Polycarbonate resin composition

Abstract

A polycarbonate resin composition which contains a polycarbonate resin containing a constituent unit having an alicyclic hydrocarbon moiety which forms a ring and in which a carbonate group is connected to two adjacent carbons, and also contains one or more types of compound selected from the group consisting of a compound having an amide bond, a sulfur compound and a phosphite ester compound, wherein the weight-average molecular weight Mw in the polycarbonate resin when measured according to size exclusion chromatography using polystyrene as a reference sample is 50,000-500,000, inclusive.

Description

[Technical field]

[0001] The present invention relates to a polycarbonate resin composition.

[0002] Aliphatic polycarbonates have been known to be useful as medical materials, engineering plastics, etc., because of their excellent properties such as impact resistance and light weight, but they have a problem of low glass transition point. On the other hand, among aliphatic polycarbonates, alicyclic polycarbonates having an alicyclic structure in the main chain structure have been actively developed because they show a higher glass transition point than other aliphatic polycarbonates. For example, a polycyclic alicyclic polycarbonate resin with a pentacyclopentadecanedimethanol skeleton and excellent transparency, heat resistance, and color tone has been disclosed (see, for example, Patent Document 1). In addition, a polycarbonate resin using isosorbide as a raw material has been disclosed, which uses not only petroleum-derived raw materials but also biomass-derived raw materials and has an excellent balance of transparency, heat resistance, water absorption, surface hardness, low birefringence, etc. (see, for example, Patent Document 2).

[0003] Among such alicyclic polycarbonate resins, poly(1,2-cyclohexene carbonate) having a cyclohexane skeleton is the simplest alicyclic polycarbonate having a saturated six-membered carbon ring corresponding to a benzene ring. It is widely known that poly(1,2-cyclohexene carbonate) can be synthesized by copolymerization of cyclohexene oxide and carbon dioxide, ring-opening polymerization of 1,2-cyclohexene carbonate, etc. (see, for example, Patent Document 3 and Non-Patent Document 1). Poly(1,2-cyclohexene carbonate) obtained as described above has the properties of transparency and complete decomposition at a certain temperature, and is expected to be used in optical materials, thermal decomposition materials, etc. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 4774610 [Patent Document 2] Patent No. 6507495 [Patent Document 3] Patent No. 5403537 [Non-patent literature]

[0005] [Non-Patent Document 1] 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]

[0006] As mentioned above, while poly(1,2-cyclohexene carbonate) has excellent transparency, there is room for improvement because it may undergo thermal decomposition during molding and the associated decrease in mechanical strength, etc. However, there have been no reports to date of sufficiently improving the thermal stability of poly(1,2-cyclohexene carbonate) while maintaining its transparency.

[0007] 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 composition having excellent thermal stability. [Means for solving the problem]

[0008] Means for Solving the Problems The present inventors have conducted intensive research to solve the above problems and have found that the thermal stability of a polycarbonate resin composition can be significantly improved by using one or more compounds selected from the group consisting of a compound having an amide bond, a sulfur compound, and a phosphite ester compound, thereby completing the present invention.

[0009] That is, the present invention is as follows. [1] a polycarbonate resin including a structural unit having an alicyclic hydrocarbon moiety that constitutes a ring and has carbonate groups linked to two adjacent carbon atoms; and one or more selected from the group consisting of a compound having an amide bond, a sulfur compound, and a phosphite ester compound, The polycarbonate resin composition has a weight average molecular weight Mw of 50,000 or more and 500,000 or less, as measured by size exclusion chromatography using polystyrene as a standard sample. [2] The polycarbonate resin composition according to [1], wherein the structural unit having an alicyclic hydrocarbon moiety is represented by the following formula (1): [ka] In formula (1), n ​​represents an integer of 1 to 6, and R 1 ~R 6 are each independently a hydrogen atom, a hydroxyl group, a phosphate group, an amino group, a vinyl group, an allyl group, an alkoxy group having 1 to 20 carbon atoms, an ester group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, which may be bonded to each other via an alkylene group or a carbonate group to form a cyclic structure, the alkylene group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, a carbonyl group may be inserted in the main chain, the alkoxy group, the ester group, the acyl group, and the alkyl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms. [3] In formula (1), R 4 ~R 6 is a hydrogen atom. [4] The polycarbonate resin composition according to any one of [1] to [3], wherein the polycarbonate resin is poly(1,2-cyclohexene carbonate). [5] The polycarbonate resin composition according to any one of [1] to [4], wherein the polycarbonate resin has a glass transition temperature Tg of 80° C. or higher and 180° C. or lower as measured by a differential scanning calorimeter. [6] The polycarbonate resin composition according to any one of [1] to [5], wherein the content of the compound having an amide bond is 500 ppm by mass to 10,000 ppm by mass. [7] The polycarbonate resin composition according to any one of [1] to [6], wherein the compound having an amide bond has a structure represented by the following formula (2): [ka] (In formula (2), R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms. [8] The polycarbonate resin composition according to any one of [1] to [6], wherein the compound having an amide bond has a structure represented by the following formula (3): [ka] (In formula (3), R 13R is an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms. 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and the alkylene group, the alkenylene group, the alkoxylene group, the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms. [9] The polycarbonate resin composition according to any one of [1] to [6], wherein the compound having an amide bond has a structure represented by the following formula (4): [ka] (In formula (4), R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and the alkylene group, the alkenylene group, the alkoxylene group, the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 6 carbon atoms, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

[10] The content of the sulfur compound is 500 ppm by mass to 10,000 ppm by mass. The polycarbonate resin composition according to any one of [1] to [9].

[11] The sulfur compound has a structure represented by the following formula (2-1): The polycarbonate resin composition according to any one of [1] to

[10] . [ka] (In formula (2-1), R 13 and R 14 R are each independently an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms. 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 2 to 30 carbon atoms, and the alkylene group, the alkenylene group, the alkoxylene group, the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

[12] The sulfur compound has a structure represented by the following formula (3-1): The polycarbonate resin composition according to any one of [1] to

[10] . [ka] (In formula (3-1), m represents an integer of 1 to 4; R 12 are each independently an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms; R 11are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 2 to 30 carbon atoms; R 13 is an m-valent hydrocarbon group which may have an alkoxy group, and the alkylene group, the alkenylene group, the alkoxylene group, the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

[13] The compound having an amide bond and the sulfur compound are contained in the compound. The polycarbonate resin composition according to any one of [1] to

[12] .

[14] the content of the compound having an amide bond and the content of the sulfur compound are each 500 ppm by mass to 10,000 ppm by mass; The polycarbonate resin composition according to any one of [1] to

[13] .

[15] The content of the phosphite ester compound is 500 ppm by mass to 10,000 ppm by mass. The polycarbonate resin composition according to any one of [1] to

[14] .

[16] The phosphite compound has a structure represented by the following formula (2-2): The polycarbonate resin composition according to any one of [1] to

[15] . [ka] In formula (2-2), m represents an integer of 0 to 3, and R 11 ~R 14are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

[17] The phosphite compound has a structure represented by the following formula (3-2): The polycarbonate resin composition according to any one of [1] to

[15] . [ka] In formula (3-2), m represents an integer of 1 to 4, and R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms; R 13 and R 14 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 2 to 30 carbon atoms; R 15 is an m-valent hydrocarbon group, and the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

[18] The composition contains the compound having an amide bond and a phosphite compound. The polycarbonate resin composition according to any one of [1] to

[17] .

[19] The content of the compound having an amide bond and the content of the phosphite ester compound are Each is 500 ppm by mass to 10,000 ppm by mass, The polycarbonate resin composition according to any one of [1] to

[18] . Effect of the Invention

[0010] According to the present invention, it is possible to provide an alicyclic polycarbonate resin composition having excellent thermal stability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, an embodiment for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. Note that the present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be carried out in various modifications within the scope of its gist.

[0012] (Polycarbonate resin composition) The polycarbonate resin composition of the present embodiment contains a polycarbonate resin containing a structural unit having an alicyclic hydrocarbon moiety that constitutes a ring and has carbonate groups linked to two adjacent carbons, and one or more compounds selected from the group consisting of compounds having an amide bond, sulfur compounds, and phosphite compounds, and the weight average molecular weight Mw of the polycarbonate resin measured by size exclusion chromatography using polystyrene as a standard sample is 50,000 or more and 500,000 or less. The polycarbonate resin composition of the present embodiment has excellent thermal stability due to the above-mentioned characteristics.

[0013] The thermal decomposition mechanism of the polycarbonate resin used in this embodiment is not clear, but it is believed to be due to the elimination of monomers by the ring-closing reaction of carbonate groups at the polymer terminals. In particular, when an alicyclic hydrocarbon portion in which a carbonate group is linked to two adjacent carbons of an alicyclic hydrocarbon is present, the ring-closing reaction is likely to proceed, but it is presumed that by adding one or more compounds selected from the group consisting of compounds having an amide bond, sulfur compounds, and phosphorous ester compounds to the polycarbonate resin, hydrogen bonding occurs between the carbonate groups at the polymer terminals and the added compounds, suppressing the ring-closing reaction of the carbonate groups. The above-mentioned mechanism is a presumption and is not limiting.

[0014] (Polycarbonate resin) The polycarbonate resin used in the polycarbonate resin composition of the present embodiment contains a structural unit having an alicyclic hydrocarbon moiety that constitutes a ring and has carbonate groups linked to two adjacent carbon atoms (hereinafter, also simply referred to as a "structural unit having an alicyclic hydrocarbon moiety"). The structural unit having an alicyclic hydrocarbon moiety is preferably represented by the following formula (1).

[0015] [ka]

[0016] In formula (1), n ​​represents an integer of 1 to 6, and R 1 ~R 6are each independently a hydrogen atom, a hydroxyl group, a phosphate group, an amino group, a vinyl group, an allyl group, an alkoxy group having 1 to 20 carbon atoms (preferably having 1 to 12 carbon atoms, more preferably having 1 to 10 carbon atoms), an ester group having 1 to 20 carbon atoms (preferably having 1 to 12 carbon atoms, more preferably having 1 to 11 carbon atoms), an acyl group having 1 to 20 carbon atoms (preferably having 1 to 12 carbon atoms, more preferably having 1 to 11 carbon atoms), or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (preferably having 1 to 12 carbon atoms, more preferably having 1 to 10 carbon atoms), and They may be bonded to each other via a carbonate group to form a cyclic structure, the alkylene group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, a carbonyl group may be inserted in the main chain, the alkoxy group, the ester group, the acyl group, and the alkyl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms. In formula (1), n ​​is 1 when the ring structure is cyclopentane, n is 2 when the ring structure is cyclohexane, n is 3 when the ring structure is cycloheptane, n is 4 when the ring structure is cyclooctane, n is 5 when the ring structure is cyclononane, and n is 6 when the ring structure is cyclodecane. In formula (1), the two wavy line portions are bonding portions of the repeating units. From the viewpoint of easy availability of raw materials, in formula (1), n ​​is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3. In formula (1), R 4 ~R 6 may be a hydrogen atom.

[0017] The polycarbonate resin used in this embodiment is A 1 and A 2 It is preferable that the copolymer contains a constitutional unit represented by the following formula (5) having a terminal structure represented by the following formula (5):

[0018] [ka]

[0019] (In formula (5), A 1 and A 2 are each independently a hydrogen atom, a hydroxyl group, a phosphate group, an amino group, a vinyl group, an allyl group, a phenyl group, a benzyl group, an alkoxy group having 1 to 10 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 10 carbon atoms. 1 and A 2 may be bonded to each other to form a ring structure. 1 and A 2 In addition, in the formula (5), n and R 1 ~R 6 is the same as in formula (1). The number of repetitions of the constitutional unit represented by formula (5) is, for example, 300 to 3,500. In formula (5), R 4 ~R 6 may be a hydrogen atom.

[0020] The polycarbonate resin used in this embodiment is preferably poly(1,2-cyclohexene carbonate). In the polycarbonate resin composition of this embodiment, when the polycarbonate resin is poly(1,2-cyclohexene carbonate), the composition tends to have excellent transparency as well as thermal stability.

[0021] (Average molecular weight of polycarbonate resin) The polycarbonate resin used in this embodiment has a weight average molecular weight Mw of 50,000 or more and 500,000 or less, measured by size exclusion chromatography using polystyrene as a standard sample. The polycarbonate resin of this embodiment is easy to mold because its Mw is within the above range. In addition, such a polycarbonate resin is more excellent in heat resistance, optical properties, and mold releasability. From the same viewpoint, Mw is more preferably 80,000 or more and 400,000 or less, and further preferably 100,000 or more and 300,0000 or less.

[0022] The number average molecular weight Mn of the polycarbonate resin used in the present embodiment, as measured by size exclusion chromatography using polystyrene as a standard sample, is preferably 50,000 or more and 500,000 or less, more preferably 80,000 or more and 400,000 or less, and even more preferably 100,000 or more and 300,0000 or less. The weight average molecular weight and number average molecular weight of the polycarbonate resin by size exclusion chromatography can be specifically measured by the method described in the Examples.

[0023] In the polycarbonate resin used in this embodiment, in order to control the weight average molecular weight Mw and number average molecular weight Mn within the above range, the ratio of the polymerizable monomer, the polymerization initiator, and the additives may be appropriately adjusted, and the polycarbonate resin may be produced by the production method described below. By reducing the ratio of the polymerization initiator to the polymerizable monomer, Mw and Mn tend to be increased. Furthermore, by performing stirring using a stirring blade or a flow mixer, Mw and Mn tend to be increased.

[0024] The glass transition temperature Tg of the polycarbonate resin used in this embodiment, measured by a differential scanning calorimeter, is preferably 80° C. or more and 180° C. or less, more preferably 90° C. or more and 180° C. or less, and even more preferably 100° C. or more and 180° C. or less. In the polycarbonate resin composition of this embodiment, when the glass transition temperature Tg of the polycarbonate resin is within the above range, the thermal stability tends to be further improved.

[0025] The method for controlling the glass transition temperature Tg of the polycarbonate resin within the above range is not particularly limited, but examples thereof include a method for controlling the weight average molecular weight and number average molecular weight of the polycarbonate resin.

[0026] When the polycarbonate resin has multiple types of structural units having an alicyclic hydrocarbon moiety, the molecular arrangement of the polycarbonate resin used in the present embodiment may be a random copolymer, an alternating copolymer, or a block copolymer, and may have two or more types of polymerization sequences.

[0027] The stereoregularity of the polycarbonate resin used in the present embodiment may be an isotactic structure, a syndiotactic structure, or an atactic structure. From the viewpoint of further improving transparency, an atactic structure which is amorphous is preferred.

[0028] (Production method of polycarbonate resin) The method for producing the polycarbonate resin used in the present embodiment is not particularly limited, and examples thereof include conventional methods such as ring-opening polymerization of an alicyclic cyclic carbonate represented by the following formula (6), copolymerization of an alicyclic cyclic oxide represented by the following formula (7) with carbon dioxide, and transesterification of an alicyclic diol represented by the following formula (8) with a carbonate precursor.

[0029] [ka] [ka] [ka]

[0030] In formulas (6) to (8), n represents an integer of 1 to 5; R 1 ~R 6 are each independently a hydrogen atom, a hydroxyl group, a phosphate group, an amino group, a vinyl group, an allyl group, an alkoxy group having 1 to 20 carbon atoms (preferably having 1 to 12 carbon atoms, more preferably having 1 to 10 carbon atoms), an ester group having 1 to 20 carbon atoms (preferably having 1 to 12 carbon atoms, more preferably having 1 to 11 carbon atoms), an acyl group having 1 to 20 carbon atoms (preferably having 1 to 12 carbon atoms, more preferably having 1 to 11 carbon atoms), or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms (preferably having 1 to 12 carbon atoms, more preferably having 1 to 10 carbon atoms), which may be bonded to each other via an alkylene group or a carbonate group to form a cyclic structure, the alkylene group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, a carbonyl group may be inserted in the main chain, and the alkoxy group, the ester group, the acyl group, or the alkyl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group. )

[0031] (ring-opening polymerization) In the method for producing the polycarbonate resin used in the present embodiment, as the cyclic carbonate used in the ring-opening polymerization, one kind of alicyclic cyclic carbonate may be used alone, and R 1 ~R 6 Any two or more kinds of alicyclic cyclic carbonates having different structures may be used in combination.

[0032] The initiator for ring-opening polymerization of alicyclic cyclic carbonate is not particularly limited, but examples thereof include acid catalysts, base catalysts, and enzyme catalysts.The base catalyst is not particularly limited, but examples thereof include alkali metals, metal alkoxides, metal organic acid salts, cyclic amines, triamine compounds, and heterocyclic compounds.Among these, alkali metals and metal alkoxides are preferred.

[0033] In the ring-opening polymerization, the method for reacting the alicyclic cyclic carbonate in the presence of an initiator is not particularly limited, and any method may be used as long as it is a commonly used polymerization method, such as batch polymerization, semi-batch polymerization, or flow polymerization.

[0034] (CO2 copolymerization) In the method for producing the polycarbonate resin used in the present embodiment, as the alicyclic cyclic oxide used in the copolymerization with carbon dioxide, one kind of alicyclic cyclic oxide may be used alone, and R 1 ~R 6 Any two or more kinds of alicyclic cyclic oxides having different groups may be used in combination.

[0035] The polymerization catalyst for copolymerizing carbon dioxide and an alicyclic cyclic oxide is not particularly limited, and examples thereof include metal catalysts such as aluminum catalysts and zinc catalysts. Among these, in view of the reactivity between an alicyclic cyclic oxide and carbon dioxide, a zinc catalyst is preferred, and an organic zinc catalyst is more preferred.

[0036] In the CO copolymerization, the method of reacting an alicyclic cyclic oxide with carbon dioxide in the presence of a polymerization catalyst is not particularly limited, but examples thereof include a method in which the alicyclic cyclic oxide and the polymerization catalyst are mixed in an autoclave, and then carbon dioxide is injected to cause the reaction.

[0037] (Transesterification) In the method for producing the polycarbonate resin used in the present embodiment, as the alicyclic cyclic diol used in the transesterification method, one kind of alicyclic cyclic diol may be used alone, and R 1 ~R 6 Any two or more kinds of alicyclic diols having different structures may be used in combination.

[0038] The carbonate precursor is not particularly limited, but for example, a carbonate ester, a carbonyl halide, etc., is used. Specific examples thereof include, but are not particularly limited to, diphenyl carbonate, dimethyl carbonate, phosgene, etc.

[0039] The polymerization catalyst for producing the alicyclic cyclic diol is not particularly limited, but examples thereof include alkali metal hydroxides, alkali metal carbonates, organic amines, etc. Among these, alkali metal hydroxides are preferred.

[0040] In the transesterification method, the method for reacting the alicyclic cyclic diol with the carbonate precursor in the presence of a polymerization catalyst is not particularly limited, and any method may be used as long as it is a commonly used polymerization method, such as melt polymerization or solid-phase polymerization.

[0041] (purification process) The method for producing the polycarbonate resin used in the present embodiment preferably includes a purification step. The purification method is not particularly limited, but may include, for example, volatilization purification by heating under reduced pressure and precipitation purification using a precipitation solvent. In addition, the above purification steps may be used alone or in combination of two kinds.

[0042] (devolatilization purification) In the purification step of the polycarbonate resin used in the present embodiment, devolatilization purification may or may not be used. The conditions of devolatilization purification are not particularly limited as long as they are within a range in which the polycarbonate resin used in the present embodiment can be purified, but the devolatilization temperature is preferably 0 to 300°C, more preferably 0 to 270°C, and even more preferably 100 to 270°C. The devolatilization pressure is preferably 0 to 80 kPaA, more preferably 0 to 50 kPaA, and even more preferably 0 to 10 kPaA.

[0043] (Precipitation purification) In the purification step of the polycarbonate resin used in the present embodiment, precipitation purification may or may not be used. The precipitation purification conditions are not particularly limited as long as they are within the range in which the polycarbonate resin used in the present embodiment can be purified, and the precipitation solvent is preferably an alcohol solvent such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, or decanol.

[0044] (Compounds having an amide bond) The polycarbonate resin composition of the present embodiment preferably contains a compound having an amide bond, particularly from the viewpoint of significantly increasing the thermal stability in nitrogen. The compound having an amide bond used in the present embodiment is not particularly limited as long as it is a compound having an amide bond in the molecule, and examples thereof include fatty acid amides, phenylamide stabilizers, and anilide oxalate stabilizers.

[0045] The compound having an amide bond is preferably a compound having a structure represented by the following formula (2), a compound having a structure represented by the following formula (3), or a compound having a structure represented by the following formula (4).

[0046] [ka] (In formula (2), R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms. [ka] (In formula (3), R 13 is an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms; R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and the alkylene group, the alkenylene group, the alkoxylene group, the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms. [ka] (In formula (4), R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and the alkylene group, the alkenylene group, the alkoxylene group, the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 6 carbon atoms, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

[0047] Examples of fatty acid amides include, but are not limited to, N-vinylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N-methylpropionamide, 2-amino-N-methylacetamide, 2-hydroxy-N-methylacetamide, N-hydroxymethylacetamide, 2-chloro-N-methylacetamide, 2-bromo-N-methylacetamide, imidazolidin-4-one hydrochloride, N,N-dimethylprop-2-ynamide, N,N-diethylprop-2-ynamide, 1,2-diacetylhydrazine, 4-oxo-4-[N'-(thiophene-2-carbonyl)-hydrazino]butyric acid, stearic acid amide, oleic acid amide, erucic acid amide, ethylene bisstearic acid amide, methylene bisstearic acid amide, and ethylene bisoleic acid amide.

[0048] Examples of the phenylamide stabilizer include, but are not limited to, N-(2H-1,2,4-triazol-5-yl)salicylamide, dodecanedioic acid bis[N2-(2-hydroxybenzoyl)hydrazide], 2',3'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, N,N'-hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide], and N,N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide.

[0049] Examples of oxalic acid anilide heat stabilizers include, but are not limited to, 2-ethoxy-2'-ethyloxalic acid bisanilide, N-(2-ethylphenyl)-N'-(2-ethoxyphenyl)oxalic acid diamide, and 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]henicosan-21-one.

[0050] From the viewpoint of more effectively and reliably achieving the effects of the present invention, particularly from the viewpoint of significantly increasing the thermal stability in nitrogen, the compound having an amide bond used in this embodiment is preferably a phenylamide stabilizer, more preferably a compound having a structure represented by the above formula (4), and even more preferably 2',3'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine. These may be used alone or in combination of two or more. By increasing the thermal stability in nitrogen, for example, the thermal stability in the solvent devolatilization process and molding process during resin production, and the thermal stability of the product in a deoxidized atmosphere such as under vacuum, tend to be improved.

[0051] From the viewpoint of significantly increasing the thermal stability in nitrogen and air, the compound having an amide bond used in this embodiment is preferably a compound having a structure represented by the above formula (2) or a compound having a structure represented by the above formula (3), more preferably N-(2H-1,2,4-triazol-5-yl)salicylamide or dodecanedioic acid bis[N2-(2-hydroxybenzoyl)hydrazide]. By increasing the thermal stability in air, for example, the thermal stability of the product in air tends to improve.

[0052] The content of the compound having an amide bond used in the polycarbonate resin composition of the present embodiment is, from the viewpoint of the added amount that satisfactorily obtains the effects of the present invention and from the viewpoint of costs, preferably 500 ppm by mass to 10,000 ppm by mass, more preferably 500 ppm by mass to 5,000 ppm by mass, and even more preferably 1,000 ppm by mass to 5,000 ppm by mass, relative to the total mass of the polycarbonate resin composition.

[0053] (Sulfur compounds) The polycarbonate resin composition of the present embodiment preferably contains a sulfur compound from the viewpoint of significantly increasing the thermal stability in air. The sulfur compound is not particularly limited as long as it is a compound having sulfur in the molecule, and examples thereof include methyl mercaptoacetate, ethyl mercaptoacetate, ethyl 2-(methylthio)acetate, methyl cysteine, methoxycarbonylsulfenyl chloride, methyl 2-ethylsulfanylacetate, methylthiomethyl acetate, methyl 2-mercaptopropionate, methyl 3-mercaptopropionate, ethyl 3-mercaptopropanoate, ethyl 2-mercaptopropionate, β-mercaptopropionic acid, methoxybutyl-3-mercaptopropionate, stearyl ester, methyl mercaptopropionate, methyl 3-mercaptopropionate, ethyl 2-mercaptopropionate, β-mercaptopropionic acid, methoxybutyl-3-mercaptopropionate, stearyl ester, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, ethyl 2-mercaptopropionate, β-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl ... n-octyl-3-mercaptopropionate, pentaerythritol-tetrakis(3-mercaptopropionate), tetraethylene glycol-bis(3-mercaptopropionate), dipentaerythritol-hexakis(3-mercaptopropionate), 3 ,3'-Thiodipropionic acid, dithiodipropionic acid, dodecylthiopropionic acid, thiodiglycolic acid, dimethyl 3-thiadipic acid, ethyl 2-[(2-methoxy-2-oxoethyl)sulfanyl]acetate, ethyl [(ethoxycarbonyl)thio]acetate, diethyl 2,2'-thiodiacetate, methyl 3-[(2-methoxy-2-oxoethyl)thio]butanoate, dilauryl-3,3'-thiodipropionate, ditridecyl 3,3'-thiobispropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'- Thiodipropionate, Pentaerythritol-tetrakis(3-laurylthiopropionate), Pentaerythritol-tetrakis(3-myristylthiopropionate), Pentaerythritol-tetrakis(3-stearylthiopropionate), Pentaerythritol tetrakis[3-(dodecylthio)propionic acid]pentaerythritol, Ethyl 2-[(2-methoxy-2-oxoethyl)sulfanyl]propanoate, Ammonium thioglycolate, Monoethanolamine thioglycolate, Diammonium dithiodiglycolate, 2,Examples include 5-thiacylenemethyl, tris[2-t-butyl-4-thio(2'-methyl-4'-hydroxy-5'-t-butyl)phenyl-5-methyl]phenyl phosphite, etc.

[0054] Among these, from the viewpoint of significantly increasing the thermal stability in air, a compound having a structure represented by the following formula (2-1) or a compound having a structure represented by the following formula (3-1) is preferred, and more preferred are ditridecyl 3,3'-thiobispropionate and pentaerythritol tetrakis[3-(dodecylthio)propionate]. These may be used alone or in combination of two or more. By increasing the thermal stability in air, for example, the thermal stability of the product in air is improved.

[0055] [ka]

[0056] In formula (2-1), R 13 and R 14 are each independently an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms. 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 2 to 30 carbon atoms, and the alkylene group, the alkenylene group, the alkoxylene group, the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

[0057] [ka]

[0058] In formula (3-1), m represents an integer of 1 to 4; 12 are each independently an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms; R 11 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 2 to 30 carbon atoms; R 13 represents an m-valent hydrocarbon group which may have an alkoxy group, and the alkylene group, the alkenylene group, the alkoxylene group, the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

[0059] When the polycarbonate resin composition of the present embodiment contains a sulfur compound, the content of the sulfur compound is, from the viewpoint of the addition amount at which the effects of the present invention can be sufficiently obtained and from the viewpoint of costs, preferably 500 ppm by mass to 10,000 ppm by mass, more preferably 500 ppm by mass to 5,000 ppm by mass, and still more preferably 1,000 ppm by mass to 5,000 ppm by mass, relative to the total mass of the polycarbonate resin composition.

[0060] From the viewpoint of significantly increasing the thermal stability in air and nitrogen, the polycarbonate resin composition of the present embodiment preferably contains a compound having an amide bond and a sulfur compound. In the case where the polycarbonate resin composition of the present embodiment contains a compound having an amide bond and a sulfur compound, the contents of the compound having an amide bond and the sulfur compound are preferably 500 ppm by mass to 10,000 ppm by mass, more preferably 500 ppm by mass to 5,000 ppm by mass, and even more preferably 1,000 ppm by mass to 5,000 ppm by mass, respectively, relative to the total mass of the polycarbonate resin composition, from the viewpoints of the added amounts at which the effects of the present invention can be sufficiently obtained and costs.

[0061] (Phosphite ester compounds) The polycarbonate resin composition of the present embodiment preferably contains a phosphite compound from the viewpoint of significantly increasing the thermal stability in nitrogen. The phosphite compound may be any compound that has a phosphite in the molecule and does not have a bulky substituent near the ether in the phosphite compound, from the viewpoint of generating sufficient interaction between the carbonate and the phosphite. Examples of the phosphite ester compound include, but are not limited to, trimethyl phosphite, triethyl phosphite, triallyl phosphite, triisopropyl phosphite, tributyl phosphite, trihexyl phosphite, tri(2-ethylhexyl) phosphite, triisodecyl phosphite, trilauryl phosphite, tris(tridecyl) phosphite, trioleyl phosphite, tristearyl phosphite, 1,2-phenylene phosphorochloridite, 2-chloro-4H-1,3,2-benzodioxaphosphorin-4-one, tris(β-chloroethyl) phosphite, diphenylmethyl phosphite, triphenyl phosphite, ethylhexyl diphenyl phosphite, decyl diphenyl phosphite, tris(p-methylphenyl) phosphite, trimethylolpropane, and the like. Panphosphite, tris(trimethylsilyl)phosphite, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tris(nonylphenyl)phosphite, tetraalkyl(C12-15)-4,4'-isopropylidene diphenyl diphosphite, diphenyl isodecyl phosphite, tetraphenyl dipropylene glycol diphosphite, bis(tridecyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2-tert-butyl-6-methyl-4-{3-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl}phenol, and the like.

[0062] In particular, from the viewpoint of significantly increasing the thermal stability in nitrogen, for example, a compound having a structure represented by the following formula (2-2) or a compound having a structure represented by the following formula (3-2) is preferable, and more preferable examples include tris(phenyl)phenyl phosphite, tetraalkyl(C12-15)-4,4'-isopropylidenediphenyl diphosphite, and the like. These may be used alone or in combination of two or more. By increasing the thermal stability in nitrogen, for example, the thermal stability during the solvent devolatilization process and molding process in the production of the resin, and the thermal stability of the product in a deoxygenated atmosphere such as under vacuum, are improved.

[0063] [ka]

[0064] In formula (2-2), m represents an integer of 0 to 3; 11 ~R 14 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group are optionally substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group are optionally substituted with an alkyl group having 1 to 20 carbon atoms.

[0065] [ka]

[0066] In formula (3-2), m represents an integer of 1 to 4; 11 and R 12are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms; R 13 and R 14 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 2 to 30 carbon atoms; R 15 is an m-valent hydrocarbon group, and the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group are optionally substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group are optionally substituted with an alkyl group having 1 to 20 carbon atoms.

[0067] When the polycarbonate resin composition of the present embodiment contains a phosphite compound, the content of the phosphite compound is, from the viewpoint of an addition amount that sufficiently obtains the effects of the present invention and from the viewpoint of costs, preferably 500 ppm by mass to 10,000 ppm by mass, more preferably 500 ppm by mass to 5,000 ppm by mass, and even more preferably 1,000 ppm by mass to 5,000 ppm by mass, relative to the total mass of the polycarbonate resin composition.

[0068] From the viewpoint of significantly increasing the thermal stability in nitrogen, the polycarbonate resin composition of the present embodiment preferably contains a compound having an amide bond and a phosphite compound. When the polycarbonate resin composition of the present embodiment contains a compound having an amide bond and a phosphite compound, the contents of the compound having an amide bond and the phosphite compound are, from the viewpoint of the added amounts at which the effects of the present invention can be sufficiently obtained and from the viewpoint of cost, preferably 500 ppm by mass to 10,000 ppm by mass, more preferably 500 ppm by mass to 5,000 ppm by mass, and even more preferably 1,000 ppm by mass to 5,000 ppm by mass, respectively, relative to the total mass of the polycarbonate resin composition.

[0069] The polycarbonate resin composition of the present embodiment may contain other additives, such as a neutralizing agent, an ultraviolet absorber, a release agent, a colorant, an antistatic agent, a slip agent, a lubricant, a plasticizer, a compatibilizer, a flame retardant, a bluing agent, and a flowability modifier.

[0070] (Method for producing polycarbonate resin composition) In this embodiment, one or more compounds selected from the group consisting of compounds having an amide bond, sulfur compounds, and phosphorous ester compounds (hereinafter, also simply referred to as "added compounds") to be blended with the polycarbonate resin, the mixing time, and the mixing method are not particularly limited. From the viewpoint of preventing thermal decomposition, the mixing time is preferably after the addition of a polymerization terminator or after precipitation purification.

[0071] (Blending method) In the present embodiment, the method of blending the additive compound into the polycarbonate resin is not particularly limited, and examples thereof include a method of kneading with a kneader, a tumbler mixer, a V-type mixer, a Nauta mixer, a Banbury mixer, a roll machine, or an extruder, or a solution blending method in which the additive compound is dissolved in a common good solvent such as acetone and mixed. However, any commonly used blending method may be used. EXAMPLES

[0072] The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples in any way. In this specification, the thermal stability of the polycarbonate resin and the polycarbonate resin composition was measured as follows.

[0073] (Molecular Weight Measurement) A solution in which tetrahydrofuran was added at a ratio of 2.0 g to 0.02 g of polycarbonate resin was used as a measurement sample, and the weight average molecular weight of the polycarbonate resin was measured using an HPLC device (manufactured by Tosoh Corporation, product name "HLC-8420GPC"). 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) manufactured by Tosoh Corporation were connected in series and used. 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 thus prepared, the number average molecular weight and weight average molecular weight of the polycarbonate resin were determined.

[0074] (Measurement of glass transition temperature Tg) The glass transition temperature Tg of the polycarbonate resin was measured using a differential scanning calorimeter (product name "DSC8500") manufactured by PerkinElmer Japan Co., Ltd. under the condition of a nitrogen gas flow rate of 20 mL / min. More specifically, after holding at 40°C for 3 minutes, the sample was first heated from 40°C to 200°C at 20°C / min to completely melt the sample. Then, the temperature was lowered from 200°C to 40°C at 50°C / min and held at 40°C for 5 minutes. Next, the intersection (midpoint glass transition temperature) of the step-like change part curve of the DSC curve drawn during the second heating from 40°C to 190°C at 10°C / min and the straight line equidistant in the vertical axis direction from the extension of each tangent was taken as the glass transition temperature (Tg).

[0075] (Measurement of thermal stability) Using a Shimadzu TG-DTA device (product name: DTG-60A) and an aluminum krypton cell, the polycarbonate resin and the polycarbonate resin composition were heated in a nitrogen gas flow and an air flow at a rate of 10°C / min. The thermal decomposition (TGA) of the polycarbonate resin composition was measured, and the thermal decomposition onset temperature was obtained from the tangent intersection of the TGA curve. With the thermal decomposition onset temperature of the polycarbonate resin test piece of Comparative Example 1 as the standard, a case in which the thermal decomposition onset temperature was higher was judged to have an improved thermal stability effect (marked as "◯" in Table 1), and a case in which the thermal decomposition onset temperature was lower was judged to have no improved thermal stability effect (marked as "×" in Table 1).

[0076] The abbreviations for the compounds used in the following Examples and Comparative Examples are as follows. (A) Polycarbonate resin A-1: A polycarbonate resin composed of 100 mol% structural units derived from poly(1,2-cyclohexene carbonate), having a weight average molecular weight of 211,000 and a glass transition temperature Tg of 120°C. (B) Compounds with an amide bond B-1: 2',3'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine B-2: N-(2H-1,2,4-triazol-5-yl)salicylamide B-3: Dodecanedioic acid bis[N2-(2-hydroxybenzoyl)hydrazide] (C) Antioxidants C-1: Hindered phenol compound (Irganox 1010, manufactured by BASF) C-2: Hindered phenol compound (BASF Irganox 1076) C-3: Hindered phenol compounds (Sumitomo Chemical Co., Ltd. SUMILIZER GA-80) C-4: Phosphite ester compound (BASF Irgafos 168) C-5: Phosphite ester compound (ADEKA STAB PEP-36) (D) Light stabilizers D-1: Hindered amine compound (ADEKA STAB LA-81)

[0077] [Example 1] 1.0 g of polycarbonate resin (A-1) and 2.0 g of acetone solution containing 1000 ppm of compound (B-1) having an amide bond were mixed using a magnetic stirrer to obtain the composition shown in Table 1, and dried for 2 hours under vacuum at 100°C to obtain a polycarbonate resin composition. The obtained polycarbonate resin composition was pressure molded using a hydraulic press at 20 MPaG to obtain a plate-shaped test piece of the polycarbonate resin composition. The results of the thermal stability measurement evaluated using the obtained test piece are shown in Table 1.

[0078] [Examples 2 to 3] A polycarbonate resin composition was obtained in the same manner as in Example 1, except that the blending ratio of the additive (compound having an amide bond) was changed as shown in Table 1. The obtained polycarbonate resin composition was molded into test pieces and then evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0079] [Comparative Example 1] 2.0 g of acetone was added to 1.0 g of polycarbonate resin (A-1), dissolved using a magnetic stirrer, dried under vacuum at 100°C for 2 hours, and pressure molded at 20 MPaG under hydraulic press to obtain a plate-shaped polycarbonate resin test piece. The obtained polycarbonate resin was evaluated after molding into a test piece in the same manner as in Example 1, and the results are shown in Table 1.

[0080] [Comparative Examples 2 to 7] A polycarbonate resin composition was obtained in the same manner as in Example 1, except that the blending ratio of additives (antioxidants or light stabilizers) was changed as shown in Table 1. The obtained polycarbonate resin composition was molded into test pieces and then evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0081] [Table 1]

[0082] From Table 1, it was found that the polycarbonate resin compositions of Examples 1 to 3 had higher thermal decomposition onset temperatures and improved thermal stability compared to the polycarbonate resins and polycarbonate resin compositions of Comparative Examples 1 to 7.

[0083] Hereinafter, the present embodiment will be described using other specific examples and comparative examples, but the present embodiment is not limited in any way to the following examples, etc.

[0084] The physical properties and characteristics of the polycarbonate resin and the polycarbonate resin composition were measured as follows.

[0085] [Physical properties and characteristics] (Measurement of molecular weight of polycarbonate resin) A solution in which tetrahydrofuran was added in a ratio of 2.0 g to 0.02 g of polycarbonate resin was used as a measurement sample, and the weight average molecular weight of the polycarbonate resin was measured using an HPLC device (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 product names manufactured by Tosoh Corporation) connected in series. The column temperature was set to 40° C., and the analysis was performed at a rate of 0.60 mL / min using tetrahydrofuran as the mobile phase. The detector used was an RI 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 thus prepared, the weight average molecular weight of the polycarbonate resin was determined.

[0086] (Measurement of glass transition temperature Tg of polycarbonate resin) The glass transition temperature Tg of the polycarbonate resin was measured using a differential scanning calorimeter (product name "DSC8500") manufactured by PerkinElmer Japan Co., Ltd. under the condition of a nitrogen gas flow rate of 20 mL / min. More specifically, after holding at 40°C for 3 minutes, the sample was first heated from 40°C to 200°C at 20°C / min to completely melt the sample. The temperature was then lowered from 200°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 (midpoint glass transition temperature) of the step-like change partial curve of the DSC curve drawn during the second heating from 40°C to 190°C at 10°C / min with a straight line equidistant in the vertical direction from the extension of each tangent.

[0087] (Measurement and evaluation of thermal stability) Using a Shimadzu TG-DTA device (product name: DTG-60A) and an aluminum krypton cell, the polycarbonate resin and the 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 the polycarbonate resin composition was measured, and the thermal decomposition onset temperature was obtained from the tangent intersection of the TGA curve. In addition, using the thermal decomposition onset temperature of the polycarbonate resin test piece of Comparative Example 8 as the standard, when the thermal decomposition onset temperature was +3°C or higher, it was evaluated as having an improved thermal stability effect (marked as "O" in Table 2), and when the thermal decomposition onset temperature was less than +3°C, it was evaluated as having no improved thermal stability effect (marked as "X" in Table 2).

[0088] [Polycarbonate resin composition] The abbreviations for the compounds used in the following Examples and Comparative Examples are as follows. ((A) Polycarbonate resin) A-1: A polycarbonate resin composed of 100 mol% structural units derived from poly(1,2-cyclohexene carbonate), having a weight average molecular weight of 211,000 and a glass transition temperature Tg of 120°C.

[0089] ((B) Sulfur compounds) B-1: Ditridecyl 3,3'-thiobispropionate B-2: Tetrakis[3-(dodecylthio)propionic acid]pentaerythritol

[0090] ((C) Antioxidants) C-1: Hindered phenol compound (Irganox 1010, manufactured by BASF) C-2: Hindered phenol compound (BASF Irganox 1076) C-3: Hindered phenol compounds (Sumitomo Chemical Co., Ltd. SUMILIZER GA-80) C-4: Phosphite ester compound (BASF Irgafos 168) C-5: Phosphite ester compound (ADEKA STAB PEP-36)

[0091] ((D) Light stabilizers) D-1: Hindered amine compound (ADEKA STAB LA-81)

[0092] [ Reference Example 1 〕 1.0 g of polycarbonate resin (A-1) and 2.0 g of an acetone solution containing 1000 ppm of sulfur compound (B-1) were mixed using a magnetic stirrer to obtain the composition shown in Table 2, and the mixture was dried under vacuum at 100°C for 2 hours to obtain a polycarbonate resin composition. The obtained polycarbonate resin composition was pressure molded using a hydraulic press at 20 MPaG to obtain a plate-shaped test piece of the polycarbonate resin composition. The thermal stability of the obtained test pieces was measured and the evaluation results are shown in Table 2.

[0093] [ Reference Example 2 〕 Except for changing the additive (sulfur compound) composition as shown in Table 2, Reference Example 1 The polycarbonate resin composition obtained was Reference Example 1 The test pieces were prepared in the same manner as in the above, and then the measurements and evaluations were carried out. The results are shown in Table 2.

[0094] Comparative Example 8 2.0 g of acetone was added to 1.0 g of polycarbonate resin (A-1), dissolved using a magnetic stirrer, dried under vacuum at 100°C for 2 hours, and molded under pressure at 20 MPaG using a hydraulic press to obtain a plate-shaped polycarbonate resin test piece. The resulting polycarbonate resin is Reference Example 1 The results are shown in Table 2.

[0095] [Comparative Examples 9 to 14] Except for the additives (antioxidants or light stabilizers) that were changed as shown in Table 2, Reference Example 1 The polycarbonate resin composition obtained was Reference Example 1 The test pieces were prepared in the same manner as in the above, and then the measurements and evaluations were carried out. The results are shown in Table 2.

[0096] [Table 2]

[0097] From Table 2, Reference Examples 1 and 2 It was found that the polycarbonate resin composition of this example had a higher thermal decomposition starting temperature and improved thermal stability, as compared with the polycarbonate resins and polycarbonate resin compositions of Comparative Examples 8 to 14.

[0098] Hereinafter, the present embodiment will be described using other specific examples and comparative examples, but the present embodiment is not limited in any way to the following examples, etc.

[0099] The physical properties and characteristics of the polycarbonate resin and the polycarbonate resin composition were measured as follows.

[0100] [Physical properties and characteristics] (Measurement of molecular weight of polycarbonate resin) A solution in which tetrahydrofuran was added in a ratio of 2.0 g to 0.02 g of polycarbonate resin was used as a measurement sample, and the weight average molecular weight of the polycarbonate resin was measured using an HPLC device (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 product names manufactured by Tosoh Corporation) connected in series. The column temperature was set to 40° C., and the analysis was performed at a rate of 0.60 mL / min using tetrahydrofuran as the mobile phase. The detector used was an RI 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 thus prepared, the weight average molecular weight of the polycarbonate resin was determined.

[0101] (Measurement of glass transition temperature Tg of polycarbonate resin) The glass transition temperature Tg of the polycarbonate resin was measured using a differential scanning calorimeter (product name "DSC8500") manufactured by PerkinElmer Japan Co., Ltd. under the condition of a nitrogen gas flow rate of 20 mL / min. More specifically, after holding at 40°C for 3 minutes, the sample was first heated from 40°C to 200°C at 20°C / min to completely melt the sample. The temperature was then lowered from 200°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 (midpoint glass transition temperature) of the step-like change partial curve of the DSC curve drawn during the second heating from 40°C to 190°C at 10°C / min with a straight line equidistant in the vertical direction from the extension of each tangent.

[0102] (Measurement and evaluation of thermal stability) Using a Shimadzu TG-DTA device (product name: DTG-60A) and an aluminum krypton cell, the polycarbonate resin and the polycarbonate resin composition were heated in a nitrogen or air stream at a rate of 10°C / min. The thermal decomposition (TGA) of the polycarbonate resin and the polycarbonate resin composition was measured, and the thermal decomposition onset temperature was obtained from the tangent intersection of the TGA curve.

[0103] [Polycarbonate resin composition] The abbreviations for the compounds used in the following Examples and Comparative Examples are as follows. ((A) Polycarbonate resin) A-1: A polycarbonate resin composed of 100 mol% structural units derived from poly(1,2-cyclohexene carbonate), having a weight average molecular weight of 211,000 and a glass transition temperature Tg of 120°C.

[0104] ((B) Compounds Having an Amide Bond) B-1: 2',3'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine B-2: N-(2H-1,2,4-triazol-5-yl)salicylamide

[0105] ((C) Sulfur compound) C-1: Tetrakis[3-(dodecylthio)propionic acid]pentaerythritol C-2: 3,3'-thiobispropionic acid ditridecyl

[0106] Example 6 1.0 g of polycarbonate resin (A-1), 2.0 g of an acetone solution containing 1000 ppm of a compound (B-1) having an amide bond, and 2.0 g of an acetone solution containing 1000 ppm of a sulfur compound (C-1) were mixed using a magnetic stirrer to obtain the composition shown in Table 3, and the mixture was dried under vacuum at 100°C for 2 hours to obtain a polycarbonate resin composition. The obtained polycarbonate resin composition was pressure molded using a hydraulic press at 20 MPaG to obtain a plate-shaped test piece of the polycarbonate resin composition. The thermal stability of the obtained test pieces was evaluated, and the results are shown in Table 3. Among the thermal stability measurement results of the test pieces of the polycarbonate resin compositions of Comparative Examples 15, 16, and 19, the one with the highest thermal decomposition onset temperature was used as the standard. When the thermal decomposition onset temperature was +3°C or higher, it was judged that there was an improved effect on thermal stability (marked with "O" in Table 3), and when the thermal decomposition onset temperature was less than +3°C, it was judged that there was no improved effect on thermal stability (marked with "X" in Table 3).

[0107] [Examples 7 to 8] A polycarbonate resin composition was obtained in the same manner as in Example 6, except that the additive composition was changed as shown in Table 4. The obtained polycarbonate resin composition was molded into test pieces and evaluated in the same manner as in Example 6. The results are shown in Table 4. Among the thermal stability measurement results of the test pieces of the polycarbonate resin compositions of Comparative Example 15 and Comparative Examples 17 to 19, those with the highest thermal decomposition onset temperature were used as the standard. When the thermal decomposition onset temperature was +3°C or higher, it was judged that there was an improvement in thermal stability (marked with "O" in Table 4), and when the thermal decomposition onset temperature was less than +3°C, it was judged that there was no improvement in thermal stability (marked with "X" in Table 4).

[0108] Comparative Example 15 4.0 g of acetone was added to 1.0 g of polycarbonate resin (A-1), dissolved using a magnetic stirrer, dried under vacuum at 100°C for 2 hours, and pressure molded at 20 MPaG under hydraulic press to obtain a plate-shaped polycarbonate resin test piece. The obtained polycarbonate resin was evaluated after molding into a test piece in the same manner as in Example 6, and the results are shown in Tables 3 and 4.

[0109] [Comparative Examples 15 to 19] A polycarbonate resin composition was obtained in the same manner as in Example 6, except that the blending of additives was changed as shown in Table 3 or Table 4. The obtained polycarbonate resin composition was molded into test pieces and then evaluated in the same manner as in Example 6, and the results are shown in Table 3 or Table 4.

[0110] [Table 3]

[0111] From Table 3, it is found that the polycarbonate resin composition of Example 6 has improved thermal stability compared to the polycarbonate resins and polycarbonate resin compositions of Comparative Examples 15, 16, and 19.

[0112] [Table 4]

[0113] From Table 4, it can be seen that the polycarbonate resin compositions of Examples 7 to 8 have a higher thermal decomposition onset temperature and improved thermal stability compared to the polycarbonate resins and polycarbonate resin compositions of Comparative Example 15 and Comparative Examples 17 to 19.

[0114] Hereinafter, the present embodiment will be described using other specific examples and comparative examples, but the present embodiment is not limited in any way to the following examples, etc.

[0115] The physical properties and characteristics of the polycarbonate resin and the polycarbonate resin composition were measured as follows.

[0116] [Physical properties and characteristics] (Measurement of molecular weight of polycarbonate resin) A solution in which tetrahydrofuran was added in a ratio of 2.0 g to 0.02 g of polycarbonate resin was used as a measurement sample, and the weight average molecular weight of the polycarbonate resin was measured using an HPLC device (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 product names manufactured by Tosoh Corporation) connected in series. The column temperature was set to 40° C., and the analysis was performed at a rate of 0.60 mL / min using tetrahydrofuran as the mobile phase. The detector used was an RI 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 thus prepared, the weight average molecular weight of the polycarbonate resin was determined.

[0117] (Measurement of glass transition temperature Tg of polycarbonate resin) The glass transition temperature Tg of the polycarbonate resin was measured using a differential scanning calorimeter (product name "DSC8500") manufactured by PerkinElmer Japan Co., Ltd. under the condition of a nitrogen gas flow rate of 20 mL / min. More specifically, after holding at 40°C for 3 minutes, the sample was first heated from 40°C to 200°C at 20°C / min to completely melt the sample. The temperature was then lowered from 200°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 (midpoint glass transition temperature) of the step-like change partial curve of the DSC curve drawn during the second heating from 40°C to 190°C at 10°C / min with a straight line equidistant in the vertical direction from the extension of each tangent.

[0118] (Measurement and evaluation of thermal stability) Using a Shimadzu TG-DTA device (product name: DTG-60A) and an aluminum krypton cell, the polycarbonate resin and the polycarbonate resin composition were heated in a nitrogen gas flow at a rate of 10°C / min. The thermal decomposition (TGA) of the polycarbonate resin and the polycarbonate resin composition was measured, and the thermal decomposition onset temperature was obtained from the tangent intersection of the TGA curve. In addition, using the thermal decomposition onset temperature of the polycarbonate resin test piece of Comparative Example 20 as the standard, when the thermal decomposition onset temperature was +3°C or higher, it was evaluated as having an improved thermal stability effect (marked as "O" in Table 5), and when the thermal decomposition onset temperature was less than +3°C, it was evaluated as having no improved thermal stability effect (marked as "X" in Table 5).

[0119] [Polycarbonate resin composition] The abbreviations for the compounds used in the following Examples and Comparative Examples are as follows. ((A) Polycarbonate resin) A-1: A polycarbonate resin composed of 100 mol% structural units derived from poly(1,2-cyclohexene carbonate), having a weight average molecular weight of 211,000 and a glass transition temperature Tg of 120°C.

[0120] ((B) Phosphite Compounds) B-1: Triphenyl phosphite B-2: Tetraalkyl(C12-15)-4,4'-isopropylidenediphenyl diphosphite B-3: Tris(phenyl)phosphite

[0121] ((C) Antioxidants) C-1: Hindered phenol compound (Irganox 1010, manufactured by BASF) C-2: Hindered phenol compound (BASF Irganox 1076) C-3: Hindered phenol compounds (Sumitomo Chemical Co., Ltd. SUMILIZER GA-80) C-4: Phosphite ester compound (BASF Irgafos 168) C-5: Phosphite ester compound (ADEKA STAB PEP-36)

[0122] ((D) Light stabilizers) D-1: Hindered amine compound (ADEKA STAB LA-81)

[0123] [ Reference Example 3 〕 1.0 g of polycarbonate resin (A-1) and 2.0 g of an acetone solution containing 1000 ppm of phosphite ester compound (B-1) were mixed using a magnetic stirrer to obtain the composition shown in Table 5, and then dried under vacuum at 100°C for 2 hours to obtain a polycarbonate resin composition. The obtained polycarbonate resin composition was pressure molded using a hydraulic press at 20 MPaG to obtain a plate-shaped test piece of the polycarbonate resin composition. The thermal stability of the obtained test pieces was measured and the evaluation results are shown in Table 5.

[0124] [ Reference Examples 4~5 〕 Except for changing the additive (phosphite ester compound) composition as shown in Table 5, Reference Example 3 The polycarbonate resin composition obtained was Reference Example 3 The test pieces were molded in the same manner as in Example 1, and then the measurements and evaluations were carried out. The results are shown in Table 5.

[0125] Comparative Example 20 2.0 g of acetone was added to 1.0 g of polycarbonate resin (A-1), dissolved using a magnetic stirrer, dried under vacuum at 100°C for 2 hours, and molded under pressure at 20 MPaG using a hydraulic press to obtain a plate-shaped polycarbonate resin test piece. The resulting polycarbonate resin is Reference Example 3 The results are shown in Table 5.

[0126] [Comparative Examples 21 to 26] Except for the additives (antioxidants or light stabilizers) added, as shown in Table 5, Reference Example 3 The polycarbonate resin composition obtained was Reference Example 3 The test pieces were molded in the same manner as in Example 1, and then the measurements and evaluations were carried out. The results are shown in Table 5.

[0127] [Table 5]

[0128] From Table 5, Reference Examples 3~5 It was found that the polycarbonate resin composition of this example had a higher thermal decomposition starting temperature and improved thermal stability, as compared with the polycarbonate resins and polycarbonate resin compositions of Comparative Examples 20 to 26.

[0129] Hereinafter, the present embodiment will be described using specific examples and comparative examples, but the present embodiment is not limited in any way to the following examples, etc.

[0130] The physical properties and characteristics of the polycarbonate resin and the polycarbonate resin composition were measured as follows.

[0131] [Physical properties and characteristics] (Measurement of molecular weight of polycarbonate resin) A solution in which tetrahydrofuran was added in a ratio of 2.0 g to 0.02 g of polycarbonate resin was used as a measurement sample, and the weight average molecular weight of the polycarbonate resin was measured using an HPLC device (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 product names manufactured by Tosoh Corporation) connected in series. The column temperature was set to 40° C., and the analysis was performed at a rate of 0.60 mL / min using tetrahydrofuran as the mobile phase. The detector used was an RI 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 thus prepared, the weight average molecular weight of the polycarbonate resin was determined.

[0132] (Measurement of glass transition temperature Tg of polycarbonate resin) The glass transition temperature Tg of the polycarbonate resin was measured using a differential scanning calorimeter (product name "DSC8500") manufactured by PerkinElmer Japan Co., Ltd. under the condition of a nitrogen gas flow rate of 20 mL / min. More specifically, after holding at 40°C for 3 minutes, the sample was first heated from 40°C to 200°C at 20°C / min to completely melt the sample. The temperature was then lowered from 200°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 (midpoint glass transition temperature) of the step-like change partial curve of the DSC curve drawn during the second heating from 40°C to 190°C at 10°C / min with a straight line equidistant in the vertical direction from the extension of each tangent.

[0133] (Measurement and evaluation of thermal stability) Using a Shimadzu TG-DTA device (product name: DTG-60A) and an aluminum krypton cell, the polycarbonate resin and the polycarbonate resin composition were heated in a nitrogen gas flow at a rate of 10°C / min. The thermal decomposition (TGA) of the polycarbonate resin and the polycarbonate resin composition was measured, and the thermal decomposition onset temperature was obtained from the tangent intersection of the TGA curve. Among the thermal stability measurements of the test pieces of Comparative Examples 27 to 31, those with the highest thermal decomposition onset temperature were used as the standard. When the thermal decomposition onset temperature was +3°C or higher, it was evaluated as having an improved thermal stability effect (marked as "O" in Table 6), and when the thermal decomposition onset temperature was less than +3°C, it was evaluated as not having an improved thermal stability effect (marked as "X" in Table 6).

[0134] [Polycarbonate resin composition] The abbreviations for the compounds used in the following Examples and Comparative Examples are as follows. ((A) Polycarbonate resin) A-1: A polycarbonate resin composed of 100 mol% structural units derived from poly(1,2-cyclohexene carbonate), having a weight average molecular weight of 211,000 and a glass transition temperature Tg of 120°C.

[0135] ((B) Compounds Having an Amide Bond) B-1: 2',3'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine

[0136] ((C) Phosphite Compounds) C-1: Triphenyl phosphite C-2: Tris(phenyl)phosphite C-3: Triisodecyl phosphite

[0137] Example 12 To obtain the composition shown in Table 6, 1.0 g of polycarbonate resin (A-1), 2.0 g of an acetone solution containing 1000 ppm of a compound (B-1) having an amide bond, and 2.0 g of an acetone solution containing 1000 ppm of a phosphite ester compound (C-1) were mixed using a magnetic stirrer and dried under vacuum at 100°C for 2 hours to obtain a polycarbonate resin composition. The obtained polycarbonate resin composition was pressure molded using a hydraulic press at 20 MPaG to obtain a plate-shaped test piece of the polycarbonate resin composition. The thermal stability of the obtained test pieces was measured and the evaluation results are shown in Table 6.

[0138] [Examples 13-14] A polycarbonate resin composition was obtained in the same manner as in Example 12, except that the blending of additives was changed as shown in Table 6. Test pieces were molded from the obtained polycarbonate resin composition in the same manner as in Example 12, and then measured and evaluated. The results are shown in Table 6.

[0139] Comparative Example 27 4.0 g of acetone was added to 1.0 g of polycarbonate resin (A-1), dissolved using a magnetic stirrer, dried under vacuum at 100°C for 2 hours, and molded under pressure at 20 MPaG using a hydraulic press to obtain a plate-shaped polycarbonate resin test piece. The obtained polycarbonate resin was measured and evaluated in the same manner as in Example 12. The results are shown in Table 6.

[0140] [Comparative Examples 28 to 31] A polycarbonate resin composition was obtained in the same manner as in Example 12, except that the blending of additives was changed as shown in Table 6. Test pieces were molded from the obtained polycarbonate resin composition in the same manner as in Example 12, and then measured and evaluated. The results are shown in Table 6.

[0141] [Table 6]

[0142] From Table 6, it was found that the polycarbonate resin compositions of Examples 12 to 14 had higher thermal decomposition onset temperatures and improved thermal stability compared to the polycarbonate resins and polycarbonate resin compositions of Comparative Examples 27 to 31.

[0143] This application is based on Japanese patent applications filed on March 30, 2021 (Patent Application No. 2021-058235), September 6, 2021 (Patent Application No. 2021-144709), September 7, 2021 (Patent Application No. 2021-145175), September 7, 2021 (Patent Application No. 2021-145177), September 7, 2021 (Patent Application No. 2021-145178), and September 7, 2021 (Patent Application No. 2021-145189), the contents of which are incorporated herein by reference. [Industrial Applicability]

[0144] INDUSTRIAL APPLICABILITY The polycarbonate resin composition of the present invention tends to have excellent thermal stability and excellent optical properties such as good moldability, hue, and transparency, and has industrial applicability in fields such as various optical materials such as optical lens materials, optical devices, materials for optical components, and display materials.

Claims

1. a polycarbonate resin including a structural unit having an alicyclic hydrocarbon moiety that constitutes a ring and has carbonate groups linked to two adjacent carbon atoms; A compound having an amide bond, The compound having an amide bond has any one of structures represented by the following formulas (2) to (4): the content of the compound having an amide bond is 500 ppm by mass to 2000 ppm by mass, The polycarbonate resin composition has a weight average molecular weight Mw of 50,000 or more and 500,000 or less, as measured by size exclusion chromatography using polystyrene as a standard sample. 【Chemistry 1】 (In formula (2), R 11 and R 12 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms; the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group; and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.) 【Chemistry 2】 In formula (3), R 13 is an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms. R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and the alkylene group, the alkenylene group, the alkoxylene group, the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphoric acid group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms. 【Chemistry 3】 (In formula (4), R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms; the alkylene group, the alkenylene group, the alkoxylene group, the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphoric acid group, an amino group, an alkoxy group, or an ester group; the aryl group and the heteroaryl group may be substituted with an alkyl group having 1 to 6 carbon atoms; and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.)

2. The polycarbonate resin composition according to claim 1 , wherein the structural unit having an alicyclic hydrocarbon moiety is represented by the following formula (1): 【Chemistry 4】 (In formula (1), n ​​represents an integer of 1 to 6, R 1 ~R 6 are each independently a hydrogen atom, a hydroxyl group, a phosphate group, an amino group, a vinyl group, an allyl group, an alkoxy group having 1 to 20 carbon atoms, an ester group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, which may be bonded to each other via an alkylene group or a carbonate group to form a cyclic structure, the alkylene group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, a carbonyl group may be inserted in the main chain, the alkoxy group, the ester group, the acyl group, and the alkyl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

3. In formula (1), R 4 ~R 6 The polycarbonate resin composition according to claim 2 , wherein is a hydrogen atom.

4. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the polycarbonate resin is poly(1,2-cyclohexene carbonate).

5. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the glass transition temperature Tg of the polycarbonate resin measured by a differential scanning calorimeter is 80°C or higher and 180°C or lower.

6. The polycarbonate resin composition according to any one of claims 1 to 5, further comprising a sulfur compound.

7. The content of the sulfur compound is 500 ppm by mass to 10,000 ppm by mass. The polycarbonate resin composition according to claim 6.

8. The sulfur compound has a structure represented by the following formula (2-1): The polycarbonate resin composition according to claim 6 or 7. 【Chemistry 5】 (In formula (2-1), R 13 and R 14 are each independently an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms. 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 2 to 30 carbon atoms, and the alkylene group, the alkenylene group, the alkoxylene group, the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

9. The sulfur compound has a structure represented by the following formula (3-1): The polycarbonate resin composition according to claim 6 or 7. 【Chemistry 6】 In formula (3-1), m represents an integer of 1 to 4, R 12 are each independently an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms; R 11 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 2 to 30 carbon atoms; R 13 is an m-valent hydrocarbon group which may have an alkoxy group, and the alkylene group, the alkenylene group, the alkoxylene group, the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

10. The polycarbonate resin composition according to any one of claims 1 to 9, further comprising a phosphite compound.

11. The content of the phosphite ester compound is 500 ppm by mass to 10,000 ppm by mass. The polycarbonate resin composition according to claim 10.

12. The phosphite compound has a structure represented by the following formula (2-2): The polycarbonate resin composition according to claim 10 or 11. 【Chemistry 7】 (In formula (2-2), m represents an integer of 0 to 3, R 11 ~R 14 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

13. The phosphite compound has a structure represented by the following formula (3-2): The polycarbonate resin composition according to claim 10 or 11. 【Chemistry 8】 (In formula (3-2), m represents an integer of 1 to 4, R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms; R 13 and R 14 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 2 to 30 carbon atoms; R 15 is a hydrocarbon group having a valence of m, and the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

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