Cyclic olefin ring-opening polymer, cyclic olefin ring-opening polymer hydride, resin composition, and resin molded article

Abstract

The purpose of the present invention is to provide: a cyclic olefin ring-opening polymer hydride which has both an Abbe number of an appropriate size and a low birefringence; and a starting material for the cyclic olefin ring-opening polymer hydride. This cyclic olefin ring-opened polymer is characterized by containing a structural unit (A) derived from a norbornene imide monomer represented by formula (1) and a structural unit (B) derived from a cyclic olefin monomer that does not have a polar group. The cyclic olefin ring-opening polymer hydride according to the present invention is characterized by being obtained by hydrogenating the cyclic olefin ring-opening polymer according to the present 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 polymers, obtained by ring-opening polymerization of cyclic olefin monomers, are hydrogenated to form cyclic olefin ring-opening polymer hydrides. Due to their excellent properties such as transparency, low moisture absorption, heat resistance, insulation, and chemical resistance, they are widely used as molding materials for optical components such as optical lenses. Therefore, in recent years, various schemes have been proposed to improve the physical properties of cyclic olefin ring-opening polymer hydrides.

[0003] For example, Patent Document 1 discloses a method for manufacturing a ring-opening metathesis polymer hydride (a cyclic olefin ring-opening polymer hydride). This method involves ring-opening metathesis polymerization of a cyclic olefin in the presence of a polymerization catalyst to obtain a ring-opening metathesis polymer, followed by hydrogenation of the polymer. A specific ruthenium compound is used as the polymerization catalyst. Furthermore, Patent Document 1 discloses that this manufacturing method can produce a ring-opening metathesis polymer hydride with excellent light transmittance.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent document 1: International Publication No. 2013 / 137398. 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 growing demand to reduce the birefringence of cyclic olefin ring-opening polymer hydrides used as molding materials for manufacturing optical components. Furthermore, from the perspective of increasing the freedom of optical design, there is a growing demand not only for developing cyclic olefin ring-opening polymer hydrides with high Abbe numbers (e.g., 50 or higher) as molding materials for optical components, but also for developing cyclic olefin ring-opening polymer hydrides with moderate Abbe numbers (e.g., 35 or higher and less than 50).

[0009] However, the cyclic olefin ring-opening polymer hydrides obtained by the above-mentioned prior art cannot simultaneously possess a moderate Abbe number and a low birefringence.

[0010] Therefore, the object of the present invention is to provide a cyclic olefin ring-opening polymer hydride and its raw materials that have both a moderate Abbe number and a low birefringence.

[0011] Furthermore, the object of the present invention is 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 a specific norbornene imide monomer and structural units from a cyclic olefin monomer without polar groups, can achieve both 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 a norbornene imide monomer represented by the following formula (1) and a structural unit (B) from a cyclic olefin monomer that does not have a polar group.

[0015] [Chemical Formula 1]

[0016]

[0017] (In formula (1), A represents an alkyl, cycloalkyl, alkoxy, or aryl group that can have substituents (excluding phenyl groups whose two adjacent positions are unsubstituents based on the bonded imide ring).)

[0018] Cyclic olefin monomers comprising structural units (A) from norbornene imide monomers represented by formula (1) and structural units (B) from cyclic olefin monomers without polar groups can be advantageously used as raw materials 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.

[0019] [2] In the cyclic olefin ring-opening polymer of [1] above, it is preferred that the above structural unit (A) is a structural unit derived from the norbornene imide monomer represented by the following formula (2).

[0020] [Chemical Formula 2]

[0021]

[0022] (In formula (2), 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. Two or more of R1 to R5 can be bonded to form a ring. At least one of R1 and R5 is not a hydrogen atom.)

[0023] If the structural unit (A) is a structural unit derived from the norbornene imide monomer specified above, it is possible to further reduce the birefringence while maintaining an appropriate Abbe number for the resulting cyclic olefin ring-opening polymer hydride.

[0024] [3] In the cyclic olefin ring-opening polymers of [1] or [2] above, it is preferable that the content of the above-mentioned structural unit (A) is 50% by mass or more and 90% by mass or less. If the content of the structural unit (A) is within the range specified above, it is possible to further reduce the birefringence while making the Abbe number of the obtained cyclic olefin ring-opening polymer hydride appropriately small.

[0025] 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.

[0026] [4] In any of the cyclic olefin ring-opening polymers described in [1] to [3] above, it is preferable that the structural unit (B) comprises a structural unit derived from a delta cyclene. If the structural unit (B) comprises a structural unit derived from a delta cyclene, it is possible to further reduce the birefringence while ensuring that the Abbe number of the resulting cyclic olefin ring-opening polymer hydride is of an appropriate size.

[0027] Furthermore, the object of the present invention is to advantageously solve the above-mentioned problems. The present invention is [5] a cyclic olefin ring-opening polymer hydride, which is obtained by hydrogenating any of the cyclic olefin ring-opening polymers [1] to [4] 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.

[0028] [6] The cyclic olefin ring-opening polymer hydride of [5] above preferably has an Abbe number of less than 50. If the Abbe number is less than 50, the cyclic olefin ring-opening polymer hydride can be suitably used for applications other than optical components with high Abbe numbers.

[0029] Furthermore, in this invention, the "Abbe number" can be measured using the method described in the embodiments.

[0030] [7] The cyclic olefin ring-opening polymer hydride described in [5] or [6] above preferably has a glass transition temperature of 120°C or higher. If the glass transition temperature is 120°C or higher, it is possible to suppress the deterioration of optical properties of the resin molded body formed using the cyclic olefin ring-opening polymer hydride due to heat deformation, etc.

[0031] Furthermore, in this invention, the "glass transition temperature" can be measured using the method described in the examples.

[0032] Furthermore, the object of the present invention is to advantageously solve the above-mentioned problems. The present invention is [8] a resin composition comprising any one of the cyclic olefin ring-opening polymer hydrides described above [5] to [7]. The resin composition comprising any one of the cyclic olefin ring-opening polymer hydrides described above can be advantageously used as a material for various molded articles such as optical elements.

[0033] Furthermore, the object of the present invention is to advantageously solve the above-mentioned problems. The present invention is [9] a resin molded article which is formed by molding the resin composition of [8] described above. The resin molded article formed using the above-described resin composition can exhibit excellent performance.

[0034] The effects of the invention

[0035] According to the present invention, it is possible to provide a cyclic olefin ring-opening polymer hydride and its raw materials that have both a moderate Abbe number and a low birefringence.

[0036] Furthermore, according to the present invention, it is possible 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. Detailed Implementation

[0037] The embodiments of the present invention will now be described in detail.

[0038] Here, the cyclic olefin ring-opening polymer of the present invention can be suitably used as a raw material, 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 a low birefringence, and can be suitably used as a material for various molded articles such as optical elements. Furthermore, the resin composition of the present invention can be suitably used as a material, for example, for manufacturing the resin molded articles of the present invention. Moreover, the resin molded articles of the present invention can be suitably used 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.

[0039] (Ring-opening polymers of cyclic olefins)

[0040] 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.

[0041] Furthermore, the cyclic olefin ring-opening polymer of the present invention comprises a structural unit (A) derived from a specified norbornene imide monomer and a structural unit (B) derived from a cyclic olefin monomer that does not have a polar group, and optionally also comprises other structural units. The structural units will be described below.

[0042] <Structural unit (A) from norbornene imide monomer>

[0043] The structural unit (A) from the norbornene imide monomer is the structural unit (hereinafter sometimes simply referred to as structural unit (A)) of the norbornene imide monomer represented by the following formula (1).

[0044] [Chemical Formula 3]

[0045]

[0046] (In formula (1), A represents an alkyl, cycloalkyl, alkoxy, or aryl group that can have substituents (excluding phenyl groups whose two adjacent positions are unsubstituents based on the bonded imide ring).)

[0047] Here, the term "alkyl group" that can form A is not particularly limited, and examples include alkyl groups with 1 or more but less than 10 carbon atoms. The term "alkyl group with 1 or more but less than 10 carbon atoms" 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.

[0048] There is no particular limitation on the term "cycloalkyl group" that can form A; examples include cycloalkyl groups with 3 or more but less than 12 carbon atoms. Examples of "cycloalkyl groups with 3 or more but less than 12 carbon atoms" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0049] The term "alkoxy group" that can form A is not particularly limited, and examples of alkoxy groups with 1 or more but less than 10 carbon atoms can be given. As for "alkoxy groups with 1 or more but less than 10 carbon atoms", they can be either straight-chain or branched, and examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, octoxy, etc.

[0050] The term "aryl group capable of having substituents (excluding phenyl groups whose two adjacent positions based on the bonded imide ring are both unsubstituents. The same applies hereinafter)" is not particularly limited, and examples of aryl groups capable of having substituents are 6 or more and 30 or less carbon atoms. Examples of aryl groups with 6 or more and 30 or less carbon atoms in the phrase "aryl group capable of having substituents" include, for example, phenyl, naphthyl, and anthraceneyl.

[0051] Here, examples of substituents in "aryl groups capable of having substituents" include: halogen atoms; hydroxyl groups; cyano groups; nitro groups; alkyl groups capable of having substituents; cycloalkyl groups capable of having substituents; alkenyl groups capable of having substituents; alkoxy groups capable of having substituents; aromatic hydrocarbon cycloyl groups capable of having substituents; and aromatic heterocyclic groups capable of having substituents. The number of substituents can be one or more. In the case of multiple substituents, they can be the same as or different from each other.

[0052] There are no particular limitations on the halogen atom that can form the substituent of the above-mentioned aryl group; examples include chlorine, fluorine, bromine, and iodine atoms.

[0053] The term "alkyl group capable of having a substituent" is not particularly limited, and examples include alkyl groups having 1 or more but less than 10 carbon atoms. Examples of alkyl groups having 1 or more but less than 10 carbon atoms in the phrase "alkyl group capable of having a substituent" include groups similar to those in A above. Methyl or isopropyl groups are preferred.

[0054] Furthermore, specific examples of "substituents" in "alkyl groups capable of having substituents" include, for example: halogen atoms such as chlorine, fluorine, bromine, and iodine; cyano; nitro; unsubstituted alkyl groups with 1 to 10 carbon atoms such as methyl, ethyl, and propyl; unsubstituted alkenyl groups with 2 to 6 carbon atoms such as vinyl and allyl; alkyl groups with 1 to 10 carbon atoms where one or more hydrogen atoms are replaced by halogen atoms such as fluorine, such as trifluoromethyl; and unsubstituted alkoxy groups with 1 to 10 carbon atoms such as methoxy, ethoxy, and isopropoxy. The number of substituents can be one or more. When multiple substituents are present, they can be the same or different from each other.

[0055] As a "cycloalkyl group capable of having a substituent" that can constitute the aforementioned aryl group, examples of cycloalkyl groups having 3 or more and 12 or less carbon atoms are given. There is no particular limitation on the cycloalkyl group having 3 or more and 12 or less carbon atoms in the phrase "cycloalkyl group capable of having a substituent," and examples can be the same group as A described above.

[0056] Furthermore, as a specific example of a substituent in "a cycloalkyl group capable of having substituents," one can cite groups that have the same substituents as those that can be present in the aforementioned "alkyl group capable of having substituents." The number of substituents can be one or more. In the case of multiple substituents, they can be the same as or different from each other.

[0057] The term "alkenyl group capable of having a substituent" as a substituent that can constitute the aforementioned aryl group is not particularly limited, and examples include alkenyl groups with 2 or more but less than 10 carbon atoms capable of having a substituent. The alkenyl group with 2 or more but less than 10 carbon atoms in the phrase "alkenyl group capable of having a substituent" can be either linear or branched, and examples include vinyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, and decenyl.

[0058] Furthermore, as a specific example of a substituent in "alkenyl groups having 2 or more and 10 or fewer carbon atoms capable of having substituents," one can cite groups that have the same substituents as those capable of having substituents in "alkyl groups capable of having substituents" described above. The number of substituents can be one or more. In the case of multiple substituents, they can be the same as or different from each other.

[0059] The term "alkynyl group capable of having a substituent" is not particularly limited, but can be exemplified by alkynyl groups having 2 or more but less than 10 carbon atoms. The alkynyl group having 2 or more but less than 10 carbon atoms in the phrase "alkynyl group capable of having a substituent" can be either linear or branched, and examples include ethynyl, propynyl, 2-propynyl (propynyl), butynyl, 2-butynyl, 3-butynyl, pentynyl, 2-pentynyl, hexynyl, 5-hexynyl, heptynyl, octyynyl, 2-octyynyl, nonynyl, decynyl, 7-decynyl, etc.

[0060] Furthermore, specific examples of substituents in "alkynyl groups having 2 or more and 10 or fewer carbon atoms that can have substituents" can be groups that have the same substituents as those that can be present in "alkyl groups that can have substituents" described above. The number of substituents can be one or more. In the case of multiple substituents, they can be the same as or different from each other.

[0061] As a substituent capable of forming the aforementioned aryl group, an alkoxy group having 1 or more but less than 10 carbon atoms can be cited as an example of an alkoxy group capable of having a substituent. As an alkoxy group capable of having 1 or more but less than 10 carbon atoms, the same group as A above can be cited.

[0062] Furthermore, as a specific example of a substituent in "alkoxy groups capable of having substituents," one can cite groups that have the same substituents as those capable of having substituents in "alkyl groups capable of having substituents" described above. The number of substituents can be one or more. In the case of multiple substituents, they can be the same as each other or different.

[0063] The term "aromatic hydrocarbon cyclic group capable of having a substituent" is not particularly limited, but can be exemplified by aromatic hydrocarbon cyclic groups having 6 or more but less than 30 carbon atoms. Examples of aromatic hydrocarbon cyclic groups having 6 or more but less than 30 carbon atoms in the phrase "aromatic hydrocarbon cyclic group capable of having a substituent" include phenyl, naphthyl, and anthracene.

[0064] As a specific example of a substituent in "an aromatic hydrocarbon cycloalloy that can have a substituent having 6 or more but less than 30 carbon atoms", a group that has the same substituents as the "alkyl group that can have a substituent" described above can be given. The number of substituents can be one or more. In the case of multiple substituents, they can be the same as each other or different.

[0065] The term "aromatic heterocyclic group capable of having a substituent" is not particularly limited, but can be exemplified by aromatic heterocyclic groups having 6 or more but less than 30 carbon atoms. Examples of aromatic hydrocarbon cyclic groups having 6 or more but less than 30 carbon atoms in the term "aromatic heterocyclic group capable of having a substituent" include: furanyl, 1-benzofuranyl, 2-benzofuranyl, pyrroleyl, indolyl, thienyl, benzo[c]thienyl, benzo[b]thienyl, pyridyl, pyrazinyl, pyrimidinyl, triazolyl, triazinyl, imidazoleyl, pyrazolyl, thiazolyl, benzothiazolyl, oxazolyl, and benzooxazolyl, etc.

[0066] As a specific example of a substituent in "an aromatic heterocyclic group having 6 or more and 30 or fewer carbon atoms capable of having a substituent", a group that has the same substituents as the "alkyl group capable of having a substituent" described above can be given. The number of substituents can be one or more. In the case of multiple substituents, they can be the same as each other or different.

[0067] When the aryl group has multiple substituents, two or more of these substituents can bond together to form a ring. The ring formed by the bonding of these multiple substituents can be a monocyclic or polycyclic ring. There is no particular limitation on the ring formed by the bonding of two or more substituents, 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.

[0068] Specific examples of aromatic hydrocarbon rings include aromatic hydrocarbon rings with 6 to 30 carbon atoms, such as benzene rings, naphthalene rings, and anthracene rings.

[0069] Specific examples of aromatic heterocycles 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.

[0070] Specific examples of non-aromatic hydrocarbon rings include cycloalkyl rings with 3 or more but less than 12 carbon atoms, such as cyclopropyl ring, cyclobutyl ring, cyclopentyl ring, cyclohexyl ring, and cyclooctyl ring.

[0071] From the viewpoint of imparting an appropriate Abbe number to the resulting cyclic olefin ring-opening polymer hydride while further reducing the birefringence, A in formula (1) is preferably a phenyl having the above-mentioned substituent. That is, the norbornene imide monomer represented by formula (1) is preferably the norbornene imide monomer represented by formula (2) below.

[0072] [Chemical Formula 4]

[0073]

[0074] (In formula (2), 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. Two or more of R1 to R5 can be bonded to form a ring. At least one of R1 and R5 is not a hydrogen atom.)

[0075] Here, the "halogen atom", "alkyl group capable of having a substituent", "cycloalkyl group capable of having a substituent", "alkenyl group capable of having a substituent", "alkynyl group capable of having a substituent", "alkoxy group capable of having a substituent", "aromatic hydrocarbon cycloyl group capable of having a substituent", "aromatic heterocyclic group capable of having a substituent", and "ring formed by bonding two or more of R1 to R5" are the same as the substituents and rings in the "aryl group capable of having a substituent" mentioned above.

[0076] From the viewpoint of imparting an appropriate Abbe number to the resulting cyclic olefin ring-opening polymer hydride while further reducing the birefringence, as the norbornene imide monomer represented by formula (2), it is preferable that one or more of R1 to R5 in formula (2) is an alkyl group having 1 or more and 10 or less carbon atoms that can have substituents, and the remainder is a hydrogen atom (wherein at least one of R1 and R5 is not a hydrogen atom. The same applies below), and more preferably that two of R1 to R5 are alkyl groups having 1 or more and 10 or less carbon atoms that can have substituents, and the remainder is a hydrogen atom.

[0077] Furthermore, from the viewpoint of further reducing the birefringence while imparting an appropriate Abbe number to the resulting cyclic olefin ring-opening polymer hydride, as the norbornene imide monomer represented by formula (2), it is preferable to be a compound in formula (2) in which one or more of R1 to R5 is methyl or isopropyl and the rest are hydrogen atoms, and more preferably a compound in formula (2) in which two of R1 to R5 are methyl or isopropyl and the rest are hydrogen atoms. In the preferred formulation (2), at least one of R1 and R5 is a methyl or isopropyl compound with the remainder being hydrogen atoms (i.e., N-2-methylphenyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), more preferably, R1 and R5 in the preferred formulation (2) are methyl or isopropyl compounds with the remainder being hydrogen atoms (i.e., N-2,6-dimethylphenyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), and even more preferably, R1 and R5 in the preferred formulation (2) are isopropyl compounds with the remainder being hydrogen atoms (i.e., N-2,6-diisopropylphenyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide).

[0078] The aforementioned norbornene imide monomers can be used alone or in combination of two or more.

[0079] [Contains percentage]

[0080] When the content of structural unit (A) is 100% by mass of all repeating units contained in the cyclic olefin ring-opening polymer, it is preferably 10% by mass or more, more preferably 25% by mass or more, even more preferably 40% by mass or more, particularly preferably 50% by mass or more, and further preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, and particularly preferably 75% by mass or less. If the content of structural unit (A) is within the above-specified range, it is possible to obtain an Abbe number of an appropriate size in the resulting cyclic olefin ring-opening polymer hydride while further reducing the birefringence.

[0081] <Structural units derived from cyclic olefin monomers without polar groups (B)>

[0082] As a "cyclic olefin monomer without polar groups" capable of forming a structural unit (B) from a cyclic olefin monomer without polar groups (hereinafter, sometimes simply referred to as structural unit (B)), there are no particular limitations as long as it has one or more olefinic unsaturated bonds capable of ring-opening polymerization and does not have polar groups. Examples include norbornene compounds without polar groups and non-norbornene compounds without polar groups. They can be used in combination. From the viewpoint of further reducing the birefringence while imparting an appropriate Abbe number to the resulting cyclic olefin ring-opening polymer hydride, the "cyclic olefin monomer without polar groups" capable of forming structural unit (B) is preferably a norbornene compound without polar groups.

[0083] [norbornene compounds without polar groups]

[0084] As a non-polar norbornene compound, there are no particular limitations as long as it is non-polar and has one or more norbornene rings, for example:

[0085] Bicyclic norbornene compounds, including bicyclic [2.2.1]hept-2-ene (common name: norbornene), 5-ethylidene-2-norbornene (common name: ethylidene norbornene), and their derivatives;

[0086] Three Rings [4.3.0.1] 2,5 ]Dec-3,7-diene (common name: dicyclopentadiene) and its derivatives, and other tricyclic norbornene compounds;

[0087] 7,8-Benzotricyclo[4.3.0.1] 2,5 ] Dec-3-ene (common name: methyl-bridged tetrahydrofluorene), tetracyclic [4.4.0.1] 2,5 .1 7 ,10Tetracyclic norbornene compounds, including dodecano-3-ene (common name: tetracyclic dodecanoene), 2-ethylidene-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (common name: ethylidene tetracyclic dodecanoene) and their derivatives.

[0088] 7,8-Benzotricyclo[4.3.0.1] 2,5 ] Dec-3-ene (common name: methyl-bridged tetrahydrofluorene, also known as tetracyclic [7.4.0.0]) 2 ,7 .1 10,13 [13-C-2,4,6,11-Tetraene), tetracyclic [4.4.0.1] 2,5 .1 7,10 Dodecyl-3-ene (common name: tetracyclic dodecylene), 8-ethylidene tetracyclo[4.4.0.1] 2,5 .1 7,10 ]-3-Dodecene and its derivatives, and other tetracyclic norbornene compounds; and

[0089] Five Rings [6.5.1.1] 3,6 .0 2,7 .0 9,13 [Pentadecano-4,10-diene, pentacyclic [9.2.1.1]] 4,7 .0 2,10 .0 3,8 [Pentadecano-5,12-diene, hexacyclic [6.6.1.1]] 3,6 .1 10,13 .0 2,7 .0 9,14 Norbornene compounds having five or more rings, such as heptadec-4-ene, 1,2,3,3a,4,6a-hexahydro-1,2,4-metenopentaren (common name: δ-cycloene) and their derivatives.

[0090] Here, a derivative refers to a substance having substituents in its ring structure. Furthermore, there are no particular limitations on the substituents that can be present in the ring structure, as long as they are not polar groups; examples include alkyl, alkylene group, alkylidene group, aryl, vinyl, and other hydrocarbon groups. Moreover, the ring structure of a derivative may have one or more of these substituents.

[0091] From the viewpoint of imparting an appropriate Abbe number to the resulting cyclic olefin ring-opening polymer hydride while further reducing the birefringence, ethylidene tetracyclododecene or δ-cycloene, and more preferably δ-cycloene, are preferred as norbornene compounds without polar groups.

[0092] In other words, structural unit (B) preferably contains structural units derived from ethylidene tetracyclododecene or δ-cycloene, more preferably from δ-cycloene, and even more preferably from δ-cycloene.

[0093] In addition, δ-cycloene is the compound represented by formula (3).

[0094] [Chemical Formula 5]

[0095]

[0096] These norbornene compounds, which do not have polar groups, can be used alone or in combination of two or more.

[0097] [Non-norbornene compounds without polar groups]

[0098] As non-norbornene compounds without polar groups, there are no particular limitations as long as they do not have polar groups and norbornene rings. Examples include: cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, cyclooctene, 3a,5,6,7a-tetrahydro-4,7-methylbridge-1H-indene, and cycloheptene, as well as other monocyclic cyclic alkenes and their derivatives.

[0099] Here, a derivative refers to a substance having substituents in its ring structure. Furthermore, there are no particular limitations on the substituents that can be present in the ring structure, as long as they are not polar groups; groups identical to those described in the section on [norbornene compounds without polar groups] can be used. Moreover, the ring structure of the derivative may have one or more of these substituents.

[0100] The above-mentioned non-norbornene compounds without polar groups can be used alone or in combination of two or more.

[0101] [Contains percentage]

[0102] When the content of structural unit (B) 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 also 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 (B) is above the above-mentioned lower limit, precipitation of the cyclic olefin ring-opening polymer after synthesis can be suppressed. Furthermore, if the content of structural unit (B) 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. In addition, if the content of structural unit (B) is below the above-mentioned upper limit, precipitation of the cyclic olefin ring-opening polymer after synthesis can be suppressed, and thermal deformation of the molded article caused by an excessively low glass transition temperature of the cyclic olefin ring-opening polymer hydride can be prevented.

[0103] <Other structural units>

[0104] Other structural units that can be arbitrarily included in the cyclic olefin ring-opening polymer are not particularly limited, as long as they do not impair the effects of the present invention and are structural units other than those described above (A) and (B).

[0105] [Contains percentage]

[0106] Moreover, 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 usually between 0% by mass and 60% by mass.

[0107] <Mass ratio of structural unit (A) to structural unit (B)>

[0108] 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 further preferably 90 / 10 or less, more preferably 75 / 25 or less.

[0109] <Methods for manufacturing cyclic olefin ring-opening polymers>

[0110] Cyclic olefin ring-opening polymers can be obtained by ring-opening polymerization of monomer compositions (mixtures) containing various monomers described in the "Cyclic olefin ring-opening polymer" item. Specifically, for example, cyclic olefin ring-opening polymers can be prepared by ring-opening polymerization of the above-mentioned monomer compositions using known ring-opening polymerization methods such as ring-opening polymerization utilizing a metathesis polymerization catalyst.

[0111] In addition, by performing ring-opening polymerization, the number of rings in each of the above monomers is reduced by at least one.

[0112] Here, there are no particular limitations on the catalyst used for metathesis polymerization, and known catalysts can be used. Specifically, examples include: catalyst systems composed of halides, nitrates, or acetylacetone compounds of metals selected from ruthenium, rhodium, palladium, osmium, iridium, and platinum, and a reducing agent; 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; 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. These catalysts can be used individually or in combination of two or more. The amount of catalyst used can be selected appropriately based on polymerization conditions, etc.

[0113] Furthermore, adding polar compounds to the above-mentioned catalyst system can improve the polymerization activity and the 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 α-methylpyridine. These polar compounds can be used individually or in combination of two or more. Moreover, the amount used can be appropriately selected, but the ratio to the metal in the catalyst, i.e., the polar compound / metal ratio (molar ratio), is typically in the range of 1 to 100,000, preferably 5 to 10,000.

[0114] 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 inactive in 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.

[0115] Polymerization conditions such as polymerization temperature, polymerization pressure, and polymerization time can be appropriately adjusted.

[0116] (Cyclic olefin ring-opening polymer hydride)

[0117] 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.

[0118] 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.

[0119] The 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 non-aromatic carbon-carbon unsaturated bonds in the cyclic olefin ring-opening polymer) is 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.

[0120] 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 achieving an appropriate Abbe number while further reducing the birefringence, it is preferable that they are not hydrogenated. Specifically, the hydrogenation rate of the aromatic carbon-carbon unsaturated bonds in the cyclic olefin ring-opening polymer hydride (the proportion of hydrogenated aromatic carbon-carbon 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).

[0121] 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.

[0122] 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.).

[0123] As hydrogenation catalysts, examples include: hydrogenation catalysts composed of organometallic compounds from groups 1 to 3 of the periodic table, such as dicyclopentadienyl titanium halides, organocarboxylic acids (nickel, cobalt, etc.); metal catalysts supported on carbon, silica, diatomaceous earth, etc., such as nickel, platinum, palladium, ruthenium, rhenium, and rhodium metal catalysts, as well as cobalt, nickel, rhodium, and ruthenium complexes; and hydrogenation compounds such as lithium aluminum hydride and p-toluenesulfonyl hydrazine. Among these, ruthenium compounds are preferred as hydrogenation catalysts from the viewpoint of avoiding isomerization and obtaining the target compound in high yield.

[0124] 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.

[0125] 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; and ether solvents such as tetrahydrofuran and ethylene glycol dimethyl ether.

[0126] 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. When the reaction temperature is too low, the hydrogenation rate is too slow; when the reaction temperature is too high, side reactions may occur.

[0127] Furthermore, the pressure of hydrogen is typically 0.01–20 MPa, preferably 0.05–15 MPa, and more preferably 0.1–10 MPa. When the hydrogen pressure is too low, the hydrogenation rate is too slow; when the hydrogen pressure is too high, it creates a limitation in terms of the need for a high-pressure-resistant reaction device.

[0128] Furthermore, the reaction time also depends on the scale of the reaction, but it is usually 0.1 to 10 hours.

[0129] 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.

[0130] <Structural Unit>

[0131] The structural unit (A) in the cyclic olefin ring-opening polymer hydride can include: a structural unit obtained by ring-opening polymerization of norbornene imide monomer, and a structural unit obtained by hydrogenation of the structural unit. Similarly, the structural unit (B) in the cyclic olefin ring-opening polymer hydride can include: a structural unit obtained by ring-opening polymerization of a cyclic olefin monomer without polar groups, and a structural unit obtained by hydrogenation of the structural unit. Furthermore, other structural units that can be arbitrarily included in the cyclic olefin ring-opening polymer hydride can include: a structural unit obtained by ring-opening polymerization of a cyclic olefin compound capable of forming other structural units, and a structural unit obtained by hydrogenation of the structural unit.

[0132] In addition, the structural units obtained by ring-opening polymerization of norbornene imide monomers, the structural units obtained by ring-opening polymerization of cyclic olefin monomers without polar groups, 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 hydride are all unhydrogenated structural units (repeating units) that were not hydrogenated during the hydrogenation of the cyclic olefin ring-opening polymer.

[0133] Furthermore, the proportion of structural unit (A) in the cyclic olefin ring-opening polymer hydride (the total proportion of structural units obtained by ring-opening polymerization of norbornene imide monomers to structural units obtained by hydrogenation of those structural units) is the same as the preferred proportion of structural unit (A) in the cyclic olefin ring-opening polymer described in the "Cyclic Olefin Ring-Opening Polymer" project. In addition, the proportion of structural unit (B) in the cyclic olefin ring-opening polymer hydride (the total proportion of structural units obtained by ring-opening polymerization of cyclic olefin monomers without polar groups to structural units obtained by hydrogenation of those structural units) is the same as the preferred proportion of structural unit (B) in the cyclic olefin ring-opening polymer described in the "Cyclic Olefin Ring-Opening Polymer" project. Furthermore, the proportion of other structural units that can be arbitrarily 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 obtained by hydrogenating such structural units) is the same as the preferred proportion of other structural units in the cyclic olefin ring-opening polymer described in the "cyclic olefin ring-opening polymer" project.

[0134] 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 described in the "cyclic olefin ring-opening polymer" project.

[0135] <weight-average molecular weight>

[0136] 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 further 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.

[0137] Furthermore, in this invention, the "weight-average molecular weight" can be determined using the method described in the examples.

[0138] 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).

[0139] Glass transition temperature

[0140] 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 further 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 caused by heat deformation due to 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.

[0141] 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.

[0142] Abbe numbers

[0143] The Abbe number (νd) of the cyclic olefin ring-opening polymer hydride of the present invention is preferably less than 50, more preferably 46 or less, even more 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 optical components with high Abbe numbers. Furthermore, the lower limit value of the Abbe number is not particularly limited and is typically around 20.

[0144] <Birefringence>

[0145] 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 75 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.

[0146] Furthermore, in this invention, the "birefringence" can be measured using the method described in the embodiments.

[0147] <Refractive index>

[0148] 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.

[0149] Furthermore, in this invention, the "refractive index" can be measured using the method described in the embodiments.

[0150] (Resin Composition)

[0151] 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.

[0152] 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 may be cited.

[0153] The resin composition preferably contains antioxidants such as phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants.

[0154] There are no particular limitations on the polymer materials and additives, as long as they can be sufficiently dispersed in the cyclic olefin ring-opening polymer hydride, and they can be mixed with the cyclic olefin ring-opening polymer hydride using any method. Specifically, the polymer materials and additives can be added at any stage in the preparation 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 they can be mixed with the cyclic olefin ring-opening polymer hydride in a molding device.

[0155] 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, it can be 0.01 parts by mass or more and 2.0 parts by mass or less relative to 100 parts by mass of the cyclic olefin ring-opening polymer hydride.

[0156] 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 0.01 parts by mass or more and 2.0 parts by mass or less relative to 100 parts by mass of the cyclic olefin ring-opening polymer hydride.

[0157] (Resin molded body)

[0158] 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.

[0159] Here, there are no particular limitations on the molding method as long as it can mold the resin composition, and methods such as 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 molding, extrusion molding, calendering, solution casting, hot pressing, and blow molding can be used. Among these, extrusion molding is preferred.

[0160] The resin molded body of the present invention is preferably an optical element, and more preferably a lens.

[0161] Moreover, the lens is not particularly limited. For example, it can be made by uniformly heating and dissolving the resin composition of the present invention to form a preform, then flowing the preform into a metal mold and cooling it to obtain the final product.

[0162] Example

[0163] 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" refer to quantities based on mass. Additionally, in polymers manufactured by copolymerizing multiple monomers, the proportion of structural units formed by polymerizing a particular monomer in the polymer is generally consistent with the proportion (feed ratio) of that particular monomer in all monomers used in the polymerization of the polymer, unless otherwise specified.

[0164] <Aggregation Conversion Rate>

[0165] 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.

[0166] <Hydrogenation rate>

[0167] 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.

[0168] <weight-average molecular weight>

[0169] 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) converted to polystyrene. Tetrahydrofuran (THF) was used as the elution solvent.

[0170] Glass transition temperature

[0171] The glass transition temperature (Tg) of the cyclic olefin ring-opening polymer hydride was measured using a differential scanning calorimeter (manufactured by SII Nanotechnology Co., Ltd., "DSC6220") based on JIS K7121 at a heating rate of 10 °C / min.

[0172] <Birefringence>

[0173] Using an injection molding apparatus (manufactured by FANUC Corporation, product number α-100B), the dried resin granules were injection molded at the following conditions: resin temperature: 20°C lower than the glass transition temperature of the cyclic olefin ring-opening polymer hydride (=Tg-20°C); metal mold temperature: 130°C lower than the glass transition temperature of the cyclic olefin ring-opening polymer hydride (=Tg-130°C); and cycle time: 1 minute, to obtain a flat resin molded body of 80mm×10mm×4mm.

[0174] For the obtained resin molded body, a birefringence meter (Photonic Lattice, product name: WPA-200(-L)) was used to linearly measure the retardation value of light with a wavelength of 543nm at a position 10mm from the gate on the resin molded body in the direction perpendicular to the resin flow direction. Then, the maximum value among the measured values ​​was taken as the birefringence.

[0175] <Refractive index>

[0176] Except for changing the obtained resin composition from 80mm×10mm×4mm to a sheet-like resin molded body of 50mm×50mm×5mm, the same procedure was followed as for the resin molded body obtained in the birefringence determination to obtain a sheet-like resin molded body with a thickness of 5mm. The obtained sheet-like resin molded body with a thickness of 5mm 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.

[0177] For the obtained test samples, the refractive index (nd, nC, nF) 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)). Table 1 shows the refractive index (nd) of light with a wavelength of 587.6nm.

[0178] Abbe numbers

[0179] Using the refractive indices (nd, nC, nF) obtained by the above refractive index determination at 25°C, the Abbe number (νd) is calculated according to the following formula (1).

[0180] [Mathematical Expression 1]

[0181]

[0182] (Example 1)

[0183] 60 parts of N-2,6-diisopropylphenyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (hereinafter sometimes referred to as "NBDII"), representing norbornene imide monomer as shown in formula (1), 40 parts of δ-cycloene (hereinafter sometimes referred to as "DCL"), a cyclic olefin monomer without polar groups, 2.5 parts of 1-hexene, 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), a polymerization catalyst, and 1000 parts of tetrahydrofuran, a solvent, were loaded into a nitrogen-purged glass pressure reactor. The entire contents were stirred at 65°C for 3 hours to carry out ring-opening polymerization. The obtained ring-opening polymer had a polymerization conversion rate of 96%, and the weight-average molecular weight of the obtained cyclic olefin ring-opening polymer was 21,100.

[0184] Next, the obtained polymerization reaction solution was placed in an autoclave and stirred for 6 hours at 150°C and a hydrogen pressure of 4.5 MPa to carry out the hydrogenation reaction. The solution was then filtered through a funnel pre-coated with radiolite to obtain the cyclic olefin ring-opening polymer hydrogenate.

[0185] 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%.

[0186] Next, 1 part of an antioxidant (tetramethylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate; Irganox 1010 manufactured by BASF Japan) was mixed into 100 parts of the obtained cyclic olefin ring-opening polymer hydride to obtain a resin composition containing the cyclic olefin ring-opening polymer hydride.

[0187] 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 stranded granulated body. This granulated body was then finely chopped using a strand pelletizer to obtain dried resin particles. The operating conditions of the twin-screw extruder are as follows.

[0188] • Barrel set temperature: 270℃~280℃

[0189] • Die head set temperature: 250℃

[0190] Screw speed: 145 rpm

[0191] • Feeder speed: 50 rpm

[0192] (Example 2)

[0193] In Example 1, 70 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 NBDII as the norbornene imide monomer represented by formula (1), and the amount of DCL was changed from 40 parts to 30 parts. Otherwise, the same procedure as in Example 1 was followed to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, resin compositions, and resin particles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0194] (Example 3)

[0195] In Example 1, the amount of NBDII was changed from 60 parts to 90 parts, and the amount of DCL was changed from 40 parts to 10 parts. Otherwise, the same procedure as in Example 1 was followed to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin particles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0196] (Example 4)

[0197] In Example 2, the amount of NBXI was changed from 70 parts to 50 parts, and the amount of DCL was changed from 30 parts to 50 parts. Otherwise, the same procedure as in Example 2 was followed to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin particles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0198] (Example 5)

[0199] In Example 1, 60 parts of N-2-methylphenyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (hereinafter sometimes simply referred to as "NBTI") were used instead of 60 parts of NBDII as the norbornene imide monomer represented by formula (1), and the amount of DCL was changed from 40 parts to 20 parts. In addition to DCL, 20 parts of 2-ethylidene-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (hereinafter sometimes simply referred to as "ETD") were further used as a cyclic olefin monomer without polar groups. Otherwise, the same procedure as in Example 1 was followed to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin particles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0200] (Example 6)

[0201] In Example 5, the amount of NBTI was changed from 60 parts to 75 parts, the amount of ETD was changed from 20 parts to 25 parts, and the amount of 1-hexene was changed from 2.5 parts to 1.0 part. DCL was not used. Otherwise, the process was the same as in Example 1 to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin particles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0202] (Example 7)

[0203] In Example 4, the amount of NBXI was changed from 50 parts to 49 parts, the amount of DCL was changed from 50 parts to 51 parts, and the amount of 1-hexene was changed from 2.5 parts to 2.0 parts. Otherwise, the same procedure as in Example 4 was followed to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin particles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0204] (Example 8)

[0205] In Example 7, the amount of NBXI was changed from 49 parts to 60 parts, the amount of DCL was changed from 51 parts to 40 parts, and the amount of 1-hexene was changed from 2.0 parts to 0.5 parts. Otherwise, the same procedure as in Example 7 was followed to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin particles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0206] (Example 9)

[0207] In Example 7, the amount of NBXI was changed from 49 parts to 60 parts, the amount of DCL was changed from 51 parts to 40 parts, and the amount of 1-hexene was changed from 2.0 parts to 0.25 parts. Otherwise, the same procedure as in Example 7 was followed to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin particles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0208] (Example 10)

[0209] In Example 7, the amount of NBXI was changed from 49 parts to 56 parts, the amount of DCL was changed from 51 parts to 44 parts, and the amount of 1-hexene was changed from 2.0 parts to 0.24 parts. Otherwise, the same procedure as in Example 7 was followed to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin particles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0210] (Example 11)

[0211] In Example 7, the amount of NBXI was changed from 49 parts to 56 parts, the amount of DCL was changed from 51 parts to 44 parts, and the amount of 1-hexene was changed from 2.0 parts to 0.18 parts. Otherwise, the same procedure as in Example 7 was followed to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin particles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0212] (Example 12)

[0213] In Example 7, the amount of NBXI was changed from 49 parts to 56 parts, the amount of DCL was changed from 51 parts to 44 parts, and the amount of 1-hexene was changed from 2.0 parts to 0.1 parts. Otherwise, the same procedure as in Example 7 was followed to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin particles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0214] (Comparative Example 1)

[0215] In Example 1, the amount of NBDII was changed from 60 parts to 100 parts, and DCL was not used. Otherwise, the same procedure as in Example 1 was followed to produce a cyclic olefin ring-opening polymer. Because the polymerization reaction solution containing the cyclic olefin ring-opening polymer contained precipitates, it was impossible to determine the weight-average molecular weight or to hydrogenate the cyclic olefin ring-opening polymer. Therefore, various measurements and evaluations could not be performed.

[0216] (Comparative Example 2)

[0217] In Example 1, 60 parts of NBDII and 40 parts of DCL were replaced with 100 parts of ETD, a cyclic olefin monomer without polar groups. Otherwise, the same procedure as in Example 1 was followed to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin particles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0218] (Comparative Example 3)

[0219] In Example 6, 75 parts of N-phenyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (hereinafter sometimes simply referred to as "NBPI"), which is a norbornene imide monomer with a phenyl bonded to the imide ring (i.e., a norbornene imide monomer where R1 and R5 are both hydrogen atoms), were used instead of 75 parts of NBTI, which is the norbornene imide monomer represented by formula (1). The amount of 1-hexene was changed from 1.0 parts to 0.75 parts. Otherwise, the same procedure as in Example 6 was followed to produce cyclic olefin ring-opening polymers, cyclic olefin ring-opening polymer hydrides, and resin particles. Various measurements and evaluations were then performed. The results are shown in Table 1.

[0220] [Table 1]

[0221]

[0222] As shown in Table 1, the cyclic olefin ring-opening polymer hydrides of Examples 1 to 12, which contain structural units (A) from the norbornene imide monomer represented by formula (1) and structural units (B) from the cyclic olefin monomer without polar groups, have both moderate Abbe numbers and low birefringence.

[0223] On the other hand, as shown in Table 1, the cyclic olefin ring-opening polymer hydride of Comparative Example 2, which does not contain the structural unit (A) from the norbornene imide monomer represented by Formula (1), has an excessively large Abbe number and a high birefringence. Furthermore, as shown in Table 1, the cyclic olefin ring-opening polymer hydride of Comparative Example 3, which replaces the structural unit (A) from the norbornene imide monomer represented by Formula (1) and contains the structural unit from the norbornene imide monomer with phenyl groups bonded to the imide ring at both ortho positions, has a moderately large Abbe number but a high birefringence.

[0224] Industrial availability

[0225] According to the present invention, it is possible to provide a cyclic olefin ring-opening polymer hydride and its raw materials that have both a moderate Abbe number and a low birefringence.

[0226] Furthermore, according to the present invention, it is possible 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.

Claims

1. A cyclic olefin ring-opening polymer comprising a structural unit (A) derived from a norbornene imide monomer represented by formula (1) and a structural unit (B) derived from a cyclic olefin monomer without a polar group, In formula (1), A represents an alkyl, cycloalkyl, alkoxy, or aryl group capable of having substituents, wherein, This excludes phenyl groups whose two adjacent positions are unsubstituent based on the bonded imide ring.

2. The cyclic olefin ring-opening polymer according to claim 1, wherein, The structural unit (A) is derived from the structural unit of the norbornene imide monomer represented by the following formula (2). In formula (2), 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. Two or more of R1 to R5 can be bonded to form a ring, wherein at least one of R1 and R5 is not a hydrogen atom.

3. The cyclic olefin ring-opening polymer according to claim 1, wherein, The structural unit (A) contains 50% by mass or more and 90% by mass or less.

4. The cyclic olefin ring-opening polymer according to claim 1, wherein, The structural unit (B) comprises structural units derived from δ-cycloenes.

5. A cyclic olefin ring-opening polymer hydride, which is obtained by hydrogenating the cyclic olefin ring-opening polymer of claim 1.

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

7. The cyclic olefin ring-opening polymer hydride according to claim 5, wherein, The glass transition temperature of the cyclic olefin ring-opening polymer hydride is above 120°C.

8. A resin composition comprising the cyclic olefin ring-opening polymer hydride of any one of claims 5 to 7.

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

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