Polycarbonate resin composition

Abstract

To provide a polycarbonate resin composition having excellent thermal stability. [Solution] A polycarbonate resin comprising a structural unit having an alicyclic hydrocarbon moiety in which two adjacent carbon atoms are linked by carbonate groups, A metal complex whose ligand is a diene structure, β-diketone structure, acyloxy structure, or phosphine structure, which coordinates to Pd, Rh, Cu, Ag, Fe, Co, Ni, or Ru, It contains, The weight-average molecular weight Mw of the polycarbonate resin is 50,000 or more and 500,000 or less. Polycarbonate resin composition.

Description

[Technical Field]

[0001] This invention relates to a polycarbonate resin composition. [Background technology]

[0002] Aliphatic polycarbonates have long been known to be useful as medical materials and engineering plastics due to their excellent properties such as impact resistance and light weight, but they have the problem of having a low glass transition temperature. On the other hand, among aliphatic polycarbonates, alicyclic polycarbonates, which have an alicyclic structure in their main chain, exhibit a higher glass transition temperature compared to other aliphatic polycarbonates, and have therefore been actively developed in recent years. For example, a polycyclic alicyclic polycarbonate resin with a pentacyclopentadecanedimethanol backbone has been disclosed, exhibiting excellent transparency, heat resistance, and color (see, for example, Patent Document 1). Furthermore, an alicyclic polycarbonate resin using isosorbide as a raw material has been disclosed, which is excellent in its balance of transparency, heat resistance, water absorption, surface hardness, and low birefringence, and is produced using biomass-derived raw materials in addition to petroleum raw materials (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, possessing a saturated six-membered carbon ring corresponding to the benzene ring. It is widely known that poly(1,2-cyclohexene carbonate) can be synthesized by copolymerization of cyclohexene oxide and carbon dioxide, or by ring-opening polymerization of 1,2-cyclohexene carbonate (see, for example, Patent Document 3 and Non-Patent Document 1). The poly(1,2-cyclohexene carbonate) obtained as described above has excellent transparency and the property of completely decomposing at a predetermined temperature, and is expected to be used in optical materials, thermal decomposition materials, and other applications. [Prior art documents] [Patent Documents]

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

[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] [Problems to be Solved by the Invention]

[0006] As described above, poly(1,2-cyclohexene carbonate) has excellent transparency. However, on the one hand, it has the problem that it may cause thermal decomposition during molding and a decrease in mechanical strength due to decomposition at a predetermined temperature. There is still no technology that sufficiently improves the thermal stability while maintaining the transparency of such poly(1,2-cyclohexene carbonate).

[0007] Therefore, in the present invention, in view of the problems of the above-described conventional technologies, an object is to provide a polycarbonate resin composition having excellent thermal stability. [Means for Solving the Problems]

[0008] As a result of intensive research to solve the problems of the above-described prior art, the inventors of the present invention have found that a polycarbonate resin composition containing a polycarbonate resin having a predetermined structure and a predetermined weight-average molecular weight and a metal complex having a predetermined structure can solve the above-described prior art, and have completed the present invention. That is, the present invention is as follows.

[0009] [1] A polycarbonate resin containing a structural unit having an alicyclic hydrocarbon moiety in which two adjacent carbons are each linked by a carbonate group, A metal complex in which a ligand has a diene structure, a β-diketone structure, an acyloxy structure, or a phosphine structure and coordinates to Pd, Rh, Cu, Ag, Fe, Co, Ni, or Ru, and containing, wherein the weight-average molecular weight Mw of the polycarbonate resin is 50,000 or more and 500,000 or less, A polycarbonate resin composition. [2] The structural unit is represented by the following formula (1), The polycarbonate resin composition according to [1] above.

[0010] [Chemical formula]

[0011] In formula (1), n represents an integer of 1 to 6, and R 1 ~R 6Each of these is independently a hydrogen atom, a hydroxyl group, a phosphate group, an amino group, a vinyl group, an allyl group, a carbon 1 to 20 alkoxy group, a carbon 1 to 20 ester group, a carbon 1 to 20 acyl group, or a linear, branched, or cyclic carbon 1 to 20 alkyl group, which may be bonded to each other via alkylene or carbonate groups 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, and a carbonyl group may be inserted into 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 a carbon 1 to 20 alkyl group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a carbon 1 to 20 alkyl group.

[0012] [3] In equation (1) above, R 4 ~R 6 is a hydrogen atom, The polycarbonate resin composition described in [2] above. [4] The polycarbonate resin is poly(1,2-cyclohexene carbonate). A polycarbonate resin composition according to any one of [1] to [3] above. [5] The glass transition temperature Tg of the polycarbonate resin, as measured by a scanning calorimeter, is between 80°C and 180°C. A polycarbonate resin composition according to any one of [1] to [4] above. [6] The ligand has an acyloxy structure, The metal content is between 50 ppm by mass and 250 ppm by mass. A polycarbonate resin composition according to any one of [1] to [5] above. [7] The metal complex has a structure represented by the following formula (2) or the following formula (3). A polycarbonate resin composition according to any one of [1] to [6] above.

[0013] [ka]

[0014] [ka]

[0015] In formula (2), M is Pd, Rh, Cu, Ag, or Fe, R is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group, m is an integer from 1 to 2, and n is an integer from 2 to 4. In formula (3), M is Pd, Rh, Cu, Ag, or Fe; R is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group; L is a monodentate or bidentate phosphine ligand; m is an integer from 1 to 2; n is an integer from 2 to 4; and l is an integer from 1 to 2.

[0016] [8] The ligand contains a metal complex that coordinates to Pd in ​​the form of a diene structure, a β-diketone structure, or a phosphine structure, and the metal content is 50 ppm by mass to 4000 ppm by mass. A polycarbonate resin composition according to any one of the above [1] to [7]. [9] The metal complex has a structure represented by the following formula (4), formula (5), formula (6), or formula (7): A polycarbonate resin composition according to any one of [1] to [8] above.

[0017] [ka]

[0018]

Chem.

[0019]

Chem.

[0020]

Chem.

[0021] In formula (4), R 1 , R 2 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group, and the combination of m and n is m = 1, n = 2 or m = 2, n = 3. In formula (5), R 1 , R 2 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group. n is 2. In formulas (6) and (7), R 1 ~R 20 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group, and n represents an integer of 1 to 3.

Advantages of the Invention

[0022] According to the present invention, a polycarbonate resin composition having excellent thermal stability can be provided.

Modes for Carrying Out the Invention

[0023] Hereinafter, modes for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. The following embodiments are illustrative examples for explaining the present invention and are not intended to limit the present invention to the following content. The present invention can be implemented in various modifications within the scope of its gist.

[0024] [Polycarbonate resin composition] The polycarbonate resin composition of this embodiment is A polycarbonate resin comprising a structural unit having an alicyclic hydrocarbon moiety in which two adjacent carbon atoms are each linked to a carbonate group, A metal complex whose ligand has a diene structure, β-diketone structure, acyloxy structure, or phosphine structure and coordinates to Pd, Rh, Cu, Ag, Fe, Co, Ni, or Ru, It contains, The weight-average molecular weight Mw of the polycarbonate resin is between 50,000 and 500,000. The weight-average molecular weight Mw can be measured by size exclusion chromatography using polystyrene as a standard sample. The polycarbonate resin composition of this embodiment, having the above-described structure, exhibits excellent thermal stability while maintaining practically good moldability.

[0025] The polycarbonate resin composition of this embodiment is considered to have excellent thermal stability due to the following reasons. First, the thermal decomposition mechanism of the polycarbonate resin used in the polycarbonate resin composition is thought to be as follows. However, the thermal decomposition mechanism of the polycarbonate resin used in this embodiment is not limited to the following. In the case of polycarbonate resins used in this embodiment, which have alicyclic hydrocarbon moieties in which a carbonate group links two adjacent carbon atoms of an alicyclic hydrocarbon, it is believed that the carbonate group in the main chain of the polymer promotes the detachment of hydrogen atoms bonded to carbon atoms adjacent to the carbon atom bonded to the carbonate group, thus causing thermal decomposition. On the other hand, by adding a metal complex to polycarbonate resin in which the ligand has a diene structure, a β-diketone structure, an acyloxy structure, or a phosphine structure and coordinates to Pd, Rh, Cu, Ag, Fe, Co, Ni, or Ru, it is thought that a coordination bond effect occurs between the carbonate groups in the polymer and the metal complex, thereby suppressing the aforementioned hydrogen detachment. This results in a polycarbonate resin composition with excellent thermal stability.

[0026] (Polycarbonate resin) The polycarbonate resin used in the polycarbonate resin composition of this embodiment includes a constituent unit having an alicyclic hydrocarbon moiety that forms a ring and has carbonate groups linked to two adjacent carbon atoms (hereinafter, it may be simply referred to as "a constituent unit having an alicyclic hydrocarbon moiety"). The constituent unit having an alicyclic hydrocarbon moiety is preferably represented by the following formula (1).

[0027] [ka]

[0028] In equation (1), n ​​represents an integer from 1 to 6, and R 1 ~R 6Each of these is independently a hydrogen atom, a hydroxyl group, a phosphate group, an amino group, a vinyl group, an allyl group, a carbon 1 to 20 alkoxy group (preferably carbon 1 to 12, more preferably carbon 1 to 10), a carbon 1 to 20 ester group (preferably carbon 1 to 12, more preferably carbon 1 to 11), a carbon 1 to 20 acyl group (preferably carbon 1 to 12, more preferably carbon 1 to 11), or a linear, branched, or cyclic carbon 1 to 20 alkyl group (preferably carbon 1 to 12, more preferably carbon 1 to 10), and is an alkylene group or a ka They may be bonded to each other via carbonate groups to form a cyclic structure, the alkylene groups may be substituted with hydroxyl groups, phosphate groups, amino groups, alkoxy groups, or ester groups, a carbonyl group may be inserted into the main chain, the alkoxy group, the ester group, the acyl group, and the alkyl group may be substituted with hydroxyl groups, phosphate groups, amino groups, alkoxy groups, or ester groups, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with alkyl groups having 1 to 20 carbon atoms.

[0029] In formula (1) above, if n is 1, it means the ring structure is cyclopentane; if n is 2, it means the ring structure is cyclohexane; if n is 3, it means the ring structure is cycloheptane; if n is 4, it means the ring structure is cyclooctane; if n is 5, it means the ring structure is cyclononane; and if n is 6, it means the ring structure is cyclodecane. Furthermore, in equation (1) above, the two dashed lines represent the connecting parts of the repeating units. From the viewpoint of the availability of raw materials, in formula (1), n ​​is preferably an integer between 1 and 4, and more preferably an integer between 1 and 3. In equation (1) above, R 4 ~R 6 It is preferable that the atom is a hydrogen atom from the viewpoint of ease of obtaining raw materials, ease of obtaining polymers, and ease of the polymerization process.

[0030] The polycarbonate resin used in the polycarbonate resin composition of this embodiment is A1 and A 2 It is preferable to include a constituent unit represented by the following formula (8) having a terminal structure represented by .

[0031] [ka]

[0032] In formula (8), A 1 and A 2 Each of these is 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. Also, A 1 and A 2 They may be joined to each other to form a ring structure. That is, A 1 and A 2 It does not have to have the terminal structure represented by . Note that in formula (8), n and R 1 ~R 6 This is the same as the one in formula (1) above. The number of repetitions of the constituent unit represented by equation (8) is, for example, between 300 and 3500. In formula (8), R 4 ~R 6 It is preferable that the atom is a hydrogen atom from the viewpoint of ease of obtaining raw materials, ease of obtaining polymers, and ease of the polymerization process.

[0033] 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), it tends to have excellent transparency.

[0034] <Weight-average molecular weight of polycarbonate resin> The polycarbonate resin used in this embodiment has a weight-average molecular weight (Mw) of 50,000 to 500,000, as measured by size exclusion chromatography using polystyrene as a standard sample. The polycarbonate resin composition of this embodiment tends to be easier to mold and process because the Mw of the polycarbonate resin is within the above range. From a similar viewpoint, the Mw is preferably 80,000 to 400,000, and more preferably 100,000 to 300,000.

[0035] In the polycarbonate resin used in this embodiment, the number-average molecular weight Mn, measured by size exclusion chromatography using polystyrene as a standard sample, is preferably 50,000 to 500,000, more preferably 80,000 to 400,000, and even more preferably 100,000 to 300,000.

[0036] The weight-average molecular weight and number-average molecular weight of polycarbonate resin can be measured by the method described in the examples below using size exclusion chromatography.

[0037] 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 polymerizable monomer, polymerization initiator, and additives can be appropriately adjusted, and the polycarbonate resin can be manufactured by the manufacturing method described later. Reducing the ratio of polymerization initiator to polymerizable monomer tends to increase Mw and Mn. Furthermore, stirring using a stirring blade or flow mixer tends to increase Mw and Mn.

[0038] <Glass transition temperature (Tg) of polycarbonate resin> The polycarbonate resin used in this embodiment preferably has a glass transition temperature Tg measured by a scanning calorimeter between 80°C and 180°C, more preferably between 90°C and 180°C, and even more preferably between 100°C and 180°C. In the polycarbonate resin composition of this embodiment, when the glass transition temperature Tg of the polycarbonate resin is within the aforementioned range, the moldability and dimensional stability tend to be even better. Methods for controlling the glass transition temperature Tg of polycarbonate resin within the above range are not limited to the following, but include, for example, methods for controlling the stereoregularity of the polycarbonate resin, and methods for copolymerizing the carbonate with an ester, lactone, or lactam.

[0039] In this embodiment, if the polycarbonate resin has multiple constituent units having alicyclic hydrocarbon moieties, it may have two or more polymerization arrangements. To further enhance transparency, it is preferable to use a random copolymer or an alternating copolymer, and to further enhance chemical resistance and mechanical strength, it is preferable to use a block copolymer.

[0040] The polycarbonate resin used in this embodiment can exhibit isotactic, syndiotactic, or atactic structures as stereoregularities. In the polycarbonate resin composition of this embodiment, an amorphous atactic structure is preferred from the viewpoint of further improving transparency.

[0041] (Method of manufacturing polycarbonate resin) The method for producing the polycarbonate resin used in this embodiment is not limited to the following, but examples of conventionally known methods include ring-opening polymerization of an alicyclic carbonate represented by formula (9) below, copolymerization of an alicyclic oxide represented by formula (10) below with carbon dioxide, and transesterification of an alicyclic diol represented by formula (11) below with a carbonate precursor.

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] In equations (9) to (11), n ​​represents an integer from 1 to 5, and R 1 ~R 6 Each of these is independently a hydrogen atom, a hydroxyl group, a phosphate group, an amino group, a vinyl group, an allyl group, a carbon 1 to 20 alkoxy group (preferably carbon 1 to 12, more preferably carbon 1 to 10), a carbon 1 to 20 ester group (preferably carbon 1 to 12, more preferably carbon 1 to 11), a carbon 1 to 20 acyl group (preferably carbon 1 to 12, more preferably carbon 1 to 11), or a linear, branched, or cyclic carbon 1 to 20 alkyl group (preferably carbon 1 to 12, more preferably carbon 1 to 10), and may be bonded to each other via alkylene groups or carbonate groups to form a cyclic structure, and the alkylene group may be substituted with a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group, and a carbonyl group may be inserted into the main chain, and 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.

[0046] <Ring-opening polymerization> In the method for producing the polycarbonate resin used in this embodiment, one type of alicyclic cyclic carbonate may be used alone as the cyclic carbonate used in ring-opening polymerization, and R in formula (9) above 1 ~R 6 Any two or more different alicyclic carbonates may be used in combination.

[0047] Initiators for ring-opening polymerization of alicyclic carbonates include, but are not limited to, acid catalysts, base catalysts, and enzyme catalysts. Examples of base catalysts include, but are not limited to, alkali metals, metal alkoxides, metal organic acid salts, cyclic amines, triamine compounds, and heterocyclic compounds. Among these, alkali metals and metal alkoxides are preferred.

[0048] In ring-opening polymerization, the method for reacting alicyclic carbonates in the presence of an initiator is not limited to the following, but any commonly used polymerization method such as batch polymerization, semi-batch polymerization, or flow polymerization may be used.

[0049] <Copolymerization with carbon dioxide> In the method for producing the polycarbonate resin used in this embodiment, one type of alicyclic cyclic oxide represented by formula (10) may be used alone as the alicyclic cyclic oxide used for copolymerization with carbon dioxide, and the R in formula (10) 1 ~R 6 Any combination of two or more different alicyclic oxides may be used.

[0050] Polymerization catalysts for copolymerizing carbon dioxide with the alicyclic oxide represented by formula (10) are not limited to the following, but examples include metal catalysts such as aluminum catalysts and zinc catalysts. Among these, zinc catalysts are preferred, and organozinc catalysts are more preferred, due to their reactivity with alicyclic oxides and carbon dioxide.

[0051] In copolymerization with carbon dioxide, the method for reacting the alicyclic oxide represented by formula (10) with carbon dioxide in the presence of a polymerization catalyst is not limited to the following, but for example, a method in which the alicyclic oxide and polymerization catalyst are mixed in an autoclave, and then carbon dioxide is injected under pressure to carry out the reaction.

[0052] <Transesterification> In the method for producing polycarbonate resin used in this embodiment, one type of alicyclic cyclic diol represented by formula (11) used in the transesterification method may be used alone, and the R in formula (11) 1 ~R 6 Any two or more different alicyclic cyclic diols may be used in combination.

[0053] Examples of carbonate precursors include, but are not limited to, carbonate esters and carbonyl halides, specifically diphenyl carbonate, dimethyl carbonate, and phosgene.

[0054] Polymerization catalysts used in the transesterification process are not limited to the following, but examples include alkali metal hydroxides, alkali metal carbonates, and organic amines. Among these, alkali metal hydroxides are preferred.

[0055] In the transesterification process, the method for reacting an alicyclic cyclic diol with a carbonate precursor in the presence of a polymerization catalyst is not limited to the following, but any commonly used polymerization method such as melt polymerization or solid-phase polymerization may be used.

[0056] <Purification process> In the method for producing the polycarbonate resin used in this embodiment, it is preferable to include a purification step. Purification methods are not limited to the following, but examples include defoliation purification by heating under reduced pressure and precipitation purification using a precipitation solvent. Furthermore, the purification process may use one type of material alone, or a combination of two types.

[0057] [Devolatilization purification] In the purification process for the polycarbonate resin used in this embodiment, defoliation purification may or may not be used. The devolatilization purification conditions are not particularly limited as long as they are within a range that allows for the purification of the polycarbonate resin used in this embodiment, 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.

[0058] [Precipitation and purification] In the purification process for the polycarbonate resin used in this embodiment, precipitation purification may or may not be used. The precipitation purification conditions are not particularly limited as long as they are within a range that can purify the polycarbonate resin used in this embodiment, but the precipitation solvent is preferably an alcohol solvent such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, or decanol.

[0059] (Metal complexes) The polycarbonate resin composition of this embodiment contains a metal complex whose ligand has a diene structure, a β-diketone structure, an acyloxy structure, or a phosphine structure, and which coordinates to Pd, Rh, Cu, Ag, Fe, Co, Ni, or Ru.

[0060] Ligands having a diene structure, a β-diketone structure, an acyloxy structure, or a phosphine structure have a lower impact on the carbonate group and the hydrogen (β-hydrogen) bonded to the carbon adjacent to the carbon bonded to it, which can cause thermal decomposition of polycarbonate resin, compared to other ligands. Therefore, in this embodiment, adding metal complexes having these ligands tends to improve the thermal stability of the polycarbonate composition. Other ligands (for example, ligands containing halogens or nitrogen) tend to promote the abstraction of β-hydrogen due to the basicity of the ligand itself and the acidity of the hydrogen halides produced by thermal decomposition.

[0061] Furthermore, in the polycarbonate resin composition of this embodiment, in addition to the type of ligand of the metal complex, the portion coordinating to the metal is specified to be a diene structure, a β-diketone structure, an acyloxy structure, or a phosphine structure. It is believed that because the portion of the ligand structure that coordinates to the metal and has the highest electronic activity is one of these structures, it tends to ensure that the decomposition of the polycarbonate resin is not accelerated. Regarding the selection of metal species, it is believed that the interaction between the metal and the polycarbonate resin is not too strong, which contributes to improving the thermal stability of the polycarbonate resin composition in this embodiment. If the interaction with the carbonyl group is too strong, such as when the ionization tendency of the metal species is too high, even with a metal complex having the above-mentioned ligand, the decomposition of the polycarbonate resin tends to be accelerated.

[0062] <Metal acyl oxy salts> From the viewpoint of significantly improving thermal stability, the polycarbonate resin composition of this embodiment preferably contains a metal complex in which the ligand has an acyloxy structure. That is, it is preferable to contain a metal acyloxy salt. The aforementioned metal acyloxy salts are not limited to the following, but include, for example, palladium acetate, silver acetate, copper(I) acetate, and copper(II) acetate.

[0063] The aforementioned ligand having an acyloxy structure, i.e., the metal acyloxy salt, is preferably a compound having a structure represented by the following formula (2) or formula (3).

[0064] [ka]

[0065] In formula (2), M is Pd, Rh, Cu, Ag, or Fe, R is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group, m is an integer from 1 to 2, and n is an integer from 2 to 4.

[0066] [ka]

[0067] In formula (3), M is Pd, Rh, Cu, Ag, or Fe; R is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group; L is a monodentate or bidentate phosphine ligand; m is an integer from 1 to 2; n is an integer from 2 to 4; and l is an integer from 1 to 2.

[0068] Examples of the aforementioned metal M include iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, and gold.

[0069] The linear or branched alkyl group having 1 to 18 carbon atoms is not limited to the following, but examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, hexyl group, octyl group, and the like. The cycloalkyl group having 3 to 18 carbon atoms is not limited to the following, but examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like. The aryl group is not limited to the following, but examples include a phenyl group, an o-methoxyphenyl group, an m-methoxyphenyl group, a p-methoxyphenyl group, a naphthyl group, and so on.

[0070] From the viewpoint of preventing a decrease in transparency and mechanical properties due to a decrease in molecular weight during the solvent degassing process and injection molding process when manufacturing polycarbonate resin, the metal acyloxy salts used in this embodiment are preferably palladium acyloxy salts, rhodium acyloxy salts, silver acyloxy salts, copper acyloxy salts, and iron acyloxy salts, and more preferably palladium(II) acetate, rhodium(II) acetate dimer, silver(I) acetate, copper(II) acetate, and iron(II) acetate.

[0071] The amount of metal complex having an acyloxy structure as a ligand, i.e., metal acyloxy salt, used in the polycarbonate resin composition of this embodiment is preferably 25 ppm to 500 ppm by mass, more preferably 25 ppm to 300 ppm by mass, and even more preferably 50 ppm to 250 ppm by mass, as the amount of metal relative to the total mass of the polycarbonate resin composition, from the viewpoint of the amount added that brings about improved thermal stability during the solvent degassing process and injection molding process during the production of the polycarbonate resin composition, and cost.

[0072] <Palladium salt> From the viewpoint of significantly improving thermal stability, the polycarbonate resin composition of this embodiment preferably contains a metal complex that coordinates to Pd in ​​the form of a diene structure, a β-diketone structure, or a phosphine structure, i.e., a palladium salt. The palladium salt used in this embodiment is not limited to the following, but examples include bis(dibenzylideneacetone)palladium(0), bis(triphenylphosphine)palladium(II) diacetate, bis(2,4-pentanedionato)palladium(II), and bis[1,2-bis(diphenylphosphino)ethane]palladium(0).

[0073] The palladium salt is preferably a compound having the structure represented by formula (4), a compound having the structure represented by formula (5), a compound having the structure represented by formula (12), a compound having the structure represented by formula (13), a compound having the structure represented by formula (6), or a compound having the structure represented by formula (7). In terms of resistance to oxidation of palladium salts, salts represented by the following formulas (5), (12), and (13) are more preferred.

[0074] [ka]

[0075] In formula (4), R 1 , R 2Each of these independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group. The possible combinations of m and n are m=1, n=2, or m=2, n=3.

[0076] The linear or branched alkyl group having 1 to 18 carbon atoms is not limited to the following, but examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, hexyl group, octyl group, and the like. The cycloalkyl group having 3 to 18 carbon atoms is not limited to the following, but examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like. The aryl group is not limited to the following, but examples include a phenyl group, an o-methoxyphenyl group, an m-methoxyphenyl group, a p-methoxyphenyl group, a naphthyl group, and so on.

[0077] [ka]

[0078] In formula (5), R 1 , R 2 Each of these independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group. n is 2.

[0079] The linear or branched alkyl group having 1 to 18 carbon atoms is not limited to the following, but examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, hexyl group, octyl group, and the like. The cycloalkyl group having 3 to 18 carbon atoms is not limited to the following, but examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like. The aryl group is not limited to the following, but examples include a phenyl group, an o-methoxyphenyl group, an m-methoxyphenyl group, a p-methoxyphenyl group, a naphthyl group, and so on.

[0080] [ka]

[0081] [ka]

[0082] In formulas (12) and (13), R 1 ~R 14 Each of these independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group, and n represents an integer from 1 to 3.

[0083] The linear or branched alkyl group having 1 to 18 carbon atoms is not limited to the following, but examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, hexyl group, octyl group, and the like. The cycloalkyl group having 3 to 18 carbon atoms is not limited to the following, but examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like. The aryl group is not limited to the following, but examples include a phenyl group, an o-methoxyphenyl group, an m-methoxyphenyl group, a p-methoxyphenyl group, a naphthyl group, and so on.

[0084] [ka]

[0085] [ka]

[0086] In formulas (6) and (7), R 1 ~R 20 Each of these independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group, and n represents an integer from 1 to 3.

[0087] The linear or branched alkyl group having 1 to 18 carbon atoms is not limited to the following, but examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, hexyl group, octyl group, and the like. The cycloalkyl group having 3 to 18 carbon atoms is not limited to the following, but examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like. The aryl group is not limited to the following, but examples include phenyl groups, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, naphthyl group, etc.

[0088] To prevent a decrease in transparency, mechanical properties, etc., due to a decrease in molecular weight during the solvent degassing process and injection molding process in resin manufacturing, the palladium salt used in this embodiment is preferably a compound having a structure represented by the above formulas (5), (12), (13), (6), or (7), and more preferably bis(dibenzylideneacetone)palladium(0), bis(2,4-pentanedionato)palladium(II), bis(triphenylphosphine)palladium(II) diacetate, and bis[1,2-bis(diphenylphosphino)ethane]palladium(0).

[0089] The amount of the palladium salt compound used in the polycarbonate resin composition of this embodiment is preferably 25 ppm to 10,000 ppm by mass, more preferably 25 ppm to 5,000 ppm by mass, and even more preferably 50 ppm to 4,000 ppm by mass, as the metal content in the polycarbonate resin composition, from the viewpoint of the amount added that brings about improved thermal stability during the solvent degassing process and injection molding process during resin production, and cost.

[0090] (Other additives) The polycarbonate resin composition of this embodiment may also contain other additives such as neutralizing agents, ultraviolet absorbers, mold release agents, colorants, antistatic agents, lubricants, plasticizers, compatibilizers, flame retardants, bluing agents, and flow modifiers.

[0091] [Method for producing polycarbonate resin composition] In this embodiment, the timing and method of mixing the metal acyloxy salt or palladium salt (hereinafter also simply referred to as "added compound") into the polycarbonate resin are not particularly limited. From the viewpoint of preventing thermal decomposition, the mixing timing is preferably, for example, after the addition of the polymerization inhibitor and after precipitation and purification.

[0092] (Blending method) In this embodiment, the method for blending the additive compound into the polycarbonate resin is not particularly limited, but examples include kneading with a kneader, tumbler mixer, V-type mixer, Nauter mixer, Bambali mixer, roll machine, or extruder, or a solution blending method in which the compound is dissolved in a common good solvent such as acetone and then mixed. Any commonly used blending method may be used. [Examples]

[0093] The embodiment will be described below using specific examples and comparative examples, but this embodiment is not limited in any way to the following examples.

[0094] [Examples 1-9, Comparative Examples 1-9] The physical properties and characteristics of the polycarbonate resin and polycarbonate resin composition in Examples 1 to 9 and Comparative Examples 1 to 9, described later, were measured as follows.

[0095] [Physical properties and characteristics] (Measurement of molecular weight of polycarbonate resin) A solution prepared by adding 2.0 g of tetrahydrofuran to 0.02 g of polycarbonate resin was used as the measurement sample, and the weight-average molecular weight of the polycarbonate resin was measured using an HPLC instrument (Tosoh Corporation, product name "HLC-8420GPC"). As columns, we used TSK Guard Columns SuperH-H, TSKgel SuperHM-H, TSKgel SuperHM-H, TSKgel SuperH2000, and TSKgel SuperH1000 (all product names of Tosoh Corporation) connected in series. The column temperature was set to 40°C, and analysis was performed at a rate of 0.60 mL / min using tetrahydrofuran as the mobile phase. An RI detector was used as the detector. A calibration curve was created using polystyrene standard samples from Polymer Standards Service (molecular weights: 2,520,000, 1,240,000, 552,000, 277,000, 130,000, 66,000, 34,800, 19,700, 8,680, 3470, 1306, 370) as standard samples. Based on the calibration curve created in this way, the weight-average molecular weight of the polycarbonate resin was determined.

[0096] (Measurement of the glass transition temperature (Tg) of polycarbonate resin) The glass transition temperature (Tg) of polycarbonate resin was measured using a differential scanning calorimetry system (product name "DSC8500") manufactured by PerkinElmer Japan Co., Ltd., under conditions of a nitrogen gas flow rate of 20 mL / min. More specifically, the sample was held at 40°C for 3 minutes, then subjected to a primary heating cycle of 20°C / min from 40°C to 200°C to completely melt it. Subsequently, it was cooled from 200°C to 40°C at 50°C / min and held at 40°C for 5 minutes. Then, the glass transition temperature (Tg) was defined as the intersection point (midpoint glass transition temperature) of the stepped transition portion of the DSC curve drawn during the secondary heating cycle of 40°C to 190°C at 10°C / min, and a straight line equidistant in the vertical direction from the extensions of each tangent line.

[0097] (Measurement and evaluation of the thermal stability of polycarbonate resin compositions to which component (B) below has been added) Using a Shimadzu TG-DTA apparatus (product name: DTG-60A) and an aluminum krypton cell, polycarbonate resin and polycarbonate resin composition were heated to 210°C at a rate of 10°C / min in a nitrogen stream and held / heated for 10 minutes. Thermal stability was evaluated by calculating the percentage change ΔMw (%) of the weight-average molecular weight before and after heating, which was calculated using the method described above. Specifically, it was calculated using the following formula (A). Furthermore, if the value Δ(ΔMw) obtained by subtracting the ΔMw measured after adding a predetermined metal complex to the polycarbonate resin in each example and comparative example from the ΔMw of the polycarbonate resin test piece in Comparative Example 1 was +5% or more, it was determined that there was an improvement in thermal stability (indicated as "〇" in the table), and if it was less than +5%, it was determined that there was no improvement in thermal stability (indicated as "×" in the table). Specifically, it was calculated using the following formula (B).

[0098] ΔMw(%) = {{(Weight-average molecular weight before heating) - (Weight-average molecular weight after heating)} / (Weight-average molecular weight before heating)} × 100 ... Equation (A)

[0099] Δ(ΔMw)(%) = ΔMw(Comparative Example 1) - ΔMw(Examples 1-9, Comparative Examples 2-9) ...(Formula B)

[0100] The abbreviations for the compounds used in Examples 1-9 and Comparative Examples 1-9 are as follows: (A) Polycarbonate resin A-1: A polycarbonate resin composed of 100 mol% structural units derived from poly(1,2-cyclohexene carbonate), with a weight-average molecular weight of 200,000 and a glass transition temperature (Tg) of 120°C.

[0101] (B) Metal acyl oxy salts B-1: Palladium(II) acetate B-2: Bis(acetato)bis(triphenylphosphine)palladium(II) B-3: Rhodium(II) acetate dimer B-4: Silver(I) acetate B-5: Copper(II) acetate B-6: Copper(I) acetate B-7: Iron(II) acetate B-8: Lithium(I) acetate B-9: Potassium acetate (I) B-10: Sodium(II) acetate B-11: Cesium(II) acetate B-12: Magnesium(II) acetate B-13: Calcium(II) acetate B-14: Scandium(III) acetate B-15: Yttrium(III) acetate

[0102] (Example 1) 1.00 g of polycarbonate resin (A-1) was dissolved in acetone to a concentration of 5% by mass. Next, palladium(II) acetate was separately dissolved in acetone to prepare a homogeneous solution, and the mass per 100 μL was measured using a micropipette to calculate the density of this solution. Then, using a micropipette, an amount of palladium(II) acetate acetone solution containing 50 ppm of palladium per 1.00 g of polycarbonate resin (A-1) was dispensed and added to the polycarbonate resin (A-1) acetone solution, and mixed using a magnetic stirrer. Subsequently, the mixture was dried under vacuum at 120°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 specimen of the polycarbonate resin composition. The results of the thermal stability measurement evaluated using the obtained test specimen are shown in Table 1 below.

[0103] (Examples 2-9) The types and proportions of metal acyl oxy salts were changed as shown in Table 1 below. If the palladium salt did not dissolve in acetone, ultrapure water was added as appropriate to prepare a homogeneous metal-containing solution, and the density was calculated in the same manner as described above. Thereafter, a polycarbonate resin composition was obtained in the same manner as in (Example 1). The obtained polycarbonate resin composition was evaluated after molding test pieces in the same manner as in Example 1, and the results are shown in Table 1 below.

[0104] (Comparative Example 1) 1.0 g of polycarbonate resin (A-1) was mixed with 2.0 g of acetone, dissolved using a magnetic stirrer, dried under vacuum at 100°C for 2 hours, and then pressure-molded with a hydraulic press at 20 MPaG to obtain a plate-shaped polycarbonate resin test specimen. The obtained polycarbonate resin was evaluated after specimen molding in the same manner as in Example 1, and the results are shown in Table 2 below.

[0105] (Comparative Examples 2-9) A polycarbonate resin composition was obtained in the same manner as in Example 1, except that the type and blending ratio of the metal acyloxy salt were changed as shown in Table 2. The obtained polycarbonate resin composition was evaluated after molding test specimens in the same manner as in Example 1, and the results are shown in Table 2 below.

[0106] [Table 1]

[0107] [Table 2]

[0108] Tables 1 and 2 show that the polycarbonate resin compositions of Examples 1 to 9 exhibited improved thermal stability, with a smaller change rate ΔMw of weight-average molecular weight before and after heating compared to the polycarbonate resins and polycarbonate resin compositions of Comparative Examples 1 to 9.

[0109] [Examples 10-16, Comparative Examples 10-14] The physical properties and characteristics of the polycarbonate resin and polycarbonate resin composition in Examples 10-16 and Comparative Examples 10-14, described later, were measured as follows.

[0110] [Physical properties and characteristics] (Measurement of molecular weight of polycarbonate resin) A solution prepared by adding 2.0 g of tetrahydrofuran to 0.02 g of polycarbonate resin was used as the measurement sample, and the weight-average molecular weight of the polycarbonate resin was measured using an HPLC instrument (Tosoh Corporation, product name "HLC-8420GPC"). As columns, we used TSK Guard Columns SuperH-H, TSKgel SuperHM-H, TSKgel SuperHM-H, TSKgel SuperH2000, and TSKgel SuperH1000 (all product names of Tosoh Corporation) connected in series. The column temperature was set to 40°C, and analysis was performed at a rate of 0.60 mL / min using tetrahydrofuran as the mobile phase. An RI detector was used as the detector. A calibration curve was created using polystyrene standard samples from Polymer Standards Service (molecular weights: 2,520,000, 1,240,000, 552,000, 277,000, 130,000, 66,000, 34,800, 19,700, 8,680, 3470, 1306, 370) as standard samples. Based on the calibration curve created in this way, the weight-average molecular weight of the polycarbonate resin was determined.

[0111] (Measurement of the glass transition temperature (Tg) of polycarbonate resin) The glass transition temperature (Tg) of polycarbonate resin was measured using a differential scanning calorimetry system (product name "DSC8500") manufactured by PerkinElmer Japan Co., Ltd., under conditions of a nitrogen gas flow rate of 20 mL / min. More specifically, the sample was held at 40°C for 3 minutes, then subjected to a primary heating cycle of 20°C / min from 40°C to 200°C to completely melt it. Subsequently, it was cooled from 200°C to 40°C at 50°C / min and held at 40°C for 5 minutes. Then, the glass transition temperature (Tg) was defined as the intersection point (midpoint glass transition temperature) of the stepped transition portion of the DSC curve drawn during the secondary heating cycle of 40°C to 190°C at 10°C / min, and a straight line equidistant in the vertical direction from the extensions of each tangent line.

[0112] (Measurement and evaluation of the thermal stability of polycarbonate resin compositions to which component (C) below has been added) Using a Shimadzu TG-DTA apparatus (product name: DTG-60A) and an aluminum krypton cell, polycarbonate resin and polycarbonate resin composition were heated to 210°C at a rate of 10°C / min in a nitrogen stream and held / heated for 10 minutes. Thermal stability was evaluated by calculating the percentage change ΔMw (%) of the weight-average molecular weight before and after heating, which was calculated using the method described above. Specifically, it was calculated using the following formula (A). Furthermore, if the value Δ(ΔMw) obtained by subtracting the ΔMw measured after adding a predetermined metal complex to the polycarbonate resin in each example and comparative example from the ΔMw of the polycarbonate resin test piece of Comparative Example 10 was +5% or more, it was determined that there was an improvement in thermal stability (indicated as "〇" in the table), and if it was less than +5%, it was determined that there was no improvement in thermal stability (indicated as "×" in the table). Specifically, it was calculated using the following formula (B).

[0113] ΔMw(%) = {{(Weight-average molecular weight before heating) - (Weight-average molecular weight after heating)} / (Weight-average molecular weight before heating)} × 100 ... Equation (A)

[0114] Δ(ΔMw)(%) = ΔMw(Comparative Example 10) - ΔMw(Examples 10-16, Comparative Examples 11-14)·····(Equation B)

[0115] The abbreviations for the compounds used in Examples 10-16 and Comparative Examples 10-14 are as follows: (A) Polycarbonate resin A-1: A polycarbonate resin composed of 100 mol% structural units derived from poly(1,2-cyclohexene carbonate), with a weight-average molecular weight of 211,000 and a glass transition temperature (Tg) of 120°C. (C) Palladium salt C-1: Bis(dibenzylideneacetone)palladium(0) C-2: Bis(2,4-pentanedionato)palladium(II) C-3: Bis[1,2-bis(diphenylphosphin)ethane]palladium(0) C-4: Palladium(II) chloride C-5: Palladium(II) trifluoroacetate C-6: Palladium(II) bromide C-7: Palladium(II) iodide

[0116] (Example 10) 1.00 g of polycarbonate resin (A-1) was dissolved in acetone to a concentration of 5 mass percent. Next, bis(dibenzylideneacetone)palladium(0) was separately dissolved in acetone to prepare a homogeneous solution. The density of this solution was calculated by measuring the weight per 100 μL using a micropipette. Subsequently, an amount of liquid containing 50 ppm of palladium per 1.00 g of polycarbonate resin (A-1) was dispensed from the palladium(II) acetate acetone solution using a micropipette and added to the polycarbonate resin (A-1) acetone solution. The mixture was then mixed using a magnetic stirrer. The mixture was then dried under vacuum at 120°C for 2 hours to obtain the polycarbonate resin composition. The obtained polycarbonate resin composition was pressure-molded using a hydraulic press at 20 MPaG to obtain plate-shaped test specimens of the polycarbonate resin composition. The results of the thermal stability measurements evaluated using the obtained test specimens are shown in Table 3 below.

[0117] (Examples 11-16) The types and proportions of palladium salts were changed as shown in Table 3 below. If the palladium salt did not dissolve in acetone, ultrapure water was added as appropriate to prepare a homogeneous metal-containing solution, and the density was calculated in the same manner as described above. Thereafter, a polycarbonate resin composition was obtained in the same manner as in Example 10. The obtained polycarbonate resin composition was evaluated after molding test specimens in the same manner as in Example 10, and the results are shown in Table 3 below.

[0118] (Comparative Example 10) 1.0 g of polycarbonate resin (A-1) was mixed with 2.0 g of acetone, dissolved using a magnetic stirrer, dried under vacuum at 100°C for 2 hours, and then pressure-molded with a hydraulic press at 20 MPaG to obtain a plate-shaped polycarbonate resin test piece. The obtained polycarbonate resin was evaluated after molding test specimens in the same manner as in Example 10, and the results are shown in Table 4 below.

[0119] (Comparative Examples 11-14) A polycarbonate resin composition was obtained in the same manner as in Example 10, except that the type and blending ratio of the metal acyl oxy salt were changed as shown in Table 4 below. The obtained polycarbonate resin composition was evaluated after molding test specimens in the same manner as in Example 10, and the results are shown in Table 4 below.

[0120] [Table 3]

[0121] [Table 4]

[0122] Tables 3 and 4 show that the polycarbonate resin compositions of Examples 10 to 16 exhibited improved thermal stability, with a smaller change rate ΔMw of weight-average molecular weight before and after heating compared to the polycarbonate resins and polycarbonate resin compositions of Comparative Examples 10 to 14. [Industrial applicability]

[0123] The polycarbonate resin composition of the present invention has industrial applicability in various fields such as optical lens materials, optical devices, optical component materials, and display materials.

Claims

1. A polycarbonate resin containing a structural unit having an alicyclic hydrocarbon moiety in which two adjacent carbon atoms are linked by carbonate groups, A metal complex whose ligand is a diene structure, β-diketone structure, acyloxy structure, or phosphine structure, which coordinates to Pd, Rh, Cu, Ag, Fe, Co, Ni, or Ru, It contains, The weight-average molecular weight Mw of the polycarbonate resin is 50,000 or more and 500,000 or less. Polycarbonate resin composition.

2. The aforementioned constituent unit is represented by the following formula (1): The polycarbonate resin composition according to claim 1. 【Chemistry 1】 (In equation (1), n ​​represents an integer from 1 to 6, R 1 ~R 6 Each of these is independently a hydrogen atom, a hydroxyl group, a phosphate group, an amino group, a vinyl group, an allyl group, a carbon 1 to 20 alkoxy group, a carbon 1 to 20 ester group, a carbon 1 to 20 acyl group, or a linear, branched, or cyclic carbon 1 to 20 alkyl group, which may be bonded to each other via alkylene or carbonate groups 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 into 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 a carbon 1 to 20 alkyl group, and the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a carbon 1 to 20 alkyl group.

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

4. The polycarbonate resin is poly(1,2-cyclohexene carbonate). The polycarbonate resin composition according to claim 3.

5. The glass transition temperature Tg of the polycarbonate resin, as measured by a scanning calorimeter, is between 80°C and 180°C. A polycarbonate resin composition according to any one of claims 1 to 4.

6. The ligand has an acyloxy structure, The metal content is between 50 ppm by mass and 250 ppm by mass. The polycarbonate resin composition according to claim 1.

7. The metal complex has a structure represented by the following formula (2) or the following formula (3). The polycarbonate resin composition according to claim 1. 【Chemistry 2】 【Transformation 3】 (In formula (2), M is Pd, Rh, Cu, Ag, or Fe, R is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group, m is an integer from 1 to 2, and n is an integer from 2 to 4.) In formula (3), M is Pd, Rh, Cu, Ag, or Fe; R is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group; L is a monodentate or bidentate phosphine ligand; m is an integer from 1 to 2; n is an integer from 2 to 4; and l is an integer from 1 to 2.

8. The ligand contains a metal complex that coordinates to Pd in ​​the form of a diene structure, a β-diketone structure, or a phosphine structure, and the metal content is 50 ppm by mass to 4000 ppm by mass. The polycarbonate resin composition according to claim 1.

9. The metal complex has a structure represented by the following formula (4), formula (5), formula (6), or formula (7): The polycarbonate resin composition according to claim 1. 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 (In formula (4), R 1 , R 2 Each of these independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group, and the combinations of m and n are m=1, n=2 or m=2, n=3. In formula (5), R 1 , R 2 Each of these independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group. n is 2. In Formula (6) and Formula (7), R 1 ~R 20 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group, and n represents an integer of 1 to 3.)

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