Polycarbonate resin, polycarbonate resin composition, optical component, and method for producing polycarbonate resin

Abstract

The present invention provides: a polycarbonate resin that includes a structural unit represented by formula (1) (in which A is an optionally substituted trivalent alicyclic moiety, and B is an optionally substituted monovalent alicyclic moiety); and a cyclic carbonate that includes a structure in which an alicyclic skeleton has been bonded to a 1,2-cycloalkylene carbonate skeleton by a single bond.

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin, a polycarbonate resin composition, an optical component, and a method for producing a polycarbonate resin. [Background technology]

[0002] Polycarbonate resin is an engineering plastic with excellent heat resistance, and there is a demand for it to be lightweight and low-cost, while also having excellent heat resistance and optical properties. To meet these demands, the development of special polycarbonate resins based on aromatic skeletons is actively underway.

[0003] On the other hand, polycarbonate resins having an aliphatic, particularly alicyclic, structure are also being developed as alternatives to aromatic polycarbonates. Alicyclic polycarbonates tend to have better light resistance and optical properties than polycarbonate resins having aromatic rings such as bisphenol A. For example, Patent Document 1 discloses a polycyclic alicyclic polycarbonate resin that is excellent in transparency, heat resistance, and color tone. Furthermore, polycarbonates using not only petroleum-derived raw materials but also biomass-derived raw materials such as plants are also being developed. For example, Patent Document 2 discloses a polycarbonate resin using isosorbide, which can be derived from starch, as a raw material.

[0004] Among such alicyclic polycarbonate resins, poly(cyclohexene carbonate) having a cyclohexane carbonate structure is the simplest polycarbonate having a saturated six-membered carbon ring corresponding to a benzene ring. It is widely known that poly(cyclohexene carbonate) can be synthesized by reacting cyclohexene oxide with carbon dioxide, as shown in Patent Document 3, for example. It is also known that poly(cyclohexene carbonate) can be obtained by ring-opening polymerization of 1,2-cyclohexene carbonate, as described in Patent Document 4 and Non-Patent Document 1. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 4774610 [Patent Document 2] Patent No. 6507495 [Patent Document 3] Patent No. 5403537 [Patent Document 4] Japanese Patent Application Publication No. 2019-108547 [Non-patent literature]

[0006] [Non-Patent Document 1] Macromolecules 2014, 47, 4230-4235. Summary of the Invention

[0007] That is, the present invention includes the following embodiments. <1> A structural unit represented by the following formula (1): [ka] (In formula (1), A is an optionally substituted trivalent alicyclic moiety, and B is an optionally substituted monovalent alicyclic moiety.) A polycarbonate resin having the formula: <2> The structural unit represented by the formula (1) is a structural unit represented by the following formula (1A): [ka] (In formula (1A), B is an optionally substituted monovalent alicyclic moiety.) having <1> The polycarbonate resin according to claim 1. <3> The alicyclic moiety B is represented by the following formula (1a): [ka] (In formula (1a), R is a substituent, n is an integer of 0 to 2, and * is a bonding site.) is a group represented by <1> or <2> The polycarbonate resin according to claim 1. <4> The alicyclic moiety B is represented by the following formula (1b): [ka] (In formula (1b), R is a substituent, n is an integer of 0 to 2, and * is a bonding site.) is a group represented by <1> or <2> The polycarbonate resin according to claim 1. <5> A structural unit represented by the following formula (1B): [ka] (In formula (1B), R is a substituent, and n is an integer of 0 to 2.) having <1> The polycarbonate resin according to claim 1. <6> A structural unit represented by the following formula (1C): [ka] (In formula (1C), R is a substituent, and n is an integer of 0 to 2.) having <1> The polycarbonate resin according to claim 1. <7> A structural unit represented by the following formula (1B-H): [ka] (In formula (1B-H), n is an integer of 0 to 1.) having <1> The polycarbonate resin according to claim 1. <8> A structural unit represented by the following formula (1C-H): [ka] (In formula (1C-H), n is an integer of 0 to 1.) having <1> The polycarbonate resin according to claim 1. <9> A structural unit represented by the following formula (2): [ka] (In formula (2), C represents an optionally substituted divalent alicyclic moiety.) having <1> ~ <8> 1. The polycarbonate resin according to claim 1 . <10> The weight average molecular weight (Mw) is 10,000 or more and 1,000,000 or less. <1> ~ <9> 1. The polycarbonate resin according to claim 1 . <11> The glass transition temperature (Tg) is 125°C or higher and 250°C or lower. <1> ~ <10> 1. The polycarbonate resin according to claim 1 . <12> The absolute value of the photoelastic coefficient is 1.5 × 10 -12 Pa -1 Below is the <1> ~ <11> 1. The polycarbonate resin according to claim 1 . <13> In the 100% uniaxially stretched film of the polycarbonate resin, the absolute value of the in-plane retardation is 100 nm or less in terms of a thickness of 100 μm. <1> ~ <12> 1. The polycarbonate resin according to claim 1 . <14> The temperature dependence of orientation birefringence (dΔn / dT) of the uniaxially stretched film under the following conditions is -0.1×10 -5 ≦dΔn / dT≦+0.1×10 -5 fulfill, <1> ~ <13> 1. The polycarbonate resin according to claim 1 . (Stretching conditions) Stretching temperature: 20°C higher than the glass transition temperature (Tg) of polycarbonate resin Stretching speed: 50mm / min Stretching ratio: 100% <15> <1> ~ <14> 10. A polycarbonate resin composition comprising the polycarbonate resin according to any one of claims 1 to 9 and an antioxidant. <16> <1> ~ <14> An optical component comprising the polycarbonate resin according to any one of claims 1 to 4. <17> <1> ~ <14> 2. Use of the polycarbonate resin according to any one of claims 1 to 11 as a material for optical components. <18> The following formula (1L): [ka] (In formula (1L), A is an optionally substituted trivalent alicyclic moiety, and B is an optionally substituted monovalent alicyclic moiety.) The method includes a polymerization step of ring-opening polymerizing a cyclic carbonate represented by the formula: A structural unit represented by the following formula (1): [ka] (In formula (1), A is an optionally substituted trivalent alicyclic moiety, and B is an optionally substituted monovalent alicyclic moiety.) A method for producing a polycarbonate resin comprising the steps of: <19> A cyclic carbonate having a structure in which an alicyclic skeleton is bonded to a 1,2-cycloalkylene carbonate skeleton via a single bond. <20> The following formula (1L): [ka] (In formula (1L), A is an optionally substituted trivalent alicyclic moiety, and B is an optionally substituted monovalent alicyclic moiety.) is expressed as <19> The cyclic carbonate according to claim 1. <21> The formula (1L) is the following (1LA): [ka] (In formula (1LA), B is an optionally substituted monovalent alicyclic moiety.) That is, <20> The cyclic carbonate according to claim 1. <22> The alicyclic moiety B is represented by the following formula (1a): [ka] (In formula (1a), R is a substituent, n is an integer of 0 to 2, and * is a bonding site.) is a group represented by <20> or <21> The cyclic carbonate according to claim 1. <23> The alicyclic moiety B is represented by the following formula (1b): [ka] (In formula (1b), R is a substituent, n is an integer of 0 to 2, and * is a bonding site.) is a group represented by <20> or <21> The cyclic carbonate according to claim 1. <24> the alicyclic moiety B is an optionally substituted norbornyl group, an optionally substituted norbornenyl group, an optionally substituted decahydro-1,4:5,8-dimethanonaphthalenyl group, or an optionally substituted octahydro-1,4:5,8-dimethanonaphthalenyl group; <20> or <21> The cyclic carbonate according to claim 1. <25> The following formula (1LB): [ka] (In formula (1LB), R is a substituent, and n is an integer of 0 to 2.) is expressed as <19> The cyclic carbonate according to claim 1. <26> The following formula (1LC): [ka] (In formula (1LC), R is a substituent, and n is an integer of 0 to 2.) is expressed as <19> The cyclic carbonate according to claim 1. <27> The following formula (1L-1): [ka] The following formula (1L-2): [ka] The following formula (1L-3): [ka] Or, the following formula (1L-4): [ka] is expressed as <19> The cyclic carbonate according to claim 1. <28> A method for producing a cyclic carbonate having a structure in which an alicyclic skeleton is bonded to a 1,2-cycloalkylene carbonate skeleton via a single bond, comprising: The following formula (2L): [ka] (In formula (2L), A is an optionally substituted trivalent alicyclic moiety.) The method for producing a cyclic carbonate includes a step of reacting a cyclic carbonate represented by the following formula (I): with a compound having a conjugated diene moiety. <29> The following formula (1L-1): [ka] Cyclic carbonates represented by the formula: The following formula (1L-2): [ka] A cyclic carbonate composition comprising a cyclic carbonate represented by the formula: <30> The following formula (1L-3): [ka] Cyclic carbonates represented by the formula: The following formula (1L-4): [ka] A cyclic carbonate composition comprising a cyclic carbonate represented by the formula: [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a polycarbonate resin having excellent heat resistance and a low photoelastic coefficient, a polycarbonate resin composition containing the same, a method for producing the polycarbonate resin, and the like. [Brief explanation of the drawings]

[0009] [Figure 1] 1 shows the H-NMR spectrum of the polycarbonate resin in Example 1. [Figure 2] 1 shows the H-NMR spectrum of the polycarbonate resin in Example 2. [Figure 3] 1 shows the H-NMR spectrum of the polycarbonate resin in Example 3. [Figure 4] 1 shows the H-NMR spectrum of the polycarbonate resin in Example 4. [Figure 5] 1 shows the H-NMR spectrum of the polycarbonate resin in Example 5. [Figure 6] 1 shows the H-NMR spectrum of the polycarbonate resin in Example 6. [Figure 7] 1 shows the H-NMR spectrum of the polycarbonate resin in Example 7. [Figure 8] 1 shows the H-NMR spectrum of the polycarbonate resin in Example 8. [Figure 9] 1 shows the 1H-NMR spectrum of the cyclic carbonate (TCDT) in Example L1. [Figure 10] 1 shows the 1H-NMR spectrum of the cyclic carbonate (NORT) in Example L2. [Figure 11] 1 shows the 1H-NMR spectrum of the cyclic carbonate (NORT-H) in Example L6. [Figure 12]1 shows the 1H-NMR spectrum of the cyclic carbonate (TCDT-H) in Example L7. [Figure 13] 1 shows the H-NMR spectrum of the cyclic carbonate (Me5NORT) in Example L11. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as "the present embodiment") will be described in detail. Note that the present invention is not limited to the present embodiment, and various modifications can be made within the scope of the gist of the present invention.

[0011] [Alicyclic polycarbonate resin] The present inventors have conducted detailed studies on conventional alicyclic polycarbonate resins, including those described in the above documents, and have found that they are insufficient in either heat resistance or optical properties.

[0012] For example, as described in Patent Document 4 and Non-Patent Document 1, the glass transition temperature of a polycarbonate resin having a cyclic cyclohexane structure in the main chain is higher than that of an aliphatic chain polycarbonate, but is lower than that of a general-purpose aromatic polycarbonate resin having a bisphenol A structure, and there has been a problem in terms of heat resistance, such as dimensional stability under high-temperature environments.

[0013] Furthermore, poly(cyclohexene carbonate) has a small photoelastic coefficient, which is a controlling factor for the birefringence that appears during use, and although it has low birefringence, further reduction of birefringence has been a challenge.

[0014] An object of the present invention is to provide a polycarbonate resin having excellent heat resistance and a low photoelastic coefficient, a polycarbonate resin composition containing the same, a method for producing the polycarbonate resin, and the like.

[0015] The present inventors have conducted extensive research to solve the above problems and have found that a polycarbonate resin having a specific cyclic structure exhibits excellent heat resistance and a low photoelastic coefficient.

[0016] The polycarbonate resin of this embodiment has a structural unit represented by the following formula (1).

[0017] [ka] (In formula (1), A is an optionally substituted trivalent alicyclic moiety, and B is an optionally substituted monovalent alicyclic moiety.)

[0018] The polycarbonate resin according to this embodiment has excellent heat resistance and a low photoelastic coefficient. The reasons for this are thought to be, but are not limited to, the following: Conventional polycarbonate resins having an alicyclic structure often contain 1,2-cycloalkylene carbonates that do not have a ring skeleton in the side chain, resulting in insufficient heat resistance and an insufficient reduction in the photoelastic coefficient. In contrast, the polycarbonate resin according to this embodiment has a structure in which an alicyclic skeleton is further bonded to the side chain of a 1,2-cycloalkylene carbonate skeleton. This is thought to improve heat resistance by increasing the proportion of ring skeletons in the molecule. Furthermore, it is thought that the increased proportion of alicyclic skeletons in the molecule reduces the flatness of the entire molecule, resulting in a low photoelastic coefficient.

[0019] The structural unit represented by formula (1) is preferably a trans isomer shown below. [ka] The above diagrams represent three-dimensional structures, and when a chiral center is included in the formula, it may be either an R-configuration or an S-configuration.

[0020] In formula (1), A represents an optionally substituted trivalent alicyclic moiety. A corresponds to the aforementioned cycloalkane-1,2-diyl group. Examples of A in formula (1) include a cyclopropane-1,2-diyl group, a cyclobutane-1,2-diyl group, a cyclopentane-1,2-diyl group, a cyclohexane-1,2-diyl group, a cycloheptane-1,2-diyl group, a cyclooctane-1,2-diyl group, a cyclononane-1,2-diyl group, and a cyclodecane-1,2-diyl group. Among these A groups, a cyclobutane-1,2-diyl group, a cyclopentane-1,2-diyl group, a cyclohexane-1,2-diyl group, a cycloheptane-1,2-diyl group, and a cyclooctane-1,2-diyl group are preferred, and a cyclobutane-1,2-diyl group, a cyclopentane-1,2-diyl group, a cyclohexane-1,2-diyl group, and a cycloheptane-1,2-diyl group are more preferred.

[0021] In formula (1), B represents an optionally substituted alicyclic skeleton. The alicyclic skeleton B is not particularly limited, but examples thereof include cyclopropane, cyclopropene, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene, cyclooctane, cyclooctene, cyclononane, cyclononene, cyclodecane, cyclodecene, a group represented by the following formula (1a), and a group represented by the following formula (1b).

[0022] [ka] (In formula (1a), R is a substituent, n is an integer of 0 to 2, and * is a bonding site.)

[0023] [ka] (In formula (1b), R is a substituent, n is an integer of 0 to 2, and * is a bonding site.)

[0024] The group represented by formula (1a) or the group represented by formula (1b) is not particularly limited, but examples thereof include norbornane, norbornene, adamantane, bicyclo[2.2.2]octane, bicyclo[2.2.2]octene, decahydronaphthalene, decahydro-1,4:5,8-dimethanonaphthalene, and octahydro-1,4:5,8-dimethanonaphthalene.

[0025] In formula (1), B is preferably cyclopropane, cyclopropene, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene, norbornane, norbornene, adamantane, bicyclo[2.2.2]octane, bicyclo[2.2.2]octene, decahydronaphthalene, decahydro-1,4:5,8-dimethanonaphthalene, or octahydro-1,4:5,8-dimethanonaphthalene. From the same viewpoint, in formula (1), B is more preferably cyclopropane, cyclopropene, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene, norbornane, norbornene, adamantane, decahydronaphthalene, decahydro-1,4:5,8-dimethanonaphthalene, or octahydro-1,4:5,8-dimethanonaphthalene. From the same viewpoint, in formula (1), B is even more preferably cyclopropane, cyclopropene, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene, norbornane, norbornene, decahydronaphthalene, decahydro-1,4:5,8-dimethanonaphthalene, or octahydro-1,4:5,8-dimethanonaphthalene.

[0026] From the viewpoint of improving heat resistance, the alicyclic moiety B is preferably a group represented by formula (1a) or a group represented by formula (1b), more preferably an optionally substituted norbornyl group, an optionally substituted norbornenyl group, an optionally substituted decahydro-1,4:5,8-dimethanonaphthalenyl group, or an optionally substituted octahydro-1,4:5,8-dimethanonaphthalenyl group, and even more preferably a norbornyl group, a norbornenyl group, a decahydro-1,4:5,8-dimethanonaphthalenyl group, or an octahydro-1,4:5,8-dimethanonaphthalenyl group.

[0027] In the present specification, when each group is substituted, the substituent is not particularly limited, and examples thereof include a hydroxyl group, a phosphate group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silyl group having 1 to 30 carbon atoms, a silylalkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 11 carbon atoms, an acyl group having 1 to 11 carbon atoms, or an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. In this embodiment, A and B may have multiple substituents, and in that case, the respective substituents may be the same or different.

[0028] In this embodiment, the substituent in formula (1) is a hydroxyl group, a phosphate group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silyl group having 1 to 30 carbon atoms, a silylalkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 11 carbon atoms, an acyl group having 1 to 11 carbon atoms, or an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. In formula (1), the substituent is preferably one or more substituents selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an ester group having 1 to 11 carbon atoms, an acyl group having 1 to 11 carbon atoms, and an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. In formula (1), the substituent is more preferably one or more substituents selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, and an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. In formula (1), the substituent is even more preferably one or more substituents selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms, and an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms.

[0029] The phosphate group described above may be unsubstituted or substituted. That is, it may be a mono-substituted phosphate group or a di-substituted phosphate group. From the viewpoint of more effectively and reliably achieving the effects of the present invention, when the phosphate group is substituted, the substituent is preferably an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. From the same viewpoint, the phosphate group in this embodiment is preferably unsubstituted.

[0030] The aryl group having 6 to 20 carbon atoms is not particularly limited, but examples thereof include unsubstituted or alkyl group-containing aryl groups such as a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, a tetramethylphenyl group, a pentamethylphenyl group, an ethylphenyl group, a propylphenyl group, and a diisopropylphenyl group; alkoxy group-containing aryl groups such as a 4-methoxyphenyl group and a 3,5-dimethoxyphenyl group; and biphenyl, naphthyl, and anthracenyl groups.

[0031] The aralkyl group having 6 to 20 carbon atoms is not particularly limited, but examples thereof include unsubstituted or alkyl group-containing aralkyl groups such as a benzyl group, a 4-methylbenzyl group, and a phenethyl group; alkoxy group-containing aralkyl groups such as a 4-methoxybenzyl group and a 3,5-dimethoxybenzyl group; and diphenylmethyl, naphthylmethyl, and anthracenylmethyl groups.

[0032] The alkoxy group having 1 to 20 carbon atoms is not particularly limited, but examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a cyclopentyloxy group, a hexyloxy group, a cyclohexyloxy group, a heptyloxy group, an octyloxy group, a nonanyloxy group, a decyloxy group, a phenoxy group, a benzyloxy group, a vinyloxy group, and an allyloxy group.

[0033] The silyl group having 1 to 30 carbon atoms is not particularly limited, but examples thereof include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, a tert-butyldimethylsilyl group, a di-tert-butylisobutylsilyl group, and a tert-butyldiphenylsilyl group.

[0034] The silylalkoxy group having 1 to 30 carbon atoms is not particularly limited, and examples thereof include a trimethylsilylmethoxy group, a trimethylsilylethoxy group, a trimethylsilylphenoxy group, a trimethylsilylbenzyloxy group, a triethylsilylmethoxy group, a triethylsilylethoxy group, a triethylsilylphenoxy group, a triethylsilylbenzyloxy group, a triisopropylsilylmethoxy group, a triisopropylsilylethoxy group, a triisopropylsilylphenoxy group, a triisopropylsilylbenzyloxy group, a triphenylsilylmethoxy group, a triphenylsilylethoxy group, a triphenylsilylphenoxy group, and a triphenylsilylbenzyloxy group. oxy group, tert-butyldimethylsilylmethoxy group, tert-butyldimethylsilylethoxy group, tert-butyldimethylsilylphenoxy group, tert-butyldimethylsilylbenzyloxy group, di-tert-butylisobutylsilylmethoxy group, di-tert-butylisobutylsilylethoxy group, di-tert-butylisobutylsilylphenoxy group, di-tert-butylisobutylsilylbenzyloxy group, tert-butyldiphenylsilylmethoxy group, tert-butyldiphenylsilylethoxy group, tert-butyldiphenylsilylphenoxy group, and tert-butyldiphenylsilylbenzyloxy group.

[0035] The ester group having 1 to 11 carbon atoms is not particularly limited, but examples thereof include a methyl ester group, an ethyl ester group, a propyl ester group, a butyl ester group, a pentyl ester group, a cyclopentyl ester group, a hexyl ester group, a cyclohexyl ester group, a heptyl ester group, an octyl ester group, a nonanyl ester group, a decyl ester group, a phenyl ester group, a benzyl ester group, a vinyl ester group, and an allyl ester group.

[0036] The above-mentioned acyl group having 1 to 11 carbon atoms is not particularly limited, but examples thereof include a formyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a benzoyl group.

[0037] Examples of the unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, a 1-norbornyl group, a 2-norbornyl group, an n-octyl group, a 1-bicyclo[2.2.2]octyl group, a 2-bicyclo[2.2.2]octyl group, an n-nonanyl group, an n-decyl group, a 1-adamantyl group, a 2-adamantyl group, a decahydronaphthyl group, and a tetracyclododecyl group.

[0038] (Terminal structure) The terminals of the polycarbonate resin of this embodiment are not particularly limited, and may be, for example, a hydrogen atom, a hydroxyl group, a phosphate group, an amino group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silyl group having 1 to 30 carbon atoms, a silylalkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 11 carbon atoms, an acyl group having 1 to 11 carbon atoms, or an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. The polycarbonate resin of this embodiment may have both terminals bonded to each other to form a cyclic structure. That is, the polycarbonate resin of this embodiment may not have a terminal structure. It is preferable that the polycarbonate resin of this embodiment has both terminals composed of hydroxyl groups.

[0039] The polycarbonate resin of the present embodiment preferably has a structure represented by the following formula (1A).

[0040] [ka] (In formula (1A), B is an optionally substituted monovalent alicyclic moiety.)

[0041] Preferred B in formula (1A) is the same as that in formula (1). In addition, examples of the substituent in formula (1A), when substituted, are the same as those in formula (1).

[0042] The polycarbonate resin of the present embodiment contains a structural unit represented by the following formula (1B): [ka] (In formula (1B), R is a substituent, and n is an integer of 0 to 2.) It is preferred that the compound has the following structure:

[0043] In order to further improve heat resistance, the polycarbonate resin of the present embodiment contains a structural unit represented by the following formula (1C): [ka] (In formula (1C), R is a substituent, and n is an integer of 0 to 2.) It is preferred that the compound has the following structure:

[0044] In formulae (1B) and (1C), n is preferably 0 or 1.

[0045] The polycarbonate resin of the present embodiment contains a structural unit represented by the following formula (1B-H): [ka] (In formula (1B-H), n is an integer of 0 to 1.) It is preferred that the compound has the following structure:

[0046] The polycarbonate resin of the present embodiment contains a structural unit represented by the following formula (1C-H): [ka] (In formula (1C-H), n is an integer of 0 to 1.) It is preferred that the compound has the following structure:

[0047] As the cyclic carbonate having a structural unit represented by formula (1B), from the viewpoint of facilitating the introduction of other substituents and obtaining a lower photoelastic coefficient, a cyclic carbonate having a structural unit represented by formula (1B-1) below is preferred: [ka] or a structural unit represented by Formula (1B-2) below: [ka] It is preferable that the compound has a structural unit represented by the following formula:

[0048] As the cyclic carbonate having a structural unit represented by formula (1C), from the viewpoint of further improving heat resistance and obtaining a lower photoelastic coefficient, a cyclic carbonate having a structural unit represented by formula (1C-1) below is preferred: [ka] or a structural unit represented by Formula (1C-2) below: [ka] It is preferable that the compound has a structural unit represented by the following formula:

[0049] The polycarbonate resin of the present embodiment may contain two or more types of structural units represented by formula (1).

[0050] The polycarbonate resin of the present embodiment may have other structural units in addition to the structural unit represented by formula (1). Other structural units include, for example, ring-opened cyclic carbonate units. More specifically, the polycarbonate resin of the present embodiment preferably contains, as another structural unit, a structural unit represented by the following formula (2): [ka] (In formula (2), C represents an optionally substituted divalent alicyclic moiety.) It has. Examples of the alicyclic moiety of C include a cyclopropane-1,2-diyl group, a cyclobutane-1,2-diyl group, a cyclopentane-1,2-diyl group, a cyclohexane-1,2-diyl group, a cycloheptane-1,2-diyl group, a cyclooctane-1,2-diyl group, a cyclononane-1,2-diyl group, and a cyclodecane-1,2-diyl group. Among these A, a cyclobutane-1,2-diyl group, a cyclopentane-1,2-diyl group, a cyclohexane-1,2-diyl group, a cycloheptane-1,2-diyl group, and a cyclooctane-1,2-diyl group are preferred, and a cyclobutane-1,2-diyl group, a cyclopentane-1,2-diyl group, a cyclohexane-1,2-diyl group, and a cycloheptane-1,2-diyl group are more preferred.

[0051] When substituted, examples of the substituents are the same as those in formula (1).

[0052] The proportion of the structural unit represented by formula (1) in the polycarbonate resin of this embodiment is not particularly limited, but is preferably, for example, 10 to 90 mol %, 20 to 80 mol %, 30 to 70 mol %, or 40 to 60 mol %.

[0053] The proportion of the structural unit represented by formula (2) in the polycarbonate resin of this embodiment is not particularly limited, but is preferably, for example, 10 to 90 mol %, 20 to 80 mol %, 30 to 70 mol %, or 40 to 60 mol %.

[0054] The weight-average molecular weight (Mw) of the polycarbonate resin of this embodiment is preferably 10,000 or more and 1,000,000 or less. When the Mw is within the above range, the polycarbonate resin of this embodiment is easily molded. Furthermore, such a polycarbonate resin has excellent heat resistance. From the same viewpoint, Mw is more preferably 10,000 or more and 950,000 or less, and even more preferably 10,000 or more and 900,000 or less. The upper limit of Mw may be 800,000. The weight-average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography, and can be specifically measured by the method described in the Examples.

[0055] In the polycarbonate resin of this embodiment, the weight-average molecular weight (Mw) can be controlled within the above range by appropriately adjusting the ratio of the polymerizable monomer to the polymerization initiator, and by producing the polycarbonate resin by the production method described below. By controlling the amount of the polymerization initiator added to the polymerizable monomer within a specific range, the polymerization reaction tends to proceed with a good conversion rate and the Mw tends to be large.

[0056] The polycarbonate resin of this embodiment preferably has a glass transition temperature (Tg) of 125°C or higher and 250°C or lower. When the Tg is 125°C or higher, the resin tends to be able to better maintain its shape even in a relatively high-temperature usage environment, resulting in excellent heat resistance. Furthermore, when the Tg is 250°C or lower, the resin tends to have even better moldability. From the same viewpoint, the glass transition temperature of the polycarbonate resin of this embodiment is more preferably 125°C or higher and 245°C or lower, and even more preferably 125°C or higher and 240°C or lower. The glass transition temperature of the polycarbonate resin is measured using a differential scanning calorimeter (DSC), and specifically, can be measured by the method described in the examples.

[0057] In order to control the glass transition temperature of the polycarbonate resin of this embodiment within the above-mentioned preferred range, A, B, and R in formula (1) may be appropriately selected. In particular, when a cyclohexane-1,2-diyl group is selected for A, a cyclohexyl group, a norbornyl group, a decahydronaphthyl group, or an octahydro-1,4:5,8-dimethanonaphthalenyl group is selected for B, and a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, or an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms is selected for R, the glass transition temperature tends to be improved and heat resistance tends to be excellent.

[0058] In the polycarbonate resin of this embodiment, the absolute value of the photoelastic coefficient is 1.5 × 10 -12 Pa -1 It is preferable that the absolute value of the photoelastic coefficient is 1.4 × 10 or less. When the absolute value of the photoelastic coefficient is within the above range, it is possible to suppress the change in retardation when strain is applied to the polycarbonate resin, and therefore the polycarbonate resin tends to exhibit even lower birefringence. From the same viewpoint, the absolute value of the photoelastic coefficient of the polycarbonate resin of this embodiment is more preferably 1.4 × 10 -12 Pa -1 and more preferably 1.3 × 10 -12 Pa -1 or less, and even more preferably 1.2 × 10 -12 Pa -1 and even more preferably 1·1×10 -12 Pa -1 In the polycarbonate resin of the present embodiment, the lower limit of the absolute value of the photoelastic coefficient is not particularly limited, but is, for example, 0.01 × 10 -12 Pa -1 The photoelastic coefficient of the polycarbonate resin can be specifically measured by the method described in the Examples. The test piece used to measure the photoelastic coefficient of the polycarbonate resin of this embodiment is formed into a film at 150°C or higher and 300°C or lower. The film thickness of the film to be produced is preferably 10 μm or higher and 1000 μm or lower.

[0059] In order to control the absolute value of the photoelastic coefficient of the polycarbonate resin of this embodiment within the above-mentioned preferred range, A, B, and R in formula (1) may be appropriately selected. In particular, when a cyclohexane-1,2-diyl group is selected for A, a cyclohexyl group, a norbornyl group, a decahydronaphthyl group, or an octahydro-1,4:5,8-dimethanonaphthalenyl group is selected for B, and a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, or an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms is selected for R, the absolute value of the photoelastic coefficient tends to be small.

[0060] In the polycarbonate resin of this embodiment, the absolute value of the in-plane retardation of the 100% uniaxially stretched film is preferably 100 nm or less in terms of a thickness of 100 μm. When the absolute value of the in-plane retardation is within the above range, the occurrence of birefringence in the polycarbonate resin due to the orientation of molecules contained in the polymer chain tends to be further suppressed. From the same viewpoint, in the polycarbonate resin of this embodiment, the absolute value of the in-plane retardation of the 100% uniaxially stretched film is more preferably 95 nm or less in terms of a thickness of 100 μm, and even more preferably 90 nm or less in terms of a thickness of 100 μm. Furthermore, the lower limit of the absolute value of the in-plane retardation is not particularly limited, and may be 0 nm in terms of a thickness of 100 μm. Specifically, the in-plane retardation of the polycarbonate resin can be measured by the method described in the Examples. The 100% uniaxially stretched polycarbonate resin film refers to a film obtained by forming a polycarbonate resin into a film by a casting method, a vacuum hot press, or the like, and then stretching the polycarbonate resin 100% in a uniaxial direction at a temperature equal to or higher than the glass transition temperature. The film before stretching is preferably formed at 150°C or higher and 300°C or lower, and the thickness of the film to be produced is preferably 10 μm or higher and 1000 μm or lower.

[0061] In order to control the absolute value of the in-plane retardation of the polycarbonate resin of this embodiment within the above-mentioned preferred range, A, B, and R in formula (1) may be appropriately selected. In particular, when a cyclohexane-1,2-diyl group is selected for A, a cyclohexyl group, a norbornyl group, a decahydronaphthyl group, or an octahydro-1,4:5,8-dimethanonaphthalenyl group is selected for B, and a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, or an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms is selected for R, the absolute value of the in-plane retardation tends to be small.

[0062] In the polycarbonate resin of this embodiment, the temperature dependence of orientation birefringence (dΔn / dT) in the stretched film uniaxially stretched under the conditions shown below is −0.1×10 -5 ≦dΔn / dT≦+0.1×10 -5 When the dΔn / dT is within the above range, the occurrence of birefringence in the polycarbonate resin due to temperature changes tends to be further suppressed. Specifically, in the case of a uniaxially stretched film having a thickness of 100 μm, dΔn / dT=0.1×10 -5 In this case, a temperature change of 10°C will cause a phase difference change of 1 nm. However, this change is generally at a level that can be seen by humans in crossed Nicol observation, so the absolute value of the temperature dependence of orientation birefringence dΔn / dT is 0.1×10 -5 From the same viewpoint, in the polycarbonate resin of the present embodiment, dΔn / dT is more preferably −0.05×10 -5 ≦dΔn / dT≦+0.05×10 -5 and more preferably −0.01×10 -5 ≦dΔn / dT≦+0.01×10 -5The temperature dependence of orientation birefringence in a stretched film obtained by uniaxially stretching a polycarbonate resin under the conditions shown below can be measured specifically by the method described in the Examples. Note that a 100% uniaxially stretched polycarbonate resin film means a film obtained by forming a polycarbonate resin into a film by a method such as casting or vacuum hot pressing, and then stretching the polycarbonate resin 100% in the uniaxial direction under a temperature condition equal to or higher than the glass transition temperature. Note that the film before stretching is formed at a temperature of 150°C to 300°C, and the film thickness of the film produced is preferably 10 μm to 1000 μm. (Stretching conditions) Stretching temperature: 20°C higher than the glass transition temperature (Tg) of polycarbonate resin Stretching speed: 50mm / min Stretching ratio: 100%

[0063] In order to control dΔn / dT within the above-mentioned preferred range in the polycarbonate resin of this embodiment, A, B, and R in formula (1) may be appropriately selected. In particular, when a cyclohexane-1,2-diyl group is selected for A, a cyclohexyl group, a norbornyl group, a decahydronaphthyl group, or an octahydro-1,4:5,8-dimethanonaphthalenyl group is selected for B, and a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, or an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms is selected for R, dΔn / dT tends to be small.

[0064] [Polycarbonate resin composition] The polycarbonate resin composition of the present embodiment contains the above-described polycarbonate resin and an antioxidant.

[0065] The polycarbonate resin composition of this embodiment contains an antioxidant, which can suppress deterioration due to heat and shear during molding processing, thereby further improving the heat resistance of the polycarbonate resin composition. Furthermore, the polycarbonate resin composition of this embodiment contains an antioxidant, which can suppress oxidation of the polycarbonate resin during use, thereby further improving the light resistance of the polycarbonate resin composition.

[0066] The antioxidant in the polycarbonate resin composition of the present embodiment is not particularly limited, but examples thereof include hindered phenol-based antioxidants and phosphorus-based antioxidants.

[0067] Examples of the hindered phenol-based antioxidant include, but are not limited to, Irganox 1010 (Irganox 1010: pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate), Irganox 1330 (Irganox 1330: 3,3',3'',5,5',5''-hexa-t-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol), Irganox 3114 (Irganox 3114: 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione), Irganox 3125 (Irganox 3125), Adekastab AO-60 (pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]), Adekastab AO-80 (3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane), Cyanox 1790, Sumilizer GA-80, Sumilizer GS (Sumilizer GS: 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate), and Sumilizer GM GM: 2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl acrylate. These may be used alone or in combination of two or more.

[0068] The phosphorus-based antioxidant is not particularly limited, but examples thereof include Irgafos 168 (Irgafos 168: tris(2,4-di-t-butylphenyl)phosphite), Irgafos 12 (Irgafos 12: tris[2-[[2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine), ADKSTAB HP-10 (ADKSTAB HP-10: 2,2'-methylenebis(4,6-di-tert-butylphenyl)octylphosphite), ADKSTAB PEP36 (ADKSTAB PEP36: bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite), ADKSTAB PEP36A (ADKSTAB Examples of suitable phosphate esters include PEP36A (bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite), Sumilizer GP (6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxaphosphepine), and GSY P101 (tetrakis(2,4-di-t-butyl-5-methylphenyl)4,4'-biphenylene diphosphonite). These may be used alone or in combination of two or more.

[0069] The polycarbonate resin in the polycarbonate resin composition of the present embodiment is the same as the polycarbonate resin described above, and preferred embodiments are also the same.

[0070] From the viewpoint of more effectively and reliably achieving the effects of the present invention, the content of the polycarbonate resin in the polycarbonate resin composition of the present embodiment is preferably 50% by mass or more and 100% by mass or less, more preferably 60% by mass or more and less than 100% by mass, and even more preferably 65% ​​by mass or more and less than 100% by mass, based on the entire resin composition.

[0071] From the viewpoint of suppressing deterioration due to heat and shear during molding processing, the content of the antioxidant in the polycarbonate resin composition of the present embodiment is preferably from 0.001% by mass to 1% by mass, more preferably from 0.003% by mass to 1% by mass, and even more preferably from 0.005% by mass to 1% by mass, based on the total mass of the resin composition.

[0072] [Optical components] The optical component of the present embodiment contains the above-mentioned polycarbonate resin or the above-mentioned polycarbonate resin composition.

[0073] The polycarbonate resin or polycarbonate resin composition contained in the optical component of this embodiment has a small photoelastic coefficient and a small in-plane retardation due to molecular orientation, so the optical component of this embodiment is less likely to exhibit stress birefringence and orientation birefringence. Therefore, the optical component of this embodiment tends to be able to suppress birefringence during use. Furthermore, as described above, the polycarbonate resin or polycarbonate resin composition contained in the optical component of this embodiment has excellent heat resistance, so the optical component of this embodiment is less likely to deteriorate over time and can be used for a longer period of time than conventional optical components.

[0074] The optical component of the present embodiment is not particularly limited, and examples thereof include optical lenses such as those used in cameras, telescopes, microscopes, projectors, and automotive lenses, as well as optical films such as diffusers, light guide plates, polarizing plates, and retardation films. The optical component of the present embodiment can be obtained by appropriately processing, such as molding, the above-mentioned polycarbonate resin or the above-mentioned polycarbonate resin composition so as to have a shape suitable for the application.

[0075] [Manufacturing method of polycarbonate resin] The method for producing the polycarbonate resin of this embodiment is not particularly limited, and examples thereof include a method for copolymerizing an epoxide with carbon dioxide, a method for ring-opening polymerization of a cyclic carbonate, and a method for condensation polymerization of a diol with carbon dioxide or a carbonate ester. From the viewpoint of more effectively and reliably achieving the effects of the present invention, it is preferable to use the method for producing a polycarbonate resin described below as the method for synthesizing the polycarbonate resin of this embodiment.

[0076] The method for producing a polycarbonate resin according to the present embodiment preferably includes a step of ring-opening polymerization of a cyclic carbonate, which will be described later.

[0077] The cyclic carbonate is preferably a cyclic carbonate represented by the following formula (1L) (hereinafter also referred to as "cyclic carbonate (A1)").

[0078] [ka]

[0079] In formula (1L), A and B are as explained in formula (1).

[0080] In the method for producing a polycarbonate resin of this embodiment, the cyclic carbonate (A1) used in the ring-opening polymerization may be one type of cyclic carbonate (A1) alone, or any two or more types of cyclic carbonates (A1) having different A or B may be used in combination.

[0081] In order to more effectively and reliably achieve the effects of the present invention, the carbonate group in the cyclic carbonate (A1) used in the ring-opening polymerization preferably forms a 1,2-trans structure.

[0082] In the method for producing a polycarbonate resin of this embodiment, other cyclic carbonates may be used in addition to the cyclic carbonate (A1). Examples of other cyclic carbonates include a cyclic carbonate represented by formula (3L) (hereinafter also referred to as "cyclic carbonate (A2)").

[0083] [ka]

[0084] In formula (3L), C is as explained in formula (2). In the method for producing a polycarbonate resin of the present embodiment, the cyclic carbonate (A2) used in the ring-opening polymerization may be one type of cyclic carbonate alone, or any two or more types of cyclic carbonates having different C may be used in combination.

[0085] (Polymerization initiator) Polymerization initiators for ring-opening polymerization of cyclic carbonates (A1) and (A2) include, but are not limited to, acid catalysts, base catalysts, and enzyme catalysts. Base catalysts include, but are not limited to, alkyl metals, metal alkoxides, metal amides, metal organic acid salts, cyclic amines such as cyclic monoamines and cyclic diamines (particularly cyclic diamine compounds having an amidine skeleton), triamine compounds having a guanidine skeleton, and heterocyclic compounds containing nitrogen atoms. Alkyl metals include, but are not limited to, organolithium compounds such as methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and phenyllithium, methylmagnesium halide, ethylmagnesium halide, propylmagnesium halide, phenylmagnesium halide, trimethylaluminum, and triethylaluminum. Among these, methyllithium, n-butyllithium, or sec-butyllithium is preferred. Metal ions in the metal alkoxide include, but are not limited to, alkali metal and alkaline earth metal ions, with alkali metals being preferred. Examples of alkoxide ions include, but are not limited to, methoxide, ethoxide, propoxide, butoxide, phenoxide, and benzyl oxide. Phenoxide and benzyl oxide may have a substituent on the aromatic ring. Examples of metal amides include, but are not limited to, lithium amide, sodium amide, potassium amide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, and potassium bis(trimethylsilyl)amide. Examples of organic acid ions in metal organic acid salts include, but are not limited to, carboxylic acid ions having 1 to 10 carbon atoms. Examples of metals in metal organic acid salts include, but are not limited to, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, and tin. Examples of base catalysts include, but are not limited to, organic bases.The organic base is not particularly limited, but examples thereof include 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), diphenylguanidine (DPG), N,N-dimethyl-4-aminopyridine (DMAP), imidazole, pyrimidine, purine, and phosphazene base. From the viewpoint of more effectively and reliably achieving the effects of the present invention, the polymerization initiator of this embodiment is preferably an alkyl metal, a metal alkoxide, or a metal amide, and more preferably a metal alkoxide or a metal amide.

[0086] The amount of polymerization initiator used in the polymerization step of the polycarbonate resin production method of this embodiment may be adjusted appropriately depending on the target molecular weight of the polycarbonate resin. From the viewpoint of controlling the weight-average molecular weight (Mw) of the polycarbonate resin within the range of 10,000 to 500,000, the amount of polymerization initiator used, calculated as the amount of substance relative to the ring-opening polymerizable monomer (the total amount of monomers such as the cyclic carbonate (A1) and the cyclic carbonate (A2)), is preferably 0.0001 mol% to 4 mol%, more preferably 0.0001 mol% to 2 mol%, and even more preferably 0.0001 mol% to 1 mol%. The above polymerization initiators may be used singly or in combination of two or more.

[0087] (polymerization terminator) In order to control the average molecular weight of the resulting polycarbonate resin, a polymerization terminator may be used in addition to the polymerization initiator. The polymerization terminator is not particularly limited, but examples thereof include inorganic acids and organic acids such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, phosphoric acid, metaphosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, lactic acid, citric acid, ascorbic acid, gluconic acid, oxalic acid, tartaric acid, Meldrum's acid, and benzoic acid.

[0088] (additives) In order to control the molecular weight of the resulting polymer and to control the terminal structure to exhibit various properties, additives may be used in addition to the polymerization initiator. Examples of the additives include, but are not limited to, monoalcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, nonanol, decanol, dodecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, 5-norbornene-2-methanol, 1-adamantanol, 2-adamantanol, trimethylsilylmethanol, phenol, benzyl alcohol, and p-methylbenzyl alcohol, dialcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexanediol, nonanediol, tetramethylene glycol, and polyethylene glycol, polyhydric alcohols such as glycerol, sorbitol, xylitol, ribitol, erythritol, and triethanolamine, and methyl lactate and ethyl lactate. The above additives may be used singly or in combination of two or more.

[0089] (Reaction temperature) In the method for producing a polycarbonate resin of this embodiment, the reaction temperature in the polymerization step is not particularly limited as long as it is within a range in which the polycarbonate resin of this embodiment can be produced, but is preferably −60° C. or higher and 150° C. or lower, more preferably −60° C. or higher and 130° C. or lower, and even more preferably −60° C. or higher and 120° C. If the reaction temperature in the polymerization step is within the above range, it becomes easier to control the weight average molecular weight of the obtained polycarbonate resin to a range of 10,000 or higher and 1,000,000 or lower.

[0090] (solvent) In the method for producing a polycarbonate resin according to the present embodiment, a solvent may or may not be used. Examples of the solvent include, but are not limited to, ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, tert-butyl methyl ether, and propylene glycol monomethyl ether acetate; halogen-based solvents such as methylene chloride, chloroform, dichloromethane, dichloroethane, and trichloroethane; saturated hydrocarbon solvents such as hexane, heptane, octane, nonane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as toluene, xylene, o-xylene, m-xylene, p-xylene, and cresol; and ketone solvents such as acetone, 2-butanone, 2-pentanone, 3-pentanone, cyclopentanone, cyclohexanone, and methyl isobutyl ketone.

[0091] [Cyclic carbonate] Polycarbonate resins are required to have various physical properties, and novel cyclic carbonates are being sought as raw materials for the resins. An object of the present embodiment is to provide novel cyclic carbonates and methods for producing the same.

[0092] The cyclic carbonate of this embodiment has a structure in which an alicyclic skeleton is bonded to a 1,2-cycloalkylene carbonate skeleton via a single bond. The cyclic carbonate of this embodiment has the above-described configuration, and by ring-opening polymerizing the cyclic carbonate, a polycarbonate with excellent heat resistance can be obtained. The reasons for this are thought to be as follows, but are not limited to: Conventional cyclic carbonates with an alicyclic structure are often 1,2-cycloalkylene carbonates that do not have a ring skeleton in the side chain, and have insufficient heat resistance. In contrast, the cyclic carbonate of this embodiment has a structure in which an alicyclic skeleton is further bonded to the side chain of the 1,2-cycloalkylene carbonate skeleton. Therefore, it is presumed that the cyclic carbonate of this embodiment has excellent heat resistance due to an increased proportion of ring skeletons in the molecule while maintaining the ring-opening polymerizability of the 1,2-cycloalkylene carbonate.

[0093] The 1,2-cycloalkylene carbonate skeleton means a skeleton in which a cyclic carbonate group is formed by a cycloalkane-1,2-diyl group and a carbonate group bonded to the 1- and 2-positions. The cycloalkane-1,2-diyl group is not particularly limited, but examples thereof include a cyclopropane-1,2-diyl group, a cyclobutane-1,2-diyl group, a cyclopentane-1,2-diyl group, a cyclohexane-1,2-diyl group, a cycloheptane-1,2-diyl group, a cyclooctane-1,2-diyl group, a cyclononane-1,2-diyl group, and a cyclodecane-1,2-diyl group.

[0094] The alicyclic skeleton refers to a moiety having a cyclic aliphatic hydrocarbon structure. The alicyclic skeleton may be a monocyclic alicyclic skeleton or a polycyclic alicyclic skeleton, but is preferably a polycyclic alicyclic skeleton. In addition, the alicyclic skeleton is preferably the alicyclic skeleton B described below.

[0095] The cyclic carbonate of this embodiment is represented by the following formula (1L). [ka]

[0096] In formula (1L), A and B are as explained in formula (1).

[0097] The structural unit represented by formula (1) is preferably a trans isomer shown below. [ka] The above diagrams represent three-dimensional structures, and when a chiral center is included in the formula, it may be either an R-configuration or an S-configuration.

[0098] The cyclic carbonate of this embodiment is preferably represented by the following formula (1LA): [ka] (In formula (1LA), B is an optionally substituted monovalent alicyclic moiety.) It is expressed as:

[0099] Preferred B in formula (1LA) is the same as that in formula (1L). In addition, examples of the substituent in formula (1LA), when substituted, are the same as those in formula (1L).

[0100] The cyclic carbonate of the present embodiment is preferably represented by the following formula (1LB) from the viewpoint of improving heat resistance and obtaining a low photoelastic coefficient. [ka]

[0101] In formula (1LB), R is a substituent, and n is an integer of 0 to 2. The substituent in formula (1LB) is the same as that in formula (1L).

[0102] The cyclic carbonate of the present embodiment is preferably represented by the following formula (1LC) from the viewpoint of improving heat resistance and obtaining a low photoelastic coefficient. [ka]

[0103] In formula (1LC), R is a substituent, and n is an integer of 0 to 2. The substituents in formula (1LB) are the same as those in formula (1L).

[0104] As the cyclic carbonate having the structure of formula (1L), from the viewpoint of further improving heat resistance and obtaining a lower photoelastic coefficient, The following formula (1L-1): [ka] The following formula (1L-2): [ka] The following formula (1L-3): [ka] Or, the following formula (1L-4): [ka] Preferably, the cyclic carbonate is a cyclic carbonate represented by the following formula:

[0105] The physical properties of the cyclic carbonates represented by the above formula (1L-1) or formula (1L-2) can be tuned by converting the functional group at the olefin moiety.

[0106] The cyclic carbonate composition of this embodiment preferably contains a cyclic carbonate represented by formula (1L-1) and a cyclic carbonate represented by formula (1L-2). By containing the cyclic carbonate represented by formula (1L-1) and the cyclic carbonate represented by formula (1L-2), the cyclic carbonate composition of this embodiment can introduce various substituents by functional group conversion of the olefin moiety, making it easy to tune physical properties such as heat resistance and photoelastic coefficient.

[0107] The molar ratio of the cyclic carbonate represented by formula (1L-1) to the cyclic carbonate represented by formula (1L-2) in the cyclic carbonate composition of this embodiment (cyclic carbonate represented by formula (1L-1) / cyclic carbonate represented by formula (1L-2)) is not particularly limited, but is preferably, for example, 10 / 90 to 90 / 10, 20 / 80 to 80 / 20, 30 / 70 to 70 / 30, or 40 / 60 to 60 / 40.

[0108] The cyclic carbonate represented by the formula (1L) is preferably a cyclic carbonate represented by the formula (1L-3) or (1L-4) from the viewpoint of further improving heat resistance.

[0109] From the viewpoint of further improving heat resistance, the cyclic carbonate composition of this embodiment preferably contains a cyclic carbonate represented by formula (1L-3) and a cyclic carbonate represented by formula (1L-4).

[0110] The molar ratio of the cyclic carbonate represented by formula (1L-3) to the cyclic carbonate represented by formula (1L-4) in the cyclic carbonate composition of this embodiment (cyclic carbonate represented by formula (1L-3) / cyclic carbonate represented by formula (1L-4)) is not particularly limited, but is preferably, for example, 10 / 90 to 90 / 10, 20 / 80 to 80 / 20, 30 / 70 to 70 / 30, or 40 / 60 to 60 / 40.

[0111] More specific examples of cyclic carbonates having the structure of formula (1L) include 4-(5-norbornen-2-yl)-trans-1,2-cyclohexene carbonate, 4-(5-norbornan-2-yl)-trans-1,2-cyclohexene carbonate, 4-(5-tetracyclododecen-2-yl)-trans-1,2-cyclohexene carbonate, 4-(5-tetracyclododecan-2-yl)-trans-1,2-cyclohexene carbonate, and 4-(1,4,5,6,7-pentamethyl-5-norbornen-2-yl)-trans-1,2-cyclohexene carbonate. Among these, from the viewpoint of further improving heat resistance and obtaining a lower photoelastic coefficient, more specifically, 4-(5-norbornen-2-yl)-trans-1,2-cyclohexene carbonate, 4-(5-norbornan-2-yl)-trans-1,2-cyclohexene carbonate, 4-(5-tetracyclododecen-2-yl)-trans-1,2-cyclohexene carbonate, and 4-(5-tetracyclododecan-2-yl)-trans-1,2-cyclohexene carbonate are more preferred.

[0112] [Method for producing cyclic carbonate] The method for producing a cyclic carbonate of the present embodiment preferably includes a step of reacting a cyclic carbonate represented by the following formula (2L) with a compound having a conjugated diene moiety.

[0113] [ka] (In formula (2L), A is an optionally substituted trivalent alicyclic moiety.)

[0114] Preferred examples of A in formula (2L) are the same as those in formula (1L). In addition, examples of the substituent in formula (2L) are the same as those in formula (1L).

[0115] The compound having a conjugated diene moiety used in the production method is not particularly limited, but examples thereof include 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, trans-3-(tert-butyldimethylsilyloxy)-N,N-dimethyl-1,3-butadien-1-amine, 1,3-pentadiene, 2,4-hexadiene, 3-methyl-1,3-pentadiene, 1,3-cyclopentadiene, and 1,3-cyclohexadiene. , 2-trimethylsilyloxy-1,3-cyclohexadiene, 1,3,5,5-tetramethyl-1,3-cyclohexadiene, α-terpinene, α-phellandrene, 1,2,3,4,5-pentamethylcyclopentadiene, 5-trimethylsilyl-1,2,3,4,5-pentamethyl-1,3-cyclopentadiene, 1,2,3,4-tetraphenyl-1,3-cyclopentadiene, 1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene, and 1,3-cyclooctadiene.

[0116] The compound having a conjugated diene moiety in this embodiment may be generated during the reaction by thermal decomposition or the like in the production process of a cyclic carbonate. For example, 1,3-cyclopentadiene generated by thermally decomposing dicyclopentadiene during the reaction may be used instead of 1,3-cyclopentadiene.

[0117] In the method for producing a cyclic carbonate according to this embodiment, the cyclic carbonate according to this embodiment can be purified from the reaction product obtained in the reaction step by purification procedures such as distillation, column chromatography, and recrystallization.

[0118] [Uses of cyclic carbonates] The cyclic carbonate according to this embodiment can be used as a raw material for polycarbonate resin. Polycarbonate resin can be obtained by ring-opening polymerization of the cyclic carbonate using an initiator such as an anionic polymerization initiator. In addition, the cyclic carbonate can be used as an electrolyte for lithium ion secondary batteries or as an additive to the electrolyte. [Example]

[0119] The present invention will be explained in more detail using examples and comparative examples, but the present invention is not limited to these examples in any way.

[0120] The various abbreviations are as follows: T6C: trans-1,2-cyclohexene carbonate VCHC: 4-vinyl-trans-1,2-cyclohexene carbonate NORT: 4-(5-norbornen-2-yl)-trans-1,2-cyclohexene carbonate NORT-H: 4-(5-norbornan-2-yl)-trans-1,2-cyclohexene carbonate TCDT: 4-(5-tetracyclododecen-2-yl)-trans-1,2-cyclohexene carbonate TCDT-H: 4-(5-tetracyclododecan-2-yl)-trans-1,2-cyclohexene carbonate Me5NORT: 4-(1,4,5,6,7-pentamethyl-5-norbornene-2-yl)-trans-1,2-cyclohexene carbonate

[0121] In this specification, the physical properties of the cyclic carbonate were measured as follows.

[0122] ( 1 H-NMR measurement) By performing NMR measurements using a JEOL NMR device (product name: ECZ400S) and a TFH probe, the 1 H-NMR spectra were obtained. Note that the base peak of the deuterated solvent was δ H = 7.26 ppm, and the number of integrations was set to 32.

[0123] (Accurate mass measurement; HR-MS) Accurate mass measurements of cyclic carbonates were performed using a GC / Q-TOFMS instrument manufactured by Agilent Technologies (product name: Agilent 7890GC / 7200 Accurate-Mass Q-TOF GC / MS). More specifically, an acetone solution of cyclic carbonates prepared to a sample concentration of 500 ppm (2500 ppm for Example L1) was analyzed using an Agilent J&W GC column (product name: DB-1) manufactured by Agilent Technologies, Inc. The column temperature was held at 40°C for 5 minutes, then increased to 300°C at 20°C / min and held at 300°C for 12 minutes. Using 20% ​​methane as the reaction gas, the exact mass of the protonated product of each cyclic carbonate was measured by chemical ionization. Calculated values ​​are reported as Calc., and measured values ​​as Found.

[0124] (Measurement of weight average molecular weight (Mw) and number average molecular weight (Mw)) The weight-average molecular weight of the polycarbonate resin was measured using a solution containing 0.02 g of polycarbonate resin and 2.0 g of tetrahydrofuran as a measurement sample using a high-speed GPC system (manufactured by Tosoh Corporation, product name "HLC-8420GPC"). The columns used were TSK guard columns SuperH-H, TSKgel SuperHM-H, TSKgel SuperHM-H, TSKgel SuperH2000, and TSKgel SuperH1000 (all products manufactured by Tosoh Corporation) connected in series. The column temperature was set to 40°C, and analysis was performed at a rate of 0.60 mL / min using tetrahydrofuran as the mobile phase. An RI detector was used as the detector. A calibration curve was prepared using polystyrene standard samples (molecular weights: 2,520,000, 1,240,000, 552,000, 277,000, 130,000, 66,000, 34,800, 19,700, 8,680, 3,470, 1,306, and 370) manufactured by Polymer Standards Service as standard samples. Based on the calibration curve prepared in this manner, the number-average molecular weight and weight-average molecular weight of the polycarbonate resin were determined.

[0125] (Measurement of glass transition temperature (Tg)) Approximately 5 mg of the polycarbonate resin obtained in the examples and comparative examples described below was used as a measurement sample, and the glass transition temperature was measured using a differential scanning calorimeter (product name "DSC8500") manufactured by PerkinElmer Japan Co., Ltd. under the condition of a nitrogen gas flow rate of 20 mL / min. More specifically, after holding at 40°C for 3 minutes, the sample was first heated from 40°C to 210°C at 20°C / min to completely melt. The temperature was then lowered from 210°C to 40°C at 50°C / min and held at 40°C for 5 minutes. The glass transition temperature (Tg) was determined by the intersection of the step-like change portion of the DSC curve drawn during the second heating from 40°C to 200°C at 10°C / min with a straight line equidistant in the vertical direction from the extension of each tangent (midpoint glass transition temperature).

[0126] (Measurement of in-plane retardation, orientation birefringence, and temperature dependence of orientation birefringence) <Preparation of unstretched and stretched samples> First, an unstretched polycarbonate resin sample was prepared using a vacuum compression molding machine. Specifically, it was prepared as follows. The polycarbonate resin was placed in a 25-150 μm thick polyimide frame and sandwiched between two polyimide films, two aluminum plates, and two iron plates to obtain a laminate. The laminate was stacked in the following order: iron plate, aluminum plate, polyimide film, polyimide frame, polyimide film, aluminum plate, and iron plate. The laminate was placed in a vacuum compression molding machine (Shindo Metal Industries, SFV-30 model) and preheated at a predetermined temperature under reduced pressure (10 kPa) for 5 minutes. After that, it was compressed at a predetermined temperature and a pressure of 10 MPa for 10 minutes while maintaining the reduced pressure. After the vacuum and press pressure were released, the compressed laminate was transferred to a cooling compression molding machine (AYS-10, manufactured by Shinto Metal Industries Co., Ltd.) and cooled to solidify, yielding a pressed film with a thickness of 20 to 250 μm. The obtained pressed film was aged for 24 hours in a constant temperature and humidity chamber at 23°C and 50% humidity to obtain an unstretched sample.

[0127] Next, the unstretched sample was cut into a width of 30 mm and a length of 50 mm and placed in a tensile test jig. The tensile test jig was set in a Shimadzu Autograph AG-5kNXPlus tester connected to a thermostatic chamber TCR1W-200T, and uniaxial free stretching was performed under the following conditions: chuck distance 30 mm, stretching temperature Tg + 20°C, stretching speed 50 mm / min, and stretch ratio 100% (meaning 2x stretching). Immediately after uniaxial free stretching, the sample was removed and cooled to room temperature and then aged for 24 hours in a constant temperature and humidity chamber at 23°C and 50% humidity to obtain a stretched film with a thickness of 10 to 500 μm. Several stretched films were produced using the above procedure. The thickness of each film was then measured using a thickness gauge (Mitutoyo Corporation, Digimatic Thickness Gauge).

[0128] <Measurement conditions for in-plane retardation and orientation birefringence> The in-plane retardation and orientation birefringence were measured using the above 100% uniaxially stretched film as follows. First, for each stretched film, the absolute value of the in-plane retardation at a wavelength of 587 nm was measured using a retardation measuring device manufactured by Oji Scientific Instruments (product name "KOBRA-WR"). Then, the orientation birefringence was calculated using the obtained absolute value of the in-plane retardation and the thickness of each stretched film. The obtained orientation birefringence was used to calculate the absolute value of the in-plane retardation per 100 μm thickness from the thickness of the stretched film, and this was taken as the absolute value of the in-plane retardation converted to a thickness of 100 μm. Note that the orientation birefringence, the absolute value of the in-plane retardation, the absolute value of the in-plane retardation converted to a thickness of 100 μm, and the thickness of the stretched film satisfy the following formulas (A), (B), and (C). Δn=nx-ny (A) Re=Δn×d (B) Re 100 (nm) = Δn × 1.0 × 10 5 (C) (Δn: orientation birefringence, nx: refractive index in the stretching direction, ny: refractive index in the direction perpendicular to the stretching direction within the sample plane, Re: absolute value of in-plane retardation, Re 100 : absolute value of in-plane retardation converted to a thickness of 100 μm, d: thickness of stretched film)

[0129] <Measurement of temperature dependence of orientation birefringence> The temperature dependence of orientation birefringence was measured using the uniaxially stretched film obtained above. First, the prepared film was set in a temperature control jig and left to stabilize at a specified temperature for 15 minutes. After that, birefringence measurements were repeatedly performed at 10°C intervals from 30°C to 60°C. Since the change in birefringence at each temperature corresponds to the temperature dependence of orientation birefringence, the temperature dependence of orientation birefringence dΔn / dT was calculated by finding the slope of the approximation line using the least squares method.

[0130] (Measurement of photoelastic coefficient) The unstretched samples obtained in the above "Preparation of Unstretched and Stretched Samples" were cut into pieces 6 mm wide and 30 mm long and used as samples to measure the photoelastic coefficient as follows. Details of the measurement method were found in Polymer Engineering and Science 1999, 39, 2349-2357. Specifically, the procedure is as follows: The sample was placed in a film tensioning device (manufactured by Imoto Manufacturing Co., Ltd.) installed in a constant temperature and humidity chamber at 23°C and 50% humidity, with a chuck spacing of 20 mm. Next, the birefringence measurement device (manufactured by Otsuka Electronics, product name "RETS-100") was positioned so that the optical path of the birefringence measurement device was positioned at the center of the sample. The birefringence of the test piece was measured at a wavelength of 550 nm while applying a stretching stress, with a chuck spacing of 20 mm and a chuck movement speed of 0.1 mm / min. From the relationship between the measured birefringence and stretching stress, the photoelastic coefficient (Pa) was calculated using the least squares method. -1 ) was calculated. For the calculation, data in which the tensile stress σ was 2.5 MPa≦σ≦10 MPa was used. The birefringence, tensile stress, and photoelastic coefficient satisfy the following formulas (D) and (E). Δn=nx-ny (D) C=Δn / σ (E) (Δn: birefringence, nx: refractive index in the stretching direction, ny: refractive index in the direction perpendicular to the stretching direction within the sample surface, C: photoelastic coefficient, σ: stretching stress)

[0131] [Synthesis example 1: VCHC] Under an argon atmosphere, 4-vinylcyclohexene oxide (485 g, 3.91 mol) and ion-exchanged water (4.85 L) were added to a 20 L five-neck flask and stirred at room temperature with a mechanical stirrer. The mixture was heated at an internal temperature of 95°C for 16 hours using a mantle heater. After cooling, the mixture was concentrated under reduced pressure using an evaporator, and toluene (4 L) was added to the concentrate to perform azeotropy. This azeotropic operation was repeated six times to obtain 4-vinyl-trans-1,2-cyclohexanediol (hereinafter also referred to as VCHDL; 551 g). Next, under an argon atmosphere, VCHDL (551 g, 3.87 mol) and tetrahydrofuran (5.52 L) were added to a five-neck flask and stirred at room temperature with a mechanical stirrer. The flask was immersed in a salt ice bath to cool, and ethyl chloroformate (842 g, 7.76 mol) and triethylamine (1060 g, 10.48 mol) were added dropwise. The flask was removed from the ice bath and allowed to warm to room temperature. After stirring at room temperature for 19 hours, the flask was again immersed in the salt ice bath to cool, and ethyl chloroformate (210 g, 1.94 mol) and triethylamine (265 g, 2.62 mol) were added dropwise. The flask was removed from the ice bath and allowed to warm to room temperature. After stirring at room temperature for 20 hours, the reaction mixture was filtered under reduced pressure, and the residue was rinsed with tetrahydrofuran / toluene = 2 / 1 (3 L x 3 times). The filtrate was concentrated under reduced pressure using an evaporator, and the resulting concentrate was dissolved in chloroform (4.5 L). Deionized water (4.5 L) was added and the mixture was stirred, followed by separation to recover the organic layer. The recovered organic layer was washed again with deionized water (4.5 L), dried over magnesium sulfate, and filtered. The organic layer was concentrated under reduced pressure using an evaporator, and the resulting concentrate was purified by silica gel column chromatography to obtain VCHC (569 g).

[0132] [Synthesis Example 2: TCDT] A 3-L autoclave was charged with VCHC (501 g, 3 mol) and dicyclopentadiene (2484 g, 18 mol). The mixture was heated to an internal temperature of 200 °C and the reaction was continued for 3 days. After cooling to an internal temperature of 60 °C, the contents were recovered and dissolved in chloroform (5.5 L). This solution was slowly poured into methanol (20 L) and stirred for 1 hour. The precipitate was removed by vacuum filtration and rinsed with methanol (1.5 L). The filtrate was concentrated under reduced pressure, and the concentrate was subjected to silica gel column chromatography to separate into two fractions, A and B. 490 g of concentrate was obtained from A, and 231 g of concentrate was obtained from B. The concentrate from fraction A (490 g) was subjected to silica gel column chromatography again, and the fraction containing the target product was concentrated. During the concentration, a white solid began to precipitate, so the concentration was stopped midway. The solid was recovered by vacuum filtration and dried under reduced pressure at 50 °C to obtain TCDT (25 g).

[0133] [Synthesis example 3: NORT] The concentrate (144 g) obtained by concentrating the filtrate after removing the white solid in Example 1 under reduced pressure was combined with the concentrate (231 g) of fraction B obtained in Example 1, and the combined concentrate was distilled under reduced pressure at 220°C / 0.6-2 hPa to obtain 168 g of a distillate. The obtained distillate was purified by silica gel column chromatography and dried under reduced pressure at 50°C to obtain NORT (102 g).

[0134] [Synthesis example 4:NORT-H] NORT (4.78 g, 20.4 mmol) and chloro(1,5-cyclooctadiene)iridium(I) dimer (0.145 g, 0.216 mmol) were weighed into a 50 mL three-neck flask, and the flask was purged with nitrogen. Toluene (Fujifilm Wako Pure Chemical Industries, Ltd., oxygen-scavenging grade; 10 mL) and 2-propanol (Fujifilm Wako Pure Chemical Industries, Ltd., oxygen-scavenging grade; 10 mL) were weighed and added to the flask. 1,2-bis(dicyclohexylphosphino)ethane (0.187 g, 0.442 mmol) was then weighed and added to the flask. The flask was then immersed in a 100 °C oil bath and heated for 6 hours with magnetic stirring. After cooling, the contents were transferred to a 50 mL flask, the solvent was removed using an evaporator, and the concentrated residue was purified by silica gel column chromatography to recover the fraction containing the target product, yielding 5.01 g of concentrate. This concentrate was dissolved in a mixed solvent of ethyl acetate (2 mL) and heptane (10 mL), transferred to a freezer at -30 °C, and allowed to stand overnight. The precipitated solid was collected by vacuum filtration, washed with heptane, and dried under reduced pressure at 60 °C to yield NORT-H (3.45 g).

[0135] [Synthesis Example 5: TCDT-H] The reaction was carried out in the same manner as in Example 3 except that TCDT (3.02 g) was used instead of NORT, to give TCDT-H (2.27 g).

[0136] [Example 1] T6C (1.05 g, 7.36 mmol) and a 2:3 NORT:TCDT mixture (2.01 g, 7.35 mmol) were weighed into a 50 mL three-neck flask, and the atmosphere inside the flask was replaced with nitrogen. Dehydrated m-xylene (11.9 g) was added to the flask and stirred using a magnetic stirrer to completely dissolve the mixture. The flask was immersed in a thermostatic bath at 25°C, and a tetrahydrofuran solution of potassium tert-butoxide (1.0 M, 28 μL, 0.028 mmol) was added and stirred at 25°C for 1 hour. Acetic acid (0.010 g) was added to terminate the reaction (polymerization solution). Subsequently, in order to evaluate the methanol-insoluble content, a reprecipitation operation was carried out as follows. The polymerization solution was diluted by adding acetone (61 g) and chloroform (31 g). The diluted solution was added to 400 g of methanol to precipitate a polycarbonate resin. The precipitated polycarbonate resin was recovered by filtration under reduced pressure and washed with methanol. The obtained polycarbonate resin was dried in a vacuum at 100°C for 2 hours to obtain a polycarbonate resin (2.54 g). 1 From the H-NMR spectrum, the proportions of T6C, NORT, and TCDT in the polycarbonate resin were calculated to be 52 mol%, 20 mol%, and 28 mol%, respectively. 1 The H-NMR spectrum is shown in Figure 1.

[0137] [Example 2] T6C (0.75 g, 5.28 mmol), a 2:3 mixture of NORT-H and TCDT-H (1.46 g, 5.29 mmol), and dehydrated m-xylene (8.71 g) were weighed into a 25 mL three-neck flask and dehydrated using 4A molecular sieves (monomer solution). After purging the atmosphere with nitrogen, the monomer solution (10.04 g) was removed and added to another 25 mL three-neck flask. The flask was immersed in a thermostatic bath at 25 °C, and a solution of potassium tert-butoxide in tetrahydrofuran (1.0 M, 20 μL, 0.020 mmol) was added and stirred at 25 °C for 30 minutes. Acetic acid (0.011 g) was added to terminate the reaction (polymerization solution). Subsequently, in order to evaluate the methanol-insoluble content, the polymerization solution was diluted with chloroform (39 g). The diluted solution was added to 284 g of methanol to precipitate a polycarbonate resin. The precipitated polycarbonate resin was collected by filtration under reduced pressure and washed with methanol. The obtained polycarbonate resin was dried in a vacuum at 100°C for 2 hours to obtain a polycarbonate resin (1.87 g). 1 From the H-NMR spectrum, the proportions of T6C, NORT-H, and TCDT-H in the polycarbonate resin were calculated to be 52 mol%, 26 mol%, and 22 mol%, respectively. 1 The H-NMR spectrum is shown in Figure 2.

[0138] [Example 3] NORT-H (3.01 g, 12.7 mmol) and dehydrated m-xylene (12.2 g) were weighed into a 50 mL three-neck flask and dehydrated using 4A molecular sieves (monomer solution). After purging the atmosphere in another 50 mL three-neck flask with nitrogen, the monomer solution (11.96 g) was removed and added. The flask was immersed in a thermostatic bath at 25°C, and a solution of potassium tert-butoxide in tetrahydrofuran (1.0 M, 33 μL, 0.033 mmol) was added and stirred at 25°C for 15 minutes. Acetic acid (0.010 g) was added to terminate the reaction (polymerization solution). Subsequently, in order to evaluate the methanol-insoluble content, the polymerization solution was diluted with m-xylene (46 g). The diluted solution was added to 482 g of methanol to precipitate a polycarbonate resin. The precipitated polycarbonate resin was recovered by filtration under reduced pressure and washed with methanol. The obtained polycarbonate resin was dried in a vacuum at 80°C for 4 hours to obtain a polycarbonate resin (2.21 g). 1 The H-NMR spectrum is shown in Figure 3.

[0139] [Example 4] T6C (0.32 g, 2.24 mmol), NORT-H (2.11 g, 8.93 mmol), and dehydrated m-xylene (9.81 g) were weighed into a 25 mL three-neck flask and dehydrated using 4A molecular sieves (monomer solution). After purging the atmosphere with nitrogen, the monomer solution (8.13 g) was removed and added to a separate 50 mL three-neck flask (the solution contained 0.21 g of T6C, 1.40 g of NORT-H, and 6.52 g of m-xylene). The flask was placed in a thermostatic bath at 25 °C, and a solution of potassium tert-butoxide in tetrahydrofuran (1.0 M, 4 μL, 0.004 mmol) was added. The mixture was stirred at 25 °C for 30 minutes. Acetic acid (0.0040 g) was added to terminate the reaction (polymerization solution). Subsequently, in order to evaluate the methanol-insoluble content, the polymerization solution was diluted with chloroform (22 g). The diluted solution was added to 287 g of methanol to precipitate a polycarbonate resin. The precipitated polycarbonate resin was collected by filtration under reduced pressure and washed with methanol. The obtained polycarbonate resin was dried in a vacuum at 100°C for 6 hours to obtain a polycarbonate resin (1.46 g). 1 From the H-NMR spectrum, the proportions of T6C and NORT-H in the polycarbonate resin were calculated to be 19 mol% and 81 mol%, respectively. 1 The H-NMR spectrum is shown in Figure 4.

[0140] [Example 5] T6C (0.77 g, 5.40 mmol), TCDT-H (0.73 g, 2.42 mmol), and dehydrated m-xylene (12.50 g) were weighed into a 25 mL three-neck flask and dehydrated using 4A molecular sieves (monomer solution). After purging the atmosphere with nitrogen, the monomer solution (10.52 g) was removed and added to a separate 50 mL three-neck flask (the solution contained 0.58 g of T6C, 0.55 g of TCDT-H, and 9.39 g of m-xylene). The flask was placed in a thermostatic bath at 25 °C, and a solution of potassium tert-butoxide in tetrahydrofuran (1.0 M, 5 μL, 0.005 mmol) was added. The mixture was stirred at 25 °C for 30 minutes. Acetic acid (0.0022 g) was added to terminate the reaction (polymerization solution). Subsequently, in order to evaluate the methanol-insoluble content, the polymerization solution was diluted with m-xylene (13 g). The diluted solution was added to 344 g of methanol to precipitate a polycarbonate resin. The precipitated polycarbonate resin was recovered by filtration under reduced pressure and washed with methanol. The obtained polycarbonate resin was dried in a vacuum at 100°C for 6 hours to obtain a polycarbonate resin (0.97 g). 1 From the H-NMR spectrum, the proportions of T6C and TCDT-H in the polycarbonate resin were calculated to be 59 mol% and 41 mol%, respectively. 1 The H-NMR spectrum is shown in Figure 5.

[0141] [Example 6] T6C (3.69 g, 25.9 mmol), NORT-H (2.03 g, 8.59 mmol), TCDT-H (1.59 g, 5.26 mmol), and dehydrated m-xylene (29.30 g) were weighed into a 50 mL three-neck flask and dehydrated using 4A molecular sieves (monomer solution). After purging the atmosphere with nitrogen, the monomer solution (31.74 g) was withdrawn and added to another 50 mL three-neck flask (the solution contained 3.19 g of T6C, 1.76 g of NORT-H, 1.38 g of TCDT-H, and 25.4 g of m-xylene). The flask was immersed in a thermostatic bath at 25 °C, and a 1.0 M solution of potassium tert-butoxide in tetrahydrofuran (17 μL, 0.017 mmol) was added and stirred at 25 °C for 1 hour. Acetic acid (0.0061 g) was added to terminate the reaction (polymerization solution). Subsequently, in order to evaluate the methanol-insoluble content, the polymerization solution was diluted with chloroform (119.56 g). The diluted solution was added to 730 g of methanol to precipitate a polycarbonate resin. The precipitated polycarbonate resin was recovered by filtration under reduced pressure and washed with methanol. The obtained polycarbonate resin was dried in a vacuum at 100°C for 4 hours to obtain a polycarbonate resin (5.42 g). 1 From the H-NMR spectrum, the proportions of T6C, NORT-H, and TCDT-H in the polycarbonate resin were calculated to be 67 mol%, 21 mol%, and 12 mol%, respectively. 1 The H-NMR spectrum is shown in Figure 6.

[0142] [Example 7] T6C (4.81 g, 33.8 mmol), NORT-H (1.01 g, 4.27 mmol), TCDT-H (1.44 g, 4.76 mmol), and dehydrated m-xylene (29.04 g) were weighed into a 50 mL three-neck flask and dehydrated using 4A molecular sieves (monomer solution). After purging the atmosphere with nitrogen, the monomer solution (32.06 g) was withdrawn and added to another 50 mL three-neck flask (the solution contained 4.25 g of T6C, 0.89 g of NORT-H, 1.28 g of TCDT-H, and 25.6 g of m-xylene). The flask was immersed in a thermostatic bath at 25 °C, and a 1.0 M solution of potassium tert-butoxide in tetrahydrofuran (19 μL, 0.019 mmol) was added and stirred at 25 °C for 1 hour. Acetic acid (0.0062 g) was added to terminate the reaction (polymerization solution). Subsequently, in order to evaluate the methanol-insoluble content, the polymerization solution was diluted with chloroform (116.26 g). The diluted solution was added to 718 g of methanol to precipitate a polycarbonate resin. The precipitated polycarbonate resin was recovered by filtration under reduced pressure and washed with methanol. The obtained polycarbonate resin was dried in a vacuum at 100°C for 4 hours to obtain a polycarbonate resin (5.33 g). 1 From the H-NMR spectrum, the proportions of T6C, NORT-H, and TCDT-H in the polycarbonate resin were calculated to be 77 mol%, 11 mol%, and 12 mol%, respectively. 1 The H-NMR spectrum is shown in Figure 7.

[0143] [Example 8] T6C (3.99 g, 28.1 mmol), TCDT-H (2.72 g, 9.00 mmol), and dehydrated m-xylene (26.93 g) were weighed into a 50 mL three-neck flask and dehydrated using 4A molecular sieves (monomer solution). After purging the atmosphere with nitrogen, the monomer solution (29.79 g) was removed and added to another 50 mL three-neck flask (the solution contained 3.54 g of T6C, 2.41 g of TCDT-H, and 23.8 g of m-xylene). The flask was immersed in a thermostatic bath at 25 °C, and a solution of potassium tert-butoxide in tetrahydrofuran (1.0 M, 16 μL, 0.016 mmol) was added and stirred at 25 °C for 1 hour. Acetic acid (0.0053 g) was added to terminate the reaction (polymerization solution). Subsequently, in order to evaluate the methanol-insoluble content, the polymerization solution was diluted with chloroform (110 g). The diluted solution was added to 799 g of methanol to precipitate a polycarbonate resin. The precipitated polycarbonate resin was recovered by filtration under reduced pressure and washed with methanol. The obtained polycarbonate resin was dried in a vacuum at 100°C for 4 hours to obtain a polycarbonate resin (5.30 g). 1 From the H-NMR spectrum, the proportions of T6C and TCDT-H in the polycarbonate resin were calculated to be 73 mol% and 27 mol%, respectively. 1 The H-NMR spectrum is shown in Figure 8.

[0144] [Comparative Example 1] A polymerization reaction and a reprecipitation operation were carried out in the same manner as in Example 3, except that T6C was used instead of NORT-H, to obtain a polycarbonate resin.

[0145] Table 1 shows the physical properties of the polycarbonate resins obtained in the examples and comparative examples.

[0146] [Table 1]

[0147] Table 1 shows that the polycarbonate resins of the Examples have significantly lower photoelastic coefficients and significantly higher glass transition temperatures than the polycarbonate resins of the Comparative Examples, and are therefore excellent in optical properties and heat resistance.

[0148] [Example L1: TCDT] A 3-L autoclave was charged with VCHC (501 g, 3 mol) and dicyclopentadiene (hereinafter referred to as DCPD; 2484 g, 18 mol). The mixture was heated to an internal temperature of 200°C, and the reaction was continued for 3 days. After allowing the mixture to cool to an internal temperature of 60°C, the contents were recovered and dissolved in chloroform (5.5 L). This solution was slowly poured into methanol (20 L) and stirred for 1 hour. The precipitate was removed by vacuum filtration and rinsed with methanol (1.5 L). The filtrate was concentrated under reduced pressure, and the concentrate was subjected to silica gel column chromatography to separate into two fractions, A and B. 490 g of concentrate was obtained from A, and 231 g of concentrate was obtained from B. The concentrate (490 g) of fraction A was subjected to silica gel chromatography again to concentrate the fraction containing the target compound. During the concentration, a white solid began to precipitate, so the concentration was stopped halfway, and the solid was recovered by vacuum filtration and dried under reduced pressure at 50 °C to obtain TCDT (25 g). 1 The H-NMR spectrum is shown in Figure 9. HR-MS: calculation for C 19 H 25 O3 [M+H + ]301.1788, found 301.1798.

[0149] [Example L2:NORT] The concentrate (144 g) obtained by concentrating the filtrate after removing the white solid in Example 1 under reduced pressure was combined with the concentrate (231 g) of fraction B obtained in Example 1, and the combined concentrate was distilled under reduced pressure at 220°C / 0.6-2 hPa to obtain 168 g of a distillate. The obtained distillate was purified by silica gel column chromatography and dried under reduced pressure at 50°C to obtain NORT (102 g). 1 The H-NMR spectrum is shown in Figure 10. HR-MS: calculation for C 14 H 19O3 [M+H + ]235.1324, found 235.1329.

[0150] [Example L3] TCDT (0.75 g, 2.5 mmol) obtained in Example 1 and NORT (1.76 g, 7.5 mmol) obtained in Example L2 were mixed to obtain a mixture of TCDT:NORT=25:75 (mol %).

[0151] [Example L4] TCDT (1.50 g, 5.0 mmol) obtained in Example L1 and NORT (1.17 g, 5.0 mmol) obtained in Example L2 were mixed to obtain a mixture of TCDT:NORT=50:50 (mol %).

[0152] [Example L5] TCDT (2.25 g, 7.5 mmol) obtained in Example L1 and NORT (0.59 g, 2.5 mmol) obtained in Example L2 were mixed to obtain a mixture of TCDT:NORT=75:25 (mol %).

[0153] Example L6: Reduction of NORT NORT (4.78 g, 20.4 mmol) and chloro(1,5-cyclooctadiene)iridium(I) dimer (0.145 g, 0.216 mmol) were weighed into a 50 mL three-neck flask, and the flask was purged with nitrogen. Toluene (Fujifilm Wako Pure Chemical Industries, Ltd., oxygen-scavenging grade; 10 mL) and 2-propanol (Fujifilm Wako Pure Chemical Industries, Ltd., oxygen-scavenging grade; 10 mL) were weighed and added to the flask. 1,2-bis(dicyclohexylphosphino)ethane (0.187 g, 0.442 mmol) was then weighed and added to the flask. The flask was then immersed in a 100 °C oil bath and heated for 6 hours with magnetic stirring. After cooling, the contents were transferred to a 50 mL flask, the solvent was removed using an evaporator, and the concentrated residue was purified by silica gel column chromatography to recover fractions containing the target product, yielding 5.01 g of concentrate. This concentrate was dissolved in a mixed solvent of ethyl acetate (2 mL) and heptane (10 mL), transferred to a freezer at -30 °C, and allowed to stand overnight. The precipitated solid was collected by vacuum filtration, washed with heptane, and dried under reduced pressure at 60 °C to yield NORT (3.45 g). 1 The H-NMR spectrum is shown in Figure 11. HR-MS: calculation for C 14 H 21 O3 [M+H + ]237.1481, found 237.1485.

[0154] Example L7: Reduction of TCDT The reaction was carried out in the same manner as in Example L2 except that TCDT (3.02 g) was used instead of NORT, to give TCDT-H (2.27 g). 1 The H-NMR spectrum is shown in Figure 12. HR-MS: calculation for C 19 H 27 O3 [M+H + ]303.1945, found 303.1955.

[0155] [Example L8] NORT-H (0.59 g, 2.5 mmol) obtained in Example L6 and TCDT-H (2.27 g, 7.5 mmol) obtained in Example L7 were mixed to obtain a mixture of NORT-H / TCDT-H=25:75 (mol %).

[0156] [Example L9] NORT-H (1.18 g, 5.0 mmol) obtained in Example L6 and TCDT-H (1.51 g, 5.0 mmol) obtained in Example L7 were mixed to obtain a mixture of NORT-H:TCDT-H=50:50 (mol %).

[0157] [Example L10] NORT-H (1.77 g, 7.5 mmol) obtained in Example L6 and TCDT-H (0.75 g, 2.5 mmol) obtained in Example L7 were mixed to obtain a mixture of NORT-H / TCDT-H=75:25 (mol %).

[0158] [Example L11: Me5NORT] VCHC (8.63 g, 51.3 mmol) was weighed into a 50 mL three-neck flask, and the atmosphere inside the flask was replaced with nitrogen. 1,2,3,4,5-pentamethylcyclopentadiene (6.99 g, 51.3 mmol) was weighed and added to the flask. The flask was then immersed in a 180 °C oil bath and heated for 14 hours with magnetic stirring. After cooling, 1,2,3,4,5-pentamethylcyclopentadiene (6.55 g, 48.1 mmol) was added to the flask, and the flask was immersed in a 180 °C oil bath and heated for an additional 20 hours. After cooling, heptane (50 mL) was added to the flask to homogenize the contents. After leaving the flask to stand for a while, a solid precipitated, so the flask was transferred to a -30 °C freezer and left to stand overnight. The precipitated solid was collected by vacuum filtration, washed with heptane (20 mL x 2), and dried under reduced pressure at 50°C to obtain Me5NORT as a white solid (4.11 g). 1 The H-NMR spectrum is shown in Figure 13. HR-MS: calculation for C 19 H 29 O3 [M+H + ]305.2105, found 305.2111.

[0159] [Usage example L1] T6C (1.05 g, 7.36 mmol) and a 2:3 NORT:TCDT mixture (2.01 g, 7.35 mmol) were weighed into a 50 mL three-neck flask, and the atmosphere inside the flask was replaced with nitrogen. Dehydrated m-xylene (11.9 g) was added to the flask and stirred using a magnetic stirrer to completely dissolve the mixture. The flask was immersed in a thermostatic bath at 25°C, and a tetrahydrofuran solution of potassium tert-butoxide (1.0 M, 28 μL, 0.028 mmol) was added and stirred at 25°C for 1 hour. Acetic acid (0.010 g) was added to terminate the reaction (polymerization solution). Subsequently, to evaluate the methanol-insoluble content, a reprecipitation operation was carried out as follows. The polymerization solution was diluted with acetone (61 g) and chloroform (31 g). The diluted solution was added to 400 g of methanol to precipitate a polycarbonate resin. The precipitated polycarbonate resin was recovered by filtration under reduced pressure and washed with methanol. The obtained polycarbonate resin was dried in a vacuum at 100°C for 2 hours to obtain a polycarbonate resin (2.54 g). The glass transition temperature of the obtained polycarbonate resin was 169°C.

[0160] [Usage example L2] T6C (0.75 g, 5.28 mmol), a 2:3 mixture of NORT-H and TCDT-H (1.46 g, 5.29 mmol), and dehydrated m-xylene (8.71 g) were weighed into a 25 mL three-neck flask and dehydrated using 4A molecular sieves (monomer solution). After purging the atmosphere with nitrogen, the monomer solution (10.04 g) was removed and added to another 25 mL three-neck flask. The flask was immersed in a thermostatic bath at 25 °C, and a solution of potassium tert-butoxide in tetrahydrofuran (1.0 M, 20 μL, 0.020 mmol) was added and stirred at 25 °C for 30 minutes. Acetic acid (0.011 g) was added to terminate the reaction (polymerization solution). Subsequently, to evaluate the methanol-insoluble content, the polymerization solution was diluted with chloroform (39 g). The diluted solution was added to 284 g of methanol to precipitate a polycarbonate resin. The precipitated polycarbonate resin was collected by filtration under reduced pressure and washed with methanol. The obtained polycarbonate resin was vacuum-dried at 100°C for 2 hours to obtain a polycarbonate resin (1.87 g). The glass transition temperature of the obtained polycarbonate resin was 170°C.

[0161] [Usage example L3] NORT-H (3.01 g, 12.7 mmol) and dehydrated m-xylene (12.2 g) were weighed into a 50 mL three-neck flask and dehydrated using 4A molecular sieves (monomer solution). After purging the atmosphere in another 50 mL three-neck flask with nitrogen, the monomer solution (11.96 g) was removed and added. The flask was immersed in a thermostatic bath at 25°C, and a solution of potassium tert-butoxide in tetrahydrofuran (1.0 M, 33 μL, 0.033 mmol) was added and stirred at 25°C for 15 minutes. Acetic acid (0.010 g) was added to terminate the reaction (polymerization solution). Subsequently, to evaluate the methanol-insoluble content, the polymerization solution was diluted with m-xylene (46 g). The diluted solution was added to 482 g of methanol to precipitate a polycarbonate resin. The precipitated polycarbonate resin was recovered by vacuum filtration and washed with methanol. The obtained polycarbonate resin was vacuum-dried at 80°C for 4 hours to obtain a polycarbonate resin (2.21 g). The glass transition temperature of the obtained polycarbonate resin was 176°C.

[0162] [Usage example L4] T6C (0.32 g, 2.24 mmol), NORT-H (2.11 g, 8.93 mmol), and dehydrated m-xylene (9.81 g) were weighed into a 25 mL three-neck flask and dehydrated using 4A molecular sieves (monomer solution). After purging the atmosphere with nitrogen, the monomer solution (8.13 g) was removed and added to a separate 50 mL three-neck flask (the solution contained 0.21 g of T6C, 1.40 g of NORT-H, and 6.52 g of m-xylene). The flask was placed in a thermostatic bath at 25 °C, and a solution of potassium tert-butoxide in tetrahydrofuran (1.0 M, 4 μL, 0.004 mmol) was added. The mixture was stirred at 25 °C for 30 minutes. Acetic acid (0.0040 g) was added to terminate the reaction (polymerization solution). Subsequently, to evaluate the methanol-insoluble content, the polymerization solution was diluted with chloroform (22 g). The diluted solution was added to 287 g of methanol to precipitate a polycarbonate resin. The precipitated polycarbonate resin was collected by filtration under reduced pressure and washed with methanol. The obtained polycarbonate resin was dried in a vacuum at 100°C for 6 hours to obtain a polycarbonate resin (1.46 g). The glass transition temperature of the obtained polycarbonate resin was 166°C.

[0163] [Usage example L5] T6C (0.77 g, 5.40 mmol), TCDT-H (0.73 g, 2.42 mmol), and dehydrated m-xylene (12.50 g) were weighed into a 25 mL three-neck flask and dehydrated using 4A molecular sieves (monomer solution). After purging the atmosphere with nitrogen, the monomer solution (10.52 g) was removed and added to a separate 50 mL three-neck flask (the solution contained 0.58 g of T6C, 0.55 g of TCDT-H, and 9.39 g of m-xylene). The flask was placed in a thermostatic bath at 25 °C, and a solution of potassium tert-butoxide in tetrahydrofuran (1.0 M, 5 μL, 0.005 mmol) was added. The mixture was stirred at 25 °C for 30 minutes. Acetic acid (0.0022 g) was added to terminate the reaction (polymerization solution). Subsequently, to evaluate the methanol-insoluble content, the polymerization solution was diluted with m-xylene (13 g). The diluted solution was added to 344 g of methanol to precipitate a polycarbonate resin. The precipitated polycarbonate resin was recovered by vacuum filtration and washed with methanol. The obtained polycarbonate resin was vacuum-dried at 100°C for 6 hours to obtain a polycarbonate resin (0.97 g). The glass transition temperature of the obtained polycarbonate resin was 164°C.

[0164] [Usage example L6] T6C (3.69 g, 25.9 mmol), NORT-H (2.03 g, 8.59 mmol), TCDT-H (1.59 g, 5.26 mmol), and dehydrated m-xylene (29.30 g) were weighed into a 50 mL three-neck flask and dehydrated using 4A molecular sieves (monomer solution). After purging the atmosphere with nitrogen, the monomer solution (31.74 g) was withdrawn and added to another 50 mL three-neck flask (the solution contained 3.19 g of T6C, 1.76 g of NORT-H, 1.38 g of TCDT-H, and 25.4 g of m-xylene). The flask was immersed in a thermostatic bath at 25 °C, and a 1.0 M solution of potassium tert-butoxide in tetrahydrofuran (17 μL, 0.017 mmol) was added and stirred at 25 °C for 1 hour. Acetic acid (0.0061 g) was added to terminate the reaction (polymerization solution). Subsequently, to evaluate the methanol-insoluble content, the polymerization solution was diluted with chloroform (119.56 g). The diluted solution was added to 730 g of methanol to precipitate a polycarbonate resin. The precipitated polycarbonate resin was collected by filtration under reduced pressure and washed with methanol. The obtained polycarbonate resin was dried in a vacuum at 100°C for 4 hours to obtain a polycarbonate resin (5.42 g). The glass transition temperature of the obtained polycarbonate resin was 150°C.

[0165] [Usage example L7] T6C (4.81 g, 33.8 mmol), NORT-H (1.01 g, 4.27 mmol), TCDT-H (1.44 g, 4.76 mmol), and dehydrated m-xylene (29.04 g) were weighed into a 50 mL three-neck flask and dehydrated using 4A molecular sieves (monomer solution). After purging the atmosphere with nitrogen, the monomer solution (32.06 g) was withdrawn and added to another 50 mL three-neck flask (the solution contained 4.25 g of T6C, 0.89 g of NORT-H, 1.28 g of TCDT-H, and 25.6 g of m-xylene). The flask was immersed in a thermostatic bath at 25 °C, and a 1.0 M solution of potassium tert-butoxide in tetrahydrofuran (19 μL, 0.019 mmol) was added and stirred at 25 °C for 1 hour. Acetic acid (0.0062 g) was added to terminate the reaction (polymerization solution). Subsequently, to evaluate the methanol-insoluble content, the polymerization solution was diluted with chloroform (116.26 g). The diluted solution was added to 718 g of methanol to precipitate a polycarbonate resin. The precipitated polycarbonate resin was collected by filtration under reduced pressure and washed with methanol. The obtained polycarbonate resin was vacuum-dried at 100°C for 4 hours to obtain a polycarbonate resin (5.33 g). The glass transition temperature of the obtained polycarbonate resin was 144°C.

[0166] [Usage example L8] T6C (3.99 g, 28.1 mmol), TCDT-H (2.72 g, 9.00 mmol), and dehydrated m-xylene (26.93 g) were weighed into a 50 mL three-neck flask and dehydrated using 4A molecular sieves (monomer solution). After purging the atmosphere with nitrogen, the monomer solution (29.79 g) was removed and added to another 50 mL three-neck flask (the solution contained 3.54 g of T6C, 2.41 g of TCDT-H, and 23.8 g of m-xylene). The flask was immersed in a thermostatic bath at 25 °C, and a solution of potassium tert-butoxide in tetrahydrofuran (1.0 M, 16 μL, 0.016 mmol) was added and stirred at 25 °C for 1 hour. Acetic acid (0.0053 g) was added to terminate the reaction (polymerization solution). Subsequently, to evaluate the methanol-insoluble content, the polymerization solution was diluted with chloroform (110 g). The diluted solution was added to 799 g of methanol to precipitate a polycarbonate resin. The precipitated polycarbonate resin was collected by filtration under reduced pressure and washed with methanol. The obtained polycarbonate resin was dried in a vacuum at 100°C for 4 hours to obtain a polycarbonate resin (5.30 g). The glass transition temperature of the obtained polycarbonate resin was 149°C.

[0167] [Comparative usage example L1] Except for using T6C instead of NORT-H, the polymerization reaction and reprecipitation procedure were carried out in the same manner as in Usage Example 3 to obtain a polycarbonate resin. The glass transition temperature of the obtained polycarbonate resin was 120°C. [Industrial Applicability]

[0168] The polycarbonate resin, polycarbonate resin composition, and optical molded articles containing them of the present invention have industrial applicability in fields such as various optical materials, such as optical lens materials, optical devices, materials for optical components, and display materials.

Claims

1. A structural unit represented by the following formula (1A)′: 【Chemical 1】 (In formula (1A)′, B represents an optionally substituted monovalent alicyclic moiety.) A polycarbonate resin having the formula:

2. The alicyclic moiety B is represented by the following formula (1a): 【Chemistry 3】 (In formula (1a), R is a substituent, n is an integer of 0 to 2, and * is a bonding site.) The polycarbonate resin according to claim 1 , wherein the aryl group is a group represented by the formula:

3. The alicyclic moiety B is represented by the following formula (1b): 【Chemistry 4】 (In formula (1b), R is a substituent, n is an integer of 0 to 2, and * is a bonding site.) The polycarbonate resin according to claim 1 , wherein the aryl group is a group represented by the formula:

4. The structural unit represented by formula (1A)' is a structural unit represented by the following formula (1B): 【Chemistry 5】 (In formula (1B), R is a substituent, and n is an integer of 0 to 2.) 2. The polycarbonate resin according to claim 1, wherein

5. The structural unit represented by formula (1A)' is a structural unit represented by the following formula (1C): 【Chemistry 6】 (In formula (1C), R is a substituent, and n is an integer of 0 to 2.) 2. The polycarbonate resin according to claim 1, wherein

6. The structural unit represented by formula (1A)' is a structural unit represented by the following formula (1B-H): 【Chemistry 7】 (In formula (1B-H), n is an integer of 0 to 1.) 2. The polycarbonate resin according to claim 1, wherein

7. The structural unit represented by formula (1A)' is a structural unit represented by the following formula (1C-H): 【Chemistry 8】 (In formula (1C-H), n is an integer of 0 to 1.) 2. The polycarbonate resin according to claim 1, wherein

8. A structural unit represented by the following formula (2): 【Chemistry 9】 (In formula (2), C represents an optionally substituted divalent alicyclic moiety.) The polycarbonate resin of claim 1 having the formula:

9. 2. The polycarbonate resin according to claim 1, having a weight average molecular weight (Mw) of 10,000 or more and 1,000,000 or less.

10. 2. The polycarbonate resin according to claim 1, which has a glass transition temperature (Tg) of 125°C or higher and 250°C or lower.

11. The absolute value of the photoelastic coefficient is 1.5 × 10 -12 Pa -1 2. The polycarbonate resin of claim 1, wherein:

12. 2. The polycarbonate resin according to claim 1, wherein the absolute value of the in-plane retardation of a 100% uniaxially stretched film of the polycarbonate resin is 100 nm or less in terms of a thickness of 100 μm.

13. The temperature dependence of orientation birefringence (dΔn / dT) of the stretched film uniaxially stretched under the following conditions is −0.1×10 -5 ≦dΔn / dT≦+0.1×10 -5 The polycarbonate resin according to claim 1, which satisfies the following: (Stretching conditions) Stretching temperature: a temperature 20°C higher than the glass transition temperature Tg of the polycarbonate resin Stretching speed: 50mm / min Stretching ratio: 100%

14. A polycarbonate resin composition comprising the polycarbonate resin according to any one of claims 1 to 13 and an antioxidant.

15. An optical part comprising the polycarbonate resin according to any one of claims 1 to 13.

16. Use of the polycarbonate resin according to any one of claims 1 to 13 as a material for optical components.

17. The following formula (1LA)': 【Chemistry 10】 (In formula (1LA)′, B represents an optionally substituted monovalent alicyclic moiety.) The method comprises a step of ring-opening polymerizing a cyclic carbonate represented by the formula: A structural unit represented by the following formula (1A)′: 【Chemistry 11】 (In formula (1A)′, B represents an optionally substituted monovalent alicyclic moiety.) A method for producing a polycarbonate resin comprising the steps of:

18. It has a structure in which an alicyclic skeleton is bonded to a 1,2-cycloalkylene carbonate skeleton via a single bond, The following formula (1LA)': 【Chemistry 12】 (In formula (1LA)′, B represents an optionally substituted monovalent alicyclic moiety.) Cyclic carbonates represented by the formula:

19. The alicyclic moiety B is represented by the following formula (1a): 【Chemistry 14】 (In formula (1a), R is a substituent, n is an integer of 0 to 2, and * is a bonding site.) The cyclic carbonate according to claim 18, wherein the cyclic carbonate is a group represented by the formula:

20. The alicyclic moiety B is represented by the following formula (1b): 【Chemistry 15】 (In formula (1b), R is a substituent, n is an integer of 0 to 2, and * is a bonding site.) The cyclic carbonate according to claim 18, wherein the cyclic carbonate is a group represented by the formula:

21. The cyclic carbonate according to claim 18, wherein the alicyclic moiety B is an optionally substituted norbornyl group, an optionally substituted norbornenyl group, an optionally substituted decahydro-1,4:5,8-dimethanonaphthalenyl group, or an optionally substituted octahydro-1,4:5,8-dimethanonaphthalenyl group.

22. The structure represented by formula (1LA)' is represented by the following formula (1LB): 【Chemistry 16】 (In formula (1LB), R is a substituent, and n is an integer of 0 to 2.) The cyclic carbonate according to claim 18, wherein the structure is represented by:

23. The structure represented by formula (1LA)' is represented by the following formula (1LC): 【Chemistry 17】 (In formula (1LC), R is a substituent, and n is an integer of 0 to 2.) The cyclic carbonate according to claim 18, wherein the structure is represented by:

24. The structure represented by formula (1LA)' is represented by the following formula (1L-1): 【Chemistry 18】 The following formula (1L-2): 【Chemistry 19】 The following formula (1L-3): 【Chemistry 20】 Or the following formula (1L-4): 【Chemical 21】 The cyclic carbonate according to claim 18, wherein the structure is represented by:

25. A method for producing a cyclic carbonate having a structure in which an alicyclic skeleton is bonded to a 1,2-cycloalkylene carbonate skeleton via a single bond, comprising: The following formula (2L)': 【Chemical 22】 The method for producing a cyclic carbonate includes a step of reacting a cyclic carbonate represented by the following formula (I): with a compound having a conjugated diene moiety.

26. The following formula (1L-1): 【Chemical 23】 Cyclic carbonates represented by the formula: The following formula (1L-2): 【Chemistry 24】 A cyclic carbonate composition comprising a cyclic carbonate represented by the formula:

27. The following formula (1L-3): 【Chemistry 25】 Cyclic carbonates represented by the formula: The following formula (1L-4): 【Chemical 26】 A cyclic carbonate composition comprising a cyclic carbonate represented by the formula:

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