JP2023160599A - Polycarbonate resin, polycarbonate resin composition, optical component, and method for producing polycarbonate resin - Google Patents

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

The present invention relates to a polycarbonate resin, a polycarbonate resin composition, an optical component, and a method for producing a polycarbonate resin.

Polycarbonate resin is an engineering plastic with excellent heat resistance, and there is a demand for it to be lightweight and low-cost, as well as having excellent heat resistance and optical properties. In order to meet such demands, special polycarbonate resins based on aromatic skeletons are being actively developed.

On the other hand, polycarbonate resins having an aliphatic structure, particularly an alicyclic structure, are being developed as resins to replace 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 has excellent transparency, heat resistance, and color tone. In addition, polycarbonate is being developed using not only petroleum raw materials but also raw materials derived from biomass such as plants. For example, Patent Document 2 discloses a polycarbonate resin using isosorbide that can be derived from starch as a raw material.

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 the reaction of cyclohexene oxide and carbon dioxide, as shown in Patent Document 3, for example. Furthermore, as described in Patent Document 4, Non-Patent Document 1, and Non-Patent Document 2, it is known that poly(cyclohexene carbonate) can be obtained by ring-opening polymerization of 1,2-cyclohexene carbonate.

Patent No. 4774610 Patent No. 6507495 Patent No. 5403537 JP 2019-108547 Publication

Macromolecules 2014, 47, 4230-4235. Yonghang Xu, Tao Zhang, Yiluan Zhou, Danmin Zhou, Zixin Shen, Limiao Lin, Polymer Degradation and Stability 168, 2019, 10 8957

As mentioned above, while poly(1,2-cyclohexene carbonate) has excellent transparency, there is room for improvement in terms of heat resistance.

The present invention was made in view of the above circumstances, and aims to provide a polycarbonate tree having excellent heat resistance, a polycarbonate resin composition, an optical component, and a method for producing a polycarbonate resin.

The present inventors conducted intensive research to solve the above problems, and as a result, they discovered that a polycarbonate resin having a sulfide bond has excellent heat resistance, and completed the present invention.

That is, the present invention includes the following embodiments.
<1>
The following formula (1):
(In formula (1),
A is an optionally substituted alicyclic moiety,
L is a direct bond or a connecting 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:
<2>
The polycarbonate resin according to <1>, wherein the A is a cyclohexane-1,2-diyl group.
<3>
The polycarbonate resin according to <1> or <2>, wherein the L is an ethylene group, a norbornylene group, or a decahydro-1,4:5,8-dimethanonaphthylene group.
<4>
The polycarbonate resin according to any one of <1> to <3>, wherein R ¹ is a cyclohexyl group, an adamantyl group, or a decyl group.
<5>
The polycarbonate resin according to any one of <1> to <4>, which has a weight average molecular weight (Mw) of 10,000 or more and 1,000,000 or less.
<6>
The polycarbonate resin according to any one of <1> to <5>, which has a glass transition temperature (Tg) of 60° C. or higher and 250° C. or lower.
<7>
A polycarbonate resin composition containing the polycarbonate resin according to any one of <1> to <6> and an antioxidant.
<8>
An optical component containing the polycarbonate resin according to any one of <1> to <6> or the polycarbonate resin composition according to <7>.
<9>
Use of the polycarbonate resin according to any one of <1> to <6> or the polycarbonate resin composition according to <7> as a material for optical components.
<10>
The following formula (1):
(In formula (1),
A is an optionally substituted alicyclic moiety,
L is a direct bond or a connecting 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):
(In formula (2),
A is an optionally substituted alicyclic moiety,
L is a direct bond or a connecting 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 obtaining the polycarbonate resin by ring-opening polymerization of a cyclic carbonate represented by the formula.
<11>
The following formula (1):
(In formula (1),
A is an optionally substituted alicyclic moiety,
L is a direct bond or a connecting 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):
(In formula (3), A is an optionally substituted alicyclic moiety, and E is an optionally substituted alkenyl group having 1 to 20 carbon atoms.)
Structural unit represented by or the following formula (3'):
(In formula (3'), A' is an optionally substituted unsaturated alicyclic moiety.)
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. .)
A method for producing a polycarbonate resin, comprising a modification step of obtaining the polycarbonate resin by mixing and stirring a mixture containing a thiol compound represented by:

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 that have excellent heat resistance.

1 shows a ¹ H-NMR spectrum of the polycarbonate resin in Example 1. 1 shows a ¹ H-NMR spectrum of the polycarbonate resin in Example 2. The ¹ H-NMR spectrum of the polycarbonate resin in Example 3 is shown. The ¹ H-NMR spectrum of the polycarbonate resin in Example 4 is shown. The ¹ H-NMR spectrum of the polycarbonate resin in Example 5 is shown. The ¹ H-NMR spectrum of the polycarbonate resin in Example 6 is shown.

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

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

The polycarbonate resin according to this embodiment exhibits excellent heat resistance by having the above configuration. This factor is considered to be as follows, but the factor is not limited to this.

Conventional cyclic carbonates with an alicyclic structure have a cyclic skeleton, but due to their highly rigid structure, there is steric space around the relatively unstable carbonate group, which is susceptible to hydrolysis etc. easy to receive.
On the other hand, since the polycarbonate resin of this embodiment has a sulfide group, the interaction between the carbonate group and the sulfide group in molecules causes steric crowding around the carbonate group, making it less susceptible to hydrolysis, etc. As a result, it is presumed that the heat resistance has improved.

In formula (1), A is an optionally substituted divalent alicyclic moiety. The alicyclic moiety is not particularly limited, but includes, for example, a cyclopropane-1,2-diyl group, a cyclobutane-1,2-diyl group, a cyclopentane-1,2-diyl group, and a cyclohexane-1,2-diyl group. , cycloheptane-1,2-diyl group, cyclooctane-1,2-diyl group, cyclononane-1,2-diyl group, and cyclodecane-1,2-diyl group. Among these A, cyclobutane-1,2-diyl group, cyclopentane-1,2-diyl group, cyclohexane-1,2-diyl group, cycloheptane-1,2-diyl group, cyclooctane-1,2 -diyl group is preferred, and cyclobutane-1,2-diyl group, cyclopentane-1,2-diyl group, cyclohexane-1,2-diyl group, and cycloheptane-1,2-diyl group are more preferred, and cyclohexane-1,2-diyl group is preferred. ,2-diyl group is more preferred.

Alicyclic moiety A may have an unsaturated bond at any position. A may have a plurality of unsaturated bonds.

Furthermore, the alicyclic moiety A may be substituted with any substituent. Substituents include, but are not particularly limited to, hydroxyl groups, phosphoric acid groups, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 6 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and 1 to 30 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 group having 1 to 30 carbon atoms. It is an alkyl group. There may be a plurality of substituents for A, and in that case, each substituent may be the same or different.

The substituent of the alicyclic moiety A is preferably a hydroxyl group, a phosphoric acid 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, or a C 1 to 20 alkoxy group. ~30 silyl group, silylalkoxy group having 1 to 30 carbon atoms, ester group having 1 to 11 carbon atoms, acyl group having 1 to 11 carbon atoms, or linear, branched, or cyclic carbon number 1 to 30 30 alkyl group, more preferably 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, or a linear, branched, or A 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. More preferably, it is an alkoxy group having 1 to 20 carbon atoms, or a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms.

The phosphate group may be unsubstituted or substituted. That is, it may be a mono-substituted phosphoric acid group or a di-substituted phosphoric acid group. When the phosphoric acid group is substituted, the substituent is preferably an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. Note that the phosphoric acid group in this embodiment is preferably unsubstituted.

The aryl group having 6 to 20 carbon atoms is not particularly limited, but includes, for example, phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, propylphenyl group. , an aryl group that is unsubstituted or has an alkyl group such as a diisopropylphenyl group, an aryl group that has an alkoxy group such as a 4-methoxyphenyl group, a 3,5-dimethoxyphenyl group, a biphenyl group, a naphthyl group, etc. , anthracenyl group.

Examples of the aralkyl group having 6 to 20 carbon atoms include, but are not particularly limited to, unsubstituted or aralkyl groups having an alkyl group such as benzyl group, 4-methylbenzyl group, and phenethyl group, and 4-methoxybenzyl group. , an aralkyl group having an alkoxy group such as a 3,5-dimethoxybenzyl group, and examples thereof include a diphenylmethyl group, a naphthylmethyl group, an anthracenylmethyl group, and the like.

The alkoxy group having 1 to 20 carbon atoms is not particularly limited, but includes, for example, 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, Examples include octyloxy group, nonanyloxy group, decyloxy group, phenoxy group, benzyloxy group, vinyloxy group, and allyloxy group.

Examples of the silyl group having 1 to 30 carbon atoms include, but are not particularly limited to, trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, triphenylsilyl group, tert-butyldimethylsilyl group, di-tert-butylisobutylsilyl group. , and tert-butyldiphenylsilyl group.

Examples of the silylalkoxy group having 1 to 30 carbon atoms include, but are not particularly limited to, a trimethylsilylmethoxy group, a trimethylsilylethoxy group, a trimethylsilylphenoxy group, a trimethylsilylbenzyloxy group, a triethylsilylmethoxy group, a triethylsilylethoxy group, and a triethylsilylphenoxy group. , triethylsilylbenzyloxy group, triisopropylsilylmethoxy group, triisopropylsilylethoxy group, triisopropylsilylphenoxy group, triisopropylsilylbenzyloxy group, triphenylsilylmethoxy group, triphenylsilylethoxy group, triphenylsilylphenoxy group, Triphenylsilylbenzyloxy 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-butyl Examples include diphenylsilylphenoxy group and tert-butyldiphenylsilylbenzyloxy group.

Examples of the ester group having 1 to 11 carbon atoms include, but are not limited to, 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, Examples include heptyl ester group, octyl ester group, nonanyl ester group, decyl ester group, phenyl ester group, benzyl ester group, vinyl ester group, and allyl ester group.

Examples of the acyl group having 1 to 11 carbon atoms include, but are not limited to, a formyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a benzoyl group.

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

In formula (1), L is a direct bond or a connecting group. Examples of the linking group include divalent alkylene groups 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, more preferably 1 to 20. The divalent alkylene group is not particularly limited, but includes, for example, 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, Decylene group, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, norbornylene group, bicyclo[2.2.2]octylene group, deca Examples include hydronaphthylene group and 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, or a cyclopropylene group. group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, norbornylene group, bicyclo[2.2.2]octylene group, decahydronaphthylene group, Decahydro-1,4:5,8-dimethanonaphthylene group, more preferably methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, hexylene group, cyclobutylene group. group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, norbornylene group, bicyclo[2.2.2]octylene group, decahydronaphthylene group, decahydro-1, 4:5,8-dimethanonaphthylene group, more preferably ethylene group, norbornylene group, or decahydro-1,4:5,8-dimethanonaphthylene group.

In formula (1), 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. R ¹ is not particularly limited, but includes, for example, 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, and a heptyl group. , octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, adamantyl group, norbornyl group, bicyclo[2.2.2]octyl group, decahydronaphthyl group, decahydro-1,4:5,8-dimethanonaphthyl group, Examples include phenyl group, benzyl group, and 3-(2-methyltetrahydro)furyl group. R ¹ is preferably a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, Cyclooctyl group, cyclononyl group, cyclodecyl group, adamantyl group, norbornyl group, bicyclo[2.2.2]octyl group, decahydronaphthyl group, decahydro-1,4:5,8-dimethanonaphthyl group, phenyl group, benzyl group , 3-(2-methyltetrahydro)furyl group, more preferably a cyclohexyl group, an adamantyl group, or a decyl group.

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

(Terminal structure)
The terminal end of the polycarbonate resin according to this embodiment is not particularly limited, but includes, for example, a hydrogen atom, a hydroxyl group, a phosphoric acid group, an amino group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, and a carbon number 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 straight It is a chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms. In addition, both ends of the polycarbonate resin according to this embodiment may be bonded to each other to form a cyclic structure. That is, the polycarbonate resin according to this embodiment does not need to have a terminal structure. The polycarbonate resin according to this embodiment preferably has hydroxyl groups at both ends.

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

L and R ¹ in formula (X1) are the same as those in formula (1).

The polycarbonate resin according to the present embodiment may have one type of structural unit represented by formula (X1), or may use a combination of multiple types.

The polycarbonate resin according to the present embodiment preferably includes a structure represented by the following formula (X1-1), (X1-2), (X1-3), or (X1-4).

The polycarbonate resin according to the present embodiment preferably has a structural unit represented by formula (X1-1) or a structural unit represented by formula (X1-2).

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

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

The polycarbonate resin according to the present embodiment preferably has a structural unit represented by formula (X1-3) or a structural unit represented by formula (X1-4).

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

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

In formulas (X1-1) and (X1-2), m is preferably an integer of 0 to 5, more preferably 1.

In formulas (X1-3) and (X1-4), n is preferably an integer of 0 to 2, more preferably 0 or 1.

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

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

Examples of the alicyclic moiety of C include cyclopropane-1,2-diyl group, cyclobutane-1,2-diyl group, cyclopentane-1,2-diyl group, cyclohexane-1,2-diyl group, and cycloheptane-1,2-diyl group. -1,2-diyl group, cyclooctane-1,2-diyl group, cyclononane-1,2-diyl group, and cyclodecane-1,2-diyl group. Among these A, cyclobutane-1,2-diyl group, cyclopentane-1,2-diyl group, cyclohexane-1,2-diyl group, cycloheptane-1,2-diyl group, cyclooctane-1,2 -diyl group is preferred, and cyclobutane-1,2-diyl group, cyclopentane-1,2-diyl group, cyclohexane-1,2-diyl group, and cycloheptane-1,2-diyl group are more preferred.

In the case of substitution, examples of the substituent are the same as those in formula (1).

The proportion of the structural unit represented by formula (1) in the polycarbonate resin according to the present embodiment is not particularly limited, but is, for example, 10 to 90 mol%, 20 to 80 mol%, 30 to 70 mol%, 40 to 60 mol%. Preferably it is mol%.

The proportion of the structural unit represented by formula (2) in the polycarbonate resin according to the present embodiment is not particularly limited, but is, for example, 10 to 90 mol%, 20 to 80 mol%, 30 to 70 mol%, 40 to 60 mol%. Preferably it is mol%.

In the polycarbonate resin according to this embodiment, the weight average molecular weight (Mw) is preferably 10,000 or more and 1,000,000 or less. The polycarbonate resin according to the present embodiment can be easily molded when the Mw is within the above range. Further, 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, still more preferably 10,000 or more and 900,000 or less. Further, 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 specifically can be measured by the method described in Examples.

In order to control the weight average molecular weight (Mw) within the above range in the polycarbonate resin according to the present embodiment, it is only necessary to adjust the ratio of the polymerizable monomer and the polymerization initiator as appropriate, and also by the manufacturing method described below. What is necessary is to manufacture polycarbonate resin. By controlling the amount of polymerization initiator added to the polymerizable monomer within a specific range, the polymerization reaction tends to proceed at a good conversion rate and the Mw can be increased.

In the polycarbonate resin according to this embodiment, the glass transition temperature (Tg) is preferably 60°C or more and 250°C or less. When the Tg is 60° C. or higher, the shape tends to be maintained even in a normal temperature usage environment, resulting in excellent heat resistance. Moreover, when Tg is 250° C. or less, moldability tends to be excellent. From the same viewpoint, the glass transition temperature of the polycarbonate resin according to this embodiment is more preferably 60°C or more and 245°C or less, and even more preferably 60°C or more and 240°C or less. The glass transition temperature of the polycarbonate resin is measured by a differential scanning calorimeter (DSC), and specifically can be measured by the method described in the Examples.

In the polycarbonate resin according to the present embodiment, in order to control the glass transition temperature within the above-mentioned preferable range, A, R ¹ and L in formula (1) may be appropriately selected. The combination of A, R ¹ and L that controls the glass transition temperature within the above preferred range is not particularly limited, but if A, R ¹ and L having a cyclic skeleton are selected, the glass transition temperature tends to increase. However, if A, R ¹ and L having a chain skeleton are selected, the glass transition temperature tends to decrease. Therefore, by appropriately combining A, R ¹ and L, a polycarbonate resin having a desired glass transition temperature can be obtained. can be manufactured. In particular, when the above-mentioned preferable A, R ¹ , L and R ² are selected, the cyclic skeleton and the chain skeleton tend to be balanced and the glass transition temperature can be controlled within the above-mentioned preferable range.

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

By containing the antioxidant, the polycarbonate resin composition according to the present embodiment can suppress deterioration due to heat and shearing during molding, so that the heat resistance of the polycarbonate resin composition can be further improved. can. In addition, the polycarbonate resin composition according to the present embodiment contains an antioxidant, which can prevent the polycarbonate resin from being oxidized during use, thereby further improving the light resistance of the polycarbonate resin composition. can be done.

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

Examples of hindered phenolic antioxidants 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''-hex-t-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol), Irganox 3114 (Irganox3114:1,3,5- Tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione), 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- Cyanox 1790 ), Sumilizer GA-80, Sumilizer GS: 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di acrylate -tert-pentylphenyl), and Sumilizer 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.

Phosphorous antioxidants are not particularly limited, but include, for example, 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 :2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite), ADKSTAB PEP36 (ADKSTAB PEP36: bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol di ADKSTAB PEP36A (bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite), Sumilizer 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-5methylphenyl)4,4'-biphenylene diphosphonite).These may be used alone or in combination of two or more. Good too.

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

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 based on the entire resin composition, from the viewpoint of more effectively and reliably achieving the effects of the present invention. It is more preferably 60% by mass or more and less than 100% by mass, and still more preferably 65% by mass or more and less than 100% by mass.

The content of the antioxidant in the polycarbonate resin composition according to the present embodiment is preferably 0.001% by mass based on the entire resin composition from the viewpoint of further preventing deterioration due to heat and shearing during molding. The content is 1% by mass or less, more preferably 0.003% by mass or more and 1% by mass or less, and still more preferably 0.005% by mass or more and 1% by mass or less.

[Optical parts]
The optical component according to this embodiment contains the above polycarbonate resin or the above polycarbonate resin composition.

Since the above-mentioned polycarbonate resin or the above-mentioned polycarbonate resin composition contained in the optical component according to the present embodiment has a small photoelastic coefficient and a small in-plane retardation due to molecular orientation, the optical component according to the present embodiment can resist stress. Less likely to exhibit birefringence and orientational birefringence. Therefore, the optical component according to this embodiment tends to be able to suppress birefringence during use. Furthermore, since the above-mentioned polycarbonate resin or the above-mentioned polycarbonate resin composition contained in the optical component according to the present embodiment has excellent heat resistance as described above, the optical component according to the present embodiment does not deteriorate over time. It is less likely to occur and can be used for a longer period of time than conventional optical components.

Optical components in this embodiment include, but are not particularly limited to, optical lenses such as cameras, telescopes, microscopes, projectors, and vehicle lenses, and optical components such as diffusers, light guide plates, polarizing plates, and retardation films. An example is film. The optical component according to the present embodiment can be obtained by appropriately processing the polycarbonate resin or the polycarbonate resin composition, such as molding, so that it has a shape suitable for its use.

[Production method of polycarbonate resin]
Methods for producing the polycarbonate resin according to the present embodiment are not particularly limited, but include, for example, a method of copolymerizing epoxide and carbon dioxide, a method of ring-opening polymerization of cyclic carbonate, and a method of copolymerizing diol and carbon dioxide or carbonic ester. Examples include a method of condensation polymerization.

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

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

In the method for producing a polycarbonate resin according to the present embodiment, as the cyclic carbonate used for ring-opening polymerization, one type of cyclic carbonate may be used alone, or any two or more types in which A, R ¹ and L are different. cyclic carbonates may be used in combination.

In the cyclic carbonate used for ring-opening polymerization, it is preferable that the carbonate group forms a 1,2-trans structure.

In the method for producing a polycarbonate resin according to the present embodiment, other cyclic carbonates may be used in addition to the cyclic carbonate (A1).
Examples of other cyclic carbonates include cyclic carbonate (A2) represented by formula (7). One type of cyclic carbonate (A2) may be used, or a combination of multiple types may be used.

In formula (7), C is as explained in formula (2). In the method for producing a polycarbonate resin according to the present embodiment, as the cyclic carbonate (A2) used in ring-opening polymerization, one type of cyclic carbonate may be used alone, or two or more types of cyclic carbonates having different C may be used alone. may be used in combination.

Examples of the polymerization initiator for ring-opening polymerization of the cyclic carbonates (A1) and (A2) include, but are not limited to, acid catalysts, base catalysts, and enzyme catalysts. Examples of the base catalyst include, but are not particularly limited to, cyclic amines such as alkyl metals, metal alkoxides, metal amides, metal organic acid salts, cyclic monoamines and cyclic diamines (particularly cyclic diamine compounds having an amidine skeleton), and guanidine skeletons. Examples include triamine compounds having a nitrogen atom, and heterocyclic compounds containing a nitrogen atom. Examples of the alkyl metal include, but are not limited to, organolithium such as methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and phenyllithium, methylmagnesium halide, ethylmagnesium halide, and propylmagnesium halide. , phenylmagnesium halide, trimethylaluminum, and triethylaluminum. Among them, methyllithium, n-butyllithium, or sec-butyllithium is preferably used. The metal ion in the metal alkoxide is not particularly limited, but includes, for example, alkali metal and alkaline earth metal ions, with alkali metal being preferred. Examples of alkoxide ions include, but are not limited to, methoxide, ethoxide, propoxide, butoxide, phenoxide, and benzyloxide. Note that 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. The organic acid ion in the metal organic acid salt is not particularly limited, but includes, for example, a carboxylic acid ion having 1 to 10 carbon atoms. Examples of the metal in the metal organic acid salt include, but are not limited to, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, and tin. Further, the base catalyst is not particularly limited, but includes, for example, an organic base. The organic base is not particularly limited, but for example, 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 bases. 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.

The amount of the polymerization initiator used in the polymerization step of the method for producing polycarbonate resin according to the present embodiment may be adjusted as appropriate 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 in the range of 10,000 to 1,000,000, the amount of the polymerization initiator used is calculated based on the amount of substance relative to the cyclic carbonate (A1), which is a ring-opening polymerizable monomer. The content is preferably 0.0001 mol% or more and 4 mol% or less, more preferably 0.0001 mol% or more and 2 mol% or less, and even more preferably 0.0001 mol% or more and 1 mol% or less. Furthermore, the above polymerization initiators may be used alone or in combination of two or more.

From the viewpoint of controlling the average molecular weight of the resulting polycarbonate resin, a polymerization terminator may be used in addition to the polymerization initiator. Examples of the polymerization terminator include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, phosphoric acid, metaphosphoric acid, formic acid, acetic acid, and propionic acid. , butyric acid, lactic acid, citric acid, ascorbic acid, gluconic acid, oxalic acid, tartaric acid, Meldrum's acid, and benzoic acid.

In addition to the above polymerization initiator, additives may be used from the viewpoint of controlling the molecular weight of the obtained polymer and from the viewpoint of expressing various properties by controlling the terminal structure. Examples of additives include, but are not limited to, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, nonanol, decanol, dodecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, 5-norbornene-2. - monoalcohols such as methanol, 1-adamantanol, 2-adamantanol, trimethylsilylmethanol, phenol, benzyl alcohol, and p-methylbenzyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, Dialcohols such as 1,3-butanediol, 1,4-butanediol, hexanediol, nonanediol, tetramethylene glycol, and polyethylene glycol, such as glycerol, sorbitol, xylitol, ribitol, erythritol, and triethanolamine Included are polyhydric alcohols, methyl lactate, and ethyl lactate. Further, the above additives may be used alone or in combination of two or more.

In the method for producing a polycarbonate resin according to the present embodiment, the reaction temperature in the polymerization step is not particularly limited as long as it is within a range that allows producing the polycarbonate resin according to the present embodiment, but is preferably -60°C or higher and 150°C. The temperature is preferably -60°C or more and 130°C or less, and even more preferably -60°C or more and 120°C or less. When 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 within the range of 10,000 or more and 1,000,000 or less.

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

<Modification process>
Examples of the method for manufacturing the polycarbonate resin according to this embodiment include, in addition to the above-mentioned manufacturing method, a manufacturing method including a modification step. In this case, the modification step may include 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 the present embodiment includes polycarbonate (B1) having a structural unit represented by the following formula (3) or a structural unit represented by the following formula (3'), and a polycarbonate (B1) having a structural unit represented by the following formula (4). It is preferable to have a step of mixing and stirring a mixture containing the represented thiol compound (B2).

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.

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

H-S-R ¹ (4)

In formula (4), R ¹ is the same as in formula (1).

One type of polycarbonate (B1) or polycarbonate (B1') may be used, or a combination of multiple types may be used.

In formula (3), E is an optionally substituted alkenyl group having 1 to 20 carbon atoms. The alkenyl group may be linear, branched, or cyclic. The alkenyl group having 1 to 20 carbon atoms is not particularly limited, but includes, for example, methylene group, ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group. group, decenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cyclohebutenyl group, cyclooctenyl group, cyclononenyl group, cyclodecenyl group, norbornenyl group, bicyclo[2.2.2]octenyl group, octahydronaphthalene Nyl group, octahydro-1,4:5,8-dimethanonaphthalenyl group. The alkenyl group having 1 to 20 carbon atoms in formula (3) is preferably a vinylidene group, ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group. group, decenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cyclohebutenyl group, cyclooctenyl group, cyclononenyl group, cyclodecenyl group, norbornenyl group, bicyclo[2.2.2]octenyl group, octahydronaphthalene Nyl group, octahydro-1,4:5,8-dimethanonaphthalenyl group, 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, cyclohebutenyl group, cyclooctenyl group, cyclononenyl group, cyclodecenyl group, norbornenyl group, bicyclo[2.2.2]octenyl group, octahydronaphthalenyl group, octahydro -1,4:5,8-dimethanonaphthalenyl group.

In formula (2'), A' is an optionally substituted unsaturated alicyclic moiety. The unsaturated alicyclic moiety preferably has a carbon-carbon double bond in the alicyclic moiety.

The terminal of the polycarbonate (B1) is preferably the same as the terminal in the polycarbonate resin according to this embodiment.

In the method for producing a polycarbonate resin according to the present embodiment, the polycarbonate (B1) preferably includes a structure represented by the following formula (Y1).

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

In the method for producing a polycarbonate resin according to the present embodiment, the polycarbonate (B1) preferably includes a structure represented by the following formula (Y1-1) or a structure represented by (Y1-2).

In formula (Y1-1), m is the same as in formula (X1-1). 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 one type or a combination of two or more types may be used.

Polycarbonate (B1) may have other structural units in addition to the structural unit represented by formula (3).
Examples of other structural units include ring-opened cyclic carbonate units. More specifically, other structural units include, for example, a structural unit represented by the following formula (2).

In formula (2), C is as described above.

The proportion of the structural unit represented by formula (3) in polycarbonate (B1) is not particularly limited, but for example, 10 to 90 mol%, 20 to 80 mol%, 30 to 70 mol%, 40 to 60 mol%. It is preferable that there be.

The proportion of the structural unit represented by formula (2) in polycarbonate (B1) is not particularly limited, but may be, for example, 10 to 90 mol%, 20 to 80 mol%, 30 to 70 mol%, 40 to 60 mol%. It is preferable that there be.

In formula (4), R ¹ is as explained in formula (1). One type of thiol compound (B2) may be used, or a combination of multiple types may be used.

The mass ratio of polycarbonate (B1) to thiol compound (B2) in the modification step is preferably 1:100 to 100:1, more preferably 1:50 to 50:1.

A solvent may be added in the modification step. Examples of the solvent include, but are not limited to, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, tert-butyl methyl ether, and propylene. Ether solvents such as glycol monomethyl ether acetate, halogen solvents such as methylene chloride, chloroform, dichloromethane, dichloroethane, and trichloroethane, saturated hydrocarbons such as hexane, heptane, octane, nonane, cyclohexane, and methylcyclohexane. Solvents, aromatic hydrocarbon solvents such as toluene, xylene, o-xylene, m-xylene, p-xylene, and cresol, as well as acetone, 2-butanone, 2-pentanone, 3-pentanone, cyclopentanone, Examples include ketone solvents such as cyclohexanone and methyl isobutyl ketone.

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

In the modification step, a radical initiator may be added. A radical initiator refers to a substance that generates radicals by heat, light, redox reaction, or the like. These include organic peroxides, azo compounds, redox initiators, photoinitiators, and the like.

Examples of the organic peroxide include, but are not limited to, benzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, and dicumyl peroxide.

Examples of the azo compound include, but are not limited to, 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.

Examples of the redox initiator include, but are not limited to, combinations of hydrogen peroxide-iron(II) salt, organic oxide-dimethylaniline, cerium(IV) salt-alcohol, and the like.

Examples of the photoinitiator include, but are not limited to, alkylphenone photoinitiators, α-aminoalkylketone photoinitiators, and phosphine oxide photoinitiators.

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.

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

Examples of the atmosphere in the modification step include an air atmosphere, a nitrogen atmosphere, and an argon atmosphere. Among these, a nitrogen atmosphere or an argon atmosphere is preferred, and a nitrogen atmosphere is more preferred.

The present invention will be explained in more detail using Examples and Comparative Examples, but the present invention is not limited by these Examples and the like.

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

[ ¹ H-NMR measurement]
A ¹ H-NMR spectrum of the cyclic carbonate was obtained by performing NMR measurement using an NMR device manufactured by JEOL Ltd. (product name: ECZ400S) and a TFH probe. Note that the reference peak of the heavy solvent was δ _H =7.26 ppm when chloroform-d was used, and the measurement was performed with the number of integrations set to 32.

[Measurement of molecular weight]
A solution prepared by adding 2.0 g of tetrahydrofuran to 0.02 g of polycarbonate resin was used as the measurement sample, and the weight of the polycarbonate resin was measured using a high-speed GPC device (manufactured by Tosoh Corporation, product name "HLC-8420GPC"). The average molecular weight was measured. As columns, TSK guard columns SuperH-H, TSKgel SuperHM-H, TSKgel SuperHM-H, TSKgel SuperH2000, and TSKgel SuperH1000 (all product names manufactured by Tosoh Corporation) were connected in series and used. The column temperature was 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 a detector. A calibration curve was created using polystyrene standard samples (molecular weight: 2520000, 1240000, 552000, 277000, 130000, 66000, 34800, 19700, 8680, 3470, 1306, 370) manufactured by Polymer Standards Service as standard samples. . Based on the calibration curve thus created, the number average molecular weight and weight average molecular weight of the polycarbonate resin were determined.

[Measurement of glass transition temperature]
Approximately 5 mg of the polycarbonate resin obtained in the Examples and Comparative Examples described later was used as a measurement sample, and a differential scanning calorimeter (product name: "DSC8500") manufactured by PerkinElmer Japan Co., Ltd. was used at a nitrogen gas flow rate of 20 mL/min. The glass transition temperature was measured under these conditions. More specifically, for example, the sample of Example 1 was held at 40°C for 3 minutes, and then the temperature was raised from 40°C to 210°C at a rate of 20°C/min to completely melt the sample. Thereafter, the temperature was lowered from 210°C to 40°C at a rate of 50°C/min and held at 40°C for 5 minutes. Next, we will compare the step-like change portion of the DSC curve drawn when the temperature is raised from 40°C to 200°C at a rate of 10°C/min and the straight line equidistant in the vertical axis direction from the extension line of each tangent. The intersection point (midpoint glass transition temperature) was defined as the glass transition temperature (Tg). The glass transition temperatures of the samples of other Examples and Comparative Examples were also measured in the same manner.

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

[Synthesis example 1: NORT]
4-vinyl-trans-1,2-cyclohexene carbonate (501 g, 3 mol) and dicyclopentadiene (2484 g, 18 mol) were added to a 3L autoclave. The reaction was continued for 3 days by heating to an internal temperature of 200°C. After cooling to an internal temperature of 60° C., the contents were collected and poured into chloroform (5.5 L) to dissolve. This solution was slowly poured into methanol (20 L) and stirred for 1 hour, then the precipitate was removed by vacuum filtration and rinsed with methanol (1.5 L). After concentrating the filtrate under reduced pressure, the concentrate was subjected to silica gel column chromatography and divided into two fractions, A and B, with 490 g of concentrate obtained from A and 231 g from B. The concentrate of fraction A (490 g) was subjected to silica gel chromatography again, and the fraction containing the target product was concentrated. A white solid began to precipitate during the concentration, so the concentration was stopped midway and the solid was removed by vacuum filtration. The concentrate (144 g) obtained by concentrating the filtrate after removing the white solid under reduced pressure 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 was obtained. The obtained distillate was purified by silica gel column chromatography and dried under reduced pressure at 50°C to produce 4-(5-norbornen-2-yl)-trans-1,2-cyclohexene carbonate (hereinafter also referred to as NORT). (102 g) was obtained.

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

[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 into a 50 mL three-necked flask, and the inside of the flask was purged with nitrogen. 2,2'-Azobisisobutyronitrile (0.08 g, 0.46 mmol) was weighed out and added to the flask, and the flask was immersed in an 80°C oil bath and stirred with a magnetic stirrer for 3 hours. Heated. After cooling, it is purified by silica gel column chromatography, and the fraction containing the target product is collected, concentrated under reduced pressure, and dried under reduced pressure at 60°C to obtain the following formula:
Compounds represented by and formula:
A mixture of compounds represented by (hereinafter also referred to as CSNT; 7.70 g) was obtained.

[Synthesis Example 4: Polymerization initiator solution]
After purging a 50 mL Schlenk tube 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.

[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 Sieve 4A (monomer solution). After purging the inside of another 100 mL three-necked flask with nitrogen, the monomer solution (45.21 g) was extracted and added. The flask was immersed in a constant temperature bath at 25°C, the polymerization initiator solution (200 μL) synthesized in Synthesis Example 4 was added, and the mixture was stirred at 25°C for 1 hour. Acetic acid (0.02 g) was added to stop the reaction (polymerization liquid).
Subsequently, chloroform (180 g) was added to the polymerization solution to dilute it. The diluted solution was added to 1600 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 reduced pressure at 100° C. for 2 hours to obtain a NORT polymer (hereinafter also referred to as p(NORT); 8.72 g).

[Synthesis Example 6: p(T6C-NORT)]
Transfer trans-1,2-cyclohexene carbonate (hereinafter also referred to as T6C; 5.05 g, 35.55 mmol), NORT synthesized in Synthesis Example 1 (8.24 g, 35.15 mmol), and dehydrated toluene (52 mmol) to a 100 mL flask. .88 g) was weighed out and dehydrated using Molecular Sieve 4A (monomer solution). After purging the inside of another 100 mL three-necked flask with nitrogen, the monomer solution (60.03 g) was extracted and added. The flask was immersed in a constant temperature bath at 25°C, the polymerization initiator solution (200 μL) synthesized in Synthesis Example 4 was added, and the mixture was stirred at 25°C for 1 hour. Acetic acid (0.01 g) was added to stop the reaction (polymerization liquid).
Subsequently, chloroform (240 g) was added to the polymerization solution to dilute it. 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 reduced pressure 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).

[Synthesis Example 7: NORTH]
Weigh NORT (4.78 g, 20.4 mmol) and chloro(1,5-cyclooctadiene)iridium(I) dimer (0.145 g, 0.216 mmol) into a 50 mL three-necked flask, and purify the inside of the flask with nitrogen. Replaced. Toluene (oxygen-absorbing grade manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.; 10 mL) and 2-propanol (oxygen-absorbing grade manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.; 10 mL) were weighed out and added to the flask. Furthermore, 1,2-bis(dicyclohexylphosphino)ethane (0.187 g, 0.442 mmol) was weighed out and added to the flask, and the flask was immersed in a 100°C oil bath while stirring with a magnetic stirrer. heated for an hour. After cooling, the contents were transferred to a 50 mL flask, the solvent was distilled off using an evaporator, the concentrated residue was purified by silica gel column chromatography, and the fraction containing the target product was collected to obtain 5.01 g of concentrate. Ta. This concentrate was dissolved in a mixed solvent of ethyl acetate (2 mL)/heptane (10 mL), transferred to a -30°C freezer, and left overnight. The precipitated solid was collected by vacuum filtration, washed with heptane, and dried under reduced pressure at 60°C to produce 4-(5-norbornan-2-yl)-trans-1,2-cyclohexene carbonate (hereinafter also referred to as NORTH). 3.45 g) was obtained.

[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 into a 50 mL three-necked flask, and the inside of the flask was purged with nitrogen. Toluene (oxygen absorbing grade manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; 15.30 g) and 2,2'-azobisisobutyronitrile (0.04 g, 0.25 mmol) were weighed out and added to the flask, and the flask was heated to 80 g. It was immersed in an oil bath at ℃ and heated for 6 hours while stirring with a magnetic stirrer (reaction liquid).
After cooling, the reaction solution was diluted with chloroform (50 g). The diluted solution was added to methanol (480 g) to precipitate the polymer. The precipitated polymer was collected by vacuum filtration and washed with methanol. The obtained polymer was dried under reduced pressure at 100° C. for 2 hours to obtain a 1-adamantanethiol adduct of p(NORT) (hereinafter also referred to as p(ASNT); 2.66 g). The ¹ H-NMR spectrum is shown in Figure 1.

[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 Sieve 4A (monomer solution). After purging the inside of another 50 mL three-necked flask with nitrogen, the monomer solution (28.53 g) was extracted and added. The flask was immersed in a constant temperature bath at 25°C, the polymerization initiator solution (400 μL) synthesized in Synthesis Example 4 was added, and the mixture was stirred at 25°C for 1 hour. Acetic acid (0.01 g) was added to stop the reaction (polymerization liquid).
Subsequently, acetone (25 g) was added to the polymerization solution to dilute it. The diluted solution was added to 960 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 reduced pressure at 100° C. for 2 hours to obtain a CSNT polymer (hereinafter also referred to as p(CSNT); 5.21 g). ^{The 1} H-NMR spectrum is shown in Figure 2.

[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 Sieve 4A (monomer solution). After purging the inside of another 50 mL three-necked flask with nitrogen, the monomer solution (26.42 g) was extracted and added. The flask was immersed in a constant temperature bath at 25°C, the polymerization initiator solution (300 μL) synthesized in Synthesis Example 4 was added, and the mixture was stirred at 25°C for 1 hour. Acetic acid (0.01 g) was added to stop the reaction (polymerization liquid).
Subsequently, acetone (50 g) was added to the polymerization solution to dilute it. The diluted solution was added to 1460 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 reduced pressure at 100° C. for 2 hours to obtain a CSVT polymer (hereinafter also referred to as p(CSVT); 4.84 g). ^{The 1} H-NMR spectrum is shown in Figure 3.

[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 into a 50 mL three-necked flask, and the inside of the flask was purged with nitrogen. Toluene (oxygen absorbing grade manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; 15.85 g) and 2,2'-azobisisobutyronitrile (0.01 g, 0.06 mmol) were weighed and added to the flask, and the flask was heated to 80 g. It was immersed in an oil bath at ℃ and heated for 3 hours while stirring with a magnetic stirrer (reaction liquid).
After cooling, chloroform (20 g) was added to the reaction solution to dilute it. The diluted solution was added to methanol (520 g) to precipitate the polymer. The precipitated polymer was collected by vacuum filtration and washed with methanol. The obtained polymer was dried under reduced pressure 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). ^{The 1} H-NMR spectrum is shown in Figure 4.

[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 into a 50 mL three-necked flask, and the inside of the flask was purged with nitrogen. Toluene (Oxygen absorbing grade manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; 17.48 g) and 2,2'-azobisisobutyronitrile (0.01 g, 0.07 mmol) were weighed and added to the flask, and the flask was heated to 80 g. It was immersed in an oil bath at ℃ and heated for 3 hours while stirring with a magnetic stirrer (reaction liquid).
After cooling, the reaction solution was diluted by adding chloroform (34 g). The diluted solution was added to methanol (550 g) to precipitate the polymer. The precipitated polymer was collected by vacuum filtration and washed with methanol. The obtained polymer was dried under reduced pressure 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). ^{The 1} H-NMR spectrum is shown in FIG.

[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 into a 50 mL three-necked flask, and the inside of the flask was purged with nitrogen. Toluene (oxygen absorbing grade manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; 19.95 g) and 2,2'-azobisisobutyronitrile (0.01 g, 0.06 mmol) were weighed and added to the flask, and the flask was heated to 80 g. It was immersed in an oil bath at ℃ and heated for 3 hours while stirring with a magnetic stirrer (reaction liquid).
After cooling, the reaction solution was diluted by adding chloroform (40 g). The diluted solution was added to methanol (560 g) to precipitate the polymer. The precipitated polymer was collected by vacuum filtration and washed with methanol. The obtained polymer was dried under reduced pressure 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). ^{The 1} H-NMR spectrum is shown in FIG. From the ¹ H-NMR spectrum of the obtained polymer, the proportions of T6C and CSNT in the polymer were calculated to be 50 mol% and 50 mol%, respectively.

[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 sieve 4A (monomer solution). After purging the inside of another 50 mL three-necked flask with nitrogen, the monomer solution (21.74 g) was extracted and added. The flask was immersed in a constant temperature bath at 25°C, the polymerization initiator solution (350 μL) synthesized in Synthesis Example 4 was added, and the mixture was stirred at 25°C for 1 hour. Acetic acid (0.01 g) was added to stop the reaction (polymerization liquid).
Subsequently, acetone (100 g) was added to the polymerization solution to dilute it. 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 reduced pressure at 100° C. for 2 hours to obtain a T6C polymer (hereinafter also referred to as p(T6C); 3.76 g).

[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-necked flask and dehydrated using Molecular Sieves 4A (monomer solution). After purging the inside of another 50 mL three-necked flask with nitrogen, the monomer solution (11.96 g) was extracted and added. The flask was immersed in a constant temperature bath at 25°C, the polymerization initiator solution (330 μL) synthesized in Synthesis Example 4 was added, and the mixture was stirred at 25°C for 15 minutes. Acetic acid (0.010 g) was added to stop the reaction (polymerization liquid).
Subsequently, m-xylene (46 g) was added to the polymerization solution to dilute it. The diluted solution was added to 482 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 reduced pressure at 100° C. for 2 hours to obtain a NORTH polymer (hereinafter also referred to as p(NORTH); 2.21 g).

Table 1 shows the physical properties of the polycarbonate resins obtained in Examples and Comparative Examples.

Table 1 shows that the polycarbonate resins of Examples had a significantly higher thermal decomposition temperature than the polycarbonate resins of Comparative Examples, and had excellent heat resistance.

The polycarbonate resin, polycarbonate resin composition, and optical molded article containing them of the present invention are industrially useful in the fields of various optical materials such as optical lens materials, optical devices, materials for optical parts, and display materials. availability.

Claims (11)

The following formula (1):
(In formula (1),
A is an optionally substituted alicyclic moiety,
L is a direct bond or a connecting 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 polycarbonate resin according to claim 1, wherein the A is a cyclohexane-1,2-diyl group. The polycarbonate resin according to claim 1, wherein the L is an ethylene group, a norbornylene group, or a decahydro-1,4:5,8-dimethanonaphthylene group. The polycarbonate resin according to claim ¹ , wherein the R 1 is a cyclohexyl group, an adamantyl group, or a decyl group. 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. The polycarbonate resin according to claim 1, having a glass transition temperature (Tg) of 60°C or more and 250°C or less. A polycarbonate resin composition comprising the polycarbonate resin according to any one of claims 1 to 6 and an antioxidant. An optical component containing the polycarbonate resin according to any one of claims 1 to 6. Use of the polycarbonate resin according to any one of claims 1 to 6 as a material for optical components. The following formula (1):
(In formula (1),
A is an optionally substituted alicyclic moiety,
L is a direct bond or a connecting 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):
(In formula (2),
A is an optionally substituted alicyclic moiety,
L is a direct bond or a connecting 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 obtaining the polycarbonate resin by ring-opening polymerization of a cyclic carbonate represented by the formula. The following formula (1):
(In formula (1),
A is an optionally substituted alicyclic moiety,
L is a direct bond or a connecting 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):
(In formula (3), A is an optionally substituted alicyclic moiety, and E is an optionally substituted alkenyl group having 1 to 20 carbon atoms.)
Structural unit represented by or the following formula (3'):
(In formula (3'), A' is an optionally substituted unsaturated alicyclic moiety.)
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. .)
A method for producing a polycarbonate resin, comprising a modification step of obtaining the polycarbonate resin by mixing and stirring a mixture containing a thiol compound represented by: