, 1 or 2, but m. A cyclic olefin-based copolymer in which q is 1 or 2 when both n and n are 0.
6. 1. 1. To 5. In the cyclic olefin-based copolymer according to any one of the above,
　when an injection-molded sheet having a thickness of 1.0 mm made of the cyclic olefin-based copolymer is produced, the Abbe number (ν) of the injection-molded sheet is increased. A cyclic olefin copolymer of 30 or more and 55 or less.
7. 1. 1. To 6. In the cyclic olefin copolymer according to any one of the above,
　the glass transition temperature (Tg) of the cyclic olefin copolymer measured by a differential scanning calorimeter (DSC) is 100 ° C. or higher and 180 ° C. or lower. A cyclic olefin copolymer.
8. 1. 1. To 7. In the cyclic olefin-based copolymer according to any one of the above, the cyclic olefin-based copolymer
　having an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.05 dl / g or more and 5.00 dl / g or less. ..
9. 1. 1. ~ 8. In the cyclic olefin-based copolymer according to any one of the above,
　when an injection-molded sheet having a thickness of 1.0 mm made of the cyclic olefin-based copolymer is produced, the compound refraction of the injection-molded sheet is 1 nm or more and 200 nm. The following cyclic olefin copolymer.
10. 1. 1. ~ 9. In the cyclic olefin copolymer according to any one of the
　above, the aromatic vinyl compound is a cyclic olefin containing at least one selected from allylbenzene, 1-vinylnaphthalene, 2-vinylnaphthalene and 9-vinylanthracene. System copolymer.
11. 1. 1. To 10. In the cyclic olefin-based copolymer according to any one of the above, the cyclic olefin-based copolymer in which
　q is 0 in the above formula (D-1).
12. 1. 1. To 11. A resin composition containing the cyclic olefin copolymer according to any one of the above.
13. 1. 1. To 11. A molded product containing the cyclic olefin copolymer according to any one of the above.
14. Optical lens 13. The molded article according to.
The scope of the claims
[Claim 1]
　Derived from a structural unit (A) derived from an α-olefin having 2 to 20 carbon atoms,
　a structural unit (B) derived from a cyclic olefin , and
　an aromatic vinyl compound represented by the general formula (C-1).
An optical lens composed of a molded product containing a cyclic olefin-based copolymer having a structural unit (C) to be obtained.
[Chemical formula 1]

[Chemical

formula 2] (In the above formula (C-1), any one of all R represented by R 1 to R 10 is a vinyl group represented by the above formula (D-1). In the above formula (D-1), * indicates a bond. In the
　above formulas (C-1) and (D-1), m, n and q are all 0 or positive. However, when m and n are both 0, q is a positive integer, and when
　m is 2 or more, a plurality of R 1 and R 4 may be the same or different, and n is 2. In the above case, the plurality of R 6 and R 9 may be the same or different, and
　R 1 to R 10 other than the hydrocarbon group having a vinyl group represented by the above formula (D-1). , And R 21 and R 22 are hydrocarbon groups having 1 to 20 carbon atoms which may be independently substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom. Yes, even if
　R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 6 and R 7 , R 7 and R 8 , and R 8 and R 9 are combined with each other to form a single ring. Often, the monocycle may have a double bond. )
[Claim 2]
　The optical lens according to claim 1, wherein the
　Abbe number (ν) is 30 or more and 55 or less.
[Claim 3]
　In the optical lens according to claim 1 or 2,
　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%. The optical lens in which the content of the structural unit (A) in the cyclic olefin copolymer is 10 mol% or more and 80 mol% or less.
[Claim 4]
　In the optical lens according to any one of claims 1 to 3, when
　the total content of the structural unit (B) and the structural unit (C) in the cyclic olefin copolymer is 100 mol%. An optical lens in which the content of the structural unit (C) in the cyclic olefin copolymer is 1 mol% or more and 95 mol% or less.
[Claim 5]
　The optical lens according to any one of claims 1 to 4,
　wherein the cyclic olefin contains a compound represented by the following formula (B-1).
[

Formula 3] (In the above formula [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R 1 to R 18 and R a and R. b is a hydrocarbon group which may be independently substituted with a hydrogen atom, a halogen atom or a halogen atom, and R 15 to R 18 may be bonded to each other to form a monocyclic or polycyclic ring. And, the monocyclic or polycyclic ring may have a double bond, and may form an alkylidene group with R 15 and R 16 or with R 17 and R 18 ).
[Claim 6]
　The optical lens according to claim 5, wherein m is a positive integer in the above formula (B-1).
[Claim 7]
　In the optical lens according to any one of claims 1 to 6, m, n and q are all 0, 1 or 2 in the general formulas (C-1) and (D-1), however. An optical lens in which q is 1 or 2 when both m and n are 0.
[Claim 8]
　In the optical lens according to any one of claims 1 to 7,
　the glass transition temperature (Tg) of the cyclic olefin copolymer measured by a differential scanning calorimeter (DSC) is 100 ° C. or higher and 180 ° C. or lower. An optical lens that is.
[Claim 9]
　In the optical lens according to any one of claims 1 to 8,
　the ultimate viscosity [η] of the cyclic olefin copolymer measured in decalin at 135 ° C. is 0.05 dl / g or more and 5.00 dl / g. The following optical lenses.
[Claim 10]
　The optical lens according to any one of claims 1 to 9, wherein the
　birefringence is 1 nm or more and 200 nm or less.
[Claim 11]
　In the optical lens according to any one of claims 1 to 10, the
　aromatic vinyl compound comprises at least one selected from allylbenzene, 1-vinylnaphthalene, 2-vinylnaphthalene and 9-vinylanthracene. lens.
[Claim 12]
　The optical lens according to any one of claims 1 to 11,
　wherein q is 0 in the above formula (D-1).