Cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, resin compositions, and resin molded articles

Abstract

The object of this invention is to provide a cyclic olefin ring-opening polymer hydride with a suitable Abbe number and low birefringence, and the raw materials thereof. The cyclic olefin ring-opening polymer of this invention is characterized by comprising structural units (A) from 1,2,3,3a,4,6a-hexahydro-1,2,4-methyl-bridged pentanene and structural units (B) from a cyclic olefin monomer having an aromatic ring structure. Furthermore, the cyclic olefin ring-opening polymer hydride of this invention is characterized by being formed by hydrogenating the cyclic olefin ring-opening polymer of this invention.

Description

Technical Field

[0001] This invention relates to cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, resin compositions, and resin molded articles. Background Technology

[0002] Cyclic olefin ring-opening polymer hydrides, obtained by ring-opening polymerization of cyclic olefin monomers and subsequent hydrogenation, are widely used as molding materials for optical components such as optical lenses due to their excellent properties, including transparency, low moisture absorption, heat resistance, insulation, and chemical resistance. Therefore, in recent years, various methods have been proposed to improve the physical properties of cyclic olefin ring-opening polymer hydrides.

[0003] For example, Patent Document 1 discloses a copolymer, a hydride of the copolymer, a molding material containing the copolymer or the hydride of the copolymer, and a resin molded body obtained by molding the molding material. The copolymer is a copolymer obtained by copolymerizing one or more cyclic olefin monomers with one or more cyclic olefin monomers, or a copolymer obtained by copolymerizing two or more cyclic olefin monomers, having a glass transition temperature of 100°C or higher, a refractive index of 1.545 or higher, and an Abbe number of 50 or higher.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent document 1: International Publication No. 2016 / 163371. Summary of the Invention

[0007] The problem the invention aims to solve

[0008] In recent years, with the improvement of the performance of optical components such as optical lenses, there has been a further demand to reduce the birefringence of cyclic olefin ring-opening polymer hydrides used as molding materials for manufacturing optical components. Furthermore, in recent years, from the perspective of increasing the freedom of optical design, cyclic olefin ring-opening polymer hydrides for molding optical components not only require high Abbe numbers (e.g., 50 or higher), but also require the development of cyclic olefin ring-opening polymer hydrides with moderate Abbe numbers (e.g., 35 or higher and less than 50).

[0009] However, the aforementioned prior art cyclic olefin ring-opening polymer hydrides do not simultaneously possess a moderate Abbe number and low birefringence.

[0010] Therefore, the present invention aims to provide a cyclic olefin ring-opening polymer hydride with a moderate Abbe number and low birefringence, and the raw material thereof.

[0011] Furthermore, the present invention aims to provide a resin composition that can be advantageously used as a material for various molded articles such as optical elements, and a resin molded article formed using the resin composition.

[0012] Solution for solving the problem

[0013] To solve the aforementioned problems, the inventors conducted in-depth research. Then, the inventors made a new discovery: a cyclic olefin ring-opening polymer hydride, obtained by hydrogenating a cyclic olefin ring-opening polymer comprising structural units from 1,2,3,3a,4,6a-hexahydro-1,2,4-methenopentalene and structural units from cyclic olefin monomers having aromatic ring structures, can achieve a balance between a moderate Abbe number and a reduction in birefringence, thus completing the present invention.

[0014] That is, the present invention was made to advantageously solve the above-mentioned problems. The present invention is [1] a cyclic olefin ring-opening polymer comprising a structural unit (A) from 1,2,3,3a,4,6a-hexahydro-1,2,4-methyl-bridged pentanene and a structural unit (B) from a cyclic olefin monomer having an aromatic ring structure. The cyclic olefin ring-opening polymer comprising the structural unit (A) from 1,2,3,3a,4,6a-hexahydro-1,2,4-methyl-bridged pentanene and the structural unit (B) from a cyclic olefin monomer having an aromatic ring structure can be advantageously used as a raw material for cyclic olefin ring-opening polymer hydrides that can achieve a moderate Abbe number (e.g., 35 or more and less than 50) and a reduction in birefringence.

[0015] [2] In the cyclic olefin ring-opening polymer of [1] above, the above structural unit (B) is preferably a structural unit derived from the monomer represented by the following formula (1).

[0016] [Chemical Formula 1]

[0017]

[0018] (In formula (1), R1 to R5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group capable of having a substituent, a cycloalkyl group capable of having a substituent, an alkenyl group capable of having a substituent, an alkoxy group capable of having a substituent, an aromatic hydrocarbon cyclogroup capable of having a substituent, or an aromatic heterocyclic group capable of having a substituent, and two or more of R1 to R5 can be bonded together to form a ring.)

[0019] If the structural unit (B) is a structural unit derived from the monomer specified above, it is possible to achieve an appropriate Abbe number in the resulting cyclic olefin ring-opening polymer hydride while further reducing the birefringence.

[0020] Furthermore, the present invention was made to advantageously solve the above-mentioned problems. The present invention is [3] a cyclic olefin ring-opening polymer hydride, which is obtained by hydrogenating the cyclic olefin ring-opening polymer of [1] or [2] above. The cyclic olefin ring-opening polymer hydride obtained by hydrogenating the above-mentioned cyclic olefin ring-opening polymer has both a moderate Abbe number and a low birefringence.

[0021] [4] In the cyclic olefin ring-opening polymer hydrides described above [3], it is preferable that the aromatic carbon-carbon unsaturated bonds present in the cyclic olefin ring-opening polymer hydrides are not hydrogenated. If the aromatic carbon-carbon unsaturated bonds present in the cyclic olefin ring-opening polymer hydrides are not hydrogenated, the Abbe number can be made to a suitable size, while further reducing the birefringence.

[0022] [5] In the cyclic olefin ring-opening polymer hydrides of [3] or [4] above, the Abbe number is preferably less than 50. If the Abbe number is less than 50, the cyclic olefin ring-opening polymer hydrides can be suitably used for applications other than optical components with high Abbe numbers.

[0023] Furthermore, in this invention, the "Abbe number" can be determined using the method described in the examples.

[0024] [6] In any of the cyclic olefin ring-opening polymer hydrides described in [3] to [5] above, the glass transition temperature is preferably 120°C or higher. If the glass transition temperature is 120°C or higher, the deterioration of optical properties of the resin molded body formed using the cyclic olefin ring-opening polymer hydride due to heat deformation and other factors can be suppressed.

[0025] Furthermore, in this invention, the "glass transition temperature" can be measured using the method described in the examples.

[0026] Furthermore, the present invention was made to advantageously solve the above-mentioned problems. The present invention is [7] a resin composition comprising the cyclic olefin ring-opening polymer hydride of any one of [3] to [6] above. The resin composition comprising the cyclic olefin ring-opening polymer hydride of any one of the above can be advantageously used as a material for various molded articles such as optical elements.

[0027] Furthermore, the present invention was made to advantageously solve the above-mentioned problems. The present invention is [8] a resin molded article, which is formed by molding the resin composition of [7] described above. The resin molded article formed using the above-described resin composition can exhibit excellent performance.

[0028] Invention Effects

[0029] According to the present invention, a cyclic olefin ring-opening polymer hydride and its raw materials with a moderate Abbe number and low birefringence can be provided.

[0030] Furthermore, according to the present invention, a resin composition that can be advantageously used as a material for various molded bodies such as optical elements can be provided, as well as a resin molded body formed using the resin composition. Detailed Implementation

[0031] The embodiments of the present invention will now be described in detail.

[0032] Here, the cyclic olefin ring-opening polymer of the present invention can be suitable as a raw material for, for example, the cyclic olefin ring-opening polymer hydride of the present invention. The cyclic olefin ring-opening polymer hydride of the present invention has a moderate Abbe number and low birefringence, and can be suitable as a material for various molded articles such as optical elements. The resin composition of the present invention can be suitable as a material for, for example, manufacturing the resin molded articles of the present invention. The resin molded articles of the present invention can be suitable as optical elements such as optical films, lenses for photographic devices such as cameras, and lenses for mobile terminals such as mobile phones or smartphones.

[0033] (Ring-opening polymers of cyclic olefins)

[0034] The cyclic olefin ring-opening polymer of the present invention can be obtained, for example, by ring-opening polymerization of a monomer composition containing a specified cyclic olefin compound (monomer) in the presence of a polymerization catalyst.

[0035] Furthermore, the cyclic olefin ring-opening polymer of the present invention comprises a structural unit (A) from 1,2,3,3a,4,6a-hexahydro-1,2,4-methyl-bridged pentanene and a structural unit (B) from a cyclic olefin monomer having an aromatic ring structure, and optionally further comprises other structural units. The structural units are described below.

[0036] <Structural unit (A) from 1,2,3,3a,4,6a-hexahydro-1,2,4-methyl-bridged pentanene>

[0037] The structural unit (A) from 1,2,3,3a,4,6a-hexahydro-1,2,4-methylbridged pentanene (hereinafter sometimes simply referred to as structural unit (A)) is derived from the structural unit of 1,2,3,3a,4,6a-hexahydro-1,2,4-methylbridged pentanene represented by the following formula (2).

[0038] [Chemical Formula 2]

[0039]

[0040] [Contains percentage]

[0041] Furthermore, when the content of structural unit (A) is 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, when the content of all repeating units contained in the cyclic olefin ring-opening polymer is 100% by mass, it is preferably 90% by mass or less, more preferably 75% by mass or less, even more preferably 60% by mass or less, and particularly preferably 50% by mass or less. If the content of structural unit (A) is below the above-mentioned upper limit, precipitation of the cyclic olefin ring-opening polymer after synthesis can be suppressed. In addition, if the content of structural unit (A) is above the above-mentioned lower limit, the glass transition temperature of the resulting cyclic olefin ring-opening polymer hydride can be prevented from becoming too high.

[0042] Furthermore, in this invention, the "content ratio of structural units" can be used 1 H-NMR or 13 The measurements were performed using nuclear magnetic resonance (NMR) methods such as C-NMR.

[0043] <Structural unit (B) from a cyclic olefin monomer with an aromatic ring structure>

[0044] The aromatic ring-structured cyclic olefin monomer capable of forming structural unit (B) (hereinafter sometimes simply referred to as structural unit (B)) from a cyclic olefin monomer with an aromatic ring structure is not particularly limited. Examples include norbornene compounds with an aromatic ring structure and non-norbornene compounds with an aromatic ring structure. These can be used in combination, but from the viewpoint of imparting an appropriate Abbe number to the resulting cyclic olefin ring-opening polymer hydride while further reducing the birefringence, the aromatic ring-structured cyclic olefin monomer capable of forming structural unit (B) is preferably a norbornene compound with an aromatic ring structure.

[0045] Here, the term "aromatic ring structure" is not particularly limited and can include aromatic hydrocarbon rings and aromatic heterocycles.

[0046] There are no particular limitations on the aromatic hydrocarbon ring; examples include aromatic hydrocarbon rings with 6 to 30 carbon atoms, such as benzene rings, naphthalene rings, and anthracene rings. Among these, benzene rings are preferred.

[0047] Furthermore, as aromatic heterocycles, there are no particular limitations, and examples include furan rings, benzofuran rings, pyrrole rings, indole rings, thiophene rings, benzothiophene rings, pyridine rings, pyrazine rings, pyrimidine rings, triazole rings, triazine rings, pyrrolidine rings, imidazole rings, pyrazole rings, thiazole rings, benzothiazole rings, thienothiazole rings, oxazole rings, and benzoxazole rings, which are aromatic heterocycles with 2 to 30 carbon atoms.

[0048] The aromatic ring structure described above can be a monocyclic structure or a polycyclic structure formed by the fusion of at least one ring selected from the aromatic hydrocarbon rings and aromatic heterocycles described above.

[0049] Furthermore, the aforementioned aromatic ring structure can have substituents. Specific examples of substituents include: halogen atoms such as chlorine, fluorine, bromine, and iodine; cyano; nitro; unsubstituted alkyl groups with 1 or more but less than 10 carbon atoms such as methyl, ethyl, and propyl; unsubstituted alkenyl groups with 2 or more but less than 6 carbon atoms such as vinyl and allyl; alkyl groups with 1 or more but less than 10 carbon atoms such as trifluoromethyl where one or more hydrogen atoms are replaced by halogen atoms such as fluorine atoms; alkoxy groups with 1 or more but less than 10 carbon atoms such as methoxy, ethoxy, and isopropoxy; etc.

[0050] The number of substituents can be one or more. When there are multiple substituents, they can be the same as each other or different from each other.

[0051] From the viewpoint of imparting an appropriate Abbe number to the obtained cyclic olefin ring-opening polymer hydride while further reducing the birefringence, the above-mentioned aromatic ring structure is preferably an aromatic hydrocarbon ring.

[0052] [norbornene compounds with aromatic ring structures]

[0053] Examples of norbornene compounds having an aromatic ring structure include compounds having one or more aromatic ring structures and one or more norbornene rings within the molecule. Furthermore, the aromatic ring structure and the norbornene ring can exist independently or form a fused ring.

[0054] Examples of norbornene compounds with aromatic ring structures include: phenyl norbornene such as 5-phenyl-2-norbornene, 5-methyl-5-phenyl-bicyclo[2.2.1]hept-2-ene, 5-benzyl-bicyclo[2.2.1]hept-2-ene, 5-tolyl-bicyclo[2.2.1]hept-2-ene [i.e., 5-(4-methylphenyl)-2-norbornene], 5-(ethylphenyl)-bicyclo[2.2.1]hept-2-ene, 5-(isopropylphenyl)-bicyclo[2.2.1]hept-2-ene, 5-methyl-5-carboxybenzylbicyclo[2.2.1]hept-2-ene, and 8-phenyl-tetracyclo[4.4.0.1²]. ,5 .1 7, ¹ 0 ]-3-Dodecene, 8-Methyl-8-phenyl-tetracyclo[4.4.0.1² ,5 .1 7, ¹ 0 ]-3-Dodecene, 8-Benzyl-Tetracyclo[4.4.0.1² ,5 .1 7, ¹0 ]-3-Dodecene, 8-Tolyl-Tetracyclo[4.4.0.1² ,5 .1 7, ¹ 0 ]-3-Dodecene, 8-(ethylphenyl)-tetracyclo[4.4.0.1² ,5 .1 7, ¹ 0 ]-3-Dodecene, 8-(isopropylphenyl)-tetracyclo[4.4.0.1² ,5 .1 7, ¹ 0 ]-3-Dodecene, 8,9-Diphenyl-tetracyclo[4.4.0.1² ,5 .1 7, ¹ 0 ]-3-Dodecene, 8-(biphenyl)-tetracyclo[4.4.0.1² ,5 .1 7, ¹ 0 ]-3-Dodecene, 8-(β-naphthyl)-tetracyclo[4.4.0.1² ,5 .1 7, ¹ 0 ]-3-Dodecene, 8-(α-naphthyl)-tetracyclo[4.4.0.1² ,5 .1 7, ¹ 0 ]-3-Dodecene, 8-(anthrayl)-tetracyclo[4.4.0.1² ,5 .1 7, ¹ 0 ]-3-Dodecene, 11-Phenyl-hexacyclo[6.6.1.1³ ,6 .1¹ 0, ¹³.0² ,7 .0 9, ¹ 4]-4-Heptadecanene, 6-(α-naphthyl)-bicyclo[2.2.1]-hept-2-ene, 5-(anthrayl)-bicyclo[2.2.1]-hept-2-ene, 5-(biphenyl)-bicyclo[2.2.1]-hept-2-ene, 5-(β-naphthyl)-bicyclo[2.2.1]-hept-2-ene, 5,6-diphenyl-bicyclo[2.2.1]-hept-2-ene, 9-(2-norbornene-5-yl)-carbazole, 1,4-methylbridged-1,4,4a,4b,5,8,8a,9a-octahydrofluorene, 1,4-methylbridged-1,4,4a,9a-tetrahydrofluorene, 1,4-methylbridged-8-methyl-1,4,4a,9a-tetrahydrofluorene, 1,4 - Methioninated-8-chloro-1,4,4a,9a-tetrahydrofluorene, 1,4-methioninated-8-bromo-1,4,4a,9a-tetrahydrofluorene, 1,4-methioninated-1,4,4a,9a-tetrahydrodibenzofuran, 1,4-methioninated-1,4,4a,9a-tetrahydrocarbazole, 1,4-methioninated-9-phenyl-1,4,4a,9a-tetrahydrocarbazole, 1,4-methioninated-1,4,4a,5,10,10a-hexahydroanthracene, 7,10-methioninated-6b,7,10,10a-tetrahydrofluoranthracene, cyclopentadiene-acenaphthene adduct, compounds obtained by further addition of cyclopentadiene to cyclopentadiene-acenaphthene adduct, 11,12-benzo-pentane [6.5.1.1³] ,6 0.0² ,7 .0 9, ¹³]-4-pentadecanene, 11,12-benzo-pentacyclo[6.6.1.1³] ,6 0.0² ,7 .0 9, ¹ 4 ]-4-Hexadecene, 14,15-benzo-heptacyclo[8.7.0.1² ,9 .1 4,7 .1¹¹ , ¹ 7 0.0³ ,8 0¹² , ¹ 6 [5-Eicosene, 5,5A,6,9,9A,10,10A,11-octahydro-4bh-5,10,6,9-dimethylbridged-benzo[B]fluorene, and their derivatives, as well as compounds represented by formula (1) below. Furthermore, a derivative refers to a substance having substituents in its ring structure. The substituents that may be present in the ring structure are not particularly limited; examples include alkyl, alkylene group, vinyl, alkoxycarbonyl, and alkylidene group. The ring structure of a derivative may have one or more of these substituents.

[0055] [Chemical Formula 3]

[0056]

[0057] (In formula (1), R1 to R5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group capable of having a substituent, a cycloalkyl group capable of having a substituent, an alkenyl group capable of having a substituent, an alkoxy group capable of having a substituent, an aromatic hydrocarbon cyclogroup capable of having a substituent, or an aromatic heterocyclic group capable of having a substituent, and two or more of R1 to R5 can be bonded together to form a ring.)

[0058] Here, there is no particular limitation on the halogen atoms that can form R1 to R5, and examples include chlorine atoms, fluorine atoms, bromine atoms, iodine atoms, etc.

[0059] The alkyl group capable of forming R1 to R5 is not particularly limited, and examples include alkyl groups with 1 to 10 carbon atoms capable of having substituents. The alkyl group with 1 to 10 carbon atoms in the phrase "alkyl group capable of having substituents" can be either straight-chain or branched, and examples include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, hexyl, octyl, nonyl, and decyl. Methyl is preferred.

[0060] Specific examples of substituents that are "alkyl groups having 1 or more but less than 10 carbon atoms" can be given, such as groups that have the same substituents as the aromatic ring structures described above. There can be one or more substituents. When there are multiple substituents, they can be the same as each other or different.

[0061] There is no particular limitation on the cycloalkyl groups that can form R1 to R5, but examples of cycloalkyl groups that can have 3 or more but less than 12 carbon atoms are possible. Examples of cycloalkyl groups that have 3 or more but less than 12 carbon atoms in the phrase "cycloalkyl groups that can have 3 or more but less than 12 carbon atoms" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0062] Specific examples of substituents that are "cycloalkyl groups having 3 or more but less than 12 carbon atoms" can be given, such as groups that have the same substituents as the aromatic ring structures described above. There can be one or more substituents. When there are multiple substituents, they can be the same as each other or different.

[0063] The alkenyl group that can form R1 to R5 and has a substituent is not particularly limited, but can be an alkenyl group with 2 or more but less than 10 carbon atoms that can have a substituent. The alkenyl group with 2 or more but less than 10 carbon atoms in the phrase "alkenyl group with 2 or more but less than 10 carbon atoms that can have a substituent" can be either linear or branched, and examples include vinyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, decenyl, etc.

[0064] Specific examples of substituents that are "alkenyl groups having 2 or more but less than 10 carbon atoms" can be given, such as groups that have the same substituents as the aromatic ring structures described above. There can be one or more substituents. When there are multiple substituents, they can be the same as each other or different.

[0065] The alkynyl group that can form R1 to R5 and has a substituent is not particularly limited, but can be any alkynyl group with 2 or more but less than 10 carbon atoms that can have a substituent. The alkynyl group with 2 or more but less than 10 carbon atoms in the phrase "alkynyl group with 2 or more but less than 10 carbon atoms that can have a substituent" can be either linear or branched, and examples include ethynyl, propynyl, 2-propynyl (propynyl), butynyl, 2-butynyl, 3-butynyl, pentyynyl, 2-pentynyl, hexynyl, 5-hexynyl, heptynyl, octyynyl, 2-octyynyl, nonynyl, decynyl, 7-decynyl, etc.

[0066] Specific examples of substituents that are "alkynyl groups with 2 or more but less than 10 carbon atoms" can be given, such as groups that have the same substituents as the aromatic ring structures described above. There can be one or more substituents. When there are multiple substituents, they can be the same as each other or different.

[0067] The alkoxy group that can form R1 to R5 is not particularly limited, and examples include alkoxy groups with 1 or more but less than 10 carbon atoms that can have substituents. The alkoxy group with 1 or more but less than 10 carbon atoms in the phrase "alkoxy group that can have substituents" can be either linear or branched, and examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, and octoxy.

[0068] Specific examples of substituents that are "alkoxy groups having 1 or more but less than 10 carbon atoms" can be given, such as groups that have the same substituents as the aromatic ring structures described above. There can be one or more substituents. When there are multiple substituents, they can be the same as each other or different.

[0069] There are no particular limitations on the aromatic hydrocarbon cyclic groups that can form R1 to R5 and have substituents; examples include aromatic hydrocarbon cyclic groups with 6 or more but less than 30 carbon atoms that can have substituents. Examples of aromatic hydrocarbon cyclic groups with 6 or more but less than 30 carbon atoms that can have substituents include phenyl, naphthyl, and anthracene.

[0070] Specific examples of substituents that are "aromatic hydrocarbon cyclic groups with 6 or more but less than 30 carbon atoms that can have substituents" can be given, such as groups that have the same substituents as the aromatic ring structures described above. There can be one or more substituents. When there are multiple substituents, they can be the same as each other or different.

[0071] There are no particular limitations on the aromatic heterocyclic groups that can form R1 to R5 and have substituents; examples include aromatic heterocyclic groups with 6 or more but less than 30 carbon atoms that can have substituents. Examples of aromatic heterocyclic groups with 6 or more but less than 30 carbon atoms that can have substituents include: furanyl, 1-benzofuranyl, 2-benzofuranyl, pyrroleyl, indolyl, thienyl, benzo[c]thienyl, benzo[b]thienyl, pyridyl, pyrazinyl, pyrimidinyl, triazolyl, triazinyl, pyrroleyl, imidazolyl, pyrazolyl, thiazolyl, benzothiazolyl, oxazolyl, and benzooxazolyl, etc.

[0072] Specific examples of substituents that are "aromatic heterocyclic groups with 6 or more but less than 30 carbon atoms" can be given, such as groups that have the same substituents as the aromatic ring structures described above. There can be one or more substituents. When there are multiple substituents, they can be the same as each other or different.

[0073] The ring formed by the bonding of two or more of R1 to R5 can be a monocyclic or polycyclic ring. There is no particular limitation on the ring formed by the bonding of two or more of R1 to R5, and examples include aromatic hydrocarbon rings, aromatic heterocycles, non-aromatic hydrocarbon rings, and polycyclic fused rings formed by the fusion of two or more of these rings.

[0074] Specific examples of the aforementioned aromatic hydrocarbon rings and aromatic heterocycles can be given by groups with the same "aromatic ring structure" as described above. Furthermore, specific examples of non-aromatic hydrocarbon rings include cyclopropyl rings, cyclobutyl rings, cyclopentyl rings, cyclohexyl rings, cyclooctyl rings, and other cycloalkyl rings with 3 or more but less than 12 carbon atoms.

[0075] From the viewpoint of imparting an appropriate Abbe number to the obtained cyclic olefin ring-opening polymer hydride while further reducing the birefringence, as a compound represented by formula (1), it is preferable that one or more of R1 to R5 in formula (1) is an alkyl group with 1 or more and 10 or less carbon atoms capable of having substituents, and the remainder is a hydrogen atom. More preferably, it is preferable that two of R1 to R5 are alkyl groups with 1 or more and 10 or less carbon atoms capable of having substituents, and the remainder is a hydrogen atom.

[0076] Furthermore, from the viewpoint of imparting an appropriate Abbe number to the obtained cyclic olefin ring-opening polymer hydride while further reducing the birefringence, as the compound represented by formula (1), it is preferable to be a compound in formula (1) where one or more of R1 to R5 is methyl and the rest are hydrogen atoms, more preferably a compound in formula (1) where two of R1 to R5 are methyl and the rest are hydrogen atoms, even more preferably a compound in formula (1) where R1 or R5 is methyl and the rest are hydrogen atoms (i.e., N-2-methylphenyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), and even more preferably a compound in formula (1) where R1 and R5 are methyl and the rest are hydrogen atoms (i.e., N-2,6-dimethylphenyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide).

[0077] Furthermore, among these norbornene compounds with aromatic ring structures, from the viewpoint of imparting an appropriate Abbe number to the resulting cyclic olefin ring-opening polymer hydride while further reducing the birefringence, the norbornene compounds with aromatic ring structures are preferably 1,4-methylbridged-1,4,4a,9a-tetrahydrofluorene, 5,5A,6,9,9A,10,10A,11-octahydro-4bh-5,10,6,9-dimethylbridged-benzo[B]fluorene, and compounds represented by formula (1), more preferably compounds represented by formula (1).

[0078] The above-mentioned norbornene compounds with aromatic ring structures can be used alone or in combination of two or more.

[0079] [Non-norbornene compounds with aromatic ring structures]

[0080] There is no particular limitation on nonnorbornene compounds having an aromatic ring structure; for example, cyclic alkenes having the aforementioned aromatic ring structure can be cited. Specific examples of cyclic alkenes in the category of "cyclic alkenes having an aromatic ring structure" include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, 1,4-cyclooctadiene, and cyclodecene.

[0081] Furthermore, specific examples of nonnorbornene compounds with aromatic ring structures include 1-phenylcyclopentene, 1-phenylcyclohexene, and 5-phenylcyclooctene.

[0082] The aforementioned nonnorbornene compounds with aromatic ring structures can be used alone or in combination of two or more.

[0083] [Contains percentage]

[0084] When the content of structural unit (B) is 10% by mass or more, more preferably 25% by mass or more, further preferably 40% by mass or more, particularly preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less, if the content of structural unit (B) is above the above-mentioned lower limit, the thermal deformation of the molded article caused by excessively low glass transition temperature of the cyclic olefin ring-opening polymer hydride can be suppressed. Furthermore, if the content of structural unit (B) is below the above-mentioned upper limit, the precipitation of the cyclic olefin ring-opening polymer after synthesis can be suppressed.

[0085] <Other structural units>

[0086] Other structural units that the cyclic olefin ring-opening polymer may optionally include are not particularly limited as long as they are not the structural units (A) and (B) described above, and examples can be found in structural units derived from cyclic olefin compounds that do not have an aromatic ring structure.

[0087] The cyclic olefin compound that does not have an aromatic ring structure, which is capable of forming structural units from cyclic olefin compounds that do not have an aromatic ring structure, is not particularly limited. Examples include norbornene compounds that do not have an aromatic ring structure and non-norbornene compounds that do not have an aromatic ring structure.

[0088] As a norbornene compound that does not possess an aromatic ring structure, there are no particular limitations; examples include tetracyclic [6.2.1.1³]. ,6 0.0² ,7 Dodecyl-4-ene (common name: tetracyclic dodecylene), 2-ethylidene-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (common name: ethylidene tetracyclic dodecylene), tricyclic [5.2.1.0²] ,6 ] Dec-3,8-diene (common name: dicyclopentadiene), 5-ethylidene bicyclo[2.2.1]hept-2-ene (common name: ethylidene norbornene), bicyclo[2.2.1]hept-2-ene (also known as "norbornene"), 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-methylene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, tetracyclo[10.2.1.0², ¹¹.0 4,9 [Pentadecyl-4,6,8,13-tetraene, 9-methyl-tetracyclo[6.2.1.1³] ,6 0.0² ,7 [dodecyl-4-ene, 9-ethyl-tetracyclo[6.2.1.1³]] ,6 0.0² ,7 Dodecyl-4-ene, 9-methylene-tetracyclo[6.2.1.1³] ,6 0.0² ,7 [dodec-4-ene, 9-ethylidene-tetracyclo[6.2.1.1³]] ,6 0.0² ,7 [dodec-4-ene, 9-vinyl-tetracyclo[6.2.1.1³]] ,6 0.0² ,7 [dodec-4-ene, 9-propenyl-tetracyclo[6.2.1.1³]] ,6 0.0² ,7 Dodecyl-4-ene, pentacyclic [9.2.1.1³] ,9 0.0² , ¹ 0 .0 4,8 [Pentadecyl-5,12-diene, tetracyclic [9.2.1.0²] , ¹ 0 0.0³ ,8 [Tetradecane-3,5,7,12-tetraene, pentacyclic [9.2.1.1³]] ,9 .0 ², ¹ 0 .0 4,8 [Pentadeca-12-ene and its derivatives, etc. Furthermore, derivatives refer to substances having substituents in their ring structure. Moreover, the substituents that can be present in the ring structure are not particularly limited as long as they do not have an aromatic ring structure; examples include alkyl, alkylene, vinyl, alkoxycarbonyl, and alkylidene groups. Furthermore, the ring structure of a derivative may have one or more of these substituents.]

[0089] Furthermore, there are no particular limitations on nonnorbornene compounds that do not have an aromatic ring structure; examples include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, 1,4-cyclooctadiene, cyclodecene, and other cycloolefins.

[0090] The aforementioned cyclic olefin compounds that do not have an aromatic ring structure can be used alone or in combination of two or more.

[0091] [Contains percentage]

[0092] Furthermore, the proportion of other structural units in all structural units (100% by mass) of the cyclic olefin ring-opening polymer (the total proportion of other structural units) is typically between 0% by mass and 60% by mass.

[0093] <Mass ratio of structural unit (A) to structural unit (B)>

[0094] From the viewpoint of imparting an appropriate Abbe number to the obtained cyclic olefin ring-opening polymer hydride while further reducing the birefringence, the mass ratio of structural unit (A) to structural unit (B) in the cyclic olefin ring-opening polymer (structural unit (A) / structural unit (B)) is preferably 10 / 90 or more, more preferably 25 / 75 or more, and preferably 90 / 10 or less, more preferably 75 / 25 or less.

[0095] <Methods for manufacturing cyclic olefin ring-opening polymers>

[0096] Cyclic olefin ring-opening polymers can be obtained by ring-opening polymerization of monomer compositions (mixtures) containing the various monomers described above in the "Cyclic olefin ring-opening polymer" category. Specifically, for example, cyclic olefin ring-opening polymers can be prepared by ring-opening polymerization of the above monomer compositions using known ring-opening polymerization methods such as ring-opening polymerization employing a metathesis polymerization catalyst.

[0097] In addition, by performing ring-opening polymerization, the number of rings in each of the above monomers is reduced by at least one.

[0098] Here, there are no particular limitations on the catalyst used for metathesis polymerization, and known catalysts can be used. Specifically, for example, catalyst systems composed of halides, nitrates, or acetylacetone compounds of metals selected from ruthenium, rhodium, palladium, osmium, iridium, and platinum, and a reducing agent can be used; catalyst systems composed of halides or acetylacetone compounds of metals selected from titanium, vanadium, zirconium, tungsten, and molybdenum, and an organoaluminum compound as a co-catalyst can be used; or, known Schrock-type or Grubbs-type active ring-opening metathesis catalysts disclosed in Japanese Patent Application Publication No. 7-179575, J.Am.Chem.Soc., 1986, 108, 733, J.Am.Chem.Soc., 1993, 115, 9858, and J.Am.Chem.Soc., 1996, 118, 100, etc., can be used. These catalysts can be used individually or in combination of two or more. The amount of catalyst used can be appropriately selected according to the polymerization conditions, etc.

[0099] Furthermore, polar compounds can be added to the above-mentioned catalyst system to improve polymerization activity or selectivity of ring-opening polymerization. Examples of polar compounds include: molecular oxygen, alcohols, ethers, peroxides, carboxylic acids, acid anhydrides, acyl chlorides, esters, ketones, nitrogen-containing compounds, sulfur-containing compounds, halogen-containing compounds, molecular iodine, and other Lewis acids. As nitrogen-containing compounds, aliphatic or aromatic tertiary amines are preferred; specific examples include triethylamine, dimethylaniline, tri-n-butylamine, pyridine, and 2-methylpyridine. These polar compounds can be used individually or in combination of two or more. The amount used can be appropriately selected, but the molar ratio (polar compound / metal ratio) is typically 1 to 100,000, preferably in the range of 5 to 10,000.

[0100] Polymerization reactions can be carried out through bulk polymerization without the use of solvents, or in solvents such as organic solvents. There are no particular restrictions on solvents as long as they are inert to the polymerization reaction. Examples include: aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclohexane; halogenated hydrocarbons such as styrene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, dichlorobenzene, and trichlorobenzene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, acetonitrile, and benzonitrile; and ether solvents such as tetrahydrofuran and ethylene glycol dimethyl ether.

[0101] Polymerization conditions such as polymerization temperature, polymerization pressure, and polymerization time can be adjusted appropriately.

[0102] (Hydrogenates of cyclic olefin ring-opening polymers)

[0103] The cyclic olefin ring-opening polymer hydride of the present invention is obtained by hydrogenating the above-mentioned cyclic olefin ring-opening polymer of the present invention, which is used as a raw material. Furthermore, the cyclic olefin ring-opening polymer hydride of the present invention possesses both a moderate Abbe number and a low birefringence.

[0104] Here, the hydrogenation of cyclic olefin ring-opening polymers can be carried out using hydrogen and a hydrogenation catalyst. The hydrogenation of cyclic olefin ring-opening polymers can be carried out using any hydrogenation catalyst and hydrogenation conditions, as long as the non-aromatic carbon-carbon unsaturated bonds such as olefinic double bonds present in the cyclic olefin ring-opening polymer can be hydrogenated.

[0105] Hydrogenation of cyclic olefin ring-opening polymers is typically carried out in such a manner that the hydrogenation rate of non-aromatic carbon-carbon unsaturated bonds, such as olefin double bonds, present in the cyclic olefin ring-opening polymer (the proportion of hydrogenated unsaturated bonds among the non-aromatic carbon-carbon unsaturated bonds in the cyclic olefin ring-opening polymer) reaches 90% or more, preferably 95% or more, and more preferably 99% or more. If the hydrogenation rate of non-aromatic carbon-carbon unsaturated bonds, such as olefin double bonds, contained in the cyclic olefin ring-opening polymer is above the aforementioned lower limit, yellowing caused by resin oxidative deterioration during molding can be suppressed.

[0106] The carbon-carbon unsaturated bonds (aromatic carbon-carbon unsaturated bonds) of the aromatic ring structure (aromatic ring and / or aromatic heterocycle) present in the cyclic olefin ring-opening polymer hydride can be hydrogenated, but from the viewpoint of making the Abbe number appropriately large and further reducing the birefringence, it is preferable that they are not hydrogenated. Specifically, the hydrogenation rate of aromatic carbon-carbon unsaturated bonds in the cyclic olefin ring-opening polymer hydride (the proportion of hydrogenated unsaturated bonds in the aromatic carbon-carbon unsaturated bonds of the cyclic olefin ring-opening polymer) is preferably 20% or less, more preferably 10% or less, and particularly preferably 0% (i.e., not hydrogenated).

[0107] Furthermore, in this invention, the hydrogenation rate of non-aromatic carbon-carbon unsaturated bonds and aromatic carbon-carbon unsaturated bonds can be determined by the method described in the examples.

[0108] Furthermore, the hydrogenation rate of non-aromatic carbon-carbon unsaturated bonds and aromatic carbon-carbon unsaturated bonds can be adjusted, for example, by changing the type and amount of hydrogenation catalyst and / or the conditions of the hydrogenation reaction (reaction temperature, etc.).

[0109] Examples of hydrogenation catalysts that can be used include: hydrogenation catalysts composed of organometallic compounds from groups 1 to 3 of the periodic table, such as dicyclopentadienyl titanium halides, organocarboxylic acids (nickel, rhenium, cobalt, etc.); metal catalysts supported on carbon, silica, diatomaceous earth, etc., such as nickel, platinum, palladium, ruthenium, rhenium, and rhodium; metal catalysts such as cobalt, nickel, rhodium, and ruthenium complexes; hydrogenation compounds such as lithium aluminum hydride and p-toluenesulfonyl hydrazine; etc. Among these, ruthenium compounds are preferred as hydrogenation catalysts from the viewpoint of preventing isomerization and obtaining the target compound in high yield.

[0110] Examples of ruthenium compounds include: RuHCl(CO)(PPh3)3, RuHCl(CO)[P(p-Me-Ph)3]3, RuHCl(CO)(PCy3)2, RuHCl(CO)[P(n-Bu)3]3, RuHCl(CO)[P(i-Pr)3]2, RuH2(CO)(PPh3)3, RuH2(CO)[P(p-Me-Ph)3]3, RuH2(CO)(PCy3)3, RuH2(CO)[P(n-Bu)3]3, RuH(OCOCH3)(CO)(PPh3)2, RuH(OCOPh)(CO)(PPh3)2, RuH(OCOPh-CH3)(CO)(PPh3)2, RuH(OCOPh-OCH3)(CO)(PPh3)2, RuH(OCOPh)(CO)(PCy3)2, etc.

[0111] Furthermore, the hydrogenation reaction of cyclic olefin ring-opening polymers can usually be carried out in inert organic solvents. Examples of inert organic solvents include: aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as pentane and hexane; alicyclic hydrocarbon solvents such as cyclohexane and decahydronaphthalene; ether solvents such as tetrahydrofuran and ethylene glycol dimethyl ether; etc.

[0112] Furthermore, the reaction temperature for hydrogenating the cyclic olefin ring-opening polymer by adding hydrogen to a system containing the cyclic olefin ring-opening polymer and a hydrogenation catalyst varies depending on the hydrogenation catalyst used, typically ranging from -20°C to 250°C, preferably from -10°C to 220°C, and more preferably from 0°C to 200°C. If the reaction temperature is too low, the hydrogenation rate may be too slow; if it is too high, side reactions may occur.

[0113] Furthermore, the hydrogen pressure is typically 0.01–20 MPa, preferably 0.05–15 MPa, and more preferably 0.1–10 MPa. If the hydrogen pressure is too low, the hydrogenation rate may be too slow; if it is too high, a high-pressure-resistant reaction device is required, which creates limitations on the equipment.

[0114] Furthermore, the reaction time also depends on the scale of the reaction, but it is usually 0.1 to 10 hours.

[0115] In addition, after the hydrogenation reaction, the obtained cyclic olefin ring-opening polymer hydride can be recovered using conventional methods. During the recovery of the hydride, catalyst residue can be removed by methods such as filtration.

[0116] <Structural Unit>

[0117] Here, structural unit (A) in the cyclic olefin ring-opening polymer hydride may include: structural units obtained by ring-opening polymerization of 1,2,3,3a,4,6a-hexahydro-1,2,4-methylbridged pentanene, and structural units formed by hydrogenating such structural units. Similarly, structural unit (B) in the cyclic olefin ring-opening polymer hydride may include: structural units obtained by ring-opening polymerization of a cyclic olefin monomer having an aromatic ring structure, and structural units formed by hydrogenating such structural units. Furthermore, other structural units optionally included in the cyclic olefin ring-opening polymer hydride may include: structural units obtained by ring-opening polymerization of a cyclic olefin compound capable of forming other structural units, and structural units formed by hydrogenating such structural units.

[0118] In addition, the structural units obtained by ring-opening polymerization of 1,2,3,3a,4,6a-hexahydro-1,2,4-methyl-bridged pentanene, the structural units obtained by ring-opening polymerization of cyclic olefin monomers with aromatic ring structures, and the structural units obtained by ring-opening polymerization of cyclic olefin compounds capable of forming other structural units in the cyclic olefin ring-opening polymer hydrides are all unhydrogenated structural units (repeating units) that were not hydrogenated during the hydrogenation of the cyclic olefin ring-opening polymer.

[0119] Furthermore, the proportion of structural unit (A) in the cyclic olefin ring-opening polymer hydride (the total proportion of structural units obtained during the ring-opening polymerization of 1,2,3,3a,4,6a-hexahydro-1,2,4-methyl-bridged pentanene and structural units formed by hydrogenation of that structural unit) is the same as the preferred proportion of structural unit (A) in the cyclic olefin ring-opening polymer described above in the "Cyclic Olefin Ring-Opening Polymer" section. In addition, the proportion of structural unit (B) in the cyclic olefin ring-opening polymer hydride (the total proportion of structural units obtained during the ring-opening polymerization of a cyclic olefin monomer having an aromatic ring structure and structural units formed by hydrogenation of that structural unit) is the same as the preferred proportion of structural unit (B) in the cyclic olefin ring-opening polymer described above in the "Cyclic Olefin Ring-Opening Polymer" section. Furthermore, the proportion of other structural units optionally included in the cyclic olefin ring-opening polymer hydride (the total proportion of structural units obtained by ring-opening polymerization of cyclic olefin compounds capable of forming other structural units and structural units formed by hydrogenation of such structural units) is the same as the preferred proportion of other structural units in the cyclic olefin ring-opening polymer described above in the item "cyclic olefin ring-opening polymer".

[0120] Furthermore, the preferred mass ratio of structural unit (A) to structural unit (B) in the cyclic olefin ring-opening polymer hydride is the same as the preferred content ratio mentioned above in the item "cyclic olefin ring-opening polymer".

[0121] <weight-average molecular weight>

[0122] The weight-average molecular weight of the cyclic olefin ring-opening polymer hydride of the present invention is preferably 10,000 or more, more preferably 15,000 or more, even more preferably 20,000 or more, particularly preferably 40,000 or more, and preferably 160,000 or less, more preferably 80,000 or less, and even more preferably 70,000 or less. If the weight-average molecular weight of the cyclic olefin ring-opening polymer hydride is above the aforementioned lower limit, the reduction in strength of the resin molded article obtained using the cyclic olefin ring-opening polymer hydride can be suppressed. Furthermore, if the weight-average molecular weight of the cyclic olefin ring-opening polymer hydride is below the aforementioned upper limit, the occurrence of molding defects due to deterioration of flowability during molding of the cyclic olefin ring-opening polymer hydride can be suppressed.

[0123] In addition, in this invention, the "weight-average molecular weight" can be determined by the method described in the examples.

[0124] Furthermore, the weight-average molecular weight of cyclic olefin ring-opening polymer hydrides can be adjusted, for example, by changing the type and / or amount of monomers used in the preparation of cyclic olefin ring-opening polymers, and the type and / or amount of molecular weight regulators (chain transfer agents).

[0125] Glass transition temperature

[0126] The glass transition temperature of the cyclic olefin ring-opening polymer hydride of the present invention is preferably 120°C or higher, more preferably 125°C or higher, even more preferably 130°C or higher, and preferably 200°C or lower, more preferably 190°C or lower, and even more preferably 180°C or lower. If the glass transition temperature of the cyclic olefin ring-opening polymer hydride is above the above-mentioned lower limit, the deterioration of optical properties due to heat deformation caused by deterioration of heat resistance can be suppressed. Furthermore, if the glass transition temperature of the cyclic olefin ring-opening polymer hydride is below the above-mentioned upper limit, the oxidative deterioration of the cyclic olefin ring-opening polymer hydride caused by excessively high processing temperature during molding can be suppressed.

[0127] The glass transition temperature of cyclic olefin ring-opening polymer hydrides can be adjusted, for example, by changing the type and / or amount of monomers used in the preparation of the cyclic olefin ring-opening polymer.

[0128] Abbe numbers

[0129] The Abbe number (vd) of the cyclic olefin ring-opening polymer hydride of the present invention is preferably less than 50, more preferably 46 or less, further preferably 45 or less, even more preferably 43 or less, and particularly preferably 42 or less. If the Abbe number of the cyclic olefin ring-opening polymer hydride is less than the above-mentioned upper limit value, the cyclic olefin ring-opening polymer hydride can be suitably used for applications other than high Abbe number optical components. Furthermore, the lower limit value of the Abbe number is not particularly limited, but is generally around 20.

[0130] <Birefringence>

[0131] The birefringence of the cyclic olefin ring-opening polymer hydride of the present invention is preferably 300 or less, more preferably 200 or less, even more preferably 100 or less, even more preferably 90 or less, and particularly preferably 85 or less. If the birefringence of the cyclic olefin ring-opening polymer hydride is below the above-mentioned upper limit, the optical properties of the resulting resin molded article as an optical element can be improved.

[0132] In addition, in this invention, the "birefringence" can be measured by the method described in the examples.

[0133] <Refractive index>

[0134] The refractive index of the cyclic olefin ring-opening polymer hydride of the present invention is preferably 1.5 or higher, more preferably 1.52 or higher, and even more preferably 1.54 or higher. If the refractive index of the cyclic olefin ring-opening polymer hydride is above the above-mentioned lower limit value, the design freedom of the obtained resin molded article as an optical element can be improved.

[0135] In addition, in this invention, the "refractive index" can be measured by the method described in the examples.

[0136] (Resin Composition)

[0137] The resin composition of the present invention comprises the above-described cyclic olefin ring-opening polymer hydride of the present invention, and optionally further comprises polymeric materials and / or various additives other than the cyclic olefin ring-opening polymer hydride of the present invention.

[0138] There are no particular limitations on the polymer materials and additives that the resin composition may contain, for example, the polymer materials and additives described in Japanese Patent Application Publication No. 10-139865.

[0139] The resin composition preferably contains antioxidants such as phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants.

[0140] There are no particular limitations on the use of polymeric materials and additives, as long as they can be sufficiently dispersed in the cyclic olefin ring-opening polymer hydride. They can be mixed with the cyclic olefin ring-opening polymer hydride using any method. Specifically, polymeric materials and additives can be added at any stage of the preparation process of the cyclic olefin ring-opening polymer hydride, or they can be mixed with the cyclic olefin ring-opening polymer hydride using a mixing machine or in a molding apparatus.

[0141] The amount of polymeric materials and additives is not particularly limited as long as it does not impair the effect of the present invention. For example, relative to 100 parts by weight of the cyclic olefin ring-opening polymer hydride, it can be more than 0.01 parts by weight and less than 2.0 parts by weight.

[0142] Furthermore, the amount of antioxidant is not particularly limited as long as it does not impair the effect of the present invention. For example, it can be more than 0.01 parts by mass and less than 2.0 parts by mass relative to 100 parts by mass of the cyclic olefin ring-opening polymer hydride.

[0143] (Resin molded body)

[0144] The resin molded article of the present invention is formed by molding the above-described resin composition of the present invention into any shape. Furthermore, since the resin molded article of the present invention contains the above-described cyclic olefin ring-opening polymer hydride of the present invention, it can exhibit excellent performance.

[0145] Here, the molding method is not particularly limited as long as it can mold the resin composition. For example, it can be injection molding, extrusion blow molding, injection blow molding, two-step blow molding, multi-layer blow molding, link blow molding, stretch blow molding, rotational molding, vacuum forming, extrusion molding, calendering, solution casting, hot pressing, inflation, etc. Among these, extrusion molding is preferred.

[0146] The resin molded body of the present invention is preferably an optical element, and more preferably a lens.

[0147] Furthermore, the lens is not particularly limited; for example, it can be obtained by uniformly heating and dissolving the resin composition of the present invention to form a preform, then flowing the preform into a mold and cooling it.

[0148] Example

[0149] The present invention will now be specifically described based on embodiments, but the present invention is not limited to these embodiments. Furthermore, in the following description, unless otherwise specified, "%" and "parts" indicating quantity refer to mass. Additionally, when copolymerizing multiple monomers to manufacture a polymer, the proportion of a structural unit formed by the polymerization of a particular monomer in the polymer is generally consistent with the proportion (feed ratio) of that monomer in all monomers used in the polymerization of the polymer, unless otherwise specified.

[0150] <Aggregation Conversion Rate>

[0151] After the polymerization reaction is completed, the residual amount of monomer in the reaction solution is determined by gas chromatography, and the amount is calculated from the value.

[0152] <Hydrogenation rate>

[0153] pass 1 H-NMR spectroscopy was used to determine the number of moles of hydrogenated carbon-carbon double bonds, and the ratio of the number of moles of carbon-carbon double bonds to the number of moles of carbon-carbon double bonds before hydrogenation was calculated. This allowed the determination of the hydrogenation rate of non-aromatic carbon-carbon unsaturated bonds and aromatic carbon-carbon unsaturated bonds in the cyclic olefin ring-opening polymer hydride.

[0154] <weight-average molecular weight>

[0155] The weight-average molecular weight (Mw) of the cyclic olefin ring-opening polymer was calculated using a gel permeation chromatography system (Tosoh Corporation, "HLC-8020", using a combination of TSKgel SuperH2000, TSKgel SuperH4000, and TSKgel SuperH5000 columns) and converted to polystyrene. Tetrahydrofuran (THF) was used as the developing solvent.

[0156] Glass transition temperature

[0157] The glass transition temperature (Tg) of the cyclic olefin ring-opening polymer hydride was measured using a differential scanning calorimeter (manufactured by Seiko Electronics Nanotechnology Co., Ltd., "DSC6220") according to JIS K7121 at a heating rate of 10°C / min.

[0158] <Birefringence>

[0159] For the resulting resin molded body, the retardation of light at a wavelength of 543 nm at a position 10 mm from the gate of the resin molded body, perpendicular to the resin flow direction, was linearly measured using a birefringence meter (Photonic Lattice, product name: WPA-200(-L)). The maximum value of the measured values ​​was then taken as the birefringence.

[0160] <Refractive index>

[0161] The resulting resin molded body was placed in an atmosphere at a temperature 15°C lower than the glass transition temperature of the cyclic olefin ring-opening polymer hydride (=Tg-15°C) for 20 hours as the test sample.

[0162] For the obtained test samples, the refractive index (n) at 25°C was measured using a precision refractometer (manufactured by Shimadzu Corporation, product name: KPR-3000, light source = He lamp (587.6nm), H2 lamp (656.3nm, 486.1nm)). d n C n F Additionally, Table 1 shows the refractive index (n) under light with a wavelength of 587.6 nm. d ).

[0163] Abbe numbers

[0164] The refractive index (n) obtained at 25°C using the above refractive index measurement d n C n F The Abbe number (ν) is calculated according to the following formula (1). d ).

[0165] [Mathematical Expression 1]

[0166]

[0167] (Example 1)

[0168] In a nitrogen-purified glass pressure reactor, 40 parts of 1,2,3,3a,4,6a-hexahydro-1,2,4-methylbridged pentaolefin (δ-cycloene; hereinafter sometimes abbreviated as "DCL"), 60 parts of N-2-methylphenyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (hereinafter sometimes abbreviated as "NBTI") as a cyclic olefin monomer with an aromatic ring structure, 3 parts of 1-hexene as a chain transfer agent, 0.025 parts of 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazolium-2-ylidene[2-(isopropoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) as a polymerization catalyst, and 1000 parts of tetrahydrofuran as a solvent were added. The entire mixture was stirred at 65°C for 3 hours to carry out ring-opening polymerization. The obtained ring-opening polymer had a polymerization conversion rate of 98%, and the weight-average molecular weight of the obtained cyclic olefin ring-opening polymer was 16,100.

[0169] Next, the obtained polymerization reaction solution was placed in an autoclave and stirred at 150°C and 4.5 MPa for 6 hours to carry out the hydrogenation reaction. The solution was then filtered through a funnel pre-coated with sodium zeolite and dried under vacuum at 150°C for 24 hours to obtain the cyclic olefin ring-opening polymer hydride.

[0170] The hydrogenation rate of the non-aromatic carbon-carbon unsaturated bonds in the obtained cyclic olefin ring-opening polymer hydrides is over 90.0%. Furthermore, the hydrogenation rate of the aromatic carbon-carbon unsaturated bonds in the obtained cyclic olefin ring-opening polymer hydrides is 0%.

[0171] Next, 100 parts of the cyclic olefin ring-opening polymer hydride were mixed with 1 part of an antioxidant (tetramethylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane; "Irganox (registered trademark) 1010" manufactured by BASF Japan Co., Ltd.) to obtain a resin composition containing the cyclic olefin ring-opening polymer hydride.

[0172] The resulting resin composition was then fed into a twin-screw extruder (Toshiba Machine Co., Ltd. "TEM-37B") with four 3mm inner diameter dies. The resin composition was then hot-melt extruded using the twin-screw extruder to form a strip-shaped profile. This profile was then pelletized using a pelletizer to obtain resin pellets. The operating conditions of the twin-screw extruder are as follows.

[0173] • Barrel set temperature: 270℃~280℃

[0174] • Die head set temperature: 250℃

[0175] Then, the dried granules obtained above were injection molded using an injection molding apparatus (manufactured by FANUC Corporation, product number α-100B) at a resin temperature 20°C lower than the glass transition temperature of the resin composition (=Tg-20°C), a mold temperature 130°C lower than the glass transition temperature of the resin composition (=Tg-130°C), and a cycle time of 1 minute to obtain a flat resin molded body of 80mm×10mm×4mm.

[0176] (Example 2)

[0177] In Example 1, except that the amount of DCL was changed from 40 parts to 20 parts, and 80 parts of N-2,6-dimethylphenyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (hereinafter sometimes simply referred to as "NBXI") were used instead of 60 parts of NBTI as the cyclic olefin monomer having an aromatic ring structure, the same procedure was followed to produce the cyclic olefin ring-opening polymer, the cyclic olefin ring-opening polymer hydride, and the resin molded article. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0178] (Example 3)

[0179] In Example 2, except that the amount of DCL was changed from 20 parts to 50 parts, the amount of NBXI was changed from 80 parts to 50 parts, and the amount of 1-hexene as a chain transfer agent was changed from 3 parts to 2.5 parts, the same procedure was followed as in Example 2 to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin molded articles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0180] (Example 4)

[0181] In Example 3, except that the amount of DCL was changed from 50 parts to 37 parts, and 5,5A,6,9,9A,10,10A,11-octahydro-4bh-5,10,6,9-dimethylbridged-benzo[B]fluorene (hereinafter sometimes simply referred to as "HNT") was used instead of 50 parts of NBXI as a cyclic olefin monomer with an aromatic ring structure, 63 parts were prepared, the same procedure as in Example 3, to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin molded articles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0182] (Example 5)

[0183] In Example 3, except that the amount of DCL was changed from 50 parts to 20 parts, replacing 50 parts of NBXI, and 60 parts of NBTI were used as a cyclic olefin monomer with an aromatic ring structure, and 20 parts of 2-ethylene-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (hereinafter sometimes simply referred to as "ETD") as a cyclic olefin monomer without an aromatic ring structure, the same procedure as in Example 3 was followed to produce a cyclic olefin ring-opening polymer, a cyclic olefin ring-opening polymer hydride, and a resin molded article. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0184] (Example 6)

[0185] In Example 2, except that the amount of DCL was changed from 20 parts to 40 parts, the amount of NBXI was changed from 80 parts to 60 parts, and the amount of 1-hexene as a chain transfer agent was changed from 3 parts to 0.5 parts, the same procedure was followed as in Example 2 to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin molded articles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0186] (Example 7)

[0187] In Example 2, except that the amount of DCL was changed from 20 parts to 40 parts, the amount of NBXI was changed from 80 parts to 60 parts, and the amount of 1-hexene as a chain transfer agent was changed from 3 parts to 0.25 parts, the same procedure was followed as in Example 2 to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin molded articles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0188] (Example 8)

[0189] In Example 2, except that the amount of DCL was changed from 20 parts to 44 parts, the amount of NBXI was changed from 80 parts to 56 parts, and the amount of 1-hexene as a chain transfer agent was changed from 3 parts to 0.24 parts, the same procedure was followed as in Example 2 to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin molded articles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0190] (Example 9)

[0191] In Example 2, except that the amount of DCL was changed from 20 parts to 44 parts, the amount of NBXI was changed from 80 parts to 56 parts, and the amount of 1-hexene as a chain transfer agent was changed from 3 parts to 0.18 parts, the same procedure was followed as in Example 2 to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin molded articles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0192] (Example 10)

[0193] In Example 2, except that the amount of DCL was changed from 20 parts to 44 parts, the amount of NBXI was changed from 80 parts to 56 parts, and the amount of 1-hexene as a chain transfer agent was changed from 3 parts to 0.1 parts, the same procedure was followed as in Example 2 to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin molded articles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0194] (Comparative Example 1)

[0195] In Example 3, the same procedure as in Example 3 was followed, except that the amount of DCL was changed from 50 parts to 100 parts and NBXI, a cyclic olefin monomer with an aromatic ring structure, was omitted. However, because the polymerization reaction solution containing the cyclic olefin ring-opening polymer contained precipitates, it was impossible to determine the weight-average molecular weight and to hydrogenate the cyclic olefin ring-opening polymer. Therefore, it was impossible to produce cyclic olefin ring-opening polymer hydrogenates and resin molded articles, and various measurements and evaluations could not be performed.

[0196] (Comparative Example 2)

[0197] In Example 3, except that DCL was not incorporated and 100 parts of 1,4-methylbridged-1,4,4a,9a-tetrahydrofluorene (hereinafter sometimes simply referred to as "MTF") were incorporated instead of 50 parts of NBXI as a cyclic olefin monomer having an aromatic ring structure, the same procedure as in Example 3 was followed to produce a cyclic olefin ring-opening polymer, a cyclic olefin ring-opening polymer hydride, and a resin molded article. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0198] (Comparative Example 3)

[0199] In Example 3, in addition to replacing 50 parts of NBXI, a tetracyclic [6.2.1.1³] was incorporated as a cyclic olefin monomer without an aromatic ring structure. ,6 0.0² ,7 Except for 50 parts of dodecyl-4-ene (hereinafter referred to as "TCD"), the same procedure as in Example 3 was followed to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin molded articles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0200] [Table 1]

[0201]

[0202] As shown in Table 1, the cyclic olefin ring-opening polymer hydrides of Examples 1 to 10, which contain structural units (A) from 1,2,3,3a,4,6a-hexahydro-1,2,4-methyl-bridged pentanene and structural units (B) from cyclic olefin monomers with aromatic ring structures, have both moderate Abbe numbers and low birefringence.

[0203] On the other hand, as shown in Table 1, the cyclic olefin ring-opening polymer hydride of Comparative Example 2, which contains structural units (B) from cyclic olefin monomers with aromatic ring structures but not structural units (A) from 1,2,3,3a,4,6a-hexahydro-1,2,4-methylbridged pentanene, has a high birefringence. Furthermore, as shown in Table 1, the cyclic olefin ring-opening polymer hydride of Comparative Example 3, which contains structural units (A) from 1,2,3,3a,4,6a-hexahydro-1,2,4-methylbridged pentanene but not structural units (B) from cyclic olefin monomers with aromatic ring structures, has an excessively high Abbe number.

[0204] Industrial availability

[0205] According to the present invention, a cyclic olefin ring-opening polymer hydride and its raw materials with a moderate Abbe number and low birefringence can be provided.

[0206] Furthermore, according to the present invention, a resin composition that can be advantageously used as a material for various molded bodies such as optical elements can be provided, as well as a resin molded body formed using the resin composition.

Claims

1. A cyclic olefin ring-opening polymer comprising a structural unit (A) from 1,2,3,3a,4,6a-hexahydro-1,2,4-methyl-bridged pentanene and a structural unit (B) from a cyclic olefin monomer having an aromatic ring structure.

2. The cyclic olefin ring-opening polymer according to claim 1, wherein, The structural unit (B) is a structural unit derived from the single unit represented by the following formula (1). In formula (1), R1 to R5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group capable of having a substituent, a cycloalkyl group capable of having a substituent, an alkenyl group capable of having a substituent, an alkoxy group capable of having a substituent, an aromatic hydrocarbon cyclogroup capable of having a substituent, or an aromatic heterocyclic group capable of having a substituent, and two or more of R1 to R5 can bond together to form a ring.

3. A cyclic olefin ring-opening polymer hydride, which is formed by hydrogenating the cyclic olefin ring-opening polymer according to claim 1.

4. The cyclic olefin ring-opening polymer hydride according to claim 3, wherein, The aromatic carbon-carbon unsaturated bonds present in the cyclic olefin ring-opening polymer hydride are not hydrogenated.

5. The cyclic olefin ring-opening polymer hydride according to claim 3, wherein the Abbe number is less than 50.

6. The cyclic olefin ring-opening polymer hydride according to claim 3 has a glass transition temperature of 120°C or higher.

7. A resin composition comprising the cyclic olefin ring-opening polymer hydride of any one of claims 3 to 6.

8. A resin molded article formed by molding the resin composition of claim 7.

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