Polycarbonate resin composition and molded article

Abstract

The present invention relates to a polycarbonate resin composition comprising a polycarbonate resin (A) and a perfluoroalkylsulfonylimide (B) represented by the following formula (1), a branching ratio of the polycarbonate resin (A) calculated by (molar amount of a structural unit derived from a branching agent) / (molar amount of a structural unit derived from a diphenol + molar amount of a structural unit derived from a branching agent + molar amount of a terminal unit) x 100 being 0.30 mol% or more and 3.0 mol% or less, and a content of the perfluoroalkylsulfonylimide (B) being 0.05 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A).

Description

Technical Field

[0001] This invention relates to polycarbonate-based resin compositions and molded articles. Background Technology

[0002] Polycarbonate resins possess excellent properties such as light transmittance, mechanical properties, thermal properties, electrical properties, and weather resistance. These properties are effectively utilized for applications in various resin-based lighting equipment covers, such as lighting masks and display covers, as well as optical molding products like lenses and transparent components in the electrical and electronic fields. For these molded products, requirements include flame retardancy, high light transmittance (high total light transmittance), and high color tint (low yellow tint and whiteness).

[0003] As for the technology involving flame-retardant polycarbonate resin compositions for such molded articles, the technologies described in Patent Documents 1 to 3 can be cited as examples.

[0004] Patent Document 1 discloses a polycarbonate resin composition containing polycarbonate resin and glass filler, wherein the average major diameter of the glass filler is 1000 μm or less, and the total amount of the organometallic salt of sulfonic acid and the organometallic salt of sulfonamide is 1% by mass or less based on the total amount of the polycarbonate resin and the glass filler. This polycarbonate resin composition has excellent flame retardancy in suppressing the burning rate after ignition and can reduce the maximum heat generation rate during combustion.

[0005] Patent document 2 discloses a polycarbonate resin composition characterized in that, relative to 100 parts by weight of (A) polycarbonate resin, it contains 0.05 to 3 parts by weight of (B) light diffusing agent and 0.01 to 0.3 parts by weight of (C) alkali metal salt of trifluoromethanesulfonate. The polycarbonate resin composition has excellent light transmittance and dispersibility and high flame retardancy.

[0006] Patent document 3 discloses a flame-retardant composition comprising a carbonate polymer and an additive metal salt containing anion selected from (a) a highly fluorinated methyl compound, (b) a highly fluorinated imide, (c) a highly fluorinated amide, and any combination thereof. This flame-retardant composition can provide flame retardancy with relatively low levels of additives, allows for a wider range of processing methods for the additive composition, and can have high transparency.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2018-170105

[0010] Patent Document 2: Japanese Patent Application Publication No. 2019-203081

[0011] Patent Document 3: Japanese Patent Publication No. 2004-521166 Summary of the Invention

[0012] The problem the invention aims to solve

[0013] According to the research of the inventors, it has been found that the polycarbonate resin compositions described in Patent Documents 1 to 3 have room for improvement in terms of thin-wall flame retardancy, i.e., the flame retardancy when the thickness of the resulting molded article is thin. In addition, molded articles formed from these polycarbonate resin compositions sometimes exhibit a yellowish or cloudy appearance, resulting in a poor color tone.

[0014] The present invention was made in view of the above circumstances, and provides a polycarbonate resin composition that can produce molded articles with suppressed yellowing and turbidity and improved thin-wall flame retardancy and light transmittance.

[0015] means for solving problems

[0016] The inventors have discovered that molded articles formed from a polycarbonate resin composition comprising a polycarbonate resin (A) with a branching rate within a specific range and a specific perfluoroalkyl sulfonamide (B) in a specific ratio exhibit suppressed yellowing and turbidity, and improved thin-wall flame retardancy and light transmittance.

[0017] That is, according to the present invention, a polycarbonate-based resin composition and a molded article as shown below are provided.

[0018] [1] A polycarbonate resin composition comprising a polycarbonate resin (A) and a perfluoroalkyl sulfonylimide (B) represented by formula (1) below.

[0019] The branching rate of the above-mentioned polycarbonate resin (A), calculated by (molar amount of structural units from the branching agent) / (molar amount of structural units from the diphenol + molar amount of structural units from the branching agent + molar amount of terminal units) × 100, is 0.30 mol% or more and 3.0 mol% or less.

[0020] The content of the perfluoroalkyl sulfonamide (B) is 0.05 parts by weight or more and 2.0 parts by weight or less per 100 parts by weight of the polycarbonate resin (A).

[0021] [Chemical Formula 1]

[0022]

[0023] (In the above formula (1), R) 31 R represents a perfluoroalkyl group having 1 to 3 carbon atoms. 32 M represents a perfluoroalkyl group having 1 to 4 carbon atoms. + This indicates a monovalent cation selected from at least one of lithium ions, sodium ions, and potassium ions.

[0024] [2] According to the polycarbonate resin composition described in [1] above, wherein,

[0025] The aforementioned polycarbonate resin (A) includes branched polycarbonate resin (A-1) and aromatic polycarbonate resin (A-2) other than the aforementioned branched polycarbonate resin (A-1).

[0026] [3] According to the polycarbonate resin composition described in [2] above, wherein,

[0027] The above-mentioned branched polycarbonate resin (A-1) has repeating units as shown in formula (I) and branched structures as shown in formula (II).

[0028] [Chemical Formula 2]

[0029]

[0030] (In the above formula (I), R) 1 and R 2 Each group independently represents a group selected from halogen atoms, alkyl groups with 1 to 18 carbon atoms, alkoxy groups with 1 to 18 carbon atoms, cycloalkyl groups with 6 to 20 carbon atoms, cycloalkoxy groups with 6 to 20 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 14 carbon atoms, aryloxy groups with 6 to 14 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, arylalkoxy groups with 7 to 20 carbon atoms, nitro, formyl, cyano, and carboxyl groups; X represents a single bond, alkylene groups with 1 to 8 carbon atoms, alkylidene groups with 2 to 8 carbon atoms, cycloalkylene groups with 5 to 15 carbon atoms, cycloalkoxy groups with 5 to 15 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, -S-, -SO-, -SO2-, -O-, or -CO-; a and b each independently represent integers from 0 to 4.

[0031] [Chemical Formula 3]

[0032]

[0033] In formula (II) above, R represents a hydrogen atom or a group selected from alkyl groups having 1 to 5 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and aryl groups having 6 to 14 carbon atoms. 11 ~R 16 Each of these characters independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. PC represents the polycarbonate moiety, and T represents the terminal group. f, g, and h represent integers.

[0034] [4] The polycarbonate resin composition according to any one of [1] to [3] above, wherein,

[0035] The viscosity-average molecular weight of the above-mentioned polycarbonate resin (A) is 10,000 or more and 50,000 or less.

[0036] [5] The polycarbonate resin composition according to any one of [1] to [4] above, wherein,

[0037] It also contains antioxidants (C),

[0038] The content of the antioxidant (C) is 0.03 parts by mass or more and 0.50 parts by mass or less per 100 parts by mass of the polycarbonate resin (A).

[0039] [6] According to the polycarbonate resin composition described in [5] above, wherein,

[0040] The antioxidant (C) mentioned above includes at least one selected from phosphorus-based antioxidants and phenolic antioxidants.

[0041] [7] The polycarbonate resin composition according to any one of [1] to [6] above, wherein,

[0042] It also contains mold release agent (D),

[0043] The content of the release agent (D) is 0.01 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of the polycarbonate resin (A).

[0044] [8] The polycarbonate resin composition according to any one of [1] to [7] above, wherein,

[0045] It also contains organosilicon compounds (E),

[0046] The content of the aforementioned organosilicon compound (E) is 0.01 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of the aforementioned polycarbonate resin (A).

[0047] [9] The polycarbonate resin composition according to any one of [1] to [8] above, wherein,

[0048] The total content of perfluoroalkane sulfonate metal salts and aromatic sulfonate metal salts is less than 0.05 parts by weight relative to 100 parts by weight of the above-mentioned polycarbonate resin (A).

[0049]

[10] The polycarbonate resin composition according to any one of [1] to [9] above,

[0050] The total light transmittance of a 5mm thick plate obtained by injection molding the above polycarbonate resin composition under the conditions of barrel temperature of 280°C, mold temperature of 80°C and cycle time of 53 seconds is more than 80%.

[0051]

[11] The polycarbonate resin composition according to any one of [1] to

[10] above,

[0052] The haze of a 5mm thick plate obtained by injection molding the above polycarbonate resin composition under the conditions of barrel temperature of 280°C, mold temperature of 80°C and cycle time of 53 seconds is less than 4.0%.

[0053]

[12] The polycarbonate resin composition according to any one of [1] to

[11] above,

[0054] The 1.5mm thick sheet obtained by injection molding the above polycarbonate resin composition under the conditions of barrel temperature of 280°C, mold temperature of 80°C and cycle time of 18 seconds has a flame retardancy of V-0 as specified in UL94 standard.

[0055]

[13] The polycarbonate resin composition according to any one of [1] to

[12] above,

[0056] The YI value of a 5mm thick plate obtained by injection molding the above polycarbonate resin composition under the conditions of barrel temperature of 280°C, mold temperature of 80°C and cycle time of 53 seconds is 6.0 or less.

[0057]

[14] The polycarbonate resin composition according to any one of [1] to

[13] above is used in a translucent molded article.

[0058]

[15] A molded article formed from any of the polycarbonate resin compositions described in any one of [1] to

[14] above.

[0059] The effects of the invention

[0060] According to the present invention, a polycarbonate-based resin composition can be provided, which can produce molded articles with suppressed yellowing and turbidity and improved thin-wall flame retardancy and light transmittance. Detailed Implementation

[0061] 1. Polycarbonate-based resin composition

[0062] The polycarbonate resin composition of the present invention comprises a polycarbonate resin (A) and a perfluoroalkyl sulfonamide (B) as shown in formula (1) below. Furthermore, the branching rate of the polycarbonate resin (A), calculated by (molar amount of structural units from the branching agent) / (molar amount of structural units from the diphenol + molar amount of structural units from the branching agent + molar amount of terminal units) × 100, is 0.30 mol% or more and 3.0 mol% or less, and the content of the perfluoroalkyl sulfonamide (B) is 0.05 parts by mass or more and 2.0 parts by mass or less relative to 100 parts by mass of the polycarbonate resin (A).

[0063] [Chemical Formula 4]

[0064]

[0065] In equation (1) above, R 31 R represents a perfluoroalkyl group having 1 to 3 carbon atoms. 32 M represents a perfluoroalkyl group having 1 to 4 carbon atoms. + It represents a monovalent cation selected from at least one of lithium ions, sodium ions, and potassium ions.

[0066] According to the polycarbonate-based resin composition of the present invention, molded articles with suppressed yellowing and turbidity, and improved thin-wall flame retardancy and light transmittance can be obtained.

[0067] The polycarbonate resin composition and its molded articles of the present invention will now be described in detail. In this specification, preferred definitions may be used arbitrarily, and combinations of preferred embodiments are even more preferred. In this specification, "XX to YY" refers to "XX or more and YY or less".

[0068] [Polycarbonate resin (A)]

[0069] The polycarbonate resin composition of the present invention comprises a polycarbonate resin (A) with a branching rate of 0.30 mol% or more and 3.0 mol% or less.

[0070] The polycarbonate resin (A) having such a branching rate preferably includes a branched polycarbonate resin (A-1), more preferably includes a branched polycarbonate resin (A-1) and an aromatic polycarbonate resin (A-2) other than the branched polycarbonate resin (A-1).

[0071] <Branched polycarbonate resin (A-1)>

[0072] Branched polycarbonate resins (A-1) are not particularly limited to any polycarbonate resin having a branched structure. For example, polycarbonate resins having repeating units as shown in formula (I) and branched structures as shown in formula (II) can be cited.

[0073] [Chemical Formula 5]

[0074]

[0075] In equation (I), R 1 and R 2 Each group independently represents a group selected from halogen atoms, alkyl groups with 1 to 18 carbon atoms, alkoxy groups with 1 to 18 carbon atoms, cycloalkyl groups with 6 to 20 carbon atoms, cycloalkoxy groups with 6 to 20 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 14 carbon atoms, aryloxy groups with 6 to 14 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, arylalkoxy groups with 7 to 20 carbon atoms, nitro, formyl, cyano, and carboxyl groups. X represents a single bond, alkylene groups with 1 to 8 carbon atoms, alkylidene groups with 2 to 8 carbon atoms, cycloalkylene groups with 5 to 15 carbon atoms, cycloalkoxy groups with 5 to 15 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, -S-, -SO-, -SO2-, -O-, or -CO-. a and b each independently represent integers from 0 to 4.

[0076] [Chemical Formula 6]

[0077]

[0078] In formula (II), R represents a hydrogen atom or a group selected from alkyl groups having 1 to 5 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and aryl groups having 6 to 14 carbon atoms. 11 ~R 16 Each of these can independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. PC represents the polycarbonate moiety, and T represents the terminal group. f, g, and h represent integers.

[0079] In the above formula (I), R is... 1 and R 2 Halogen atoms that can be represented independently include fluorine, chlorine, bromine, and iodine atoms.

[0080] As R 1 and R 2 Alkyl groups, individually represented, include methyl, ethyl, n-propyl, isopropyl, various butyl groups (“various” means including both straight-chain and all branched groups. The same applies in the following description.), various pentyl groups, and various hexyl groups. As R 1 and R 2 Alkoxy groups, which can be represented independently, include those having the aforementioned alkyl group as the alkyl group.

[0081] Examples of alkyl groups represented by X include methylene, ethylene, trimethylene, tetramethylene, and hexamethylene, with alkyl groups having 1 to 5 carbon atoms being preferred. Examples of alkylidene groups represented by X include ethoxylide and isopropylidene. Examples of cycloalkylene groups represented by X include cyclopentanediyl, cyclohexanediyl, and cyclooctanediyl, with cycloalkylene groups having 5 to 10 carbon atoms being preferred. Examples of cycloalkylidene groups represented by X include cyclohexylidene, 3,5,5-trimethylcyclohexylidene, and 2-adamantaneidene, with cycloalkylidene groups having 5 to 10 carbon atoms being preferred, and more preferably cycloalkylidene groups having 5 to 8 carbon atoms.

[0082] a and b each independently represent an integer from 0 to 4, preferably from 0 to 2, and more preferably 0 or 1. Preferably, a and b are 0 and X is a single bond or an alkyl group with 1 to 8 carbons, or a and b are 0 and X is an alkylidene group with 3 carbons, especially an isopropylidene group.

[0083] Next, the branched structure shown in equation (II) above will be explained.

[0084] In formula (II) above, examples of alkyl groups having 1 to 5 carbon atoms, represented by R, include methyl, ethyl, n-propyl, n-butyl, or n-pentyl. 11 ~R 16 Alkyl groups having 1 to 5 carbon atoms can be represented by, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, etc. Halogen atoms can be represented by, for example, chlorine, bromine, fluorine, etc.

[0085] In formula (II) above, the polycarbonate portion represented by PC has the repeating unit shown in formula (I) above. As an example, the polycarbonate portion represented by PC has the repeating unit derived from bisphenol A shown in formula (III) below.

[0086] [Chemical Formula 7]

[0087]

[0088] It should be noted that (PC) in equation (II) above f (PC) g and (PC) h In one of the polycarbonate portions, the carbon atom of the -OC(=O)- group in one of the terminal polycarbonate portions is bonded to the adjacent oxygen atom in formula (II) above, and the oxygen atom in the other terminal polycarbonate portion is bonded to the adjacent terminal group.

[0089] The terminal group (also called the terminal unit) represented by T is derived from the capping agent.

[0090] The branching agent and the raw material diphenol used in obtaining the branched polycarbonate resin (A-1) will be described later.

[0091] The branched polycarbonate resin (A-1) preferably has the branched structure shown in formula (II) above, with a branching rate of 0.30 mol% or more and 3.0 mol% or less. By achieving a branching rate within the above range for the branched polycarbonate resin (A-1), the flame retardancy of the polycarbonate resin composition of the present invention can be further improved, it is less prone to gelation during polymerization, and it is easier to manufacture polycarbonate. The branching rate of the branched polycarbonate resin (A-1) refers to the molar amount of structural units derived from the branching agent (molar amount of structural units derived from the branching agent / (total molar amount of structural units derived from the branching agent + structural units derived from the branching agent + terminal units) used in the manufacture of the branched polycarbonate resin (A-1) × 100 (expressed in mol%), relative to the total molar amount of structural units derived from the branching agent, structural units derived from the branching agent, and terminal units used in the manufacture of the branched polycarbonate resin (A-1). The branching rate can be determined by... 1 Actual measurements were performed using H-NMR.

[0092] In the manufacture of polycarbonate resins, by adding 0.30 mol% and 3.0 mol% of the branching agent (described later) relative to the total molar amount of the diphenol compound, branching agent and end-capping agent added as needed as raw materials for branched polycarbonate resins (A-1), a branched polycarbonate resin having a branching rate within the above range can be obtained.

[0093] From the viewpoint of further improving the flame retardancy of thin-walled polycarbonate resin (A-1), the branching rate is preferably 0.35 mol% or more, more preferably 0.40 mol% or more, even more preferably 0.43 mol% or more, and even more preferably 0.45 mol% or more. From the viewpoint of obtaining good flame retardancy, light transmittance, mechanical properties, formability, and flowability of thin-walled polycarbonate resin (A-1), it is preferably 2.5 mol% or less, more preferably 2.0 mol% or less, even more preferably 1.5 mol% or less, and even more preferably 1.0 mol% or less. The branched structure can be derived from a single branching agent or from two or more branching agents. More preferably, the branched structure shown in formula (II) above has R being methyl and R... 11 ~R 16 Each hydrogen atom is a branched structure derived from the structure of 1,1,1-tris(4-hydroxyphenyl)ethane.

[0094] The branched polycarbonate resin (A-1) preferably has a viscosity-average molecular weight (Mv) of 10,000 to 50,000, more preferably 15,000 to 30,000, and even more preferably 17,000 to 28,000. The above viscosity-average molecular weight can be adjusted by using a molecular weight regulator (end-capping agent) or by adjusting the reaction conditions. If the viscosity-average molecular weight of the branched polycarbonate resin (A-1) is within the above range, a polycarbonate resin composition that further improves the balance of flame retardancy, light transmittance, and mechanical properties, and also exhibits superior formability, can be obtained.

[0095] The viscosity-average molecular weight (Mv) mentioned above is the intrinsic viscosity [η] of a dichloromethane solution (concentration unit: g / L) at 20°C, calculated according to the following Schnell formula.

[0096] [Mathematical Expression 1]

[0097] [η] = 1.23 × 10 -5 ×Mv 0.83

[0098] <Aromatic polycarbonate resin (A-2)>

[0099] The aromatic polycarbonate resin (A-2) is a non-branched polycarbonate resin other than the branched polycarbonate resin (A-1) described above, and preferably has repeating units as shown in the following formula (IV).

[0100] [Chemical Formula 8]

[0101]

[0102] In equation (IV), R 21 and R 22 Each of these groups independently represents a group selected from halogen atoms, alkyl groups with 1 to 18 carbon atoms, alkoxy groups with 1 to 18 carbon atoms, cycloalkyl groups with 6 to 20 carbon atoms, cycloalkoxy groups with 6 to 20 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 14 carbon atoms, aryloxy groups with 6 to 14 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, arylalkoxy groups with 7 to 20 carbon atoms, nitro, formyl, cyano, and carboxyl groups. X' represents a single bond, alkylene groups with 1 to 8 carbon atoms, alkylidene groups with 2 to 8 carbon atoms, cycloalkylene groups with 5 to 15 carbon atoms, cycloalkoxy groups with 5 to 15 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, -S-, -SO-, -SO2-, -O-, or -CO-. t and u each independently represent an integer from 0 to 4.

[0103] R in equation (IV) above 21 and R 22 The specific examples of the halogen atoms, alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 6 carbon atoms represented by each are the same as those for R mentioned above.1 and R 2 The groups described are the same. Specific examples of alkylene groups with 1 to 8 carbons, alkylidene groups with 2 to 8 carbons, cycloalkylene groups with 5 to 15 carbons, and cycloalkylidene groups with 5 to 15 carbons represented by X' are the same as those described above for X. t and u each independently represent an integer from 0 to 4, preferably 0 to 2, more preferably 0 or 1.

[0104] Preferably, t and u are 0, and X' is a single bond or an alkyl group with 1 to 8 carbon atoms, or t and u are 0, and X' is an alkylidene group, especially an isopropylidene group. As an aromatic polycarbonate resin (A-2), it may contain two or more polycarbonate blocks.

[0105] As an aromatic polycarbonate resin (A-2), it is preferred that the content of repeating units in the above formula (IV) where t and u are 0 and X' is isopropylidene is preferably 90% by mass or more, more preferably 90.9% by mass or more, even more preferably 93.3% by mass or more, even more preferably 95% by mass or more, and even more preferably 100% by mass is the resin.

[0106] The viscosity-average molecular weight (Mv) of the aromatic polycarbonate resin (A-2) is typically 10,000 to 50,000, preferably 13,000 to 35,000, and more preferably 14,000 to 28,000.

[0107] The viscosity-average molecular weight (Mv) was calculated using Schnell's formula, just like that of branched polycarbonate resins (A-1).

[0108] <Polycarbonate Resin (A)>

[0109] In the case where the polycarbonate resin (A) of the present invention comprises, for example, a branched polycarbonate resin (A-1) and an aromatic polycarbonate resin (A-2) other than the branched polycarbonate resin (A-1), the content of the branched polycarbonate resin (A-1) is preferably 40% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, and can be 100% by mass. The content of the aromatic polycarbonate resin (A-2) is the remaining portion of the branched polycarbonate resin (A-1).

[0110] The branching rate of the polycarbonate resin (A) is 0.30 mol% or more and 3.0 mol% or less. From the viewpoint of further improving the thin-wall flame retardancy, it is preferably 0.35 mol% or more, more preferably 0.40 mol% or more, even more preferably 0.43 mol% or more, and even more preferably 0.45 mol% or more. From the viewpoint of obtaining good thin-wall flame retardancy, light transmittance, mechanical properties, formability, and flowability, it is preferably 2.5 mol% or less, even more preferably 2.0 mol% or less, even more preferably 1.5 mol% or less, and even more preferably 1.0 mol% or less.

[0111] The branching rate of polycarbonate resin (A) refers to the molar amount of structural units derived from the branching agent (expressed as mol%) relative to the total molar amount of structural units derived from the branching agent, structural units derived from the branching agent, and terminal units used in the manufacture of branched polycarbonate resin (A-1) and aromatic polycarbonate resin (A-2). The molar amount of structural units derived from the branching agent is calculated as (molar amount of structural units derived from the branching agent / (total molar amount of structural units derived from the branching agent + structural units derived from the branching agent + terminal units) × 100 (expressed as mol%)). The branching rate can be determined by... 1 Actual measurements were performed using H-NMR.

[0112] When two or more resins are used as polycarbonate resin (A), the branching rate of the mixture of the two or more resins is taken as the branching rate of polycarbonate resin (A).

[0113] The viscosity-average molecular weight of the polycarbonate resin (A) is preferably 10,000 to 50,000, more preferably 13,000 to 35,000, even more preferably 15,000 to 30,000, even more preferably 17,000 to 28,000, and even more preferably 20,000 to 25,000. If the viscosity-average molecular weight of the polycarbonate resin (A) is within the above range, a polycarbonate resin composition that can further improve the balance of flame retardancy, light transmittance, and mechanical properties, and has better formability, can be obtained. The viscosity-average molecular weight, like that of the branched polycarbonate resin (A-1), is a value calculated using Schnell's formula.

[0114] When two or more resins are used as polycarbonate resin (A), the viscosity-average molecular weight of the mixture of the two or more resins is taken as the viscosity-average molecular weight of polycarbonate resin (A).

[0115] <Manufacturing Method of Polycarbonate Resin (A)>

[0116] The polycarbonate resin (A) is not particularly limited and can be manufactured by known methods.

[0117] As a method for manufacturing polycarbonate resin (A), examples include methods that use bisphenols and carbonate precursors as raw materials to manufacture it via solution method (interfacial polycondensation) or melt method (transesterification). That is, polycarbonate resin (A) can be manufactured in the presence of a capping agent as needed via interfacial polycondensation, in which bisphenols react with carbonate precursors such as alkyl chloride, or via transesterification, in the presence of bisphenols and carbonate precursors such as diphenyl carbonate.

[0118] The interfacial polycondensation method is not particularly limited. It can be a one-step method in which a diphenol reacts with a carbonate precursor to obtain a polycarbonate resin, or a two-step method in which a diphenol reacts with a carbonate precursor to produce a polycarbonate oligomer, and then the obtained polycarbonate oligomer is reacted with a diphenol added as needed to obtain a polycarbonate resin.

[0119] The following is a detailed explanation of a two-step method in the interfacial polycondensation process that reacts diphenols with carbonyl chloride.

[0120] The branched polycarbonate resin (A-1) and aromatic polycarbonate resin (A-2) constituting the polycarbonate resin (A) can each be manufactured as follows: by a step (1) of producing a polycarbonate oligomer by reacting a diphenol with a carbonyl chloride in an organic solvent, followed by a step (2) of reacting the polycarbonate oligomer, the diphenol, and a capping agent added as needed to produce a polycarbonate resin.

[0121] (Process (1))

[0122] In this process, a polycarbonate oligomer with chloroformate groups is produced by reacting a diphenol with a carbonyl chloride in an organic solvent.

[0123] As a diphenol, in the case of branched polycarbonate resin (A-1), the compound shown in formula (i) below is preferred, and in the case of aromatic polycarbonate resin (A-2), the compound shown in formula (ii) below is preferred.

[0124] [Chemical Formula 9]

[0125]

[0126] In equation (i), R 1 R 2 a, b, and X are the same as those recorded above.

[0127] [Chemical Formula 10]

[0128]

[0129] In equation (ii), R 21 R22 The values ​​t, u, and X' are the same as those recorded above.

[0130] Examples of diphenols represented by formulas (i) and (ii) above include: 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane and other bis(hydroxyphenyl)alkanes, 4,4′-dihydroxybiphenyl, bis(4-hydroxyphenyl)cycloalkanes, bis(4-hydroxyphenyl) ethers, bis(4-hydroxyphenyl) sulfides, bis(4-hydroxyphenyl) sulfones, bis(4-hydroxyphenyl) sulfoxides, bis(4-hydroxyphenyl) ketones, etc. These diphenols can be used individually or in combination of two or more.

[0131] Among them, bis(hydroxyphenyl)alkane-based diphenols are preferred, and bisphenol A is more preferred. When using bisphenol A as the diphenol, a branched polycarbonate resin (A-1) in formula (i) above, in which X is isopropylidene and a = b = 0, and an aromatic polycarbonate resin (A-2) in formula (ii) above, in which X' is isopropylidene and t = u = 0, can be obtained.

[0132] Examples of diphenols other than bisphenol A include bis(hydroxyaryl)alkanes, bis(hydroxyaryl)cycloalkanes, dihydroxyaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, dihydroxydiaryl sulfones, dihydroxybiphenyls, dihydroxydiarylfluorenes, and dihydroxydiaryl fumonisins. These diphenols can be used individually or in combination of two or more.

[0133] Examples of bis(hydroxyaryl)alkanes include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, and 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane.

[0134] Examples of bis(hydroxyaryl)cycloalkanes include 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)norbornene, and 1,1-bis(4-hydroxyphenyl)cyclododecane. Examples of dihydroxyaryl ethers include 4,4′-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether.

[0135] Examples of dihydroxy diaryl sulfides include 4,4′-dihydroxydiphenyl sulfide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide. Examples of dihydroxy diaryl sulfoxides include 4,4′-dihydroxydiphenyl sulfoxide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide. Examples of dihydroxy diaryl sulfones include 4,4′-dihydroxydiphenyl sulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone.

[0136] Examples of dihydroxybiphenyl derivatives include 4,4′-dihydroxybiphenyl. Examples of dihydroxydiarylfluorene derivatives include 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Examples of dihydroxydiaryl fluorane derivatives include 1,3-bis(4-hydroxyphenyl)adamantane, 2,2-bis(4-hydroxyphenyl)adamantane, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

[0137] Examples of diphenols other than those mentioned above include 4,4'-[1,3-phenylenebis(1-methylethoxy)]bisphenol, 10,10-bis(4-hydroxyphenyl)-9-anthrone, and 1,5-bis(4-hydroxyphenylthio)-2,3-dioxapentane.

[0138] Carbonyl chloride is typically obtained by reacting chlorine and carbon monoxide with activated carbon as a catalyst in a ratio of 1.01 to 1.3 moles of carbon monoxide to chlorine. When using carbonyl chloride gas, a gaseous carbonyl chloride containing approximately 1 to 30% by volume of unreacted carbon monoxide can be used. Alternatively, liquefied carbonyl chloride can also be used.

[0139] In step (1), to produce polycarbonate oligomers, an alkaline aqueous solution of diphenol, carbonyl chloride, and an organic solvent are introduced into a reactor for reaction. Ideally, the amount of organic solvent used is selected such that the volume ratio of the organic solvent phase to the aqueous phase is 5 / 1 to 1 / 7, preferably 2 / 1 to 1 / 4. In the reactor, the temperature of the reaction product rises due to the heat generated by the chloroformation reaction of the terminal groups of the diphenol using carbonyl chloride and the decomposition reaction of carbonyl chloride using alkali. Therefore, it is preferable to cool the reaction product so that the temperature is 0 to 50°C, preferably 5 to 40°C. Regarding the amount of carbonyl chloride used, it is preferable to use an excess of 1.1 to 1.5 moles of carbonyl chloride relative to 1 mole of diphenol. The reaction solution obtained after the reaction is separated into an aqueous phase and an organic phase, yielding an organic phase containing polycarbonate oligomers. The weight-average molecular weight of the obtained polycarbonate oligomers is typically 5000 or less, and the degree of polymerization is typically 20 polymers or less, preferably 2 to 10 polymers.

[0140] In the manufacture of the aforementioned polycarbonate oligomers, an amine polymerization catalyst used in the subsequent step (2) can be used to promote the reaction. End-capping agents, which are used as molecular weight regulators for polycarbonate, can be used. Examples of compounds used as end-capping agents include monohydric phenols such as phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, 3-pentadecanylphenol, bromophenol, tribromophenol, and nonylphenol. Among these, p-tert-butylphenol, p-cumylphenol, and phenol are preferred from the perspectives of economy and ease of acquisition. Furthermore, by using 3-pentadecanylphenol, the flowability of the obtained polycarbonate can be significantly improved.

[0141] The reactor used in the manufacture of polycarbonate oligomers is preferably a static mixer. A static mixer is preferably a tubular reactor containing internal units that divide, switch, and reverse the fluid flow. Following the static mixer, further use of a trough-type stirred tank with a stirrer can promote oligomerization; therefore, it is preferable to use such reactors in combination.

[0142] Through step (1), a reaction mixture containing polycarbonate oligomers with chloroformate groups is obtained. The reaction mixture is separated into an organic phase containing polycarbonate oligomers and an aqueous phase by means of separation methods such as static separation. The organic phase containing polycarbonate oligomers is used in step (2) described later.

[0143] (Process (2))

[0144] In step (2), the polycarbonate oligomer obtained in step (1), a desired diphenol, and a desired end-capping agent are reacted to produce a polycarbonate resin. The polycarbonate oligomer and diphenol are subjected to a polycondensation reaction to adjust the molecular weight to the target molecular weight range. The polycondensation reaction is carried out until the viscosity-average molecular weight of the obtained polycarbonate resin is within the above range.

[0145] Specifically, the organic solvent phase containing polycarbonate oligomers separated in step (1), the end-capping agent to be used as needed, the polymerization catalyst to be used as needed, the organic solvent, the alkaline aqueous solution and the alkaline aqueous solution of the diphenol are mixed and interfacial polycondensation is carried out at a temperature typically in the range of 0 to 50°C, preferably 20 to 40°C.

[0146] The alkali, organic solvent, and capping agent used in the alkaline aqueous solution in this process can be the same substances described in step (1) above. The amount of organic solvent used in step (2) is usually selected such that the volume ratio of the organic phase to the aqueous phase is preferably 7 / 1 to 1 / 1, more preferably 5 / 1 to 2 / 1.

[0147] The reactor used in step (2) can be completed using only one reactor, depending on the reactor's processing capacity. If necessary, multiple reactors, such as a second reactor and a third reactor, can be used. These reactors can be stirred tanks, multi-stage tower-type stirred tanks, stirred tankless tanks, static mixers, pipeline mixers, orifice plate mixers, and / or piping, etc.

[0148] The resulting reaction solution contains an organic solvent phase containing polycarbonate resin and an aqueous phase containing unreacted diphenols; therefore, oil-water separation is performed. Examples of separation devices include a settling tank and a centrifuge. The separated organic solvent phase containing polycarbonate resin is then subjected to alkali washing, acid washing, and pure water washing sequentially to obtain a purified organic solvent phase containing polycarbonate resin. This purified organic solvent phase is then concentrated as needed, followed by kneading and warm water granulation to obtain polycarbonate resin powder. Since the obtained polycarbonate resin powder contains residual organic solvent, it is dried by heat treatment or other methods to obtain polycarbonate resin powder with the organic solvent removed. The obtained polycarbonate resin powder can be granulated using a granulator and other methods to form various molded shapes.

[0149] (Branching agent)

[0150] By adding any branching agent, a branched polycarbonate resin (A-1) can be manufactured. By not adding a branching agent, an aromatic polycarbonate resin (A-2) can be manufactured. The branching agent can be added in both steps (1) and / or (2) above. When added in step (1), it is added together with the diphenol and carbonyl chloride and reacted. Although it varies depending on the branching agent used, the branching agent shown in formula (iii) described later is soluble in alkaline aqueous solution, so it is desirable to dissolve it in alkaline aqueous solution before introduction. In addition, for branching agents that are difficult to dissolve in alkaline aqueous solution, it is desirable to dissolve them in organic solvents such as dichloromethane before introduction.

[0151] The branching agent can be added in either step (1) or step (2), or in both steps (1) and (2). The branching agent can also be further added in step (2). Regarding the amount of branching agent added, based on the total amount of branching agent added in steps (1) and (2), relative to the total molar amount of the diphenol compound, branching agent, and end-capping agent added as needed, it is preferable to ultimately add 0.30 mol% or more and 3.0 mol% or less. By setting the above-mentioned amount, a branched polycarbonate resin (A-1) having the above-mentioned preferred branching rate can be obtained. Relative to the total molar amount of the diphenol compound, branching agent, and end-capping agent added as needed, the amount of the branching agent added is preferably 0.35 mol% or more, more preferably 0.40 mol% or more, even more preferably 0.43 mol% or more, and even more preferably 0.45 mol% or more, from the viewpoint of obtaining good thin-wall flame retardancy, light transmittance, mechanical properties, formability, and flowability, preferably 2.5 mol% or less, even more preferably 2.0 mol% or less, even more preferably 1.5 mol% or less, and even more preferably 1.0 mol% or less.

[0152] Specifically, when manufacturing a branched polycarbonate resin having the branched structure shown in formula (II) above, a branching agent shown in formula (iii) below is used.

[0153] [Chemical Formula 11]

[0154]

[0155] In formula (iii), R represents a hydrogen atom or a group selected from alkyl groups having 1 to 5 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and aryl groups having 6 to 14 carbon atoms. 11 ~R 16 Each can independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.

[0156] The branching agent shown in formula (iii) above will be described in further detail.

[0157] R represents an alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, or n-pentyl. As R... 11 ~R 16 Alkyl groups having 1 to 5 carbon atoms can be represented by, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, etc., and halogen atoms can be represented by, for example, chlorine, bromine, fluorine, etc.

[0158] More specifically, the branching agent shown in formula (iii) above is 1,1,1-tris(4-hydroxyphenyl)methane; 1,1,1-tris(4-hydroxyphenyl)ethane; 1,1,1-tris(4-hydroxyphenyl)propane; 1,1,1-tris(2-methyl-4-hydroxyphenyl)methane; 1,1,1-tris(2-methyl-4-hydroxyphenyl)ethane; 1,1,1-tris(3-methyl-4-hydroxyphenyl)methane; 1,1,1-tris(3-methyl-4-hydroxyphenyl)ethane; 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)methane; 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane; 1,1,1-tris(3-chloro-4-hydroxyphenyl)methane; 1,1,1-tris(3-chloro-4-hydroxyphenyl)ethane; 1,1,1-tris(3,5-dichloro-4-hydroxyphenyl)ethane; 1,1,1-tris(3,5-dichloro-4-hydroxyphenyl)ethane; 1,1,1-Tris(3,5-dichloro-4-hydroxyphenyl)methane; 1,1,1-Tris(3-bromo-4-hydroxyphenyl)methane; 1,1,1-Tris(3-bromo-4-hydroxyphenyl)methane; 1,1,1-Tris(3-bromo-4-hydroxyphenyl)methane; 1,1,1-Tris(3,5-dibromo-4-hydroxyphenyl)methane; 1,1,1-Tris(3,5-dibromo-4-hydroxyphenyl)methane, 4,4'-[1-[4-] 1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethide]bisphenol; α,α',α”-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene; 1-[α-methyl-α-(4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(4”-hydroxyphenyl)ethyl]benzene; phloroglucinol, trimellitic acid, indigo bibis(o-cresol), and other compounds having three or more functional groups. Among these, from the viewpoints of availability, reactivity, and economy, 1,1,1-tris(4-hydroxyphenyl)ethane (hereinafter sometimes abbreviated as THPE) is preferred.

[0159] By using the branching agent shown in formula (iii) above, a polycarbonate resin having the branched structure shown in formula (II) above can be manufactured. The polycarbonate resin obtained by the above manufacturing method includes at least a branched polycarbonate resin having one structural unit derived from the branching agent shown in formula (iii), and may also include a branched polycarbonate resin having two or more structural units derived from the branching agent shown in formula (iii). The case of a branched polycarbonate resin containing two or more structural units derived from such a branching agent also falls under the category of branched polycarbonate resin (A-1), and its branching rate can be determined by… 1 Actual measurements were performed using H-NMR.

[0160] <Polymerization Catalyst>

[0161] In both steps (1) and (2) above, a polymerization catalyst can be used, for example, an amine catalyst.

[0162] As amine-based catalysts, tertiary amines or their salts, or quaternary ammonium salts, can be used. Examples of tertiary amines include triethylamine, tributylamine, N,N-dimethylcyclohexylamine, pyridine, and dimethylaniline. Examples of tertiary amine salts include hydrochlorides and bromates of these tertiary amines. Examples of quaternary ammonium salts include trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, and tetrabutylammonium bromide. Tertiary amines are preferred as amine-based catalysts, and triethylamine is particularly preferred. If these catalysts are in a liquid state, they can be directly introduced, or dissolved in an organic solvent or water before introduction. Alternatively, solid catalysts can be dissolved in an organic solvent or water before introduction.

[0163] When a polymerization catalyst is used in step (2), the amount of polymerization catalyst, in molar ratio to the chloroformate groups of the polycarbonate oligomer obtained from step (1), is, for example, 0.0005 or more and 0.030 or less. If the amount of polymerization catalyst added in step (2) is within the above range, the flame retardancy of the obtained polycarbonate resin can be improved.

[0164] The amount of polymerization catalyst added in step (2), relative to the chloroformate groups of the polycarbonate oligomer, is more preferably 0.001 or more, more preferably 0.002 or more, more preferably 0.004 or more, more preferably 0.006 or more, more preferably 0.025 or less, and more preferably 0.020 or less.

[0165] [Perfluoroalkyl sulfonamide (B)]

[0166] In the polycarbonate resin composition of the present invention, the content of the perfluoroalkyl sulfonamide (B) (hereinafter also referred to as "perfluoroalkyl sulfonamide (B)") shown in formula (1) is 0.05 parts by mass or more and 2.0 parts by mass or less relative to 100 parts by mass of the polycarbonate resin (A). As the perfluoroalkyl sulfonamide (B) described above, only one type may be used alone, or two or more types may be used in combination.

[0167] [Chemical Formula 12]

[0168]

[0169] In equation (1), R 31 R represents a perfluoroalkyl group having 1 to 3 carbon atoms. 32 M represents a perfluoroalkyl group having 1 to 4 carbon atoms. + It represents a monovalent cation selected from at least one of lithium ions, sodium ions, and potassium ions.

[0170] From the perspective of further improving the flame retardancy of thin-walled structures, R 31 Preferably, it is a perfluoroalkyl group having 1 or 2 carbon atoms, more preferably a perfluoroalkyl group having 1 carbon atom, R 32 Preferably, it is a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a perfluoroalkyl group having 1 or 2 carbon atoms, and even more preferably a perfluoroalkyl group having 1 carbon atom.

[0171] The perfluoroalkyl group with 1 carbon atom is perfluoromethyl (-CF3 group), the perfluoroalkyl group with 2 carbon atom is perfluoroethyl (-CF2CF3 group), and the perfluoroalkyl group with 3 carbon atom is perfluorobutyl (-CF2CF2CF3 group).

[0172] From the perspective of improving the flame retardancy of thin-walled structures and suppressing yellowing, M + The ion is selected from at least one of lithium ions, sodium ions, and potassium ions, preferably selected from at least one of lithium ions and potassium ions, and more preferably potassium ions.

[0173] As the perfluoroalkyl sulfonyl imide (B) shown in formula (1) above, it is preferably selected from at least one of bis(trifluoromethanesulfonyl)imide potassium, bis(trifluoromethanesulfonyl)imide lithium, bis(trifluoromethanesulfonyl)imide sodium, nonafluoro-N-[(trifluoromethane)sulfonyl]butanesulfonamide potassium, nonafluoro-N-[(trifluoromethane)sulfonyl]butanesulfonamide sodium and nonafluoro-N-[(trifluoromethane)sulfonyl]butanesulfonamide lithium, more preferably selected from at least one of bis(trifluoromethanesulfonyl)imide potassium, bis(trifluoromethanesulfonyl)imide lithium and bis(trifluoromethanesulfonyl)imide sodium, further preferably selected from at least one of bis(trifluoromethanesulfonyl)imide potassium and bis(trifluoromethanesulfonyl)imide lithium, and even more preferably bis(trifluoromethanesulfonyl)imide potassium.

[0174] These compounds are available in commercially available form, for example, using the EF-N series manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.

[0175] In the polycarbonate resin composition of the present invention, the content of perfluoroalkyl sulfonamide (B) is 0.05 parts by weight or more and 2.0 parts by weight or less per 100 parts by weight of polycarbonate resin (A).

[0176] From the viewpoint of further improving thin-wall flame retardancy, the content of perfluoroalkyl sulfonamide (B) in the polycarbonate resin composition of the present invention is preferably 0.06 parts by weight or more relative to 100 parts by weight of polycarbonate resin (A), more preferably 0.07 parts by weight or more, even more preferably 0.09 parts by weight or more, even more preferably 0.13 parts by weight or more, even more preferably 0.18 parts by weight or more, and from the viewpoint of obtaining good light transmittance, color tone, and mechanical properties, preferably 1.8 parts by weight or less, more preferably 1.5 parts by weight or less, and even more preferably 1.2 parts by weight or less. When two or more perfluoroalkyl sulfonamides (B) are included, the total amount falls within the above range.

[0177] Regarding the total content of polycarbonate resin (A) and perfluoroalkyl sulfonamide (B) in the polycarbonate resin composition of the present invention, when the total content of the polycarbonate resin composition is set to 100% by mass, from the viewpoints of further suppressing the yellowing and cloudiness of the obtained molded article and further improving the flame retardancy and light transmittance of thin-walled parts, it is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, further preferably 98% by mass or more, and further preferably 99% by mass or more. The upper limit of the total content of polycarbonate resin (A) and perfluoroalkyl sulfonamide (B) is not particularly limited, for example, it is 100% by mass or less.

[0178] [Antioxidant (C)]

[0179] From the viewpoints of further suppressing yellowing and turbidity and further improving thin-wall flame retardancy and light transmittance, the polycarbonate resin composition of the present invention preferably further includes an antioxidant (C). As the antioxidant (C), known antioxidants can be used, and preferably at least one selected from phosphorus-based antioxidants and phenolic antioxidants.

[0180] Examples of phosphorus-based antioxidants include triphenyl phosphite, diphenyl(nonyl) phosphite, diphenyl(2-ethylhexyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, diphenyl(isooctyl) phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, diphenyl(isodecyl) phosphite, diphenylmon(tetrazyl) phosphite, phenyl(diisodecyl) phosphite, phenyldi(tetrazyl) phosphite, and so on. Tris(2-ethylhexyl) phosphate, Tris(isodecyl) phosphite, Tri(tridecyl) phosphite, Dibutyl hydrogen phosphite, Trilauryl trithiophosphite, Tetra(2,4-di-tert-butylphenyl)-4,4'-biphenyl diphosphite, 4,4'-isopropylidene diphenol dodecyl phosphite, 4,4'-isopropylidene diphenol tridecyl phosphite, 4,4'-isopropylidene diphenol tetradecyl phosphite, 4,4'-isopropylidene diphenol pentadecyl phosphite, 4,4'-butylidene bis( 3-Methyl-6-tert-butylphenyl) bis(tetrazyl) phosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, distearate pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetraphenyl dipropylene glycol diphosphite, 1,1,3-tris(2-methyl-4-bis(tetrazyl) phosphite-5-tert-butylphenyl)butane, 3,4,5,6-dibenzo-1,2-oxaphosphine, triphenylphosphine, diphenyl Butylphosphine, diphenyloctadecylphosphine, tris(p-tolyl)phosphine, tris(p-nonylphenyl)phosphine, tris(naphthyl)phosphine, diphenyl(hydroxymethyl)phosphine, diphenyl(acetoxymethyl)phosphine, diphenyl(β-ethylcarboxyethyl)phosphine, tris(p-chlorophenyl)phosphine, tris(p-fluorophenyl)phosphine, benzyldiphenylphosphine, diphenyl(β-cyanoethyl)phosphine, diphenyl(p-hydroxyphenyl)phosphine, diphenyl(1,4-dihydroxyphenyl)-2-phosphine, phenylnaphthylbenzylphosphine, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, etc.

[0181] Specifically, examples of phosphorus-based antioxidants include "Irgafos 168" (manufactured and trademarked by BASF JAPAN, Inc.), "Irgafos 12" (manufactured and trademarked by BASF JAPAN, Inc.), "Irgafos 38" (manufactured and trademarked by BASF JAPAN, Inc.), "ADKSTAB 329K" (manufactured and trademarked by ADEKA, Inc.), "ADKSTAB PEP-36" (manufactured and trademarked by ADEKA, Inc.), "ADKSTAB PEP-8" (manufactured and trademarked by ADEKA, Inc.), "ADKSTAB 2112" (manufactured and trademarked by ADEKA, Inc.), "Sandstab P-EPQ" (manufactured and trademarked by Clariant, Inc.), "Weston 618" (manufactured and trademarked by SI Group, Inc.), "Weston 619G" (manufactured and trademarked by SI Group, Inc.), "Weston 624" (manufactured and trademarked by SI Group, Inc.), and "Doverphos". Commercially available products include S-9228PC (manufactured by Dover Chemical Company).

[0182] Examples of phenolic antioxidants include triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. Tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoamide), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane, etc.

[0183] Specifically, commercially available products that serve as phenolic antioxidants include "Irganox 1010" (manufactured and trademarked by BASF JAPAN Co., Ltd.), "Irganox 1076" (manufactured and trademarked by BASF JAPAN Co., Ltd.), "Irganox 1330" (manufactured and trademarked by BASF JAPAN Co., Ltd.), "Irganox 3114" (manufactured and trademarked by BASF JAPAN Co., Ltd.), "Irganox 3125" (manufactured and trademarked by BASF JAPAN Co., Ltd.), "BHT" (manufactured and trademarked by Takeda Pharmaceutical Company Ltd.), "Cyanox 1790" (manufactured and trademarked by Solvay Corporation), and "Sumilizer GA-80" (manufactured and trademarked by Sumitomo Chemical Co., Ltd.).

[0184] The antioxidant (C) can be used alone or in combination of two or more. From the viewpoint of further suppressing yellowing and turbidity and further improving thin-wall flame retardancy and light transmittance, the content of the antioxidant (C) in the polycarbonate resin composition of the present invention is preferably 0.03 parts by weight or more, more preferably 0.05 parts by weight or more, even more preferably 0.07 parts by weight or more, and even more preferably 0.08 parts by weight or more, relative to 100 parts by weight of the polycarbonate resin (A). From the viewpoint of further improving thin-wall flame retardancy and obtaining good light transmittance, color tone, and mechanical properties, it is preferably 0.50 parts by weight or less, more preferably 0.20 parts by weight or less, and even more preferably 0.18 parts by weight or less. When using two or more antioxidants (C), the total amount falls within the above range.

[0185] [Mold Release Agent (D)]

[0186] From the viewpoint of improving demolding performance, the polycarbonate resin composition of the present invention preferably further comprises a mold release agent (D). As the mold release agent (D), there are no particular limitations as long as it can be combined with the polycarbonate resin and improve the demolding performance during molding. For example, beeswax, glyceryl monostearate, glyceryl tristearate, pentaerythritol monostearate, pentaerythritol tristearate, pentaerythritol tetrastearate, lignite wax, carboxylic acid esters, etc. can be used.

[0187] The release agent (D) may be used alone in one kind, or may be used in combination of two or more kinds. With respect to 100 parts by mass of the polycarbonate resin (A), the content of the release agent (D) in the polycarbonate-based resin composition of the present invention is preferably 0.01 part by mass or more, more preferably 0.02 part by mass or more, still more preferably 0.03 part by mass or more from the viewpoint of improving release performance; and from the viewpoint of further improving thin-wall flame retardancy and obtaining good light transmittance, hue and mechanical properties, the content is preferably 5.0 parts by mass or less, more preferably 2.0 parts by mass or less, still more preferably 1.0 part by mass or less, and further more preferably 0.5 part by mass or less. When two or more release agents (D) are used, the total amount shall fall within the above range.

[0188] [Silicone compound (E)]

[0189] The polycarbonate-based resin composition of the present invention preferably further comprises a silicone compound (E). When granulating the polycarbonate-based resin composition of the present invention, the silicone compound (E) has the effects of exerting lubricity, inhibiting yellowing, improving flame retardancy, and preventing appearance defects such as silver streaks during molding.

[0190] When the polycarbonate-based resin composition is used for optical applications, the difference in refractive index between the silicone compound (E) and the polycarbonate-based resin is preferably reduced. The refractive index of the silicone compound (E) is preferably 1.45 to 1.65, more preferably 1.48 to 1.60.

[0191] As the silicone compound (E), a silicone compound having a hydrocarbyl group with 1 to 12 carbon atoms bonded to a silicon atom can be used.

[0192] As the silicone compound (E), both the non-functional group-containing silicone compound (e1) and the functional group-containing silicone compound (e2) can be used.

[0193] In one embodiment of the present invention, the non-functional group-containing silicone compound (e1) is preferably used as the silicone compound (E).

[0194] The non-functional group-containing silicone compound (e1) is composed of (R S2 ) r SiO (4-r) / 2 [wherein, R S2 each independently represent a hydrocarbyl group having 1 to 12 carbon atoms, and r is an integer satisfying 0 < r ≤ 3.] a polymer or copolymer formed from the structural unit represented by. Examples of the hydrocarbyl group represented by R S2 include methyl, ethyl, phenyl and the like.

[0195] Specific examples of organosilicon compounds (e1) having no functional group include polydimethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydimethyldiphenylsiloxane, etc. Among them, from the viewpoints of maintaining transparency by adjusting compatibility with polycarbonate and refractive index, and improving the flame retardancy of molded articles, phenyl-containing polysiloxanes such as polymethylphenylsiloxane and polydimethyldiphenylsiloxane are preferably used.

[0196] In another aspect of the present invention, as the organosilicon compound (E), an organosilicon compound (e2) having a functional group is preferably used.

[0197] The organosilicon compound (e2) having a functional group is represented by (R S1 ) p (R S2 ) q SiO (4-p-q) / 2 [wherein R S1 each independently represents a functional group, R S2 each independently represents a hydrocarbyl group having 1 to 12 carbon atoms. In addition, p and q are each integers satisfying 0 < p ≤ 3, 0 ≤ q < 3, and 0 < p+q ≤ 3.] is a polymer or copolymer formed from the structural unit represented. Examples of the functional group represented by R S1 include alkoxy, aryloxy, polyalkyleneoxy, hydrido, hydroxyl, carboxyl, silanol, amino, mercapto, epoxy, vinyl, etc. Among them, alkoxy, hydrido, hydroxyl, epoxy and vinyl are preferred, and methoxy and vinyl are more preferred. Examples of the hydrocarbyl group represented by R S2 include methyl, ethyl, phenyl, etc.

[0198] Among the above organosilicon compounds (e2) having functional groups, the particularly useful compounds are functional group-containing organosilicon compounds formed from structural units containing phenyl as the hydrocarbyl group represented by R S2 in the above formula. The compound may contain one type of functional group as the functional group represented by R S1 in the above formula, or may contain multiple different types of functional groups as the functional group represented by R S1 in the above formula, or may be a mixture of these compounds. Compounds wherein the ratio of the functional group (R S1 ) / hydrocarbyl (R S2 ) in the above formula is 0.1 to 3, preferably 0.3 to 2, are preferred. The functional group-containing organosilicon compound may be in liquid form or in powder form. In the case of liquid compounds, those having a viscosity at room temperature of about 10 to 500,000 cSt are preferred.

[0199] Specifically, examples of organosilicon compounds (E) include commercially available products such as "KR-511" (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), "KR-2710" (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), "TSF437" (manufactured by Momentive Performance Material Co., Ltd., trade name), "TSF431" (manufactured by Momentive Performance Material Co., Ltd., trade name), "TSF433" (manufactured by Momentive Performance Material Co., Ltd., trade name), "TSF4300" (manufactured by Momentive Performance Material Co., Ltd., trade name), and "SFR320" (manufactured by Momentive Performance Material Co., Ltd., trade name).

[0200] The organosilicon compound (E) can be used alone or in combination of two or more. Regarding the content of the organosilicon compound (E) in the polycarbonate resin composition of the present invention, relative to 100 parts by weight of the polycarbonate resin (A), from the viewpoint of acting as a lubricant and inhibiting yellowing during granulation of the polycarbonate resin composition of the present invention, and from the viewpoint of preventing appearance defects such as silver streaks during molding, it is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, further preferably 0.10 parts by weight or more, and even more preferably 0.20 parts by weight or more. From the viewpoint of further improving the flame retardancy of thin walls, it is preferably 0.05 parts by weight or more, more preferably 0.10 parts by weight or more, further preferably 0.30 parts by weight or more, and even more preferably 0.50 parts by weight or more. From the viewpoint of obtaining good light transmittance, color tone, and mechanical properties, it is preferably 5.0 parts by weight or less, more preferably 2.0 parts by weight or less, and even more preferably 1.2 parts by weight or less. From the perspective of obtaining good light transmittance, color tone and mechanical properties, the content of organosilicon compound (E) can be less than 1.0 parts by weight or less than 0.5 parts by weight relative to 100 parts by weight of polycarbonate resin (A).

[0201] When the organosilicon compound (E) is a non-functional organosilicon compound (e1), from the viewpoint of balancing thin-wall flame retardancy with good light transmittance and color tone, its content relative to 100 parts by weight of polycarbonate resin (A) is preferably 0.10 parts by weight or more and 2.0 parts by weight or less, more preferably 0.30 parts by weight or more and 1.2 parts by weight or less, and even more preferably 0.60 parts by weight or more and 1.2 parts by weight or less. When the organosilicon compound (E) is a functional organosilicon compound (e2), its content is preferably 0.05 parts by weight or more and 1.0 parts by weight or less, more preferably 0.10 parts by weight or more and 0.50 parts by weight or less.

[0202] When using two or more organosilicon compounds (E), the total amount shall be within the range described above.

[0203] [Other Additives]

[0204] In the polycarbonate resin composition of the present invention, in addition to the components (A) to (E) described above, various additives may be included within a range that does not adversely affect the color, thin-wall flame retardancy, light transmittance, etc. of the obtained molded article. Examples of such additives include flame retardants other than perfluoroalkyl sulfonamide (B), polyethers, polytetrafluoroethylene, alicyclic epoxy compounds, ultraviolet absorbers, and diffusing agents.

[0205] Furthermore, in the polycarbonate resin composition of the present invention, from the viewpoint of improving light transmittance and color tone, the total content of the perfluoroalkane sulfonate metal salt and the aromatic sulfonate metal salt, which are flame retardants, is preferably less than 0.05 parts by weight, more preferably less than 0.03 parts by weight, even more preferably less than 0.01 parts by weight, even more preferably less than 0.005 parts by weight, even more preferably less than 0.001 parts by weight, and even more preferably the polycarbonate resin composition of the present invention does not contain the perfluoroalkane sulfonate metal salt and the aromatic sulfonate metal salt.

[0206] Examples of perfluoroalkane sulfonate metal salts include potassium trifluoromethanesulfonate, potassium nonafluorobutyrate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, sodium perfluorobutyrate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutyrate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutyrate, cesium perfluorooctanesulfonate, cesium perfluorohexanesulfonate, rubidium perfluorobutyrate, and rubidium perfluorohexanesulfonate.

[0207] Examples of aromatic sulfonic acid metal salts include, for example, disodium diphenyl sulfide-4,4'-disulfonate, dipotassium diphenyl sulfide-4,4'-disulfonate, potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, poly(ethylene terephthalate) polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, poly(2,6-dimethylphenylene ether) polysulfonate, poly(1,3-phenylene ether) polysulfonate, poly(1,4-phenylene ether) polysulfonate, poly(2,6-diphenylene ether) polysulfonate, lithium poly(2-fluoro-6-butylphenylene ether) polysulfonate, potassium benzenesulfonate, and benzene... Sodium sulfonate, sodium p-toluenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzene disulfonate, dipotassium naphthalene-2,6-disulfonate, calcium biphenyl-3,3'-disulfonate, sodium diphenyl sulfone-3-sulfonate, potassium diphenyl sulfone-3-sulfonate, dipotassium diphenyl sulfone-3,3'-disulfonate, dipotassium diphenyl sulfone-3,4'-disulfonate, sodium α,α,α-trifluoroacetophenone-4-sulfonate, dipotassium benzophenone-3,3'-disulfonate, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, sodium benzothiophene sulfonate, potassium diphenyl sulfoxide-4-sulfonate, formaldehyde condensates of sodium naphthalenesulfonate, and formaldehyde condensates of sodium anthracenesulfonate, etc.

[0208] The polycarbonate-based resin composition of the present invention can suppress the yellowing and cloudiness of the resulting molded articles and can improve the flame retardancy and light transmittance of thin-walled articles. Although it will be described in detail in the examples, it is specifically described here.

[0209] <Light transmittance>

[0210] From the viewpoint of further improving light transmittance, the total light transmittance of the 3mm thick portion of the three-section plate obtained by injection molding the polycarbonate resin composition of the present invention under the conditions of barrel temperature of 280°C, mold temperature of 80°C, and cycle time of 31 seconds is preferably 80% or more, more preferably 85% or more, further preferably 87% or more, and even more preferably 88% or more. From the viewpoint of light transmittance, the higher the above-mentioned total light transmittance, the more preferred it is; therefore, there is no particular upper limit, for example, it can be 100% or less, 95% or less, or 92% or less.

[0211] Furthermore, the total light transmittance of a 5mm thick plate obtained by injection molding the polycarbonate resin composition of the present invention under conditions of barrel temperature of 280°C, mold temperature of 80°C, and cycle time of 53 seconds is preferably 80% or more, more preferably 85% or more, even more preferably 87% or more, and even more preferably 88% or more.

[0212] From the viewpoint of light transmittance, the higher the total light transmittance described above is, the more preferable it is. Therefore, the upper limit is not particularly limited, and it is, for example, 100% or less, may be 95% or less, or may be 92% or less.

[0213] The above total light transmittance can be measured in accordance with JIS K7375:2008.

[0214] <YI value>

[0215] From the viewpoint of further suppressing the yellow tint of the resulting molded article, the YI value of the 3 mm thick portion of a three-step plate obtained by injection molding the polycarbonate resin composition of the present invention under the conditions of a cylinder temperature of 280°C, a mold temperature of 80°C, and a cycle time of 31 seconds is preferably 3.5 or less, more preferably 3.0 or less, and still more preferably 2.5 or less. From the viewpoint of further suppressing the yellow tint, the lower the above YI value is, the more preferable it is. Therefore, the lower limit is not particularly limited, and it is, for example, 0.1 or more, and may be 0.5 or more.

[0216] In addition, the YI value of a 5 mm thick plate obtained by injection molding the polycarbonate resin composition of the present invention under the conditions of a cylinder temperature of 280°C, a mold temperature of 80°C, and a cycle time of 53 seconds is preferably 6.0 or less, more preferably 5.5 or less, still more preferably 5.0 or less, and even more preferably 4.5 or less. From the viewpoint of further suppressing the yellow tint, the lower the above YI value is, the more preferable it is. Therefore, the lower limit is not particularly limited, and it is, for example, 0.1 or more, and may be 0.5 or more.

[0217] <Haze>

[0218] From the viewpoint of further suppressing the clouding of the resulting molded article, the haze of the 3 mm thick portion of a three-step plate obtained by injection molding the polycarbonate resin composition of the present invention under the conditions of a cylinder temperature of 280°C, a mold temperature of 80°C, and a cycle time of 31 seconds is preferably 3.0% or less, more preferably 2.0% or less, still more preferably 1.5% or less, and even more preferably 1.2% or less. From the viewpoint of further suppressing clouding, the lower the above haze is, the more preferable it is. Therefore, the lower limit is not particularly limited, and it is, for example, 0.01% or more, and may be 0.10% or more.

[0219] Furthermore, from the viewpoint of further suppressing the cloudiness of the obtained molded article, the haze of a 5mm thick sheet obtained by injection molding the polycarbonate resin composition of the present invention under conditions of barrel temperature of 280°C, mold temperature of 80°C, and cycle time of 53 seconds is preferably 4.0% or less, more preferably 3.0% or less, even more preferably 2.0% or less, and even more preferably 1.5% or less. From the viewpoint of further suppressing cloudiness, the lower the haze, the more preferred it is; therefore, the lower limit value is not particularly limited, for example, it can be 0.01% or more, or 0.10% or more.

[0220] The above-mentioned haze can be measured according to JIS K7375:2008.

[0221] <Thin-wall flame retardancy>

[0222] From the viewpoint of further improving the flame retardancy of thin-walled structures, the flame retardancy of a 1.5 mm thick sheet obtained by injection molding the polycarbonate resin composition of the present invention under conditions of barrel temperature of 280°C, mold temperature of 80°C, and cycle time of 18 seconds is preferably V-0 as specified in the UL94 standard. That is, the polycarbonate resin composition of the present invention can achieve a very high degree of flame retardancy for thin-walled structures.

[0223] 2. Method for manufacturing polycarbonate-based resin compositions

[0224] The polycarbonate resin composition of the present invention can be obtained by combining and mixing the above-mentioned components.

[0225] There are no particular limitations on the method of mixing or compounding; for example, methods such as using a belt mixer, Henschel mixer, Banbury mixer, drum mixer, single-screw extruder, twin-screw extruder, kneader, and multi-screw extruder can be used. Furthermore, the heating temperature during compounding is typically selected within the range of 240–330°C, preferably 250–320°C.

[0226] At this point, it is preferable to formulate the polycarbonate resin (A) such that the branching rate is 0.30 mol% or more and 3.0 mol% or less. For the branched polycarbonate resin (A-1) and the aromatic polycarbonate resin (A-2) other than the branched polycarbonate resin (A-1), from the viewpoint of further improving the thin-wall flame retardancy, the formulation can be such that the branching rate of the polycarbonate resin (A) is preferably 0.35 mol% or more, more preferably 0.40 mol% or more, even more preferably 0.43 mol% or more, even more preferably 0.45 mol% or more, and from the viewpoint of obtaining good thin-wall flame retardancy, light transmittance, mechanical properties, formability, and flowability, it is preferably 2.5 mol% or less, even more preferably 2.0 mol% or less, even more preferably 1.5 mol% or less, and even more preferably 1.0 mol% or less.

[0227] Other components besides polycarbonate resin (A) can also be pre-melted with polycarbonate resin or other thermoplastic resin, i.e. added in the form of masterbatch.

[0228] 3. Molded products

[0229] The polycarbonate-based resin composition of the present invention is preferably used to form molded articles. That is, the polycarbonate-based resin composition of the present invention is preferably used for molded articles, more preferably for translucent molded articles, and even more preferably for transparent molded articles.

[0230] The molded articles of the present invention are formed from the polycarbonate-based resin composition of the present invention.

[0231] That is, the molded articles of the present invention can be obtained by molding the polycarbonate-based resin composition of the present invention.

[0232] As a forming method, various well-known forming methods can be used, such as injection molding, injection compression molding, extrusion molding, profile extrusion molding, blow molding, stamping, vacuum forming, and foam forming.

[0233] Other components besides polycarbonate resin (A) can also be pre-melted and blended with polycarbonate resin (A) or other thermoplastic resins, i.e., added in the form of masterbatch.

[0234] It is preferable to granulate the polycarbonate resin composition and use the granules for molding. Various molded articles can be manufactured using conventional molding methods such as injection molding, injection compression molding, or extrusion molding, as well as special molding methods such as gas-assisted molding and profile extrusion molding.

[0235] When the molded article of the present invention is used as an appearance component, it is preferable to use molding techniques that improve the appearance, such as thermal cycling molding, high-temperature molds, and heat-insulating molds.

[0236] Due to its excellent flame retardancy, light transmittance, and color tone, the molded articles of this invention can be appropriately used as various resin lighting equipment covers, lenses, etc., such as lighting covers and display covers.

[0237] Furthermore, the molded articles of the present invention are preferably light-transmitting molded articles, and more preferably transparent molded articles.

[0238] Example

[0239] The present invention will be further described in detail below through embodiments, but the present invention is not limited to these embodiments.

[0240] 1. Manufacturing of branched polycarbonate resins

[0241] Manufacturing Example 1 (Manufacturing of Branched PC1: THPE 0.90 mol%)

[0242] (Polycarbon oligomer (i) synthesis process)

[0243] A sodium hydroxide aqueous solution of BPA was prepared by adding sodium dithionite at a concentration of 2000 ppm relative to the amount of BPA (bisphenol A) subsequently dissolved in a 5.6 wt% sodium hydroxide aqueous solution to dissolve BPA to a concentration of 13.5 wt%.

[0244] A sodium hydroxide aqueous solution of THPE was prepared by adding sodium dithionite at a concentration of 2000 ppm relative to the amount of THPE (1,1,1-tris(4-hydroxyphenylethane)) subsequently dissolved in a 5.6 wt% sodium hydroxide aqueous solution to dissolve THPE to a concentration of 11.3 wt%.

[0245] The above-mentioned sodium hydroxide aqueous solution of BPA was continuously fed into a tubular reactor with an inner diameter of 6 mm and a length of 30 m at a flow rate of 42 L / hr, sodium hydroxide aqueous solution of THPE at a flow rate of 0.87 L / hr, dichloromethane at a flow rate of 15 L / hr, and carbonyl chloride at a flow rate of 4.0 kg / hr. The tubular reactor has a jacketed section, and cooling water is circulated into the jacket to maintain the temperature of the reaction solution below 40°C.

[0246] The reaction liquid from the tubular reactor was continuously introduced into a trough reactor with baffles and swept blades, with an internal volume of 40L. Further additions were made to the reactor, including an aqueous solution of BPA in sodium hydroxide at 2.8L / hr, an aqueous solution of 25wt% sodium hydroxide at 0.07L / hr, water at 17L / hr, an aqueous solution of 1wt% triethylamine at 0.69L / hr, and a dichloromethane solution of PTBP (4.0wt%) at 4.6L / hr.

[0247] The reaction liquid overflowing from the trough reactor was continuously pumped out and allowed to stand, thereby separating and removing the aqueous phase and collecting the dichloromethane phase.

[0248] The obtained polycarbonate oligomer had a concentration of 330 g / L and a chloroformate group concentration of 0.72 mol / L.

[0249] (Manufacturing process of polycarbonate resins)

[0250] In a 50L trough reactor equipped with baffles, paddle-type stirring blades and a cooling jacket, 15L of the previously obtained polycarbonate oligomer solution, 10.2L of dichloromethane and 2.8mL of triethylamine were added and mixed.

[0251] A sodium hydroxide aqueous solution of BPA (prepared by dissolving 1166g of BPA in an aqueous solution of 639g NaOH and 2.3g sodium dithionite in 9.3L of water) was added to the mixture, and a polymerization reaction was carried out for 60 minutes.

[0252] To dilute, 10 L of dichloromethane was added and stirred for 10 minutes. The mixture was then separated into an organic phase containing polycarbonate resin and an aqueous phase containing excess BPA and NaOH. The organic phase was then separated.

[0253] The obtained polycarbonate dichloromethane solution was washed sequentially with 15% (v / v) of 0.03 mol / L sodium hydroxide aqueous solution and 0.2 N hydrochloric acid, followed by repeated washing with pure water until the conductivity of the aqueous phase after washing was below 0.01 μS / m. The resulting polycarbonate resin dichloromethane solution was concentrated and pulverized, and the resulting sheet was dried under reduced pressure at 120 °C.

[0254] The obtained branched PC1 through 1 The branching rate determined by H-NMR was 0.90 mol%, and the viscosity-average molecular weight Mv determined according to ISO 1628-4 (1999) was 22800.

[0255] 2. Physical property determination of polycarbonate resin (A)

[0256] (1) Branching rate of polycarbonate resin (A)

[0257] Regarding the branching rate of polycarbonate resin (A), by... 1 The result was determined by H-NMR. It was calculated as the molar amount of structural units from the branching agent / (total molar amount of structural units from the diphenol + structural units from the branching agent + terminal units) × 100 (expressed as mol%).

[0258] (2) Viscosity-average molecular weight of polycarbonate resin (A)

[0259] The viscosity-average molecular weight Mv of polycarbonate resin (A) was determined by measuring the intrinsic viscosity [η] of a dichloromethane solution (concentration unit: g / L) at 20°C using an Ubbelohde viscometer and calculated using the following Schnell formula.

[0260] In Tables 1-5, the actual value calculated based on the measured intrinsic viscosity is rounded to the nearest multiple of 1000 and shown as the viscosity-average molecular weight Mv.

[0261] [Mathematical Expression 2]

[0262] [η] = 1.23 × 10 -5 ×Mv 0.83

[0263] 3. Raw materials used (resin and additives)

[0264] The following raw materials were used in the examples and comparative examples.

[0265] (A) Polycarbonate (PC) resin

[0266] (A-1) Branched polycarbonate resin (branched PC)

[0267] • Branched PC1: Manufacturing Example 1 above

[0268] (A-2): Aromatic polycarbonate resins

[0269] •PC1: TARFLON FN1700 [Made by Idemitsu Kosan Co., Ltd., a homopolymer carbonate made from bisphenol A, with a viscosity-average molecular weight of 17,700]

[0270] •PC2: TARFLON FN2200 [Manufactured by Idemitsu Kosan Co., Ltd., a homopolymer carbonate made from bisphenol A, with a viscosity-average molecular weight of 21,300]

[0271] •PC3: TARFLON FN2500 [Manufactured by Idemitsu Kosan Co., Ltd., a homopolymer carbonate made from bisphenol A, with a viscosity-average molecular weight of 23,500]

[0272] (B): Perfluoroalkyl sulfonyl imide

[0273] ·PFSI1: EF-N112 [Made by Mitsubishi Materials Electronic Chemicals Co., Ltd., potassium bis(trifluoromethanesulfonyl)imine]

[0274] ·PFSI2: EF-N115 [Made by Mitsubishi Materials Electronic Chemicals Co., Ltd., Lithium Bis(trifluoromethanesulfonyl)imide]

[0275] (B'): Flame retardants other than the perfluoroalkyl sulfonamide (B) shown in formula (1).

[0276] Flame retardant 1: KFBS [Made by Mitsubishi Materials Electronic Chemicals Co., Ltd., potassium nonafluorobutyrate]

[0277] Flame retardant 2: KSS [Made by Metropolitan Eximchem Pvt. Ltd, potassium diphenyl sulfone-3-sulfonate]

[0278] Flame retardant 3: EF-N442 [Made by Mitsubishi Materials Electronic Chemicals Co., Ltd., N,N-bis(nonafluorobutyryl)imine potassium]

[0279] Flame retardant 4: EF-N444 [Made by Mitsubishi Materials Electronic Chemicals Co., Ltd., bis(nonafluorobutanesulfonyl)imine ammonium]

[0280] Flame retardant 5: P12N111 [Made by Mitsubishi Materials Corporation, 1-ethyl-1-methylpyrrolidone bis(trifluoromethanesulfonyl)imide]

[0281] Flame retardant 6: TEATFSI [Made by Mitsubishi Materials Corporation, tetraethylammonium bis(trifluoromethanesulfonyl)imide]

[0282] Flame retardant 7: MTOAT FSI [Made by Mitsubishi Materials Corporation, methyltrioctylammonium bis(trifluoromethanesulfonyl)imide]

[0283] Flame retardant 8: EMIN111 [Made by Mitsubishi Materials Corporation, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide]

[0284] (C) Antioxidants

[0285] • Antioxidant 1: Irgafos 168 [manufactured by BASF JAPAN Corporation, tris(2,4-di-tert-butylphenyl) phosphite, abbreviated as Irg168 in the table]

[0286] • Antioxidant 2: Irganox 1076 [(manufactured by BASF JAPAN Corporation, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, abbreviated as Irg1076 in the table)]

[0287] • Antioxidant 3: Doverphos S-9228PC [manufactured by Dover Chemical, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, abbreviated as Doverphos in the table]

[0288] (D) Release agent

[0289] • Release agent 1: EW-440A [Manufactured by Riken Vitamins Co., Ltd., pentaerythritol tetrastearate]

[0290] • Release agent 2: S-100A [Manufactured by Riken Vitamins Co., Ltd., Glyceryl monostearate]

[0291] (E) Organosilicon compounds

[0292] • Organosilicon 1: KR-511 [Manufactured by Shin-Etsu Chemical Industry Co., Ltd., a reactive organosilicon compound containing phenyl, methoxy, and vinyl groups, refractive index = 1.518]

[0293] • Organosilicon 2: TSF437 [Made by Momentive Performance Material Co., Ltd., polydimethyldiphenylsiloxane, refractive index = 1.499]

[0294] • Organosilicon 3: SFR320 [Made by Momentive Performance Material Co., Ltd., polymethylphenylsiloxane, refractive index = 1.536]

[0295] 4. Examples and Comparative Examples

[0296] (4.1) Examples 1-17 and Comparative Examples 1-16

[0297] (1) Evaluation of the production of granules

[0298] The components were mixed in the proportions shown in Tables 1 to 4 and fed into a vented twin-screw extruder [Toshiba Machine Co., Ltd.: TEM-35]. The mixture was melt-mixed at a barrel temperature of 270–280°C, a screw speed of 250 rpm, and a discharge rate of 25 kg / hr to obtain granular samples for evaluation.

[0299] Here, the unit of the proportions of each component shown in Tables 1 to 4 is parts by mass.

[0300] (2) Evaluation of the production of molded products

[0301] (Test piece for evaluating the flame retardancy of thin-walled plates)

[0302] The evaluation granules obtained in each embodiment and comparative example were dried at 120°C for 5 hours, and then injection molded using an injection molding machine [manufactured by Toshiba Machine Co., Ltd., EC75PNII] at a barrel temperature of 280°C, a mold temperature of 80°C, and a cycle time of 18 seconds to produce plate-shaped test pieces with a length of 125 mm, a width of 13 mm, and a thickness of 1.5 mm.

[0303] (A three-segment plate was used to measure total transmittance, haze, and YI value)

[0304] The evaluation granules obtained in each embodiment and comparative example were dried at 120°C for 5 hours and then injection molded using an injection molding machine [NIIGATA MACHINE TECHNO Co., Ltd., MD50X] at a barrel temperature of 280°C, a mold temperature of 80°C, and a cycle time of 31 seconds to produce a 90mm × 50mm three-section plate (3mm thick section: 45mm × 50mm, 2mm thick section: 22.5mm × 50mm, 1mm thick section: 22.5mm × 50mm).

[0305] (Total transmittance, haze, and YI value were measured using a 5mm thick plate)

[0306] The evaluation granules obtained in each embodiment and comparative example were dried at 120°C for 5 hours, and then injection molded using an injection molding machine [Nissei Resin Kogyo Co., Ltd., ES1000] at a barrel temperature of 280°C, a mold temperature of 80°C, and a cycle time of 53 seconds to produce a 5mm thick plate of 90mm × 50mm.

[0307] (3) Evaluation

[0308] The following evaluations were conducted using the molded articles obtained in (2) above. The results are shown in Tables 1 to 4.

[0309] Thin-walled flame retardancy

[0310] Vertical burning tests were conducted on the 1.5mm plate-shaped test discs prepared above, according to UL94 standard. Based on the test results, flame retardancy was evaluated by classifying the discs into V-0, V-1, and V-2 grades. The case where no grade was met was designated V-out.

[0311] It should be noted that the UL94 standard refers to a method for evaluating flame retardancy based on the afterflame time after a test piece of a specified size, kept vertical, has been in contact with a burner flame for 10 seconds.

[0312] Total transmittance

[0313] The total light transmittance of the 3mm thick section and the 5mm thick section of the three-section board prepared above was measured. The total light transmittance was measured using an NDH 5000 testing machine manufactured by Nippon Denshoku Kogyo Co., Ltd., in accordance with JIS K7375:2008.

[0314] · Haze

[0315] The haze of the 3mm thick section and the 5mm thick section of the three-section board prepared above were measured. The haze was measured using an NDH 5000 testing machine manufactured by Nippon Denshoku Kogyo Co., Ltd., in accordance with JISK7375:2008.

[0316] ·YI value

[0317] For the 3mm thick section and the 5mm thick section of the 3-segment board prepared above, the YI value was measured using a SE2000 testing machine manufactured by Nippon Denshoku Kogyo Co., Ltd. under C light source and 2-degree field of view conditions.

[0318] [Table 1]

[0319]

[0320] [Table 2]

[0321]

[0322] [Table 3]

[0323]

[0324] [Table 4]

[0325]

[0326] (4.2) Examples 18-21

[0327] (1) Evaluation of the production of granules

[0328] The components were mixed in the proportions shown in Table 5, and granular samples for evaluation were obtained in the same manner as in Example 1.

[0329] (2) Evaluation of the production of molded products

[0330] Similar to Example 1, a 1.5 mm thick plate-shaped test piece and a 5 mm thick plate were prepared.

[0331] In addition, the evaluation granules obtained in each embodiment were dried at 120°C for 5 hours, and then injection molded using an injection molding machine [manufactured by Toshiba Machine Co., Ltd., EC75PNII] at a barrel temperature of 280°C, a mold temperature of 40°C, and a cycle time of 18 seconds to form a plate-shaped test piece with a length of 125 mm, a width of 13 mm, and a thickness of 1.2 mm.

[0332] (3) Evaluation

[0333] Thin-walled flame retardancy

[0334] Similar to Example 1, the thin-walled flame retardancy was evaluated using plate-shaped test pieces with a thickness of 1.5 mm.

[0335] In addition, the thin-walled flame retardancy was evaluated in the same way as that of the 1.2 mm thick plate-shaped test piece prepared above.

[0336] Total transmittance, haze, and YI value

[0337] Similar to Example 1, the total transmittance, haze, and YI value were measured for a 5 mm thick plate.

[0338] [Table 5]

[0339] Table 5

[0340]

[0341] As shown in Tables 1-5, the molded articles formed from the polycarbonate resin compositions of the examples have low YI values ​​and haze, and yellowing and turbidity are suppressed. Furthermore, it is shown that even under thin-wall conditions such as 1.5 mm or 1.2 mm thickness, the molded articles of the examples exhibit a flame retardancy of V-0 as specified in the UL94 standard, demonstrating good thin-wall flame retardancy. Based on the above, it can be understood that using the polycarbonate resin compositions of the present invention, molded articles with suppressed yellowing and turbidity, and improved thin-wall flame retardancy and light transmittance can be obtained.

[0342] Several embodiments and / or examples of the present invention have been described in detail above. Those skilled in the art can readily make various modifications to these exemplary embodiments and / or examples without substantially departing from the novel teachings and effects of the present invention. Therefore, these various modifications are also included within the scope of the present invention.

[0343] The full disclosure of the document described in this specification and the full disclosure of the specification of Japanese Patent Application No. 2021-064310, which claims priority in this application, are incorporated herein by reference.

Claims

1. A polycarbonate resin composition comprising a polycarbonate resin (A), a perfluoroalkyl sulfonylimide (B) as shown in formula (1) below, and an antioxidant (C), The branching rate of the polycarbonate resin (A), calculated by (molar amount of structural units from the branching agent) / (molar amount of structural units from the diphenol + molar amount of structural units from the branching agent + molar amount of terminal units) × 100, is 0.30 mol% or more and 3.0 mol% or less. The antioxidant (C) comprises phosphorus-based antioxidants and phenolic antioxidants. The phosphorus-based antioxidant comprises a variety selected from triphenyl phosphite, diphenyl(nonyl) phosphite, diphenyl(2-ethylhexyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, diphenyl(isooctyl) phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, diphenyl(isodecyl) phosphite, diphenylmono(tetrazyl) phosphite, and benzene phosphite. Di(isodecyl) ester, phenyl di(tridecyl) phosphite, tri(2-ethylhexyl) phosphite, tri(isodecyl) phosphite, tri(tridecyl) phosphite, dibutyl hydrogen phosphite, trilauryl trithiophosphite, tetra(2,4-di-tert-butylphenyl)-4,4'-biphenyl diphosphite, 4,4'-isopropylidene diphenol dodecyl phosphite, 4,4'-isopropylidene diphenol tridecyl phosphite, 4 4'-Isopropylidene diphenol tetradecyl phosphite, 4,4'-isopropylidene diphenol pentadecyl phosphite, 4,4'-butylidene bis(3-methyl-6-tert-butylphenyl) phosphite di(tetrazyl) ester, 1,1,3-tris(2-methyl-4-phosphite di(tetrazyl) ester-5-tert-butylphenyl)butane, 3,4,5,6-dibenzo-1,2-oxaphosphine, triphenylphosphine, diphenylbutylphosphine, diphenyloctadecyl At least one of alkylphosphine, tris(p-tolyl)phosphine, tris(p-nonylphenyl)phosphine, tris(naphthyl)phosphine, diphenyl(hydroxymethyl)phosphine, diphenyl(acetoxymethyl)phosphine, diphenyl(β-ethylcarboxyethyl)phosphine, tris(p-chlorophenyl)phosphine, tris(p-fluorophenyl)phosphine, benzyldiphenylphosphine, diphenyl(β-cyanoethyl)phosphine, diphenyl(p-hydroxyphenyl)phosphine, diphenyl(1,4-dihydroxyphenyl)-2-phosphine, and phenylnaphthylbenzylphosphine. The content of the perfluoroalkyl sulfonamide (B) is 0.05 parts by weight or more and 2.0 parts by weight or less per 100 parts by weight of the polycarbonate resin (A). The content of the antioxidant (C) is 0.03 parts by weight or more and 0.50 parts by weight or less per 100 parts by weight of the polycarbonate resin (A). The total content of perfluoroalkane sulfonate metal salts and aromatic sulfonate metal salts is less than 0.05 parts by weight relative to 100 parts by weight of the polycarbonate resin (A). In the above formula (1), R 31 R represents a perfluoroalkyl group having 1 to 3 carbon atoms. 32 M represents a perfluoroalkyl group having 1 to 4 carbon atoms. ＋ It represents a monovalent cation selected from at least one of lithium ions, sodium ions, and potassium ions.

2. The polycarbonate-based resin composition according to claim 1, wherein, The polycarbonate resin (A) comprises a branched polycarbonate resin (A-1).

3. The polycarbonate-based resin composition according to claim 1, wherein, The polycarbonate resin (A) comprises a branched polycarbonate resin (A-1) and an aromatic polycarbonate resin (A-2) other than the branched polycarbonate resin (A-1).

4. The polycarbonate-based resin composition according to claim 2, wherein, The branched polycarbonate resin (A-1) has repeating units as shown in formula (I) and branched structures as shown in formula (II). In the aforementioned formula (I), R 1 and R 2 Each group independently represents a group selected from halogen atoms, alkyl groups with 1 to 18 carbon atoms, alkoxy groups with 1 to 18 carbon atoms, cycloalkyl groups with 6 to 20 carbon atoms, cycloalkoxy groups with 6 to 20 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 14 carbon atoms, aryloxy groups with 6 to 14 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, arylalkoxy groups with 7 to 20 carbon atoms, nitro, formyl, cyano, and carboxyl groups; X represents a single bond, alkylene groups with 1 to 8 carbon atoms, alkylidene groups with 2 to 8 carbon atoms, cycloalkylene groups with 5 to 15 carbon atoms, cycloalkylidene groups with 5 to 15 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, -S-, -SO-, -SO2-, -O-, or -CO-; a and b each independently represent integers from 0 to 4. In formula (II), R represents a hydrogen atom or a group selected from alkyl groups having 1 to 5 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and aryl groups having 6 to 14 carbon atoms. 11 ~R 16 Each of these elements independently represents a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a halogen atom. PC represents the polycarbonate moiety, T represents the terminal group, and f, g, and h represent integers.

5. The polycarbonate-based resin composition according to claim 4, wherein, In the formula (I), a and b are 0, and X is a single bond or an alkyl group with 1 to 8 carbon atoms.

6. The polycarbonate-based resin composition according to claim 4, wherein, In the formula (I), a and b are 0, and X is an alkylidene group with 3 carbon atoms.

7. The polycarbonate-based resin composition according to claim 4, wherein, In the formula (I), a and b are 0, and X is isopropylidene.

8. The polycarbonate-based resin composition according to any one of claims 4 to 7, wherein, In formula (II), the polycarbonate portion represented by PC has repeating units derived from bisphenol A as shown in formula (III) below. 。 9. The polycarbonate-based resin composition according to any one of claims 4 to 7, wherein, The branched structure shown in formula (II) is a branched structure derived from 1,1,1-tris(4-hydroxyphenyl)ethane.

10. The polycarbonate-based resin composition according to any one of claims 4 to 7, wherein, In formula (II), T is a terminal group derived from a capping agent selected from phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, 3-pentadecanylphenol, bromophenol, tribromophenol, and nonylphenol.

11. The polycarbonate-based resin composition according to any one of claims 2 to 7, wherein, The branched polycarbonate resin (A-1) has a branching rate of 0.35 mol% or more and 2.5 mol% or less.

12. The polycarbonate-based resin composition according to any one of claims 2 to 7, wherein, The branched polycarbonate resin (A-1) has a branching rate of 0.45 mol% or more and 1.0 mol% or less.

13. The polycarbonate-based resin composition according to any one of claims 2 to 7, wherein, The branched polycarbonate resin (A-1) has a viscosity-average molecular weight of 10,000 to 50,000.

14. The polycarbonate-based resin composition according to any one of claims 2 to 7, wherein, The branched polycarbonate resin (A-1) has a viscosity-average molecular weight of 17,000 to 28,000.

15. The polycarbonate-based resin composition according to claim 3, wherein, The aromatic polycarbonate resin (A-2) is a non-branched polycarbonate resin other than the branched polycarbonate resin (A-1).

16. The polycarbonate-based resin composition according to claim 3, wherein, The aromatic polycarbonate resin (A-2) has repeating units as shown in formula (IV). In equation (IV), R 21 and R 22 Each of these groups independently represents a group selected from halogen atoms, alkyl groups with 1 to 18 carbon atoms, alkoxy groups with 1 to 18 carbon atoms, cycloalkyl groups with 6 to 20 carbon atoms, cycloalkoxy groups with 6 to 20 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 14 carbon atoms, aryloxy groups with 6 to 14 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, arylalkoxy groups with 7 to 20 carbon atoms, nitro, formyl, cyano, and carboxyl groups. X' represents a single bond, alkylene groups with 1 to 8 carbon atoms, alkylidene groups with 2 to 8 carbon atoms, cycloalkylene groups with 5 to 15 carbon atoms, cycloalkoxy groups with 5 to 15 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, -S-, -SO-, -SO2-, -O-, or -CO-. t and u each independently represent an integer from 0 to 4.

17. The polycarbonate-based resin composition according to claim 16, wherein, In formula (IV), t and u are 0, and X' is a single bond or an alkyl group with 1 to 8 carbon atoms.

18. The polycarbonate-based resin composition according to claim 16, wherein, In formula (IV), t and u are 0, and X' is an alkylidene group with 3 carbon atoms.

19. The polycarbonate-based resin composition according to claim 16, wherein, In formula (IV), t and u are 0, and X' is isopropylidene.

20. The polycarbonate-based resin composition according to claim 19, wherein, In the aromatic polycarbonate resin (A-2), the content of repeating units of formula (IV) where t and u are 0 and X' is isopropylidene is 90% or more by mass.

21. The polycarbonate-based resin composition according to claim 19, wherein, In the aromatic polycarbonate resin (A-2), the content of repeating units of formula (IV) with t and u being 0 and X' being isopropylidene groups is 100 by mass.

22. The polycarbonate-based resin composition according to claim 3, wherein, The viscosity-average molecular weight (Mv) of aromatic polycarbonate resin (A-2) is 10,000 to 50,000.

23. The polycarbonate-based resin composition according to claim 3, wherein, The viscosity-average molecular weight (Mv) of the aromatic polycarbonate resin (A-2) is 14,000 to 28,000.

24. The polycarbonate-based resin composition according to claim 3, wherein, The content of branched polycarbonate resin (A-1) in the polycarbonate resin (A) is 40% by mass or more, and the content of aromatic polycarbonate resin (A-2) is the remaining part of the branched polycarbonate resin (A-1).

25. The polycarbonate-based resin composition according to claim 3, wherein, The content of the branched polycarbonate resin (A-1) in the polycarbonate resin (A) is 50% by mass or more, and the content of the aromatic polycarbonate resin (A-2) is the remaining portion of the branched polycarbonate resin (A-1).

26. The polycarbonate-based resin composition according to claim 2, wherein, The content of the branched polycarbonate resin (A-1) in the polycarbonate resin (A) is 100% by mass.

27. The polycarbonate-based resin composition according to any one of claims 1 to 7, wherein, The branching rate of the polycarbonate resin (A) is 0.35 mol% or more and 2.5 mol% or less.

28. The polycarbonate-based resin composition according to any one of claims 1 to 7, wherein, The branching rate of the polycarbonate resin (A) is 0.45 mol% or more and 1.0 mol% or less.

29. The polycarbonate-based resin composition according to any one of claims 1 to 7, wherein, The viscosity-average molecular weight of the polycarbonate resin (A) is 10,000 to 50,000.

30. The polycarbonate-based resin composition according to any one of claims 1 to 7, wherein, The viscosity-average molecular weight of the polycarbonate resin (A) is 20,000 to 25,000.

31. The polycarbonate-based resin composition according to any one of claims 1 to 7, wherein, The polycarbonate resin (A) is a polycarbonate resin manufactured by interfacial polycondensation of a bisphenol with a carbonyl chloride or by transesterification of a bisphenol with a diphenyl carbonate in the presence of a capping agent added as needed.

32. The polycarbonate-based resin composition according to any one of claims 1 to 7, wherein, The perfluoroalkyl sulfonylimide (B) is selected from at least one of bis(trifluoromethanesulfonyl)imide potassium, bis(trifluoromethanesulfonyl)imide lithium, bis(trifluoromethanesulfonyl)imide sodium, nonafluoro-N-[(trifluoromethane)sulfonyl]butanesulfonamide potassium, nonafluoro-N-[(trifluoromethane)sulfonyl]butanesulfonamide sodium, and nonafluoro-N-[(trifluoromethane)sulfonyl]butanesulfonamide lithium.

33. The polycarbonate-based resin composition according to any one of claims 1 to 7, wherein, The content of the perfluoroalkyl sulfonamide (B) is 0.18 parts by weight or more and 1.2 parts by weight or less per 100 parts by weight of the polycarbonate resin (A).

34. The polycarbonate-based resin composition according to any one of claims 1 to 7, wherein, The total content of the polycarbonate resin (A) and the perfluoroalkyl sulfonamide (B) is 50% by mass or more relative to 100% by mass of the polycarbonate resin composition.

35. The polycarbonate-based resin composition according to any one of claims 1 to 7, wherein, The combined content of the polycarbonate resin (A) and the perfluoroalkyl sulfonamide (B) is 99% by mass or more relative to 100% by mass of the polycarbonate resin composition.

36. The polycarbonate-based resin composition according to any one of claims 1 to 7, wherein, The phenolic antioxidant is selected from triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. At least one of the following: (-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoamide), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, and 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane.

37. The polycarbonate-based resin composition according to any one of claims 1 to 7, wherein, The content of the antioxidant (C) is 0.08 parts by mass and less than 0.18 parts by mass relative to 100 parts by mass of the polycarbonate resin (A).

38. The polycarbonate-based resin composition according to any one of claims 1 to 7, wherein, It also contains mold release agent (D), The content of the release agent (D) is 0.01 parts by weight or more and 5.0 parts by weight or less per 100 parts by weight of the polycarbonate resin (A).

39. The polycarbonate-based resin composition according to claim 38, wherein, The release agent (D) is selected from one or more of beeswax, glyceryl monostearate, glyceryl tristearate, pentaerythritol monostearate, pentaerythritol tristearate, pentaerythritol tetrastearate, lignite ester wax and carboxylic acid esters.

40. The polycarbonate-based resin composition according to claim 38, wherein, The content of the release agent (D) is 0.03 parts by mass and less than 0.5 parts by mass relative to 100 parts by mass of the polycarbonate resin (A).

41. The polycarbonate-based resin composition according to any one of claims 1 to 7, wherein, It also contains organosilicon compounds (E), The content of the organosilicon compound (E) is 0.01 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of the polycarbonate resin (A).

42. The polycarbonate-based resin composition according to claim 41, wherein, The refractive index of the organosilicon compound (E) is 1.48 to 1.

60.

43. The polycarbonate-based resin composition according to claim 41, wherein, Organosilicon compounds (E) are organosilicon compounds with hydrocarbon groups having 1 to 12 carbon atoms bonded to silicon atoms.

44. The polycarbonate-based resin composition according to claim 41, wherein, The organosilicon compound (E) is selected from one or more organosilicon compounds (e1) without functional groups and organosilicon compounds (e2) with functional groups.

45. The polycarbonate-based resin composition according to claim 44, wherein, The organosilicon compound (e1) without functional groups is a polymer or copolymer formed from structural units shown in the following formula. (R S2 ) r SiO (4-r) / 2 In the formula, R S2 Each of the following groups independently represents a hydrocarbon group with 1 to 12 carbon atoms, where r is an integer satisfying 0 < r ≤ 3.

46. ​​The polycarbonate-based resin composition according to claim 44, wherein, The organosilicon compound (e1) without functional groups is selected from one or more of polydimethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane and polydimethyldiphenylsiloxane.

47. The polycarbonate-based resin composition according to claim 44, wherein, The organosilicon compound (e2) having functional groups is a polymer or copolymer formed from structural units shown in the following formula. (R S1 ) p (R S2 ) q SiO (4-p-q) / 2 In the formula, R S1 Each group independently represents a functional group selected from alkoxy, aryloxy, polyoxyalkylene, hydrogen, hydroxyl, carboxyl, silanol, amino, mercapto, epoxy, and vinyl groups. S2 Each of the groups independently represents a hydrocarbon group with 1 to 12 carbon atoms, and p and q are integers that satisfy 0 < p ≤ 3, 0 ≤ q < 3, and 0 < p + q ≤ 3, respectively.

48. The polycarbonate-based resin composition according to claim 47, wherein, In the organosilicon compound (e2) having functional groups, the functional group (R) S1 ) / hydrocarbon group (R S2 The value of ) is 0.3 to 2.

49. The polycarbonate-based resin composition according to claim 44, 47 or 48, wherein, The organosilicon compound (e2) with functional groups is a liquid or powder with a viscosity of 10 to 500,000 cSt at room temperature.

50. The polycarbonate-based resin composition according to claim 41, wherein, The content of the organosilicon compound (E) is 0.20 parts by mass or more and 1.2 parts by mass or less per 100 parts by mass of the polycarbonate resin (A).

51. The polycarbonate-based resin composition according to claim 41, wherein, The content of the organosilicon compound (E) is 0.20 parts by mass and less than 0.5 parts by mass relative to 100 parts by mass of the polycarbonate resin (A).

52. The polycarbonate-based resin composition according to claim 44, wherein, The content of the organosilicon compound (e1) without functional groups is 0.60 parts by mass or more and 1.2 parts by mass or less.

53. The polycarbonate-based resin composition according to claim 44, wherein, The content of the organosilicon compound (e2) having a functional group is 0.10 parts by mass or more and 0.50 parts by mass or less.

54. The polycarbonate-based resin composition according to any one of claims 1 to 7, wherein, It also contains additives selected from flame retardants other than perfluoroalkyl sulfonamides (B), polyethers, polytetrafluoroethylene, alicyclic epoxy compounds, ultraviolet absorbers, and diffusing agents.

55. The polycarbonate-based resin composition according to claim 54, wherein, Flame retardants other than perfluoroalkyl sulfonylimide (B) are flame retardants selected from perfluoroalkane sulfonate metal salts and aromatic sulfonate metal salts.

56. The polycarbonate-based resin composition according to any one of claims 1 to 7, wherein, It does not contain perfluoroalkane sulfonate metal salts or aromatic sulfonate metal salts.

57. The polycarbonate-based resin composition according to claim 55, wherein, The perfluoroalkane sulfonate metal salts are selected from potassium trifluoromethanesulfonate, potassium nonafluorobutyrate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, sodium perfluorobutyrate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutyrate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutyrate, cesium perfluorooctanesulfonate, cesium perfluorohexanesulfonate, rubidium perfluorobutyrate, and rubidium perfluorohexanesulfonate. Aromatic sulfonate metal salts are selected from disodium diphenyl sulfide-4,4'-disulfonate, dipotassium diphenyl sulfide-4,4'-disulfonate, potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, poly(ethylene terephthalate) polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, poly(2,6-dimethylphenylene ether) polysulfonate, poly(1,3-phenylene ether) polysulfonate, poly(1,4-phenylene ether) polysulfonate, poly(2,6-diphenylene ether) polysulfonate, lithium poly(2-fluoro-6-butylphenylene ether) polysulfonate, potassium benzenesulfonate, and sodium benzenesulfonate. Formaldehyde condensates of sodium p-toluenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzene disulfonate, dipotassium naphthalene-2,6-disulfonate, calcium biphenyl-3,3'-disulfonate, sodium diphenyl sulfone-3-sulfonate, potassium diphenyl sulfone-3-sulfonate, dipotassium diphenyl sulfone-3,3'-disulfonate, dipotassium diphenyl sulfone-3,4'-disulfonate, sodium α,α,α-trifluoroacetophenone-4-sulfonate, dipotassium benzophenone-3,3'-disulfonate, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, sodium benzothiophene sulfonate, potassium diphenyl sulfoxide-4-sulfonate, sodium naphthalenesulfonate, and sodium anthracenesulfonate.

58. The polycarbonate resin composition according to any one of claims 1 to 7, wherein the total light transmittance of the 3mm thick portion of the three-section plate obtained by injection molding the polycarbonate resin composition under the conditions of barrel temperature of 280°C, mold temperature of 80°C and cycle time of 31 seconds is 80% or more.

59. The polycarbonate-based resin composition according to claim 58, wherein, The total light transmittance of the 3mm thick section of the 3-section plate obtained by injection molding under the conditions of barrel temperature of 280℃, mold temperature of 80℃, and cycle time of 31 seconds is above 88% and below 92%.

60. The polycarbonate-based resin composition according to any one of claims 1 to 7, The total light transmittance of a 5mm thick plate obtained by injection molding the polycarbonate resin composition under the conditions of barrel temperature of 280°C, mold temperature of 80°C, and cycle time of 53 seconds is more than 80%.

61. The polycarbonate-based resin composition according to claim 60, wherein, The total light transmittance of the 5mm thick plate obtained by injection molding under the conditions of barrel temperature of 280℃, mold temperature of 80℃, and cycle time of 53 seconds is above 88% and below 92%.

62. The polycarbonate-based resin composition according to claim 58, wherein, Total transmittance was measured according to JIS K7375:2008.

63. The polycarbonate-based resin composition according to any one of claims 1 to 7, The haze of the 3mm thick section of the three-section plate obtained by injection molding the polycarbonate resin composition under the conditions of barrel temperature of 280°C, mold temperature of 80°C and cycle time of 31 seconds is less than 3.0%.

64. The polycarbonate-based resin composition according to claim 63, wherein, The haze of the 3mm thick section of the 3-segment plate obtained by injection molding under the conditions of barrel temperature of 280℃, mold temperature of 80℃, and cycle time of 31 seconds is above 0.10% and below 1.2%.

65. The polycarbonate resin composition according to any one of claims 1 to 7, wherein the haze of a 5 mm thick plate obtained by injection molding the polycarbonate resin composition under conditions of a barrel temperature of 280°C, a mold temperature of 80°C, and a cycle time of 53 seconds is 4.0% or less.

66. The polycarbonate-based resin composition according to claim 65, wherein, The haze of the 5mm thick plate obtained by injection molding under the conditions of barrel temperature of 280℃, mold temperature of 80℃, and cycle time of 53 seconds is above 0.10% and below 1.5%.

67. The polycarbonate-based resin composition according to claim 63, wherein, The haze was measured according to JIS K7375:2008.

68. The polycarbonate resin composition according to any one of claims 1 to 7, wherein a 1.5 mm thick sheet obtained by injection molding the polycarbonate resin composition under conditions of barrel temperature of 280°C, mold temperature of 80°C, and cycle time of 18 seconds has a flame retardancy of V-0 as specified in UL94 standard.

69. The polycarbonate-based resin composition according to any one of claims 1 to 7, The YI value of the 3mm thick portion of the three-section plate obtained by injection molding the polycarbonate resin composition under the conditions of barrel temperature of 280°C, mold temperature of 80°C and cycle time of 31 seconds is less than 3.

5.

70. The polycarbonate-based resin composition according to claim 69, wherein, The YI value of the 3mm thick section of the 3-segment plate obtained by injection molding under the conditions of barrel temperature of 280℃, mold temperature of 80℃, and cycle time of 31 seconds is above 0.5 and below 2.

5.

71. The polycarbonate resin composition according to any one of claims 1 to 7, wherein the YI value of a 5 mm thick plate obtained by injection molding the polycarbonate resin composition under the conditions of a barrel temperature of 280°C, a mold temperature of 80°C, and a cycle time of 53 seconds is 6.0 or less.

72. The polycarbonate-based resin composition according to claim 71, wherein, The YI value of the 5mm thick plate obtained by injection molding under the conditions of barrel temperature of 280℃, mold temperature of 80℃, and cycle time of 53 seconds is above 0.5 and below 4.

5.

73. Use of the polycarbonate resin composition according to any one of claims 1 to 72 for forming molded articles.

74. Use of the polycarbonate resin composition according to any one of claims 1 to 72 for forming translucent molded articles.

75. Use of the polycarbonate resin composition according to any one of claims 1 to 72 for forming transparent molded articles.

76. A method for manufacturing a polycarbonate resin composition, comprising the steps of combining and mixing and / or kneading a polycarbonate resin (A), a perfluoroalkyl sulfonamide (B) as shown in formula (1) below, and an antioxidant (C). The branching rate of the polycarbonate resin (A), calculated by (molar amount of structural units from the branching agent) / (molar amount of structural units from the diphenol + molar amount of structural units from the branching agent + molar amount of terminal units) × 100, is 0.30 mol% or more and 3.0 mol% or less. The content of the perfluoroalkyl sulfonamide (B) is 0.05 parts by weight or more and 2.0 parts by weight or less per 100 parts by weight of the polycarbonate resin (A). In the above formula (1), R 31 R represents a perfluoroalkyl group having 1 to 3 carbon atoms. 32 M represents a perfluoroalkyl group having 1 to 4 carbon atoms. ＋ It represents a monovalent cation selected from at least one of lithium ions, sodium ions, and potassium ions.

77. The method for manufacturing the polycarbonate-based resin composition according to claim 76, wherein, The mixing and / or compounding method is the use of a belt mixer, Henschel mixer, Banbury mixer, drum mixer, single-screw extruder, twin-screw extruder, kneader, or multi-screw extruder.

78. The method for manufacturing the polycarbonate-based resin composition according to claim 76, wherein, The heating temperature during mixing is 240℃~330℃.

79. The method for manufacturing the polycarbonate-based resin composition according to claim 76, wherein, The branching rate of the polycarbonate resin (A) is ≥0.45 mol% and ≤1.0 mol%.

80. A molded article formed from any one of the polycarbonate-based resin compositions according to claims 1 to 72.

81. The molded article according to claim 80, wherein it is an illumination cover or a lens.

82. The molded article according to claim 80, wherein it is a translucent molded article.

83. The molded article according to claim 80, wherein it is a transparent molded article.

84. The molded article according to claim 80, wherein it is a resin lighting device cover.

85. A method for manufacturing a molded article, comprising: a step of molding a polycarbonate-based resin composition according to any one of claims 1 to 72.

86. The method for manufacturing a molded article according to claim 85, wherein, The forming methods include injection molding, injection compression molding, extrusion molding, profile extrusion molding, blow molding, stamping, vacuum forming, or foaming molding.

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