WO2020137709A1 - Cyclic olefin copolymer for optical member, cyclic olefin copolymer composition for optical member, and molded article - Google Patents

Abstract

This cyclic olefin copolymer for an optical member is a cyclic olefin copolymer that has an aromatic ring and contains a structural unit (A) shown in specific formula (III).

Description

Cyclic olefin copolymer for optical member, cyclic olefin copolymer composition for optical member, and molded article

The present invention relates to a cyclic olefin copolymer for optical members, a cyclic olefin copolymer composition for optical members, and a molded product.

In recent years, in optical materials such as mobile phones and camera lenses for automobiles, the development of resins with excellent optical properties that can substitute for glass is progressing. In addition, among the glass-substituting resins, attention is focused on cyclic olefin ring-opening polymer hydrides and cyclic olefin addition copolymers, which have lower water absorption and less dimensional change than resins such as PC (polycarbonate) and PMMA (polymethyl methacrylate). There is.

For example, regarding hydrogenated cyclic olefin ring-opening polymer, in Patent Document 1 and Patent Document 2, high refractive index, yellowing resistance, and moldability are obtained by ring-opening metathesis polymerization of tetracyclododecene and a monomer derived from a norbornene compound. Excellent resins are mentioned. Further, Patent Document 3 describes that a resin having good breaking strength can be obtained by ring-opening metathesis polymerization of a 3-membered cyclopentene monomer. In Patent Document 4, a precision optical lens made of a norbornene-based resin having an aromatic ring of 1 molar equivalent/200 g or more and a weight average molecular weight of 25,000 to 45,000 has excellent moldability and mechanical strength even if the thickness is small. It is said to be excellent. Regarding the production of a hydride of a cyclic olefin ring-opening polymer, Patent Document 5 discloses that an aliphatic carbon-carbon double bond in a polymer obtained by polymerizing a polycyclic norbornene-based monomer having three or more rings. Is described using a specific hydrogenation catalyst to produce a polymer hydride.

JP 2007-137935A International Publication No. 2016/052302 International Publication No. 2017/051819 JP, 2007-206363, A JP, 2006-063141, A

However, according to the studies by the present inventors, a cyclic olefin copolymer capable of obtaining a molded product having a high glass transition temperature and a high refractive index cannot be obtained by the technique disclosed above. There wasn't. The present invention has been made in view of such circumstances. That is, the present invention provides a cyclic olefin copolymer for optical members, which has a high glass transition temperature, a high refractive index, a small amount of birefringence, and is capable of obtaining a molded body with little discoloration due to heat. Is.

The inventors of the present invention have conducted extensive studies and found that the above problem can be solved by a cyclic olefin copolymer containing a specific structural unit (A) having an aromatic ring.

That is, according to the present invention, there are provided the following cyclic olefin copolymer for optical members, cyclic olefin copolymer composition for optical members, and molded products.

[1]
A cyclic olefin copolymer having an aromatic ring,
A cyclic olefin copolymer for optical members, which comprises the structural unit (A) of the following (III).

(In the above formula (III), n is 0, 1 or 2, m is 1, 2 or 3, and R ⁵⁵ to R ⁶⁸ are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or fluorine. A hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding atoms, and when m=1, R ⁶⁵ and R ⁶⁷ , R ⁶⁷ and R ⁶⁸ , R ⁶⁸ and R ⁶⁶ are mutually They may be bonded to each other to form a monocycle or a polycycle, and when m=2 or 3, R ⁶⁵ and R ⁶⁵ , R ⁶⁵ and R ⁶⁷ , R ⁶⁷ and R ⁶⁸ , R ⁶⁸ and R ⁶⁶ , R ^66. And R ⁶⁶ may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic or polycyclic ring may have a double bond, and the monocyclic or polycyclic ring may be aromatic. It may be a group ring.)
[2]
In the cyclic olefin copolymer described in [1],
A cyclic olefin copolymer for optical members, wherein the content of the structural unit (A) is 0.2 mol% or more and 100 mol% or less.
[3]
In the cyclic olefin copolymer according to [1] or [2],
Further, a cyclic olefin copolymer for optical members, which contains a structural unit (B) derived from an olefin having 2 to 20 carbon atoms.
[4]
In the cyclic olefin copolymer described in [3],
The cyclic olefin copolymer for optical members, wherein the structural unit (B) has an alicyclic structure.
[5]
In the cyclic olefin copolymer according to [3] or [4],
When the total content of the structural unit (A) and the structural unit (B) is 100 mol %, the content of the structural unit (A) in the cyclic olefin copolymer is 0.5 mol% or more and 100 or more. A cyclic olefin copolymer for optical members, which is at most mol %.
[6]
In the cyclic olefin copolymer described in any one of [1] to [5],
A cyclic olefin copolymer for optical members, wherein the glass transition temperature (Tg) of the cyclic olefin copolymer is 100° C. or more and 200° C. or less as measured by a differential scanning calorimeter (DSC).
[7]
In the cyclic olefin copolymer according to any one of [1] to [6],
When a 3.0 mm-thick injection-molded sheet made of the cyclic olefin copolymer is prepared, the injection-molded sheet has a refractive index of 1.534 to 1.590 at a wavelength of 589 nm. Polymer.
[8]
In the cyclic olefin copolymer according to any one of [1] to [7],
A cyclic olefin copolymer for optical members, which has an Abbe number (ν) of the injection molded sheet of 30 or more and 55 or less when an injection molded sheet of 3.0 mm in thickness made of the cyclic olefin copolymer is prepared.
[9]
The cyclic olefin copolymer according to any one of [1] to [8],
The cyclic olefin copolymer for optical members, wherein the structural unit (A) is derived from benzonorbornadiene.
[10]
A cyclic olefin copolymer composition for optical members, which comprises the cyclic olefin copolymer for optical members according to any one of [1] to [9].
[11]
A molded product containing the cyclic olefin copolymer for an optical member according to any one of [1] to [10].
[12]
The molded product according to [11], which is an optical lens.

According to the present invention, a cyclic olefin copolymer for optical members, which has a high glass transition temperature, a high refractive index, a small birefringence amount, and is capable of obtaining a molded product with little discoloration due to heat, for optical members A cyclic olefin copolymer composition and a molded product can be provided.

Hereinafter, the present invention will be described based on the embodiments. In the present embodiment, “A to B” indicating a numerical range indicates A or more and B or less unless otherwise specified.

[Cyclic olefin copolymer]
First, the cyclic olefin copolymer (P) for optical members according to the present embodiment will be described.
The cyclic olefin copolymer for optical members (P) according to this embodiment is a cyclic olefin copolymer having an aromatic ring, and is a cyclic olefin copolymer containing a structural unit (A). According to the cyclic olefin copolymer for an optical member of the present invention, by containing the structural unit (A) having an aromatic ring, it has the properties generally required for an optical member, the glass transition temperature is high, and the refractive index is high. It becomes a cyclic olefin copolymer for optical members which can obtain a high molded product.
The cyclic olefin copolymer (P) according to the invention of the present application is a cyclic olefin copolymer (P) for optical members, and the above-mentioned properties generally required for optical members are, specifically, Good moldability means that the molded product has high transparency and appropriate Abbe number and density.
Hereinafter, the cyclic olefin copolymer for optical members is also simply referred to as a cyclic olefin copolymer.

The structural unit (A) according to this embodiment will be described below.
The structural unit (A) according to this embodiment includes the following structural unit (III).

In the above formula (III), n is 0, 1 or 2, and m is 1, 2 or 3. R ⁵⁵ to R ⁶⁸ are each independently a hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom. When m=1, R ⁶⁵ and R ⁶⁷ , R ⁶⁷ and R ⁶⁸ , and R ⁶⁸ and R ⁶⁶ may be bonded to each other to form a monocyclic or polycyclic ring. ⁶⁵ and R ⁶⁵ , R ⁶⁵ and R ⁶⁷ , R ⁶⁷ and R ⁶⁸ , R ⁶⁸ and R ⁶⁶ , and R ⁶⁶ and R ⁶⁶ may be bonded to each other to form a monocycle or a polycycle. The polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

In addition, examples of the hydrocarbon group having 1 to 20 carbon atoms include, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group, each independently. To be More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group, and the cycloalkyl group includes cyclohexyl. Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a naphthyl group, a benzyl group and a phenylethyl group, or an aralkyl group. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.
The general formula (III) includes each resonance structure.

Among these, the structural unit (A) according to the present embodiment is preferably a structural unit derived from benzonorbornadiene, for example.

The structural unit derived from benzonorbornadiene specifically means a structural unit represented by the following formula (A-3).
That is, the structural unit (A) according to this embodiment is preferably a structural unit represented by the following formula (A-3).

(Structural unit (B) derived from olefin having 2 to 20 carbon atoms)
The cyclic olefin copolymer according to this embodiment may also include an olefin-derived structural unit (B) having 2 to 20 carbon atoms. The structural unit (B) can be a structural unit derived from a cyclic olefin having no aromatic ring.

The structural unit (B) preferably has an alicyclic structure. When the structural unit (B) has an alicyclic structure, a cyclic olefin copolymer for an optical member can be obtained which has a high glass transition temperature and a high refractive index.
Further, the structural unit (B) more preferably has a 5-membered alicyclic structure. When the structural unit (B) is a structural unit having a 5-membered alicyclic structure, the time required for the reaction to form the structural unit (A) and the time required for the reaction to form the structural unit (B) are Since they can be made to be approximately the same, a cyclic olefin copolymer having the structural unit (A) and the structural unit (B) can be efficiently produced, which is preferable in terms of production.

The structural unit (B) according to the present embodiment has the following formula (B- from the viewpoint of a cyclic olefin copolymer for an optical member, which can give a molded product having a high glass transition temperature and a high refractive index. It preferably contains a structural unit derived from the compound represented by 1).

(In the above formula [B-1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ¹ to R ¹⁸ and R ^a and R ^b are respectively Independently, it is a hydrogen atom, a halogen atom or a hydrocarbon group which may be substituted with a halogen atom, R ¹⁵ to R ¹⁸ may be bonded to each other to form a monocyclic ring or a polycyclic ring, and The monocycle or polycycle may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group, including an aromatic ring. Absent.)

Among these, as the structural unit (B) according to the present embodiment, a structural unit derived from bicyclo[2.2.1]-2-heptene (abbreviation: NB), tetracyclo[4.4.0.1 ^{2] , 5} . 1 ^7,10] -3-dodecene (abbreviation: TD) structural units derived from, hexacyclo ^{[6,6,1,1 3,6,} 1 ^10,13, 0 ^{2,7, 0 9,14]} heptadecene - 4, a structural unit derived from ethyl norbornene (abbreviation: ENB), a structural unit derived from dicyclopentadiene (abbreviation: DCPD), a structural unit derived from a hydride of DCPD and tricycloundecene (abbreviation) TCU, 1,4,4a,5,6,7,8,8a-Octahydro-1,4-methanonaphthalene) is preferably contained at least one structural unit selected from structural units derived from 2.2.1]-2-Heptene-derived structural units and tetracyclo[4.4.0.1 ^2,5 . It is more preferable to include at least one structural unit selected from structural units derived from 1 ^7,10 ]-3-dodecene, and tetracyclo[4.4.0.1 ^2,5 . It is particularly preferable to include a structural unit derived from 1 ^7,10 ]-3-dodecene.

In addition, tetracyclo[4.4.0.1 ^2,5 . The structural unit derived from 1 ^7,10 ]-3-dodecene specifically means a structural unit represented by the following formula (B-2). That is, the structural unit (B) according to this embodiment preferably contains a structural unit represented by the following formula (B-2).

The structural unit derived from DCPD specifically means a structural unit represented by the following formula (B-3) or formula (B-4).

In the cyclic olefin copolymer (P) according to this embodiment, the content of the structural unit (A) is preferably 0.2 mol% or more and 100 mol% or less, and 3 mol% or more and 100 mol% or less. Is more preferable, and more preferably 8 mol% or more and 80 mol% or less.

In the cyclic olefin copolymer (P), when the total content of the structural unit (A) and the structural unit (B) is 100 mol %, the structural unit (A in the cyclic olefin copolymer is Is preferably 0.5 mol% or more and 100 mol% or less, more preferably 3 mol% or more and 100 mol% or less, and further preferably 8 mol% or more and 80 mol% or less. ..
In the present embodiment, the content of the structural unit (A) and the structural unit (B) can be measured by, for example, ¹ H-NMR or ¹³ C-NMR.
By using the content of each structural unit contained in the cyclic olefin copolymer (P) within the above numerical range, an optical member for which a molded product having a high glass transition temperature and a high refractive index can be obtained It can be a cyclic olefin copolymer.

In the cyclic olefin copolymer (P) according to this embodiment, the aromatic ring content is preferably 0.01 mol% or more and 71 mol% or less, and 0.1 mol% or more and 65 mol% or less. Is more preferable, and more preferably 0.2 mol% or more and 60 mol% or less. The content of the aromatic ring was calculated by calculating the peak area of the hydrogen peak derived from the aromatic ring (6.7 to 7.3 ppm) with respect to the total area of all the hydrogen derived peaks detected by ¹ H-NMR. Desired.
By setting the content of the aromatic ring contained in the cyclic olefin copolymer (P) within the above numerical range, it is possible to obtain a molded article having a high glass transition temperature and a high refractive index. It can be an olefin copolymer.

The copolymerization type of the cyclic olefin copolymer (P) according to the present embodiment is not particularly limited, but examples thereof include a random copolymer and a block copolymer. In the present embodiment, the cyclic olefin copolymer according to the present embodiment (from the viewpoint of a glass olefin copolymer having a high glass transition temperature and capable of obtaining a molded product having a high refractive index for an optical member) P) is preferably a random copolymer.

[Method for producing cyclic olefin copolymer]
The method for producing the cyclic olefin copolymer (P) according to this embodiment is not particularly limited as long as the cyclic olefin copolymer containing the structural unit (A) of (III) above can be obtained. It can be obtained by a step of obtaining a body polymer (precursor polymer polymerization step) and a step of partially hydrogenating the obtained precursor polymer (partial hydrogenation step).
That is, it is common to carry out a hydrogenation step in the production of a cyclic olefin ring-opening polymer. Further, in the case of passing through the hydrogenation step, even if the raw material monomer or the precursor polymer as an intermediate has an aromatic ring (for example, a benzyl group), the benzyl group is reduced to a cyclohexane group in the hydrogenation step. Therefore, no aromatic ring remained in the obtained cyclic olefin copolymer. The cyclic olefin copolymer (P) according to the present invention uses, for example, a monomer having a benzyl functional group as a raw material, is partially hydrogenated, and has a main chain of the cyclic olefin copolymer and side chains of benzyl. A cycloolefin copolymer for an optical member, which is capable of obtaining a molded product having a high glass transition temperature and a high refractive index by obtaining a cycloolefin copolymer containing a specific structural unit (A) having a group It is thought that it can be realized.

[Precursor polymer polymerization step]
The precursor polymer according to this embodiment is disclosed in, for example, JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, JP-A-61-115916, and JP-A-61-115916. JP-A-61-271308, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407, JP-A-2007-314806, JP-A-2010-241932, etc. It can be produced by appropriately selecting the conditions according to the method of.

[Partial hydrogenation process]
The method of partially hydrogenating the obtained precursor polymer is described in, for example, Stephen F. Hahn,
An Improvmnet Method for the Diimide Hydrogenation of Butadiene and Isoprene Contining Polymers, 19 high-pressure slurries and Journal of Polymer syr.

The glass transition temperature (Tg) of the cyclic olefin copolymer (P) according to the present embodiment, which is measured by a differential scanning calorimeter (DSC), has good heat resistance while maintaining good transparency of the obtained molded article. From the viewpoint of further improvement, the temperature is preferably 80° C. or higher and 200° C. or lower, more preferably 100° C. or higher and 190° C. or lower, and further preferably 110° C. or higher and 180° C. or lower.

The intrinsic viscosity [η] (in decalin at 135° C.) of the cyclic olefin copolymer (P) according to the present embodiment is, for example, 0.05 to 5.0 dl/g, preferably 0.1 to 4.0 dl/g. g, more preferably 0.2 to 2.0 dl/g, and particularly preferably 0.3 to 1.0 dl/g.
When the intrinsic viscosity [η] is not less than the above lower limit, the mechanical strength of the molded product can be improved. Further, when the intrinsic viscosity [η] is not more than the above upper limit value, the moldability can be improved.

[Cyclic Olefin Copolymer Composition]
The cyclic olefin copolymer composition for optical members according to the present embodiment contains the cyclic olefin copolymer for optical members (P) according to the present embodiment, and, if necessary, the cyclic olefin copolymer for optical members (P Other components other than) may be included. In the present embodiment, even when the cyclic olefin copolymer composition for optical members according to the present embodiment contains only the cyclic olefin copolymer (P) for optical members, the cyclic olefin copolymer composition for optical members is also included. Call.

Further, the content of the cyclic olefin copolymer for optical members (P) in the cyclic olefin copolymer composition for optical members according to the present embodiment depends on the transparency, heat resistance, and density of the obtained molded product. From the viewpoint of further improving the performance balance, when the total amount of the cyclic olefin copolymer composition for optical members is 100% by mass, preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more. It is 100 mass% or less, more preferably 80 mass% or more and 100 mass% or less, and particularly preferably 90 mass% or more and 100 mass% or less.
The cyclic olefin copolymer composition for optical members according to the present embodiment contains the cyclic olefin copolymer (P) for optical members in the above ratio, and thus has a high glass transition temperature and a high refractive index. It becomes possible to gain a body.

(Other ingredients)
The cyclic olefin copolymer composition according to the present embodiment, if necessary, a weather resistance stabilizer, a heat resistance stabilizer, an antioxidant, a hydrophilic stabilizer, a metal deactivator, a hydrochloric acid absorbent, an antistatic agent, Flame retardants, slip agents, anti-blocking agents, anti-fog agents, lubricants, natural oils, synthetic oils, waxes, organic or inorganic fillers, etc. can be added to such an extent that the object of the present invention is not impaired, and the mixing ratio thereof. Is an appropriate amount.

The cyclic olefin copolymer composition according to the present embodiment may include a hindered amine compound [C], if necessary.
As the hindered amine compound [C] (hereinafter, also simply referred to as compound [C] or [C]), a hindered amine structure (specifically, a partial structure represented by the following formula (b1)) is used. A compound having one or two or more can be appropriately used.
In formula (b1), * represents a bond with another chemical structure.

As the compound [C], specifically, a compound known as a known hindered amine light stabilizer (Hindered Amine Light Stabilizers: HALS) can be used.

Examples of the compound [C] include hindered amine compounds described in paragraphs 0058 to 0082 of WO 2006/112434, hindered amine compounds described in paragraphs 0124 to 0186 of WO 2008/047468, and international publication nos. Examples thereof include the piperidine derivatives or salts thereof described in paragraphs 0187 to 0226 of 2008/047468, and the polyamine derivatives or salts thereof described in JP-A-2006-321793.

Also, Chimassorb 2020, Chimassorb 944, Tinuvin 622, Tinuvin PA144 Tinuvin 765, Tinuvin 770 (above, manufactured by BASF), Cyasorb UVs-Cyorb UV-3853, Cyasorb UVs-Cab, Cyasorb UVs-Cab, Cyasorb UVs-Cab, Cyasorb UVs-Cab, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs, Cyasorb UVs-Cabs. Made), Adeka Stab LA-52, Adeka Stab LA-57, Adeka Stab LA-63P, Adeka Stub LA-68, Adeka Stub LA-72, Adeka Stub LA-77Y, Adeka Stub LA-81, Adeka Stab LA-82, Adeka Stab LA-87, Adeka Stab LA-87 and above. A commercial product such as ADEKA) can be used.

In this embodiment, the compound [C] is preferably a compound having a structural unit represented by the following general formula (b2).
The compound is typically a polymer or oligomer. By using a compound [C] that is a polymer or an oligomer, such as this compound, it is considered that the compatibility with the cyclic olefin copolymer (P) can be increased and the composition can be made more uniform. In addition, it is considered that the structure does not easily change into a structure having characteristic absorption by irradiation. It is considered that this makes it possible to further reduce discoloration due to electron beam or gamma ray irradiation, and to reduce generation of radicals due to electron beam or gamma ray irradiation.

In the general formula (b2), X ₁ and X ₂ each independently represent a divalent linking group.
Examples of the divalent linking group for X ₁ and X ₂ include an alkylene group, a cycloalkylene group, an arylene group, and a group in which these groups are linked. Among these, an alkylene group is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is more preferable.
As the compound having the structural unit represented by the general formula (b2), a commercially available product may be used, or the compound may be obtained by polycondensing a corresponding diol, dicarboxylic acid or the like.

About compound [C], only 1 type may be used and 2 or more types may be used.
The content of the compound [C] in the composition is, for example, 0.01 to 2.0 parts by mass, preferably 0.05 to 1 when the content of the cyclic olefin copolymer (P) is 100 parts by mass. 0.5 parts by mass, more preferably 0.10 to 1.0 parts by mass. Within this range, discoloration due to electron beam or gamma ray irradiation, generation of radicals, etc. can be effectively reduced while maintaining other performances (for example, moldability and mechanical strength).

The cyclic olefin copolymer composition according to the present embodiment may contain a phosphorus compound [D], if necessary.
There is no particular limitation on the phosphorus compound [D] that can be used (hereinafter, also simply referred to as the compound [D] or [D]). For example, a known phosphorus-based antioxidant can be used.

The phosphorus-based antioxidant is not particularly limited, and conventionally known phosphorus-based antioxidants (for example, phosphite-based antioxidants) can be used.
Specifically, triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, tris(nonylphenyl)phosphite, tris(dinonylphenyl)phosphite, tris(2,4-di-t-butylphenyl) ) Phosphite, tris(2-t-butyl-4-methylphenyl)phosphite, tris(cyclohexylphenyl)phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, 9 ,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10- Monophosphite compounds such as phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene; 4,4'-butylidene-bis(3-methyl-6-) t-butylphenyl-di-tridecylphosphite), 4,4'-isopropylidene-bis(phenyl-di-alkyl(C12-C15)phosphite), 4,4'-isopropylidene-bis(diphenylmonoalkyl) (C12-C15) phosphite), 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane, tetrakis(2,4-di-t-butyl) Phenyl)-4,4'-biphenylenediphosphite, cyclic neopentanetetraylbis(isodecylphosphite), cyclic neopentanetetraylbis(nonylphenylphosphite), cyclic neopentanetetraylbis(2 ,4-di-t-butylphenylphosphite), cyclic neopentanetetraylbis(2,4-dimethylphenylphosphite), cyclic neopentanetetraylbis(2,6-di-t-butylphenylphosphite) And a diphosphite compound such as phyto).

The compound [D] used preferably is a trivalent organic phosphorus compound. More specifically, the compound [D] is a compound having a structure in which three hydrogen atoms of phosphorous acid (P(OH) ₃ ) are each substituted with the same or different organic groups.
More specifically, the compound [D] is preferably a compound represented by the following general formula (c1), (c2) or (c3).

In the general formulas (c1), (c2) and (c3),
R ¹ independently represents an alkyl group when a plurality of R ^1's are present,
R ^2's each independently represent an aromatic group when a plurality of R ^2's are present;
R ³ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group,
X represents a single bond or a divalent linking group.

The alkyl group of R ¹ preferably has 1 to 10 carbon atoms, and more preferably a t-butyl group.
Examples of the aromatic group of R ² include a phenyl group, a naphthyl group, a group in which these are substituted with an alkyl group and the like.
The carbon number of R ³ is preferably 1 to 30, more preferably 3 to 20, and further preferably 6 to 18.
R ³ is preferably an aryl group or an aralkyl group, and more preferably an aralkyl group. These aryl groups or aralkyl groups may be further substituted with a substituent (for example, an alkyl group having 1 to 6 carbon atoms or a hydroxy group).
When X is a divalent linking group, specific examples thereof include an alkylene group (such as a methylene group) and an ether group (—O—). X is preferably a single bond.

About compound [D], only 1 type may be used and 2 or more types may be used.
The content of the compound [D] in the composition is, for example, 0.01 to 1.5 parts by mass, preferably 0.02 to 1.2, when the amount of the cyclic olefin copolymer (P) is 100 parts by mass. It is 0 part by mass, more preferably 0.05 to 0.5 part by mass. Within this range, discoloration due to electron beam or gamma ray irradiation, generation of radicals, etc. can be effectively reduced while maintaining other performances (for example, moldability and mechanical strength).

On the other hand, as another viewpoint, when the amount of the cyclic olefin copolymer (P) is 100 parts by mass, the content of the phosphorus compound [D] is 100 parts by mass of the content of the cyclic olefin copolymer (P). Is less than 0.05 part by mass, more preferably 0.03 part by mass or less, still more preferably 0.02 part by mass or less.

The cyclic olefin copolymer composition according to the present embodiment may include a phenolic stabilizer as a weathering stabilizer, if necessary.
Examples of the phenolic stabilizer include 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(methylene-2,4,6-triyl) Tri-p-cresol, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl)benzylbenzene, pentaerythritol tetrakis[3-(3,5 -Di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di- tert-butyl-4-hydroxyphenyl)propionate] and other hindered phenolic stabilizers; 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate , 2,4-di-t-amyl-6-(1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl)phenyl acrylate and the like are disclosed in JP-A-63-179953 and JP-A-1. Acrylate-based phenol compounds described in JP-A-168643; 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, octadecyl-3-(3 5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 4,4'-butylidene-bis(6-t-butyl-) m-cresol), 4,4′-thiobis(3-methyl-6-t-butylphenol), bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane, 3,9-bis(2-(3 -(3-t-Butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,1 ,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-) Hydroxybenzyl)benzene, tetrakis(methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenylpropionate)methane [ie pentaerythrimethyl-tetrakis(3-(3,5- Di-t-butyl-4-hydroxyphenylpropionate)], triethylene glycol bis(3-(3-t -Butyl-4-hydroxy-5-methylphenyl)propionate), an alkyl-substituted phenolic compound such as tocophenol; 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bisoctylthio -1,3,5-triazine, 6-(4-hydroxy-3,5-dimethylanilino)-2,4-bisoctylthio-1,3,5-triazine, 6-(4-hydroxy-3- Methyl-5-t-butylanilino)-2,4-bisoctylthio-1,3,5-triazine, 2-octylthio-4,6-bis-(3,5-di-t-butyl-4-oxyanilino) And triazine group-containing phenolic compounds such as -1,3,5-triazine; and the like.
The content of the phenolic stabilizer is preferably less than 0.05 parts by mass, more preferably 0.03 parts by mass or less, and further preferably, when the content of the cyclic olefin copolymer (P) is 100 parts by mass. It is 0.02 parts by mass or less.

The cyclic olefin copolymer composition according to the present embodiment is a method in which the cyclic olefin copolymer (P) and other components are melt-kneaded using a known kneading device such as an extruder and a Banbury mixer; A method of dissolving the polymer (P) and the other components in a common solvent and then evaporating the solvent; a method of adding a solution of the cyclic olefin copolymer (P) and the other components to a poor solvent to cause precipitation; and the like. Can be obtained.

[Molded body]
The molded product according to the present embodiment is a molded product containing the cyclic olefin copolymer for optical members (P) according to the present embodiment.

Further, the content of the cyclic olefin copolymer for optical members (P) in the molded body according to the present embodiment is 100% by mass of the entire molded body from the viewpoint of further improving the performance balance of the molded body. Is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, further preferably 80% by mass or more and 100% by mass or less, particularly preferably 90% by mass. % To 100% by mass.

The molded product according to this embodiment can be obtained by molding a resin composition containing the cyclic olefin copolymer (P) into a predetermined shape. The method of molding the resin composition containing the cyclic olefin copolymer (P) to obtain a molded product is not particularly limited, and a known method can be used. Depending on its application and shape, for example, extrusion molding, injection molding, compression molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calender molding, foam molding, etc. Is applicable. Among these, the injection molding method is preferable from the viewpoint of moldability and productivity. The molding conditions are appropriately selected depending on the purpose of use or the molding method. For example, the resin temperature in injection molding is usually 150°C to 400°C, preferably 200°C to 350°C, more preferably 230°C to 330°C. The range is appropriately selected.

In the cyclic olefin copolymer (P) according to the present embodiment, when a molded product made of the cyclic olefin copolymer (P) is produced, the density measured by the water substitution method at 23° C. based on JIS K7112 is: It is preferably 1.010 g/cm ³ or more and 1.090 g/cm ³ or less, more preferably more than 1.020 g/cm ³ and 1.090 g/cm ³ or less, still more preferably 1.030 g/cm ³ or more 1. 090 g/cm ³ or less, and even more preferably 1.040 g/cm ³ or more and 1.090 g/cm ³ or less.

Further, in the cyclic olefin copolymer (P) according to the present embodiment, from the viewpoint of further improving the transparency of the obtained molded product, an injection-molded sheet made of the cyclic olefin copolymer (P) and having a thickness of 3.0 mm The haze of the injection-molded sheet measured in accordance with JIS K7136 is preferably less than 5%.

In the cyclic olefin copolymer (P) according to the present embodiment, when a 3.0 mm-thick injection molded sheet made of the cyclic olefin copolymer (P) is produced, the injection molding is measured according to ASTM D542. The refractive index (nd) at a wavelength of 589 nm of the sheet is preferably 1.534 or more and 1.590 or less, preferably 1.538 or more and 1.590 or less, and more preferably 1.540 or more and 1.590 or less. ..

When the refractive index is within the above range, the molded product obtained by using the cyclic olefin copolymer (P) according to the present embodiment can have a thinner thickness while maintaining good optical characteristics.
In the optical member, the optical design requires precision in controlling the refractive index, and it may be controlled up to the third and fourth digits after the decimal point. In the cyclic olefin copolymer (P) according to this embodiment, the required refractive index can be precisely controlled.

Further, in the cyclic olefin copolymer (P) according to the present embodiment, from the viewpoint of adjusting the Abbe number (ν) of the obtained molded product to a more suitable range, the thickness of the cyclic olefin copolymer (P) When a 3.0 mm injection-molded sheet is produced, the Abbe number (ν) of the injection-molded sheet is preferably 30 or more and 55 or less, more preferably 33 or more and 53 or less, and further preferably 35 or more and 51 or less.
The Abbe number (ν) of the injection-molded sheet can be calculated from the refractive index of the injection-molded sheet at 23° C. at wavelengths of 486 nm, 589 nm and 656 nm using the following formula.
ν=(nD-1)/(nF-nC)
nD: Refractive index at wavelength 589 nm nC: Refractive index at wavelength 656 nm nF: Refractive index at wavelength 486 nm

Further, in the cyclic olefin copolymer (P) according to the present embodiment, from the viewpoint of adjusting the birefringence amount of the obtained molded product to a more suitable range, the thickness of the cyclic olefin copolymer (P) When a 3.0 mm injection-molded sheet is produced, the amount of birefringence of the injection-molded sheet is preferably −20 nm or more and 20 nm or less.
In the present embodiment, the amount of birefringence of the injection-molded sheet is an average value of phase differences measured at measurement wavelengths of 523 nm, 543 nm and 575 nm using a wide range birefringence evaluation system WPA-200 manufactured by Photonic Lattice. ..

Since the molded product according to this embodiment contains the cyclic olefin copolymer for optical members (P) according to this embodiment, it has good moldability at the time of molding, high transparency, and an appropriate Abbe number and density. In addition to the above, the molded product has excellent heat resistance and a high refractive index. Therefore, it is suitable for optical member applications. The molded body according to this embodiment can be, for example, an optical lens.

As an optical member application, for example, it can be suitably used as an optical lens such as a spectacle lens, an fθ lens, a pickup lens, an imaging lens, a lens for various sensors, a prism, a light guide plate, an in-vehicle camera lens, and a high refractive index Since it has an Abbe number lower than that of a conventional resin material, it can be particularly suitably used as an imaging lens.

The molded body according to the present embodiment can be used in various forms such as a lens shape, a spherical shape, a rod shape, a plate shape, a column shape, a cylinder shape, a tube shape, a fiber shape, a film shape or a sheet shape.

The optical lens according to the present embodiment may be combined with an optical lens different from the above optical lens to form an optical lens system.
That is, the optical lens system according to the present embodiment is different from the first optical lens configured by the molded body containing the cyclic olefin copolymer (P) according to the present embodiment and the first optical lens different from the first optical lens. 2 optical lenses.

The second optical lens is not particularly limited, but for example, an optical lens made of at least one resin selected from polycarbonate resin, polyester resin, and polyolefin resin or glass can be used.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.
Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the scope of achieving the object of the present invention are included in the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

<Production of cyclic olefin copolymer>
First, a precursor polymer of a cyclic olefin copolymer was obtained by the following method.

[Production Example 1]
8.7 ml of tetracyclododecene, 6.7 ml of benzonorbornadiene (see the following formula (3), hereinafter also referred to as BNBD), 140 ml of dehydrated toluene, and 0.11 ml of hexadiene were placed in a 500-ml glass reactor sufficiently replaced with nitrogen. The temperature is raised to ℃ and stirred. 5.9 mg of Grubbs Catalyst ^™ 2nd Generation was added as a catalyst, and the mixture was reacted with stirring. After 10 minutes, 1 ml of butyraldehyde was added dropwise to terminate the reaction.
About 150 ml of the solution obtained after the reaction was dropped into 1400 ml of acetone for crystallization, filtered through Kiriyama filter paper (5B), and dried under reduced pressure at 80° C. to obtain 13 g of a polymer. Hereinafter, this polymer is referred to as RTD-BNBD50.

[Production Example 2]
8.7 ml of tetracyclododecene, 0.2 ml of benzonorbornadiene (refer to the following formula (3), hereinafter also referred to as BNBD), 140 ml of dehydrated toluene, and 0.11 ml of hexadiene were placed in a 500 ml glass reactor which had been sufficiently replaced with nitrogen. The temperature is raised to ℃ and stirred. 5.9 mg of Grubbs Catalyst ^™ 2nd Generation was added as a catalyst, and the mixture was reacted with stirring. After 10 minutes, 1 ml of butyraldehyde was added dropwise to terminate the reaction.
About 150 ml of the solution obtained after the reaction was dropped into 1400 ml of acetone for crystallization, filtered through Kiriyama filter paper (5B), and dried under reduced pressure at 80° C. to obtain 13 g of a polymer. Hereinafter, this polymer is referred to as RTD-BNBD1.

[Production Example 3]
16 ml of benzonorbornadiene, 140 ml of dehydrated toluene and 0.11 ml of hexadiene are placed in a 500 ml glass reactor which has been sufficiently replaced with nitrogen, and the mixture is heated to 50° C. and stirred. 5.9 mg of Grubbs Catalyst ^™ 2nd Generation was added as a catalyst, and the mixture was reacted with stirring. After 10 minutes, 1 ml of butyraldehyde was added dropwise to terminate the reaction.
About 150 ml of the solution obtained after the reaction was dropped into 1400 ml of acetone for crystallization, filtered through Kiriyama filter paper (5B), and dried under reduced pressure at 80° C. to obtain 13 g of a polymer. Hereinafter, this polymer is referred to as RBNBD.

[Production Example 4]
Tetracyclododecene (tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene in a 500 ml glass reactor sufficiently replaced with nitrogen, see formula (1) below. ) 17.3 ml, 140 ml of dehydrated toluene and 0.11 ml of hexadiene are added, the temperature is raised to 50° C. and the mixture is stirred. 5.9 mg of Grubbs Catalyst ^™ 2nd Generation was added as a catalyst, and the mixture was reacted with stirring. After 10 minutes, 1 ml of butyraldehyde was added dropwise to terminate the reaction.
About 150 ml of the solution obtained after the reaction was dropped into 1400 ml of acetone for crystallization, filtered through Kiriyama filter paper (5B), and dried under reduced pressure at 80° C. to obtain 13 g of a polymer. Hereinafter, this polymer is referred to as RTD.

[Production Example 5]
Tetracyclododecene 15.6 ml and indene norbornene (1,4,4a,9a tetrahydro 1,4 methanofluorene, refer to the following formula (2), hereinafter also referred to as IndNB) are placed in a 500 ml glass reactor which is sufficiently replaced with nitrogen. 1.9 ml, 140 ml of dehydrated toluene and 0.11 ml of hexadiene are added, the temperature is raised to 50° C. and the mixture is stirred. 5.9 mg of Grubbs Catalyst ^™ 2nd Generation was added as a catalyst, and the mixture was reacted with stirring. After 10 minutes, 1 ml of butyraldehyde was added dropwise to terminate the reaction.
About 150 ml of the solution obtained after the reaction was dropped into 1400 ml of acetone for crystallization, filtered through Kiriyama filter paper (5B), and dried under reduced pressure at 80° C. to obtain 13 g of a polymer. Hereinafter, this polymer is referred to as RTD-IndNB10.

[Production Example 6]
Tetracyclododecene (13.9 ml), indenenorbornene (3.8 ml), dehydrated toluene (140 ml) and hexadiene (0.11 ml) were placed in a 500 ml glass reactor which had been sufficiently replaced with nitrogen, and the mixture was heated to 50° C. and stirred. 5.9 mg of Grubbs Catalyst ^™ 2nd Generation was added as a catalyst, and the mixture was reacted with stirring. After 10 minutes, 1 ml of butyraldehyde was added dropwise to terminate the reaction.
About 150 ml of the solution obtained after the reaction was dropped into 1400 ml of acetone for crystallization, filtered through Kiriyama filter paper (5B), and dried under reduced pressure at 80° C. to obtain 13 g of a polymer. Hereinafter, this polymer is referred to as RTD-IndNB20.

[Production Example 7]
Tetracyclododecene (8.7 ml), indenenorbornene (9.4 ml), dehydrated toluene (140 ml) and hexadiene (0.11 ml) were placed in a 500 ml glass reactor which had been sufficiently replaced with nitrogen, and the mixture was heated to 50° C. and stirred. 5.9 mg of Grubbs Catalyst ^™ 2nd Generation was added as a catalyst, and the mixture was reacted with stirring. After 10 minutes, 1 ml of butyraldehyde was added dropwise to terminate the reaction.
About 150 ml of the solution obtained after the reaction was dropped into 1400 ml of acetone for crystallization, filtered through Kiriyama filter paper (5B), and dried under reduced pressure at 80° C. to obtain 13 g of a polymer. Hereinafter, this polymer is referred to as RTD-IndNB50.

[Production Example 8]
16 ml of indene norbornene, 140 ml of dehydrated toluene and 0.11 ml of hexadiene are put into a 500 ml glass reactor which has been sufficiently replaced with nitrogen, and the mixture is heated to 50° and stirred. 5.9 mg of Grubbs Catalyst ^™ 2nd Generation was added as a catalyst, and the mixture was reacted with stirring. After 10 minutes, 1 ml of butyraldehyde was added dropwise to terminate the reaction.
About 150 ml of the solution obtained after the reaction was dropped into 1400 ml of acetone for crystallization, filtered through Kiriyama filter paper (5B), and dried under reduced pressure at 80° C. to obtain 13 g of a polymer. Hereinafter, this polymer is referred to as RIndNB.

[Production Example 9]
Tetracyclododecene (8.7 mL), methylphenylnorbornene (see the following formula (4), hereinafter also referred to as MePhNB) 8.0 mL, dehydrated toluene 140 mL, and hexadiene 0.11 mL were placed in a 500-mL glass reactor sufficiently replaced with nitrogen. Then, the mixture is heated to 50° C. and stirred. 5.9 mg of Grubbs Catalyst ^™ 2nd Generation was added as a catalyst, and the mixture was reacted with stirring. After 10 minutes, 1 ml of butyraldehyde was added dropwise to terminate the reaction.
About 150 ml of the solution obtained after the reaction was added dropwise to 1400 ml of acetone for crystallization, filtered through Kiriyama filter paper (5B), and dried under reduced pressure at 80° C. to obtain 13 g of a polymer. Hereinafter, this polymer is referred to as RTD-MPNB50.

[Production Example 10]
16 ml of methylphenyl norbornene (see the following formula (4), hereinafter also referred to as MePhNB)), 140 ml of dehydrated toluene, and 0.11 ml of hexadiene are put into a 500 ml glass reactor sufficiently replaced with nitrogen, and heated to 50° C. and stirred. .. 5.9 mg of Grubbs Catalyst ^™ 2nd Generation was added as a catalyst, and the mixture was reacted with stirring. After 10 minutes, 1 ml of butyraldehyde was added dropwise to terminate the reaction.
About 150 ml of the solution obtained after the reaction was dropped into 1400 ml of acetone for crystallization, filtered through Kiriyama filter paper (5B), and dried under reduced pressure at 80° C. to obtain 13 g of a polymer. Hereinafter, this polymer is referred to as RMPNB.

The precursor polymer shown in Table 1 was obtained by the above method. Then, the obtained precursor polymer was partially hydrogenated or wholly hydrogenated by the following method.

(Example 1)
[Production of Cyclic Olefin Polymer P-1 (Partial Hydrogenation)]
13 g of RTD-BNBD50 and 600 ml of o-xylene were placed in a 1 L glass reactor which had been sufficiently replaced with nitrogen, and the mixture was dissolved and heated to 140° C. with stirring and refluxed. Then, 30.5 g of p-toluenesulfonyl hydrazide and 23.4 g of tri-n-propylamine were added to start the reaction. After 4 hours from the start of the reaction, the temperature was lowered to room temperature to terminate the reaction, and about 600 ml of a reaction solution was obtained. This reaction solution was added dropwise to 1800 ml of acetone for crystallization in the same manner as in the above Production Example, filtered with Kiriyama filter paper (5B), and dried under reduced pressure at 80° C. to obtain 13 g of a polymer.
When this polymer was observed by NMR, the aromatic ring remained, but other double bonds were almost lost.

(Examples 2 to 3, Comparative Examples 1 to 6)
[Production of Cyclic Olefin Polymers P-2 to P-9]
A partial hydrogenation step was carried out in the same manner as in the production of the cyclic olefin polymer P-1 except that the polymers shown in Table 1 were used instead of the RTD-BNBD50 to obtain the cyclic olefin polymers P-2 to P-9. It was When the cyclic olefin polymers P-2 to P-9 were observed by NMR as in the case of the cyclic olefin polymer P-1, aromatic rings remained, but other double bonds were almost eliminated.

(Comparative Example 7)
[Production of cyclic olefin polymer P-10 (total hydrogenation)]
13 g of RTD, 277 g of cyclohexane, 0.08 g of bis(tricyclohexylphosphine)benzilidineruthenium(IV) dichloride and 4.7 g of ethyl vinyl ether were put into an autoclave which had been sufficiently replaced with nitrogen, and hydrogen pressure was applied to 8 atm to 120°C. The temperature was raised and the reaction was carried out for 10 hours.
This reaction solution was added dropwise to 1800 ml of acetone for crystallization in the same manner as in the above Production Example, filtered with Kiriyama filter paper (5B), and dried under reduced pressure at 80° C. to obtain 13 g of a polymer.
When this polymer was observed by NMR, aromatic rings and other double bonds were almost eliminated.

(Comparative Examples 8 to 11)
[Production of Cyclic Olefin Polymers P-11 to P-14]
The hydrogenation step (total hydrogenation) was carried out in the same manner as in the production of the cyclic olefin polymer P-10 except that the polymer shown in Table 1 was used instead of the RTD, and the cyclic olefin polymers P-11 to P-14 Got When the cyclic olefin polymers P-11 to P-14 were observed by NMR as in the case of the cyclic olefin polymer P-10, aromatic rings and other double bonds were almost eliminated.

(Evaluation of cyclic olefin polymer)
[Intrinsic viscosity]
The intrinsic viscosity ([η]) was measured in decalin at 135°C.
Specifically, the resin (about 20 mg) was dissolved in a decalin solvent (15 ml), and the specific viscosity η _sp was measured in an oil bath at 135°C. A decalin solvent (5 ml) was added to the decalin solution to dilute it, and then the specific viscosity η _sp was measured in the same manner as in the above-described method. This dilution operation was repeated twice more, and the value of η _sp /C when the concentration (C) of the sample was extrapolated to 0 was defined as the intrinsic viscosity [η].
Intrinsic viscosity [η]=lim (η _sp /C) (C→0)

[Glass transition temperature Tg (°C)]
It was determined by performing DSC measurement under the following conditions.
・Device: DSC7000 manufactured by SII Nano Technology Co., Ltd.
-Measurement conditions: Under a nitrogen atmosphere, the temperature was raised from room temperature to 260°C at a rate of 10°C/min, and then held for 5 minutes. Then, the temperature was lowered to 30° C. at a temperature lowering rate of 10° C./min, and then held for 5 minutes. Then, a DSC curve in the process of heating up to 260° C. at a temperature rising rate of 10° C./min was acquired.

In the obtained DSC curve, the temperature at the point where a straight line that is equidistant from the extended straight line of each baseline in the vertical axis direction and the curve of the stepwise change portion of the glass transition intersect was defined as the glass transition temperature.

[ ¹ H-NMR measurement]
¹ H-NMR measurement of the cyclic olefin polymer was carried out by the following method to confirm the presence or absence of an aromatic ring and the presence or absence of a double bond.
Measured at 0.5 ppm to 8 ppm by ¹ H-NMR manufactured by JEOL Ltd. to check for the presence of hydrogen peaks from aromatic rings (6.7 to 7.3 ppm) and other double bond-derived peaks. confirmed.
In addition, the content of the structural unit (A) in the cyclic olefin copolymer and the cyclic olefin copolymer when the total content of the structural unit (A) and the structural unit (B) is 100 mol% by the following method. The aromatic ring content in the polymer was calculated.
The peak area of the hydrogen peak derived from the aromatic ring (6.7 to 7.3 ppm) relative to the total area of all the hydrogen derived peaks detected at 0.5 ppm to 8 ppm by ¹ H-NMR manufactured by JEOL Ltd. By calculating, the amount of hydrogen in the aromatic ring contained in the polymer was calculated.

(Evaluation of molded body)
[Pelletization]
The cyclic olefin polymers P-1 to P-14 were set using a twin-screw extruder BT-30 (screw diameter 30 mmφ, L/D=46) manufactured by Plastic Engineering Laboratory, a preset temperature of 270° C., a resin extrusion rate of 80 g/min, and Granulation was carried out under the condition of a screw rotation speed of 200 rpm to obtain pellets for various measurements.

[Injection molding]
Using the injection molding machine IS-55 manufactured by Toshiba Machine Co., Ltd., the pellets obtained above are cylinder temperature=270 to 290° C., injection speed=70 to 90%, screw rotation speed 70 to 100 rpm, mold temperature 120. Injection molding was carried out under the condition of °C to prepare injection square plates each having a thickness of 3.0 mm.

[transparency]
The internal haze of the obtained square plate test piece having a thickness of 3.0 mm was measured, and the transparency was evaluated according to the following criteria.
The internal haze was measured in benzyl alcohol using a haze meter (NDH-20D manufactured by Nippon Denshoku Industries Co., Ltd.).
◯: Internal haze is less than 6.0% ×: The test piece is visually cloudy, or the internal haze is 6.0% or more.

[discoloration]
The color change of the pellets obtained from the cyclic olefin polymers P-1 to P-7 before and after pelletization was visually observed.
The cyclic olefin polymers P-1 to P-7 were colorless and transparent. A change in color due to heat (270° C.) during pelletization was observed.
Comparative Examples 1 to 4 turned yellow. It is considered that the discoloration is likely to be caused by heat because the benzyl position of IndNB is a secondary carbon.

[density]
The density of the square plate test piece having a thickness of 3.0 mm obtained above was measured at 23° C. based on JIS K7112. The density was measured by the underwater substitution method.

[Refractive index]
The 30 mm×30 mm×3.0 mm thick square plate test piece obtained above was measured for a refractive index (nd) at a wavelength of 589 nm using a refractometer (KPR200 manufactured by Shimadzu Science Co., Ltd.) according to ASTM D542. did.

[Abbe number (ν)]
About the square plate test piece of 30 mm × 30 mm × thickness 3.0 mm obtained above, the refractive index at wavelengths of 486 nm, 589 nm and 656 nm at 23° C. was measured using an Abbe refractometer, and the following formula was used. Abbe number (ν) was calculated.
ν=(nD-1)/(nF-nC)
nD: Refractive index at wavelength 589 nm nC: Refractive index at wavelength 656 nm nF: Refractive index at wavelength 486 nm

[Amount of birefringence]
Photographs of 30 mm x 30 mm x 3.0 mm square plate test pieces obtained from cyclic olefin polymers P-1, P-2, P-3, P-6, P-7, P-12 and P-13. Using a wide range birefringence evaluation system WPA-200 manufactured by Nick Lattice Co., Ltd., an average value of phase differences measured at measurement wavelengths of 523 nm, 543 nm and 575 nm was calculated.

This application claims the priority on the basis of Japanese application Japanese Patent Application No. 2018-244496 filed on Dec. 27, 2018, and incorporates all the disclosure thereof.

Claims (12)

1. A cyclic olefin copolymer having an aromatic ring,
   A cyclic olefin copolymer for optical members, which comprises the structural unit (A) of the following (III).
   

   

   (In the above formula (III), n is 0, 1 or 2, m is 1, 2 or 3, and R ⁵⁵ to R ⁶⁸ are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or fluorine. A hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding atoms, and when m=1, R ⁶⁵ and R ⁶⁷ , R ⁶⁷ and R ⁶⁸ , R ⁶⁸ and R ⁶⁶ are mutually They may combine to form a monocyclic or polycyclic ring, and when m=2 or 3, R ⁶⁵ and R ⁶⁵ , R ⁶⁵ and R ⁶⁷ , R ⁶⁷ and R ⁶⁸ , R ⁶⁸ and R ⁶⁶ , R ^66. And R ⁶⁶ may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic or polycyclic ring may have a double bond, and the monocyclic or polycyclic ring may be aromatic. It may be a group ring.)
2. The cyclic olefin copolymer according to claim 1, wherein
   A cyclic olefin copolymer for optical members, wherein the content of the structural unit (A) is 0.2 mol% or more and 100 mol% or less.
3. The cyclic olefin copolymer according to claim 1 or 2,
   Further, a cyclic olefin copolymer for optical members, which contains a structural unit (B) derived from an olefin having 2 to 20 carbon atoms.
4. The cyclic olefin copolymer according to claim 3,
   The cyclic olefin copolymer for optical members, wherein the structural unit (B) has an alicyclic structure.
5. The cyclic olefin copolymer according to claim 3 or 4,
   When the total content of the structural unit (A) and the structural unit (B) is 100 mol %, the content of the structural unit (A) in the cyclic olefin copolymer is 0.5 mol% or more and 100 or more. A cyclic olefin copolymer for optical members, which is at most mol %.
6. The cyclic olefin copolymer according to any one of claims 1 to 5,
   A cyclic olefin copolymer for optical members, wherein the glass transition temperature (Tg) of the cyclic olefin copolymer is 100° C. or more and 200° C. or less as measured by a differential scanning calorimeter (DSC).
7. The cyclic olefin copolymer according to any one of claims 1 to 6,
   When a 3.0 mm-thick injection-molded sheet made of the cyclic olefin copolymer is prepared, the injection-molded sheet has a refractive index of 1.534 to 1.590 at a wavelength of 589 nm. Polymer.
8. The cyclic olefin copolymer according to any one of claims 1 to 7,
   A cyclic olefin copolymer for optical members, which has an Abbe number (ν) of the injection molded sheet of 30 or more and 55 or less when an injection molded sheet of 3.0 mm in thickness made of the cyclic olefin copolymer is prepared.
9. The cyclic olefin copolymer according to any one of claims 1 to 8,
   The cyclic olefin copolymer for optical members, wherein the structural unit (A) is derived from benzonorbornadiene.
10. A cyclic olefin copolymer composition for optical members, comprising the cyclic olefin copolymer for optical members according to any one of claims 1 to 9.
11. A molded product comprising the cyclic olefin copolymer for optical members according to any one of claims 1 to 9.
12. The molded product according to claim 11, which is an optical lens.