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

Abstract

To provide a polycarbonate resin with superior heat resistance, a polycarbonate resin composition, an optical component, and a method for producing a polycarbonate resin.SOLUTION: The present invention relates to a polycarbonate resin with a structural unit represented by the following formula (1) (where, A is an optionally substituted alicyclic site, L represents a direct bond or a linking group, R1 is an optionally substituted C1-20 aliphatic hydrocarbon group or an optionally substituted C6-20 aromatic hydrocarbon group).SELECTED DRAWING: None

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, Non-Patent Document 1, and Non-Patent Document 2. [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. [Non-patent document 2] Yonghang Xu, Tao Zhang, Yiluan Zhou, Danmin Zhou, Zixin Shen, Limiao Lin, Polymer Degradation and Stability 168,2019,108957 Summary of the Invention [Problem to be solved by the invention]

[0007] As described above, poly(1,2-cyclohexene carbonate) has excellent transparency, but has room for improvement in terms of heat resistance.

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polycarbonate resin having excellent heat resistance, a polycarbonate resin composition, an optical part, and a method for producing a polycarbonate resin. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above problems and have found that polycarbonate resins having sulfide bonds have excellent heat resistance, leading to the completion of the present invention.

[0010] That is, the present invention includes the following embodiments. <1> The following formula (1): [ka] (In formula (1), A is an optionally substituted alicyclic moiety; L is a direct bond or a linking group; R 1 is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. A polycarbonate resin having a structural unit represented by the formula: <2> A is a cyclohexane-1,2-diyl group. <1> The polycarbonate resin according to claim 1. <3> L is an ethylene group, a norbornylene group, or a decahydro-1,4:5,8-dimethanonaphthylene group; <1> or <2> The polycarbonate resin according to claim 1. <4> R 1 is a cyclohexyl group, an adamantyl group, or a decyl group; <1> ~ <3> 1. The polycarbonate resin according to claim 1 . <5> The weight average molecular weight (Mw) is 10,000 or more and 1,000,000 or less. <1> ~ <4> 1. The polycarbonate resin according to claim 1 . <6> The glass transition temperature (Tg) is 60°C or higher and 250°C or lower. <1> ~ <5> 1. The polycarbonate resin according to claim 1 . <7> <1> ~ <6> 10. A polycarbonate resin composition comprising the polycarbonate resin according to any one of claims 1 to 9 and an antioxidant. <8> <1> ~ <6> The polycarbonate resin according to any one of the above items, or <7> An optical part comprising the polycarbonate resin composition according to claim 1. <9> <1> ~ <6> The polycarbonate resin according to any one of the above items, or <7> 2. Use of the polycarbonate resin composition according to claim 1 as a material for optical parts. <10> The following formula (1): [ka] (In formula (1), A is an optionally substituted alicyclic moiety; L is a direct bond or a linking group; R 1 is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. A method for producing a polycarbonate resin having a structural unit represented by The following formula (2): [ka] (In formula (2), A is an optionally substituted alicyclic moiety; L is a direct bond or a linking group; R 1 is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. A method for producing a polycarbonate resin, comprising a polymerization step of ring-opening polymerizing a cyclic carbonate represented by the following formula: <11> The following formula (1): [ka] (In formula (1), A is an optionally substituted alicyclic moiety; L is a direct bond or a linking group; R 1 is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. A method for producing a polycarbonate resin having a structural unit represented by The following formula (3): [ka] (In formula (3), A is an optionally substituted alicyclic moiety, and E is an optionally substituted alkenyl group having 1 to 20 carbon atoms.) or a structural unit represented by The following formula (3'): [ka] (In formula (3'), A' is an optionally substituted unsaturated alicyclic moiety.) A polycarbonate having a structural unit represented by The following formula (4): HSR 1 (4) (In formula (4), R 1 is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. and a thiol compound represented by the formula (I): [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a polycarbonate resin, a polycarbonate resin composition, an optical component, and a method for producing a polycarbonate resin, all of which have excellent heat resistance. [Brief explanation of the drawings]

[0012] [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. DETAILED DESCRIPTION OF THE INVENTION

[0013] 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.

[0014] [Polycarbonate resin] The polycarbonate resin according to this embodiment has a structural unit represented by the following formula (1).

[0015] [ka]

[0016] The polycarbonate resin according to this embodiment has the above-described structure and exhibits excellent heat resistance. This is thought to be due to the following reasons, but is not limited to these.

[0017] Conventional cyclic carbonates having an alicyclic structure have a cyclic skeleton, but due to their highly rigid structure, the carbonate group, which is relatively less stable, is sterically open, making them susceptible to hydrolysis and other effects. In contrast, since the polycarbonate resin of the present embodiment has sulfide groups, the carbonate groups and sulfide groups interact with each other intermolecularly, causing three-dimensional crowding around the carbonate groups, making the resin less susceptible to the effects of hydrolysis and the like, which is presumably why heat resistance is improved.

[0018] In formula (1), A represents an optionally substituted divalent alicyclic moiety. The alicyclic moiety 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. 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, 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, and a cyclohexane-1,2-diyl group is even more preferred.

[0019] The alicyclic moiety A may have an unsaturated bond at any position. A may have a plurality of unsaturated bonds.

[0020] The alicyclic moiety A may be substituted with any substituent. The substituent is not particularly limited, but 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 a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. A may have multiple substituents, and in that case, the respective substituents may be the same or different.

[0021] The substituent of the alicyclic moiety A is preferably 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 a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, more preferably a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, Preferably, the alkyl group is a hydroxyl group, an ester group having 1 to 11 carbon atoms, an acyl group having 1 to 11 carbon atoms, or a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, more preferably a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, and even more preferably an alkoxy group having 1 to 20 carbon atoms, or a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms.

[0022] The phosphate group may be unsubstituted or substituted. That is, it may be a mono-substituted phosphate group or a di-substituted phosphate group. When the phosphate group is substituted, the substituent is preferably an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. In this embodiment, the phosphate group is preferably unsubstituted.

[0023] The aryl group having 6 to 20 carbon atoms is not particularly limited, and 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.

[0024] 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 benzyl group, 4-methylbenzyl group, and phenethyl group; alkoxy group-containing aralkyl groups such as 4-methoxybenzyl group and 3,5-dimethoxybenzyl group; and diphenylmethyl group, naphthylmethyl group, and anthracenylmethyl group.

[0025] 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.

[0026] 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.

[0027] 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. group, a tert-butyldimethylsilylmethoxy group, a tert-butyldimethylsilylethoxy group, a tert-butyldimethylsilylphenoxy group, a tert-butyldimethylsilylbenzyloxy group, a di-tert-butylisobutylsilylmethoxy group, a di-tert-butylisobutylsilylethoxy group, a di-tert-butylisobutylsilylphenoxy group, a di-tert-butylisobutylsilylbenzyloxy group, a tert-butyldiphenylsilylmethoxy group, a tert-butyldiphenylsilylethoxy group, a tert-butyldiphenylsilylphenoxy group, and a tert-butyldiphenylsilylbenzyloxy group.

[0028] 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.

[0029] The 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.

[0030] Examples of the 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.

[0031] In formula (1), L is a direct bond or a linking group. Examples of the linking group include a divalent alkylene group that may be linear, branched, or cyclic. The number of carbon atoms in the linking group is not particularly limited, but is preferably 1 to 30, and more preferably 1 to 20. The divalent alkylene group is not particularly limited, but examples thereof include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a norbornylene group, a bicyclo[2.2.2]octylene group, a decahydronaphthylene group, and a decahydro-1,4:5,8-dimethanonaphthylene group. Among these, L is preferably a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a norbornylene group, a bicyclo[2.2.2]octylene group, a decahydronaphthylene group, or a decahydro-1,4:5,8-dimethanonaphthylene group, more preferably Preferably, it is a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, a hexylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a norbornylene group, a bicyclo[2.2.2]octylene group, a decahydronaphthylene group, or a decahydro-1,4:5,8-dimethanonaphthylene group, and more preferably an ethylene group, a norbornylene group, or a decahydro-1,4:5,8-dimethanonaphthylene group.

[0032] In formula (1), R 1 R is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. 1Examples of R include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, an adamantyl group, a norbornyl group, a bicyclo[2.2.2]octyl group, a decahydronaphthyl group, a decahydro-1,4:5,8-dimethanonaphthyl group, a phenyl group, a benzyl group, and a 3-(2-methyltetrahydro)furyl group. 1 is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a cyclopropyl group, a cyclobutyl ... Examples of the alkyl group include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, norbornyl, bicyclo[2.2.2]octyl, decahydronaphthyl, decahydro-1,4:5,8-dimethanonaphthyl, phenyl, benzyl, and 3-(2-methyltetrahydro)furyl groups, and more preferably cyclohexyl, adamantyl, or decyl.

[0033] The polycarbonate resin according to this embodiment may have one or more types of structural units represented by formula (1).

[0034] (Terminal structure) The terminals of the polycarbonate resin according to 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 according to this embodiment may have both terminals bonded to each other to form a cyclic structure. That is, the polycarbonate resin according to this embodiment may not have a terminal structure. It is preferable that the polycarbonate resin according to this embodiment has both terminals being hydroxyl groups.

[0035] The polycarbonate resin according to this embodiment has a structure represented by the following formula (X1).

[0036] [ka]

[0037] L and R in formula (X1) 1 is the same as in equation (1).

[0038] The structural unit represented by formula (X1) contained in the polycarbonate resin according to this embodiment may be of one type, or a combination of two or more types may be used.

[0039] The polycarbonate resin according to this embodiment preferably contains a structure represented by the following formula (X1-1), (X1-2), (X1-3), or (X1-4).

[0040] The polycarbonate resin according to this embodiment preferably has a structural unit represented by formula (X1-1) or a structural unit represented by formula (X1-2).

[0041] [ka]

[0042] In formula (X1-1), m is an integer of 0 to 18, and R 1 is the same as in equation (1).

[0043] [ka]

[0044] In formula (X1-2), m is an integer of 0 to 18, and R 1 is the same as in equation (1).

[0045] The polycarbonate resin according to this embodiment preferably has a structural unit represented by formula (X1-3) or a structural unit represented by formula (X1-4).

[0046] [ka]

[0047] In formula (X1-3), n is an integer of 0 to 3, and R 1 is the same as in equation (1).

[0048] [ka]

[0049] In formula (X1-4), n is an integer of 0 to 3, and R 1 is the same as in equation (1).

[0050] In the formulae (X1-1) and (X1-2), m is preferably an integer of 0 to 5, and more preferably 1.

[0051] In the formulae (X1-3) and (X1-4), n is preferably an integer of 0 to 2, and more preferably 0 or 1.

[0052] The polycarbonate resin according to this embodiment may have other structural units in addition to the structural unit represented by formula (1). Examples of the other structural units include ring-opened cyclic carbonate units. More specifically, the other structural units preferably have a structural unit represented by the following formula (2):

[0053] [ka]

[0054] In formula (2), C is an optionally substituted divalent alicyclic moiety.

[0055] 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.

[0056] When substituted, examples of the substituents are the same as those in formula (1).

[0057] The proportion of the structural unit represented by formula (1) in the polycarbonate resin according to 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 %.

[0058] The proportion of the structural unit represented by formula (2) in the polycarbonate resin according to 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 %.

[0059] The weight-average molecular weight (Mw) of the polycarbonate resin according to this embodiment is preferably 10,000 or more and 1,000,000 or less. The polycarbonate resin according to this embodiment, having an Mw within the above range, is easily moldable. Furthermore, such a polycarbonate resin exhibits 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.

[0060] In the polycarbonate resin according to this embodiment, the weight-average molecular weight (Mw) can be controlled within the above range by appropriately adjusting the ratio of the polymerizable monomer and 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.

[0061] The polycarbonate resin according to this embodiment preferably has a glass transition temperature (Tg) of 60°C or higher and 250°C or lower. When the Tg is 60°C or higher, the resin tends to be able to maintain its shape even in a room temperature usage environment, and has excellent heat resistance. When the Tg is 250°C or lower, the resin tends to have excellent moldability. From the same viewpoint, the glass transition temperature of the polycarbonate resin according to this embodiment is more preferably 60°C or higher and 245°C or lower, and even more preferably 60°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.

[0062] In the polycarbonate resin according to this embodiment, in order to control the glass transition temperature within the above-mentioned preferred range, it is necessary to 1 A, R and L may be appropriately selected so as to control the glass transition temperature within the above-mentioned preferred range. 1 The combination of A, R and L is not particularly limited. 1 When A and R are selected, the glass transition temperature tends to increase. 1 When A and R are selected, the glass transition temperature tends to decrease. 1 By appropriately combining A, R, and L, a polycarbonate resin having a desired glass transition temperature can be produced. 1 , and L and R 2 By selecting the above, the cyclic skeleton and the chain skeleton are well balanced, and the glass transition temperature tends to be controlled within the above preferred range.

[0063] [Polycarbonate resin composition] The polycarbonate resin composition according to this embodiment contains the above-described polycarbonate resin and an antioxidant.

[0064] The polycarbonate resin composition according to 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 according to 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.

[0065] The antioxidant in the polycarbonate resin composition according to this embodiment is not particularly limited, but examples thereof include hindered phenol-based antioxidants and phosphorus-based antioxidants.

[0066] 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.

[0067] 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.

[0068] The polycarbonate resin in the polycarbonate resin composition according to this embodiment is the same as the polycarbonate resin described above, and preferred embodiments are also the same.

[0069] 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 according to 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.

[0070] From the viewpoint of further preventing deterioration due to heat and shear during molding processing, the content of the antioxidant in the polycarbonate resin composition according to this 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.

[0071] [Optical components] The optical component according to this embodiment contains the above-mentioned polycarbonate resin or the above-mentioned polycarbonate resin composition.

[0072] The polycarbonate resin or polycarbonate resin composition contained in the optical component according to this embodiment has a small photoelastic coefficient and a small in-plane retardation due to molecular orientation, so the optical component according to this embodiment is less likely to exhibit stress birefringence and orientation birefringence. Therefore, the optical component according to this embodiment tends to be able to suppress birefringence during use. Furthermore, the polycarbonate resin or polycarbonate resin composition contained in the optical component according to this embodiment has excellent heat resistance as described above, so the optical component according to this embodiment is less likely to deteriorate over time and can be used for a longer period of time than conventional optical components.

[0073] The optical component according to 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 according to the present embodiment can be obtained by appropriately processing, such as molding, the polycarbonate resin or the polycarbonate resin composition described above so as to have a shape suitable for the intended use.

[0074] [Manufacturing method of polycarbonate resin] The method for producing the polycarbonate resin according to the present embodiment is not particularly limited, but examples thereof include a method of copolymerizing an epoxide with carbon dioxide, a method of ring-opening polymerization of a cyclic carbonate, and a method of condensation polymerization of a diol with carbon dioxide or a carbonate ester.

[0075] <Polymerization process> The method for producing a polycarbonate resin according to this embodiment preferably includes a step of ring-opening polymerizing a cyclic carbonate (A1) represented by the following formula (2).

[0076] [ka]

[0077] In formula (2), A, R 1 , and L are as explained in equation (1).

[0078] In the method for producing a polycarbonate resin according to this embodiment, the cyclic carbonate used in the ring-opening polymerization may be one type of cyclic carbonate alone, or a combination of A, R 1 Any two or more kinds of cyclic carbonates having different cyclic groups and L may be used in combination.

[0079] In the cyclic carbonate used in the ring-opening polymerization, the carbonate group preferably forms a 1,2-trans structure.

[0080] In the method for producing a polycarbonate resin according to this embodiment, other cyclic carbonates may be used in addition to the cyclic carbonate (A1). Examples of other cyclic carbonates include cyclic carbonates (A2) represented by formula (7): The cyclic carbonates (A2) may be used alone or in combination of two or more.

[0081] [ka]

[0082] In formula (7), C is as explained in formula (2). In the method for producing a polycarbonate resin according to this 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.

[0083] 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.Examples of organic bases include, but are not limited to, 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. The polymerization initiator according to this embodiment is preferably an alkyl metal, a metal alkoxide, or a metal amide, and more preferably a metal alkoxide or a metal amide.

[0084] The amount of polymerization initiator used in the polymerization step of the polycarbonate resin production method according to 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 1,000,000, the amount of polymerization initiator used, calculated as the amount of substance relative to the cyclic carbonate (A1) as the ring-opening polymerizable monomer, 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.

[0085] 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.

[0086] 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.

[0087] In the method for producing a polycarbonate resin according to 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 according to 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 resulting polycarbonate resin to a range of 10,000 or higher and 1,000,000 or lower.

[0088] In the method for producing a polycarbonate resin according to this embodiment, a solvent may or may not be used. The solvent is not particularly limited, but examples thereof include 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.

[0089] <Modification process> In addition to the above-described production method, the polycarbonate resin according to this embodiment may also be produced by a production method including a modification step. In this case, the modification step may be preceded by a polymerization step to obtain a polycarbonate having a structural unit represented by the following formula (3) or a polycarbonate having a structural unit represented by the following formula (3'): The method for producing a polycarbonate resin according to this embodiment preferably includes a step of mixing and stirring a mixture containing a polycarbonate (B1) having a structural unit represented by the following formula (3) or a structural unit represented by the following formula (3') and a thiol compound (B2) represented by the following formula (4).

[0090] [ka]

[0091] In formula (3), A is the same as in formula (1), and E is an optionally substituted alkenyl group having 1 to 20 carbon atoms.

[0092] [ka]

[0093] In formula (3'), A' is an optionally substituted unsaturated alicyclic moiety.

[0094] HSR 1 (4)

[0095] In formula (4), R 1 is the same as in equation (1).

[0096] The polycarbonate (B1) or polycarbonate (B1') may be used alone or in combination of two or more kinds.

[0097] In formula (3), E represents an optionally substituted alkenyl group having 1 to 20 carbon atoms. The alkenyl group may be linear, branched, or cyclic. Examples of the alkenyl group having 1 to 20 carbon atoms include, but are not limited to, methylene, ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, norbornenyl, bicyclo[2.2.2]octenyl, octahydronaphthalenyl, and octahydro-1,4:5,8-dimethanonaphthalenyl. The alkenyl group having 1 to 20 carbon atoms in the formula (3) is preferably a vinylidene group, an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclononenyl group, a cyclodecenyl group, a norbornenyl group, a bicyclo[2.2.2]octenyl group, an octahydronaphthalenyl group, an octahydro and octahydro-1,4:5,8-dimethanonaphthalenyl group, and more preferably vinylidene group, ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclononenyl group, cyclodecenyl group, norbornenyl group, bicyclo[2.2.2]octenyl group, octahydronaphthalenyl group, and octahydro-1,4:5,8-dimethanonaphthalenyl group.

[0098] In formula (2'), A' is an optionally substituted unsaturated alicyclic moiety, which preferably has a carbon-carbon double bond therein.

[0099] The terminals of the polycarbonate (B1) are preferably the same as the terminals of the polycarbonate resin according to this embodiment.

[0100] In the method for producing a polycarbonate resin according to this embodiment, the polycarbonate (B1) preferably contains a structure represented by the following formula (Y1).

[0101] [ka]

[0102] E in formula (Y1) is the same as that in formula (3). In the polycarbonate (B1), the structure represented by formula (Y1) may be of one type, or a combination of two or more types may be used.

[0103] In the method for producing a polycarbonate resin according to this embodiment, the polycarbonate (B1) preferably contains a structure represented by the following formula (Y1-1) or (Y1-2).

[0104] [ka] [ka]

[0105] In formula (Y1-1), m is the same as in formula (X1-1), and in formula (Y-2), n is the same as in formula (X1-3). In the polycarbonate (B1), the structure represented by formula (Y1-1) and the structure represented by formula (Y1-2) may be of one type, or a combination of two or more types may be used.

[0106] The polycarbonate (B1) may have other structural units in addition to the structural unit represented by formula (3). Examples of the other structural units include ring-opened cyclic carbonate units. More specifically, examples of the other structural units include structural units represented by the following formula (2):

[0107] [ka]

[0108] In the formula (2), C is as described above.

[0109] The proportion of the structural unit represented by formula (3) in the polycarbonate (B1) 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 %.

[0110] The proportion of the structural unit represented by formula (2) in the polycarbonate (B1) 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 %.

[0111] In formula (4), R 1 is as explained in formula (1). The thiol compound (B2) may be used alone or in combination of two or more kinds.

[0112] In the modification step, the mass ratio of the polycarbonate (B1) to the thiol compound (B2) is preferably 1:100 to 100:1, and more preferably 1:50 to 50:1.

[0113] In the modification step, a solvent may be added. 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.

[0114] The mass ratio of the polycarbonate (B1) to the solvent in the modification step is preferably from 100:1 to 1:100, and more preferably from 90:1 to 1:90.

[0115] In the modification step, a radical initiator may be added. A radical initiator is one that generates radicals by heat, light, or a redox reaction. Examples of such initiators include organic peroxides, azo compounds, redox initiators, and photoinitiators.

[0116] The organic peroxide is not particularly limited, but examples thereof include benzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, and dicumyl peroxide.

[0117] The azo compound is not particularly limited, but examples thereof include 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo(methylethyl)diacetate, 2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2'-azobisisobutyronitrile (AIBN), methyl 2,2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, 3,5-dihydroxymethylphenylazo-2-methylmalonodinitrile, 2,2'-azobis-2-methylvaleronitrile, dimethyl 4,4'-azobis-4-cyanovalerate, and 2,2'-azobis-2,4-dimethylvaleronitrile.

[0118] The redox initiator is not particularly limited, but examples thereof include combinations of hydrogen peroxide and iron (II) salt, organic peroxide and dimethylaniline, and cerium (IV) salt and alcohol.

[0119] The photoinitiator is not particularly limited, but examples thereof include alkylphenone-based photoinitiators, α-amino alkyl ketone-based photoinitiators, and phosphine oxide-based photoinitiators.

[0120] The molar ratio of the thiol compound (B2) to the radical initiator in the modification step is preferably 10:1 to 10,000:1, more preferably 20:1 to 5,000:1.

[0121] The temperature in the modification step is preferably 0°C to 150°C, and more preferably 20°C to 120°C.

[0122] The atmosphere in the modification step may be an air atmosphere, a nitrogen atmosphere, or an argon atmosphere. Of these, a nitrogen atmosphere or an argon atmosphere is preferred, and a nitrogen atmosphere is more preferred. [Example]

[0123] 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.

[0124] In this specification, various physical properties were measured as follows.

[0125] [ 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.

[0126] [Molecular weight measurement] 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.

[0127] [Measurement of glass transition temperature] 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 a nitrogen gas flow rate of 20 mL / min. More specifically, for example, for the sample in Example 1, the sample was held at 40°C for 3 minutes, then heated at 20°C / min from 40°C to 210°C for a first time until the sample was completely melted. The sample was then cooled 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 line equidistant along the vertical axis from the extension of each tangent (midpoint glass transition temperature). The glass transition temperatures of the samples in the other examples and comparative examples were also measured in the same manner.

[0128] [Measurement of thermal decomposition onset temperature] Using a Shimadzu TG-DTA device (product name: DTG-60A) and an aluminum krypton cell, the polycarbonate resin and polycarbonate resin composition were heated in an air stream at a rate of 10°C / min. The thermal decomposition (TGA) of the polycarbonate resin and polycarbonate resin composition was measured, and the thermal decomposition onset temperature was obtained from the tangent intersection of the TGA curve.

[0129] [Synthesis example 1: NORT] A 3-L autoclave was charged with 4-vinyl-trans-1,2-cyclohexene carbonate (501 g, 3 mol) and dicyclopentadiene (2484 g, 18 mol). The mixture was heated to an internal temperature of 200°C and allowed to react for 3 days. After allowing the mixture to cool to 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 chromatography again, and the fraction containing the target product was concentrated. During the concentration process, a white solid began to precipitate, so the concentration was stopped and the solid was removed by vacuum filtration. The filtrate after removing the white solid was concentrated under reduced pressure to obtain a concentrate (144 g) and the concentrate of fraction B (231 g) were combined and 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 4-(5-norbornen-2-yl)-trans-1,2-cyclohexene carbonate (hereinafter also referred to as NORT; 102 g).

[0130] [Synthesis example 2: CSNT] The NORT (5.40 g, 23.05 mmol) and cyclohexanethiol (2.77 g, 23.86 mmol) synthesized in Synthesis Example 1 were weighed and placed in a 50 mL three-neck flask, and the atmosphere in the flask was replaced with nitrogen. Toluene (Fujifilm Wako Pure Chemical Industries, Ltd., oxygen-scavenging grade; 4 g) and 2,2'-azobisisobutyronitrile (0.05 g, 0.30 mmol) were weighed and added to the flask, and the flask was immersed in an 80°C oil bath and heated for 3 hours while stirring with a magnetic stirrer. After cooling, the mixture was purified by silica gel column chromatography, and the fraction containing the target product was collected, concentrated under reduced pressure, and dried under reduced pressure at 60°C to obtain the product represented by the following formula: [ka] A compound represented by the formula: formula: [ka] A mixture of compounds represented by the following formula (hereinafter also referred to as CSNT; 7.70 g) was obtained.

[0131] [Synthesis example 3: CSVT] 4-Vinyl-trans-1,2-cyclohexene carbonate (7.64 g, 45.42 mol) and cyclohexanethiol (7.93 g, 63.81 mmol) were weighed and placed in a 50 mL three-neck flask, and the atmosphere in the flask was replaced with nitrogen. 2,2'-Azobisisobutyronitrile (0.08 g, 0.46 mmol) was weighed and added to the flask, and the flask was immersed in an 80°C oil bath and heated for 3 hours while stirring with a magnetic stirrer. After cooling, the mixture was purified by silica gel column chromatography, and the fraction containing the target product was collected, concentrated under reduced pressure, and dried under reduced pressure at 60°C to obtain the product of the following formula: [ka] A compound represented by the formula: formula: [ka] A mixture of compounds represented by the following formula (hereinafter also referred to as CSNT; 7.70 g) was obtained.

[0132] [Synthesis Example 4: Polymerization initiator solution] After replacing the atmosphere in a 50 mL Schlenk flask with nitrogen, a tetrahydrofuran solution of potassium tert-butoxide (1.0 M, 2.4 mL, 2.4 mmol), benzyl alcohol (0.52 g, 4.81 mmol), and dehydrated m-xylene (21.00 mL) were added and stirred at room temperature for 30 minutes to prepare a polymerization initiator solution.

[0133] [Synthesis example 5: p(NORT)] NORT (10.03 g, 42.80 mmol) synthesized in Synthesis Example 1 and dehydrated m-xylene (40.01 g) were weighed into a 100 mL flask and dehydrated using molecular sieves 4A (monomer solution). After purging the atmosphere in another 100 mL three-neck flask with nitrogen, the monomer solution (45.21 g) was removed and added. The flask was immersed in a thermostatic bath at 25°C, and the polymerization initiator solution (200 μL) synthesized in Synthesis Example 4 was added, followed by stirring at 25°C for 1 hour. Acetic acid (0.02 g) was added to terminate the reaction (polymerization solution). Subsequently, the polymerization solution was diluted with chloroform (180 g). The diluted solution was added to 1600 g of methanol to precipitate a polymer. The precipitated polymer was collected by filtration under reduced pressure and washed with methanol. The obtained polymer was dried under reduced pressure at 100°C for 2 hours to obtain a NORT polymer (hereinafter also referred to as p(NORT); 8.72 g).

[0134] [Synthesis example 6: p(T6C-NORT)] Trans-1,2-cyclohexene carbonate (hereinafter also referred to as T6C; 5.05 g, 35.55 mmol), NORT (8.24 g, 35.15 mmol) synthesized in Synthesis Example 1, and dehydrated toluene (52.88 g) were weighed into a 100 mL flask and dehydrated using molecular sieves 4A (monomer solution). After purging the atmosphere in another 100 mL three-neck flask with nitrogen, the monomer solution (60.03 g) was removed and added. The flask was immersed in a thermostatic bath at 25°C, and the polymerization initiator solution (200 μL) synthesized in Synthesis Example 4 was added. The mixture was stirred at 25°C for 1 hour. Acetic acid (0.01 g) was added to terminate the reaction (polymerization solution). Subsequently, the polymerization solution was diluted with chloroform (240 g). The diluted solution was added to methanol (2100 g) to precipitate the polymer. The precipitated polymer was collected by vacuum filtration and washed with methanol. The obtained polymer was dried under vacuum at 100°C for 2 hours to obtain a copolymer of T6C and NORT (hereinafter also referred to as p(T6C-NORT); 11.27 g).

[0135] [Synthesis example 7: NORTH] 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. The fraction containing the target product was recovered, 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 obtain 4-(5-norbornan-2-yl)-trans-1,2-cyclohexene carbonate (hereinafter also referred to as NORTH; 3.45 g).

[0136] [Example 1: p(ASNT)] p(NORT) (1.65 g) synthesized in Synthesis Example 5 and 1-adamantanethiol (1.78 g, 10.59 mmol) were weighed and placed in a 50 mL three-neck flask, and the atmosphere in the flask was replaced with nitrogen. Toluene (Fujifilm Wako Pure Chemical Industries, deoxidizing grade; 15.30 g) and 2,2'-azobisisobutyronitrile (0.04 g, 0.25 mmol) were weighed and added to the flask, and the flask was immersed in an 80°C oil bath and heated for 6 hours while stirring with a magnetic stirrer (reaction solution). After cooling, the reaction solution was diluted with chloroform (50 g). The diluted solution was added to methanol (480 g) to precipitate a polymer. The precipitated polymer was collected by vacuum filtration and washed with methanol. The resulting polymer was dried under vacuum at 100°C for 2 hours to obtain a 1-adamantanthiol adduct of p(NORT) (hereinafter also referred to as p(ASNT); 2.66 g). 1 The H-NMR spectrum is shown in Figure 1.

[0137] Example 2: p(CSNT) CSNT (6.98 g, 19.91 mmol) synthesized in Synthesis Example 2 and dehydrated m-xylene (28.91 g) were weighed into a 50 mL flask and dehydrated using molecular sieves 4A (monomer solution). After purging the atmosphere in another 50 mL three-neck flask with nitrogen, the monomer solution (28.53 g) was removed and added. The flask was immersed in a thermostatic bath at 25°C, and the polymerization initiator solution (400 μL) synthesized in Synthesis Example 4 was added, followed by stirring at 25°C for 1 hour. Acetic acid (0.01 g) was added to terminate the reaction (polymerization solution). Subsequently, the polymerization solution was diluted with acetone (25 g). The diluted solution was added to 960 g of methanol to precipitate a polymer. The precipitated polymer was collected by filtration under reduced pressure and washed with methanol. The obtained polymer was dried under reduced pressure at 100°C for 2 hours to obtain a CSNT polymer (hereinafter also referred to as p(CSNT); 5.21 g). 1 The H-NMR spectrum is shown in Figure 2.

[0138] [Example 3: p(CSVT)] CVNT (9.92 g, 34.88 mmol) synthesized in Synthesis Example 3 and dehydrated m-xylene (39.70 g) were weighed into a 50 mL flask and dehydrated using molecular sieves 4A (monomer solution). After replacing the atmosphere in another 50 mL three-neck flask with nitrogen, the monomer solution (26.42 g) was removed and added. The flask was immersed in a thermostatic bath at 25°C, and the polymerization initiator solution (300 μL) synthesized in Synthesis Example 4 was added, followed by stirring at 25°C for 1 hour. Acetic acid (0.01 g) was added to terminate the reaction (polymerization solution). Subsequently, the polymerization solution was diluted with acetone (50 g). The diluted solution was added to 1,460 g of methanol to precipitate the polymer. The precipitated polymer was collected by vacuum filtration and washed with methanol. The obtained polymer was dried under vacuum at 100°C for 2 hours to obtain a CSVT polymer (hereinafter also referred to as p(CSVT); 4.84 g). 1 The H-NMR spectrum is shown in Figure 3.

[0139] [Example 4: p(PSNT)] p(NORT) (1.49 g) synthesized in Synthesis Example 5 and 1-pentanethiol (0.65 g, 6.19 mmol) were weighed and placed in a 50 mL three-neck flask, and the atmosphere in the flask was replaced with nitrogen. Toluene (Fujifilm Wako Pure Chemical Industries, deoxidizing grade; 15.85 g) and 2,2'-azobisisobutyronitrile (0.01 g, 0.06 mmol) were weighed and added to the flask, and the flask was immersed in an 80°C oil bath and heated for 3 hours while stirring with a magnetic stirrer (reaction solution). After cooling, the reaction solution was diluted with chloroform (20 g). The diluted solution was added to methanol (520 g) to precipitate a polymer. The precipitated polymer was collected by vacuum filtration and washed with methanol. The resulting polymer was dried under vacuum at 100°C for 2 hours to obtain a 1-pentanethiol adduct of p(NORT) (hereinafter also referred to as p(PSNT); 1.95 g). 1 The H-NMR spectrum is shown in Figure 4.

[0140] [Example 5: p(IBSNT)] p(NORT) (1.66 g) synthesized in Synthesis Example 5 and isobutyl mercaptan (1.73 g, 19.14 mmol) were weighed and placed in a 50 mL three-neck flask, and the atmosphere in the flask was replaced with nitrogen. Toluene (Fujifilm Wako Pure Chemical Industries, deoxidizing grade; 17.48 g) and 2,2'-azobisisobutyronitrile (0.01 g, 0.07 mmol) were weighed and added to the flask, and the flask was immersed in an 80°C oil bath and heated for 3 hours while stirring with a magnetic stirrer (reaction solution). After cooling, the reaction solution was diluted with chloroform (34 g). The diluted solution was added to methanol (550 g) to precipitate a polymer. The precipitated polymer was collected by vacuum filtration and washed with methanol. The resulting polymer was dried under vacuum at 100°C for 2 hours to obtain an isobutyl mercaptan adduct of p(NORT) (hereinafter also referred to as p(IBSNT); 2.22 g). 1 The H-NMR spectrum is shown in Figure 5.

[0141] Example 6: p(T6C-CSNT) p(T6C-NORT) (2.00 g) synthesized in Synthesis Example 6 and cyclohexanethiol (1.95 g, 16.75 mmol) were weighed and placed in a 50 mL three-neck flask, and the atmosphere in the flask was replaced with nitrogen. Toluene (Fujifilm Wako Pure Chemical Industries, deoxidizing grade; 19.95 g) and 2,2'-azobisisobutyronitrile (0.01 g, 0.06 mmol) were weighed and added to the flask, and the flask was immersed in an 80°C oil bath and heated for 3 hours while stirring with a magnetic stirrer (reaction solution). After cooling, the reaction mixture was diluted with chloroform (40 g). The diluted solution was added to methanol (560 g) to precipitate a polymer. The precipitated polymer was collected by vacuum filtration and washed with methanol. The resulting polymer was dried under vacuum at 100°C for 2 hours to obtain a p(T6C-NORT) cyclohexanethiol adduct (hereinafter also referred to as p(T6C-CSNT); 2.51 g). 1 The H-NMR spectrum of the obtained polymer is shown in Figure 6. 1 From the H-NMR spectrum, the proportions of T6C and CSNT in the polymer were calculated to be 50 mol% and 50 mol%, respectively.

[0142] [Comparative example 1: p(T6C)] T6C (10.06 g, 70.78 mmol) and dehydrated m-xylene (38.40 g) were weighed into a 50 mL flask and dehydrated using molecular sieves 4A (monomer solution). After purging the atmosphere in a separate 50 mL three-neck flask with nitrogen, the monomer solution (21.74 g) was removed and added. The flask was immersed in a thermostatic bath at 25°C, and the polymerization initiator solution (350 μL) synthesized in Synthesis Example 4 was added. The mixture was stirred at 25°C for 1 hour. Acetic acid (0.01 g) was added to terminate the reaction (polymerization solution). Subsequently, the polymerization solution was diluted with acetone (100 g). The diluted solution was added to 1260 g of methanol to precipitate the polymer. The precipitated polymer was collected by vacuum filtration and washed with methanol. The obtained polymer was dried under vacuum at 100°C for 2 hours to obtain a T6C polymer (hereinafter also referred to as p(T6C); 3.76 g).

[0143] [Comparative example 2: p(NORTH)] NORTH (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 molecular sieves 4A (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 the polymerization initiator solution (330 μL) synthesized in Synthesis Example 4 was added, followed by stirring at 25°C for 15 minutes. Acetic acid (0.010 g) was added to terminate the reaction (polymerization solution). Subsequently, the polymerization solution was diluted with m-xylene (46 g). The diluted solution was added to 482 g of methanol to precipitate a polymer. The precipitated polymer was collected by vacuum filtration and washed with methanol. The obtained polymer was dried under vacuum at 100°C for 2 hours to obtain a NORTH polymer (hereinafter also referred to as p(NORTH); 2.21 g).

[0144] Table 1 shows the physical properties of the polycarbonate resins obtained in the examples and comparative examples.

[0145] [Table 1]

[0146] Table 1 shows that the polycarbonate resins of the Examples have significantly higher thermal decomposition temperatures than the polycarbonate resins of the Comparative Examples, and are therefore superior in heat resistance. [Industrial Applicability]

[0147] 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. The following formula (1): 【Chemistry 1】 (In formula (1), A is an optionally substituted alicyclic moiety; L is a direct bond or a linking group; R 1 is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. A polycarbonate resin having a structural unit represented by the formula:

2. 2. The polycarbonate resin according to claim 1, wherein L is an ethylene group, a norbornylene group, or a decahydro-1,4:5,8-dimethanonaphthylene group.

3. The R 1 The polycarbonate resin according to claim 1 , wherein is a cyclohexyl group, an adamantyl group, or a decyl group.

4. 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.

5. 2. The polycarbonate resin according to claim 1, which has a glass transition temperature (Tg) of 60°C or higher and 250°C or lower.

6. A polycarbonate resin composition comprising the polycarbonate resin according to any one of claims 1 to 5 and an antioxidant.

7. An optical component comprising the polycarbonate resin according to any one of claims 1 to 5.

8. Use of the polycarbonate resin according to any one of claims 1 to 5 as a material for optical parts.

9. The following formula (1): 【Chemistry 2】 (In formula (1), A is an optionally substituted alicyclic moiety; L is a direct bond or a linking group; R 1 is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. A method for producing a polycarbonate resin having a structural unit represented by The following formula (2): 【Transformation 3】 (In formula (2), A is an optionally substituted alicyclic moiety; L is a direct bond or a linking group; R 1 is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. A method for producing a polycarbonate resin, comprising a polymerization step of ring-opening polymerizing a cyclic carbonate represented by the following formula:

10. The following formula (1): 【Chemistry 4】 (In formula (1), A is an optionally substituted alicyclic moiety; L is a direct bond or a linking group; R 1 is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. A method for producing a polycarbonate resin having a structural unit represented by The following formula (3): 【Transformation 5】 (In formula (3), A is an optionally substituted alicyclic moiety, and E is an optionally substituted alkenyl group having 1 to 20 carbon atoms.) or a structural unit represented by The following formula (3'): 【Transformation 6】 (In formula (3'), A' is an unsaturated alicyclic moiety which may be substituted.) A polycarbonate having a structural unit represented by The following formula (4): H-S-R 1 (4) (In formula (4), R 1 is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. and a thiol compound represented by the formula (I):

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