JP2016141721A - Polycarbonate resin composition and polycarbonate resin molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition capable of enhancing fire retardancy and heat resistance at the same time and a molded body thereof.SOLUTION: There is provided a polycarbonate resin composition containing a polycarbonate resin (A) containing at least a structural unit derived from a dihydroxy compound (a) and a metal salt compound (B), where the dihydroxy compound (a) is a dihydroxy compound represented by the formula (1), a percentage of the structural unit derived from the dihydroxy compound (a) of the structural unit derived from all dihydroxy compounds in the polycarbonate resin (A) is 10 to 50 mass%, and the metal salt compound (B) is 0.01 to 1.00 pts.mass based on 100 pts.mass of the polycarbonate resin (A).SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition and a polycarbonate resin molded body. More specifically, the present invention relates to a polycarbonate resin composition and a polycarbonate resin molded article excellent in flame retardancy and heat resistance.

  Polycarbonate resins are resins having excellent heat resistance, mechanical properties, and electrical characteristics, and are widely used, for example, as automotive materials, electrical and electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields. In particular, the flame-retardant polycarbonate resin composition is suitably used as a member of OA / information equipment such as computers, notebook computers, mobile phones, printers, and copying machines.

As means for imparting flame retardancy to a polycarbonate resin, conventionally, a halogen-based flame retardant or a phosphorus-based flame retardant has been added to the polycarbonate resin.
However, a polycarbonate resin composition containing a halogen-based flame retardant containing chlorine or bromine may lead to a decrease in thermal stability or corrosion of a molding machine screw or molding die during molding processing. there were.

  In addition, the polycarbonate resin composition containing a phosphorus-based flame retardant inhibits the high transparency that is characteristic of the polycarbonate resin and causes a decrease in impact resistance and heat resistance, so that its use is limited. was there. Specifically, in recent years, as the electrical and electrical equipment becomes shorter, lighter and thinner, the equipment temperature may increase, and the flame retardant polycarbonate resin used is also required to have further heat resistance. Then, such a request could not be met.

In addition, these halogen-based flame retardants and phosphorus-based flame retardants may cause environmental pollution at the time of product disposal and recovery, and in recent years, these flame retardants can be made flame retardant without using these flame retardants. It is desired.
Under such circumstances, in recent years, metal salt compounds typified by organic alkali metal salt compounds and organic alkaline earth metal salt compounds have been studied as useful flame retardants. Examples of the flame retardant technology of polycarbonate using such a metal salt compound include, for example, a method using an alkali metal salt of perfluoroalkylsulfonic acid having 4 to 8 carbon atoms (see Patent Document 1), non-halogen aromatic sulfonic acid. Examples include a method of imparting flame retardancy to an aromatic polycarbonate resin composition using an alkali metal salt compound of an aromatic sulfonic acid, such as a method of containing a sodium salt (see Patent Document 2).

Furthermore, a technique for improving flame retardancy by applying a branched polycarbonate resin to a part of the polycarbonate resin has been proposed. (For example, see publicly known document 3)
On the other hand, Patent Document 4 describes a polycarbonate resin composition obtained by making a polycarbonate resin made from a specific monomer a raw material with a phosphorus flame retardant.

Japanese Patent Publication No. 47-40445 JP 2000-169696 A JP 2000-336260 A US Pat. No. 6,174,942

  However, the flame retardancy imparted to the polycarbonate resin by the metal salt compound as described above is catalytic, and even if the blending amount is increased in order to obtain high flame retardancy, no effect is obtained or On the contrary, there is a problem that flame retardancy deteriorates, and a polycarbonate resin composition containing a branched polycarbonate resin has not yet been satisfactory with respect to the thin flame retardance required in recent years.

Further, a polycarbonate resin composition obtained by making a polycarbonate resin made from a specific monomer a flame retardant with a phosphorus-based flame retardant also has a drawback that it cannot withstand actual use because its heat resistance is remarkably lowered.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a polycarbonate resin composition and a molded body thereof that can simultaneously improve flame retardancy and heat resistance.

The inventors of the present invention have intensively studied to solve the above problems, and as a result, it is possible to improve both flame retardancy and heat resistance by adding a predetermined amount of a metal salt compound to a polycarbonate resin containing a specific structure. The headline and the present invention were completed.
That is, the gist of the present invention resides in the polycarbonate resin composition and the polycarbonate resin molded article according to the following [1] to [12].

[1] A polycarbonate resin composition containing at least a polycarbonate resin (A) containing a structural unit derived from a dihydroxy compound (a) and a metal salt compound (B),
The dihydroxy compound (a) is a dihydroxy compound represented by the following formula (1), and is derived from the dihydroxy compound (a) among structural units derived from all the dihydroxy compounds in the polycarbonate resin (A). The proportion of the structural unit is 10 to 50% by mass, and the metal salt compound (B) is 0.01 to 1.00 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). A polycarbonate resin composition.

(In the above formula (1), R ¹ and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom, and n Represents an integer of 0 to 2. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 6 carbon atoms, and R ⁷ and R ⁸ each independently represents a hydrogen atom. And represents an alkyl group having 1 to 6 carbon atoms.)
[2] The polycarbonate resin composition according to [1], wherein the dihydroxy compound (a) is a dihydroxy compound represented by the following formula (2).

[3] The structural unit derived from the dihydroxy compound (b) represented by the structural unit derived from the dihydroxy compound (a) represented by the above formula (1) and the polycarbonate resin (A). And a polycarbonate resin (A-1) having a molar ratio of 100/0 to 10/90 in a molar ratio of the dihydroxy compound (a) and the dihydroxy compound (b), and the polycarbonate resin (A-1) The polycarbonate resin composition according to [1], which is a polycarbonate resin made of other polycarbonate resin (A-2) different from).

(In said formula (3), R <^9> , R < ¹⁰ > shows a hydrogen atom, a C1-C20 alkyl group, or an aryl group each independently. The coupling group X is a single bond, a carbonyl group, an alkylidene group, Represents a sulfur atom or an oxygen atom, and n represents an integer of 0 to 4.)
[4] The polycarbonate resin composition according to [3], wherein the dihydroxy compound (a) is a dihydroxy compound represented by the above formula (2).
[5] The polycarbonate resin composition according to [3] or [4], wherein the dihydroxy compound (b) is a dihydroxy compound represented by the following formula (4).

[6] The polycarbonate resin composition according to [3] or [4], wherein the dihydroxy compound (b) is a dihydroxy compound represented by the following formula (5).

[7] The polycarbonate resin (A-2) according to any one of [3] to [6], including 20 to 100% by mass of a polycarbonate resin (A-3) having a structural viscosity index N of 1.2 or more. Polycarbonate resin composition.
[8] The polycarbonate resin composition according to [3] to [7], wherein the polycarbonate resin (A-2) is a polycarbonate resin containing a structural unit derived from the dihydroxy compound represented by the formula (4).
[9] The polycarbonate resin composition according to any one of [1] to [8], wherein the metal salt compound (B) is an alkali metal salt of an organic sulfonic acid.
[10] The polycarbonate resin composition according to [9], wherein the alkali metal salt of organic sulfonic acid is an alkali metal salt of fluorine-containing aliphatic sulfonic acid.
[11] The polycarbonate resin composition according to [10], wherein the alkali metal salt of the fluorinated aliphatic sulfonic acid is an alkali metal salt of perfluoroalkanesulfonic acid.
[12] A polycarbonate resin molded article obtained by molding the polycarbonate resin composition according to any one of [1] to [11].

  According to the polycarbonate resin composition of the present invention, higher flame retardancy and heat resistance can be realized.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples described below, and may be arbitrarily selected without departing from the scope of the present invention. You can change it to
The polycarbonate resin composition of the present invention contains at least a polycarbonate resin having a specific structure and a metal salt compound. Moreover, the polycarbonate resin composition of this invention may contain the other component as needed.

[1. Polycarbonate resin (A)]
The polycarbonate resin (A) used in the polycarbonate resin composition of the present invention is a polymer (polymer) having a carbonic acid bond represented by the following formula (6).

In the formula (6), the linking group A bonded to the oxygen atom is not particularly limited as long as it is a hydrocarbon group, but a carbon atom having a hetero atom or a hetero bond in the hydrocarbon group of the linking group A for imparting various properties. Hydrogen group A may be used.
Such a polycarbonate resin (A) is obtained by polymerizing a dihydroxy compound and a carbonate-forming compound. The polycarbonate resin (A) used in the polycarbonate resin composition of the present invention contains at least the following formula (1). And a structural unit derived from the dihydroxy compound (a) represented. By including such a dihydroxy compound (a), the flame retardancy and heat resistance of the polycarbonate resin composition of the present invention can be effectively enhanced.

In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom, and n Represents an integer of 0-2. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 6 carbon atoms, and R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Represents.

The ^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7 and ^{R 8} Oite, alkyl group having 1 to 6 carbon atoms in the formula (1), a methyl group, an ethyl group Propyl group, isopropyl group, n-butyl group, t-butyl group, sec-butyl group, pentyl group, hexyl group and the like.
In R ¹ and R ² in the above formula (1), examples of the aryl group include a phenyl group, a tolyl group, a dimethylphenyl group, a t-butylphenyl group, a di-t-butylphenyl group, and a naphthyl group.

In R ¹ and R ² in the above formula (1), examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.
In R ¹ and R ² in the above formula (1), examples of the halogen atom include a chlorine atom, a bromine atom, and a fluorine atom.
R ¹ and R ² in the above formula (1) are preferably at least one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms among the above-mentioned substituents. It is more preferably an atom or a methyl group, and most preferably a hydrogen atom.

R ³ , R ⁴ , R ⁵ and R ⁶ in the above formula (1) are at least one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms among the above substituents. It is preferably a hydrogen atom or a methyl group, and most preferably a methyl group.
R ⁷ and R ⁸ in the above formula (1) are preferably at least one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms among the above-mentioned substituents. It is more preferably an atom or a methyl group, and most preferably a hydrogen atom.

  In the dihydroxy compound (a) represented by the above formula (1), as a specific compound, for example, a dihydroxy compound having a structure such as the following formulas (2), (7), (8), (9) is preferable. It is mentioned as a thing. Among these specific dihydroxy compounds, the heat resistance and flame retardancy of the polycarbonate resin composition of the present invention can be improved more effectively, and the dihydroxy compound as a raw material for producing the polycarbonate resin (A) Is used, the dihydroxy compound represented by the following formula (2) may be used as the dihydroxy compound (a) of the polycarbonate resin (A) of the polycarbonate resin composition of the present invention because it is easy to polymerize. Further preferred.

  Specific examples of the dihydroxy compound (a) represented by the above formula (2) include dihydroxy compounds having the structures of the following formulas (10), (11), and (12). The dihydroxy compound represented by the following formula (10) is preferable because good mechanical properties are easily obtained because the property can be secured, and the thermal stability of the obtained polycarbonate resin is good and gelation is easily suppressed.

The dihydroxy compounds of the above formulas (1), (2), (7) to (12) can be produced by a known method (for example, JP-A-2014-114281). The dihydroxy compound obtained by these methods is purified as necessary and applied to the dihydroxy compound (a) contained as a structural unit in the polycarbonate resin (A) contained in the polycarbonate resin composition of the present invention.

In the polycarbonate resin composition of the present invention, among the structural units derived from all the dihydroxy compounds in the polycarbonate resin (A), the proportion of the structural units derived from the dihydroxy compound (a) is 10 to 50% by mass. It is characterized by that. When the ratio of this dihydroxy compound (a) is less than 10 mass%, there exists a possibility that the heat resistance and flame retardance of the polycarbonate resin composition of this invention may fall. Moreover, when the ratio of a dihydroxy compound (a) exceeds the said upper limit, there exists a possibility that the mechanical physical property of the polycarbonate resin composition of this invention may fall remarkably, and also a moldability may fall. For such reasons, the proportion of the above-mentioned dihydroxy compound (a) in the structural units derived from all dihydroxy compounds in the polycarbonate resin (A) is preferably 12% by mass or more, more preferably, It is 13 mass% or more, More preferably, it is 15 mass% or more, Preferably, it is 40 mass% or less, More preferably, it is 35 mass% or less, More preferably, it is 30 mass% or less.
As the dihydroxy compound (a), only a single compound having the same structure may be used, or two or more compounds having different structures may be used in combination.

  The polycarbonate resin (A) used in the polycarbonate resin composition of the present invention comprises a structural unit derived from the dihydroxy compound (a) represented by the above formula (1) and a dihydroxy compound (b) represented by the following formula (3). A polycarbonate resin (A-1) containing a structural unit derived from the above and having a molar ratio of the dihydroxy compound (a) and the dihydroxy compound (b) of 100/0 to 10/90, and the polycarbonate It is preferable that it is a polycarbonate resin which consists of other polycarbonate resin (A-2) different from resin (A-1).

In said formula (3), R <^9> , R < ¹⁰ > shows a hydrogen atom, a C1-C20 alkyl group, or an aryl group each independently. X represents a single bond, a carbonyl group, an alkylidene group, a sulfur atom, or an oxygen atom. n represents an integer of 0 to 4. Note that the alkyl group, aryl group, and alkylidene group described above may have a substituent.
In the above formula (3), R ⁹ and R ¹⁰ are preferably an alkyl group having 1 to 20 carbon atoms. Specifically, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Examples include n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like. Among these, a methyl group, an ethyl group, and an n-propyl group are more preferable, and a methyl group is still more preferable.

In the above formula (3), the linking group X represents a single bond, a carbonyl group, an alkylidene group, a sulfur atom, or an oxygen atom, and the alkylidene group, sulfur atom, or oxygen atom may have a substituent. Among these, an alkylidene group is preferable, and is specifically represented by the following formula (13) or the following formula (14). The X is the case of sulfur atom, for example, -S -, - SO ₂ - and the like.

In the formula (13), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group. In the formula (14), Z is a carbon atom. An alkylene group of formula 4 to 20 is shown. The alkyl group, aryl group, and alkylene group here may each have a substituent.
In the above formula (13), when R ¹¹ and R ¹² are alkyl groups having 1 to 20 carbon atoms, specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl Group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like. When R ¹¹ and R ¹² are aryl groups, specific examples include a phenyl group, a benzyl group, a tolyl group, a 4-methylphenyl group, and a naphthyl group.

Among these specific examples, in the above formula (13), R ¹¹ and R ¹² are preferably a methyl group, an ethyl group, an n-propyl group, or a 4-methylphenyl group, more preferably a methyl group, , R ¹¹ and R ¹² are both methyl groups, that is, the linking group X in the formula (3) is preferably an isopropylidene group.
In the above formula (14), Z may form a substituted or unsubstituted divalent carbocycle in the formula (3) by combining the linking group X with the carbon bonding the two phenyl groups. It is preferably a substituent that can be used. The divalent carbocycle is, for example, a cycloalkylidene group such as a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group (preferably the number of carbon atoms 5-8). Examples of the substituted ones include those having these methyl substituents and ethyl substituents. Among these, a methyl-substituted product of a cyclohexylidene group, a cyclohexylidene group, or a cyclododecylidene group is preferable.

Among the polycarbonate resins (A) used in the polycarbonate resin composition of the present invention, the structural unit derived from the dihydroxy compound (a) represented by the above formula (1) and the dihydroxy compound represented by the above formula (3) ( Specific examples of the dihydroxy compound (b) represented by the above formula (3) in the polycarbonate resin (A-1) containing the structural unit derived from b) include 2,5-dihydroxybiphenyl, Dihydroxybiphenyls such as 2,2′-dihydroxybiphenyl and 4,4′-dihydroxybiphenyl; 2,2′-dihydroxydiphenyl ether, 3,3′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ether, 4,4′- Dihydroxy-3,3′-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenyl Enoxy) benzene, 1,3-bis (4-hydroxyphenoxy) benzene and other dihydroxydiaryl ethers; 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “bisphenol A” or “BPA”) 1), 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane (hereinafter abbreviated as “bisphenol C” or “BPC”) ), 2,2-bis (3-methoxy-4-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane, 1,1-bis (3 -Tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) Lopan, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane, α, α'-bis (4 -Hydroxyphenyl) -1,4-diisopropylbenzene, 1,3-bis [2-
(4-hydroxyphenyl) -2-propyl] benzene, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) cyclohexylmethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) ( 4-propenylphenyl) methane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) naphthylmethane, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) ethane, 1, 1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-naphthylethane, 1-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxy) Phenyl) butane, 2,2-bis (4-hydroxypheny) L) pentane, 1,1-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) hexane, 1-bis (4-hydroxyphenyl) octane, 2-bis (4-hydroxyphenyl) Octane, 1-bis (4-hydroxyphenyl) hexane, 2-bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) nonane, Bis (hydroxyaryl) alkanes such as 10-bis (4-hydroxyphenyl) decane and 1-bis (4-hydroxyphenyl) dodecane; 1-bis (4-hydroxyphenyl) cyclopentane, 1-bis (4- Hydroxyphenyl) cyclohexane, 4-bis (4-hydroxyphenyl) cyclohexane, 1,1 Bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane, 1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane, , 1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) ) -3-tert-butyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3-pheny Bis (hydroxyaryl) cycloalkanes such as cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane, and the like; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4 Bisphenols containing a cardo structure such as -hydroxy-3-methylphenyl) fluorene; dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; Dihydroxydiaryl sulfoxides such as 4′-dihydroxydiphenyl sulfoxide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide; 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′- Dimethyldiphenyl sulfone Dihydroxydiaryl sulfones such as; The production method of these dihydroxy compounds is not particularly limited as long as it is a known method, but it can usually be obtained by synthesizing, neutralizing and purifying phenols and ketones or aldehydes under acid catalyst conditions. it can.

  As the dihydroxy compound (b) represented by the above formula (3), bis (hydroxyaryl) alkanes are preferable among these, and bis (4-hydroxyphenyl) alkanes are particularly preferable. Particularly, impact resistance, From the viewpoint of heat resistance, 2,2-bis (4-hydroxyphenyl) propane (BPA) represented by the following formula (4) is preferable. From the viewpoint of hardness and flame retardancy, it is represented by the following formula (5). 2,2-bis (3-methyl-4-hydroxyphenyl) propane (BPC) is preferred. BPA and BPC can be obtained from commercial products or known production methods. As the dihydroxy compound (b), only a single compound may be used, or two or more compounds having different structures may be used in combination.

  Among the polycarbonate resins (A) used in the polycarbonate resin composition of the present invention, the structural unit derived from the dihydroxy compound (a) represented by the above formula (1) and the dihydroxy compound represented by the above formula (3) ( The proportion of the dihydroxy compound (a) and the dihydroxy compound (b) in the polycarbonate resin (A-1) containing the structural unit derived from b) is preferably 100/0 to 10/90 in molar ratio. However, More preferably, it is 90 / 10-20 / 80, More preferably, it is 80 / 20-30 / 70. By setting this range, not only the productivity of the polycarbonate resin (A-1) is improved, but the mixing property of the polycarbonate resin (A-1) and the polycarbonate resin (A-2) described later is improved. There exists a tendency for the flame retardance of the polycarbonate resin composition of this invention to improve.

The polycarbonate resin (A) used in the polycarbonate resin composition of the present invention is a polycarbonate resin composed of the polycarbonate resin (A-1) and a polycarbonate resin (A-2) different from the polycarbonate resin (A-1). It is preferable. “Different from the polycarbonate resin (A-1)” means that the abundance, type and structure of the dihydroxy compound which is a component derived from the structural unit contained in the polycarbonate resin (A-1) are different. say.

  Although there is no restriction | limiting in particular as a dihydroxy compound used for polycarbonate resin (A-2), It is preferable that it is the above-mentioned dihydroxy compound (b), Especially, bis (hydroxyaryl) alkane is more preferable, and bis (4- Hydroxyphenyl) alkanes are more preferable, and 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A) represented by the above formula (4) is most preferable from the viewpoint of impact resistance and heat resistance. As the dihydroxy compound (b), only a single compound may be used, or two or more compounds having different structures may be used in combination.

  In the polycarbonate resin (A) used for the polycarbonate resin composition of the present invention, the blending ratio when the polycarbonate resin (A-1) and the polycarbonate resin (A-2) are used is represented by the above formula (1). If the ratio of the structural unit derived from the dihydroxy compound (a) is 10 to 50% by mass among the structural units derived from all the dihydroxy compounds in the polycarbonate resin (A), the dihydroxy compound (a) is particularly limited. Usually, the mass ratio (polycarbonate resin (A-1) / polycarbonate resin (A-2)) is 90/10 to 20/80, preferably 80/20 to 25/75, more preferably. Preferably, it is 70 / 30-30 / 70, More preferably, it is 60 / 40-40 / 60. If it is this range, the mixing property of polycarbonate resin (A-1) and polycarbonate resin (A-2) will improve, and it exists in the tendency for the flame retardance and mechanical property of the polycarbonate resin of this invention to improve.

  The polycarbonate resin (A) used in the polycarbonate resin composition of the present invention is obtained by polymerizing a dihydroxy compound and a carbonate-forming product. Examples of carbonate-forming compounds include carbonyl halides and carbonate esters. used. In addition, a carbonate forming compound may use a single compound, or may use 2 or more types of different compounds together in arbitrary combinations and ratios.

Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformate of dihydroxy compounds and monochloroformate of dihydroxy compounds.
Specific examples of the carbonate ester include aryl carbonates represented by the following formula (15), dialkyl carbonates, biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, carbonates of dihydroxy compounds such as cyclic carbonates, and the like. Examples include the body.

In formula (15), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group, or an arylalkyl group. Hereinafter, when R ¹³ and R ¹⁴ are an alkyl group or an arylalkyl group, they may be referred to as dialkyl carbonate, and when they are an aryl group, they may be referred to as diaryl carbonate. Among these, from the viewpoint of reactivity with the dihydroxy compound, both R ¹³ and R ¹⁴ are preferably aryl groups, and more preferably diaryl carbonates represented by the following formula (16).

In formula (16), R ¹⁵ and R ¹⁶ each independently represent a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, or 4 carbon atoms. A cycloalkyl group having 20 carbon atoms and an aryl group having 6-20 carbon atoms, and p and q each independently represents an integer of 0-5.
Specific examples of such carbonate esters include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, diphenyl carbonate (hereinafter sometimes referred to as “DPC”), and bis (4-methyl). Phenyl) carbonate, bis (4-chlorophenyl) carbonate, bis (4-fluorophenyl) carbonate, bis (2-chlorophenyl) carbonate, bis (2,4-difluorophenyl) carbonate, bis (4-nitrophenyl) carbonate, bis (Substituted) diaryl carbonates such as (2-nitrophenyl) carbonate, bis (methylsalicylphenyl) carbonate, and ditolyl carbonate are exemplified, and among them, diphenyl carbonate is preferable. In addition, these carbonate ester can be used individually or in mixture of 2 or more types.

  In addition, the carbonate ester may be preferably substituted with dicarboxylic acid or dicarboxylic acid ester in an amount of 50 mol% or less, more preferably 30 mol% or less. Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

  These carbonate esters (including the above-mentioned substituted dicarboxylic acid or dicarboxylic acid ester; the same shall apply hereinafter) are usually used in excess with respect to the dihydroxy compound when polymerized with a dihydroxy compound to obtain a polycarbonate resin. That is, the carbonate ester is used in an amount of 1.01-1.30 times (molar ratio), preferably 1.02-1.20 times (molar ratio), relative to the dihydroxy compound. When the molar ratio is too small, the terminal OH groups of the obtained polycarbonate resin increase, and the thermal stability of the resin tends to deteriorate. On the other hand, if the molar ratio is too large, the transesterification reaction rate decreases, and it becomes difficult to produce a polycarbonate resin having a desired molecular weight, or the residual amount of carbonic acid diester in the resin increases. May cause odor when used as a product.

[2. Production method of polycarbonate resin (A)]
The manufacturing method of polycarbonate resin (A) is not specifically limited, Arbitrary methods are employable. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Hereinafter, a particularly preferable one of these methods will be specifically described.

<Interfacial polymerization method>
First, the case where a polycarbonate resin (A) is manufactured by an interfacial polymerization method will be described. In the interfacial polymerization method, a dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher. Polycarbonate resin is obtained by interfacial polymerization in the presence. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present as necessary, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

The dihydroxy compound and carbonate-forming compound used as the raw material for the polycarbonate resin (A) are as described above. Of the carbonate-forming compounds, phosgene is preferably used, and the method using phosgene is particularly called the phosgene method.
Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; It is done. In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate. Among them, sodium hydroxide and Potassium hydroxide is preferred. In addition, an alkali compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the dihydroxy compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. In particular, it is preferably set to 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Formula tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. Pyridine; guanine; guanidine salt; and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the molecular weight regulator include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides, and the like. Among them, aromatic phenols are preferable. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as 0-oxine benzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

The amount of the molecular weight regulator used is usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol or less, relative to 100 mol of the dihydroxy compound as a raw material. By making the usage-amount of a molecular weight modifier into this range, when using the obtained polycarbonate resin (A) for a polycarbonate resin composition, thermal stability and hydrolysis resistance can be improved.

In the polymerization reaction, the order of mixing the reaction substrate (raw material), the reaction solvent, the catalyst, the additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. For example, when phosgene is used as the carbonate-forming compound, the molecular weight regulator can be mixed at any time as long as it is from the time of the reaction (phosgenation) of the dihydroxy compound and phosgene to the start of the polymerization reaction.
In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

<Melted ester exchange method>
Next, a case where the polycarbonate resin (A) is produced by the melt transesterification method will be described. In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.
As the dihydroxy compound and the carbonate ester, those described above are used, and as the carbonate ester to be used, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is more preferable. In addition, carbonate ester may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
The ratio of the dihydroxy compound and the carbonate ester is arbitrary as long as the desired polycarbonate resin is obtained, but it is preferable to use an equimolar amount or more of the carbonate ester with respect to 1 mol of the dihydroxy compound, and in particular, 1.01 mol or more is used. It is more preferable. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In the polycarbonate resin (A), the amount of terminal hydroxyl groups tends to have a great influence on the thermal stability, hydrolysis stability, color tone, and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the transesterification reaction, the polycarbonate resin (A) in which the amount of terminal hydroxyl groups is adjusted can be usually obtained by adjusting the mixing ratio of carbonate ester and dihydroxy compound; the degree of vacuum during the transesterification reaction, and the like. In addition, the molecular weight of the polycarbonate resin (A) usually obtained can also be adjusted by this operation.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonate ester and the dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, and carbonate esters. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When the polycarbonate resin (A) is produced by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.
The melt polycondensation reaction can be performed by either a batch method or a continuous method. When performing by a batch type, the order which mixes a reaction substrate (raw material), a reaction solvent, a catalyst, an additive, etc. is arbitrary as long as a desired polycarbonate resin (A) is obtained, and if an appropriate order is set arbitrarily Good. However, in view of the stability of the polycarbonate resin (A) and the polycarbonate resin composition, the melt polycondensation reaction is preferably carried out continuously.

In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to polycarbonate resin, and is 100 ppm or less normally, Preferably it is 50 ppm or less.

The polycarbonate resin (A) used in the polycarbonate resin composition in the present invention preferably contains a certain percentage or more of a polycarbonate resin having a structural viscosity index N in a predetermined range.
The structural viscosity index N is an index for evaluating the flow characteristics of the melt. Usually, the melting characteristics of polycarbonate resin can be expressed by the formula: γ = a · σ ^N. In the above formula, γ: shear rate, a: constant, σ: stress, N: structural viscosity index.

  In the above formula, when N = 1, Newtonian fluidity is shown, and the non-Newtonian fluidity increases as the value of N increases. That is, the flow characteristics of the melt are evaluated by the magnitude of the structural viscosity index N. In general, a polycarbonate resin having a large structural viscosity index N tends to have a high melt viscosity in a low shear region. For this reason, when a polycarbonate resin having a large structural viscosity index N is mixed with another polycarbonate resin, dripping at the time of combustion of the obtained polycarbonate resin composition can be suppressed, and flame retardancy can be improved.

  In the polycarbonate resin composition of the present invention, the structural viscosity index N of the polycarbonate resin (A-2) is 1.2 or more, preferably 1.25 or more, more preferably 1.28 or more, and 1.8 Hereinafter, it is preferable to contain a polycarbonate resin of 1.7 or less in a certain ratio or more. By including a polycarbonate resin having a high structural viscosity index N as described above, dripping during combustion of the polycarbonate resin composition of the present invention can be suppressed and flame retardancy can be improved. Moreover, the moldability of the polycarbonate resin composition of this invention can be maintained in a favorable range by making structural viscosity index N below the upper limit of the said range.

The “structural viscosity index N” is expressed by Log η _a = [(1−N) / N] × Log γ + C, which is derived from the above formula, for example, as described in Japanese Patent Application Laid-Open No. 2005-232442. It is also possible. In the above formula, N: structural viscosity index, γ: shear rate, C: constant, η _a : apparent viscosity. As can be seen from this equation, the N value can also be evaluated from γ and ηa in _a low shear region in which the viscosity behavior is greatly different. For example, the N value can be determined from η _a at γ = 12.16 sec ⁻¹ and γ = 24.32 sec ⁻¹ .

When the polycarbonate resin (A) used in the polycarbonate resin composition of the present invention is composed of the polycarbonate resin (A-1) and the polycarbonate resin (A-2), the polycarbonate resin (A-2) is The polycarbonate resin (A-3) having a structural viscosity index N of 1.2 or more is preferably a polycarbonate resin containing 20% by mass or more based on the polycarbonate resin (A). By carrying out like this, the synergistic effect peculiar to polycarbonate resin (A-1) which has the specific structural unit which concerns on this invention, and a metal salt can be exhibited notably. The content of the polycarbonate resin (A-3) is more preferably 30% by mass or more, and further preferably 50% by mass or more. In addition, there is no restriction | limiting in an upper limit, Although it is 100 mass% or less normally, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less.

  In order to produce the polycarbonate resin (A-3) having the above structural viscosity index N of 1.2 or more, for example, when using BPC or BPA as a raw material dihydroxy compound, the above-mentioned polycarbonate resin ( A polycarbonate resin having a structural viscosity index N of 1.2 or more can be obtained by producing according to the production method of A), but preferably a polycarbonate resin having a branched structure (hereinafter referred to as “branched polycarbonate resin” as appropriate). Is preferable because it is easy to obtain a polycarbonate resin having a structural viscosity index N of 1.2 or more. This is because the branched polycarbonate resin tends to have a high structural viscosity index N.

  Examples of the method for producing the branched polycarbonate resin include the methods described in JP-A-8-259687, JP-A-8-245782, and the like. In the methods described in these documents, when the dihydroxy compound and the carbonic acid diester are reacted by the melt transesterification method, the structural viscosity index can be obtained without using a branching agent by selecting the catalyst conditions or production conditions. An aromatic polycarbonate resin that is high and excellent in hydrolysis stability can be obtained.

Further, as another method for producing a branched polycarbonate resin, a trifunctional or higher polyfunctional compound (branching agent) is used in addition to the dihydroxy compound and the carbonate-forming compound which are the raw materials of the polycarbonate resin (A) described above. And a method of copolymerizing them by an interfacial polymerization method or a melt transesterification method.
Examples of the trifunctional or higher functional compound include 1,3,5-trihydroxybenzene (phloroglucin), 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4 , 6-Dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri Polyhydroxy compounds such as (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane; 3,3-bis (4-hydroxyaryl) oxyindole (ie, isatin) Bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferable.

The polyfunctional compound can be used by substituting a part of the dihydroxy compound. The usage-amount of a polyfunctional aromatic compound is 0.01 mol% or more normally with respect to all the dihydroxy compounds of the raw material which manufactures (A-3), Preferably it is 0.1 mol% or more, and usually It is 10 mol% or less, preferably 3 mol% or less.
In addition, a polyfunctional compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the branched structure contained in the branched polycarbonate resin obtained by the melt transesterification method include structures of the following formulas (17) to (20) when the raw dihydroxy compound is BPA. In the following formulas (17) to (20), X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, cycloalkylidene group having 5 to 15 carbon atoms, or,, -O -, - S - , - CO -, - SO -, - SO 2 - in showing what is selected from the group consisting of divalent groups represented.

As a method for producing a branched polycarbonate resin, among the methods described above, a production method for producing a branched polycarbonate resin by the above-described melt transesterification method is particularly preferable. This is because it can be manufactured from a relatively inexpensive and easily available industrial material. For this reason, the polycarbonate resin is also preferably produced by a melt transesterification method.
As the polycarbonate resin (A-3) having a structural viscosity index N of 1.2 or more, a single resin may be used, or two or more different resins may be used in any combination and ratio.

  Further, the polycarbonate resin (A-2) includes a polycarbonate resin having a structural viscosity index N outside the predetermined range in addition to the polycarbonate resin (A-3) having the structural viscosity index N in the predetermined range. Also good. Although there is no restriction | limiting in the kind, A linear polycarbonate resin is preferable especially. By combining a polycarbonate resin having a structural viscosity index N within a predetermined range and a linear polycarbonate resin, it is easy to balance the flame retardancy (anti-dripping property) and moldability (fluidity) of the resulting polycarbonate resin composition. The advantage is obtained. From this viewpoint, it is particularly preferable to use a polycarbonate resin composed of an aromatic polycarbonate resin having a structural viscosity index N in a predetermined range and a linear aromatic polycarbonate resin.

[3. Other matters regarding polycarbonate resin (A)]
The molecular weight of the polycarbonate resin (A) used in the polycarbonate resin composition of the present invention is arbitrary and may be appropriately selected and determined, but the viscosity average molecular weight [Mv] converted from the solution viscosity is usually 10,000 or more, Preferably it is 16000 or more, More preferably, it is 18000 or more, and is 40000 or less normally, Preferably it is 30000 or less. By setting the viscosity average molecular weight to be equal to or higher than the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, which is more preferable when used for applications requiring high mechanical strength. On the other hand, by setting the viscosity average molecular weight to be equal to or lower than the upper limit of the above range, the polycarbonate resin composition of the present invention can be suppressed and improved in fluidity, and the molding processability can be improved and the molding process can be easily performed. Two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used, and in this case, a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed.

The viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. , Η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

  The terminal hydroxyl group concentration of the polycarbonate resin (A) is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 1500 ppm or less, more preferably 1000 ppm or less. Thereby, the residence heat stability and color tone of the polycarbonate resin composition of the present invention can be further improved. Moreover, the lower limit is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more in the polycarbonate resin (A) produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of the polycarbonate resin composition of this invention can be improved more.

In addition, the unit of the terminal hydroxyl group concentration represents the weight of the terminal hydroxyl group with respect to the weight of the polycarbonate resin (A) in ppm. The measurement method is colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.
In addition, the polycarbonate resin (A) may contain a polycarbonate oligomer in order to improve the appearance and fluidity of the molded product. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and is usually 9500 or less, preferably 9000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by weight or less of the polycarbonate resin (including the polycarbonate oligomer).

  Further, the polycarbonate resin (A) may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin). Examples of the used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.

  However, the regenerated polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less in the polycarbonate resin (A) contained in the polycarbonate resin composition of the present invention. The reason for this is that the recycled polycarbonate resin is likely to have undergone deterioration such as thermal deterioration and aging deterioration. This is because the physical properties may be lowered.

[4. Metal salt compound (B)]
The polycarbonate resin composition of the present invention contains a metal salt compound (B). Thus, the flame retardance of the polycarbonate resin composition of this invention can be improved by containing a metal salt compound.
As a kind of metal which a metal salt compound (B) has, it is preferable that they are an alkali metal or an alkaline-earth metal. The polycarbonate resin composition of the present invention can promote the formation of a carbonized layer at the time of combustion, can further enhance the flame retardancy, and has mechanical properties such as impact resistance possessed by the polycarbonate resin (A) itself, heat resistance, electricity This is because the properties such as the mechanical characteristics can be maintained well. Accordingly, the metal of the metal salt compound (B) is preferably a metal salt compound containing at least one metal selected from the group consisting of alkali metal salts and alkaline earth metal salts, and more preferably alkali metal salts.

Examples of the metal salt compound include an organic metal salt compound and an inorganic metal salt compound, and an organic metal salt compound is preferable from the viewpoint of good dispersibility in a polycarbonate resin.
Examples of the organic metal salt compound include organic sulfonic acid metal salts, organic sulfonamide metal salts, organic carboxylic acid metal salts, organic boric acid metal salts, and organic phosphoric acid metal salts. Among these, from the viewpoint of thermal stability when mixed with the polycarbonate resin (A), an organic sulfonic acid metal salt, an organic sulfonamide metal salt, and an organic phosphoric acid metal salt are preferable, and an organic sulfonic acid metal salt is particularly preferable.

  The metal of the metal salt compound includes alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs); magnesium (Mg), calcium (Ca), strontium (Sr), alkaline earth metals such as barium (Ba); and aluminum (Al), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn ), Zirconium (Zr), molybdenum (Mo) and the like. Of these, alkali metals and alkaline earth metals are preferred, alkali metals are more preferred, and sodium, potassium, and cesium are most preferred from the viewpoint of better flame retardancy.

  Examples of organic sulfonic acid metal salts include organic sulfonic acid lithium (Li) salt, organic sulfonic acid sodium (Na) salt, organic sulfonic acid potassium (K) salt, organic sulfonic acid rubidium (Rb) salt, organic sulfonic acid Examples thereof include a cesium (Cs) salt, an organic magnesium sulfonate (Mg) salt, an organic calcium sulfonate (Ca) salt, an organic sulfonic acid strontium (Sr) salt, and an organic sulfonic acid barium (Ba) salt. Among these, organic sulfonic acid alkali metal salts such as organic sulfonic acid sodium (Na) salt, organic sulfonic acid potassium (K) salt compound, and organic sulfonic acid cesium (Cs) salt compound are particularly preferable.

Among the organic sulfonic acid metal salts, preferred examples include fluorine-containing aliphatic sulfonic acid or aromatic sulfonic acid metal salts and aromatic sulfonamide metal salts. Specific examples of preferable ones include potassium perfluorobutane sulfonate, lithium perfluorobutane sulfonate, sodium perfluorobutane sulfonate, cesium perfluorobutane sulfonate, and the like. Alkali metal salt of fluorine-containing aliphatic sulfonic acid having a bond; magnesium perfluorobutanesulfonate, calcium perfluorobutanesulfonate, barium perfluorobutanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, trifluoromethanesulfone Fluorine-containing aliphatic sulfonic acid alkaline earth metal salt having at least one C—F bond in the molecule, such as barium acid; Lufon-3,3′-disulfonate dipotassium, diphenylsulfone-3-sulfonate potassium, sodium benzenesulfonate, sodium (poly) styrenesulfonate, sodium paratoluenesulfonate, sodium (branched) dodecylbenzenesulfonate, trichlorobenzene Sodium sulfonate, potassium benzenesulfonate, potassium styrenesulfonate, potassium (poly) styrenesulfonate, potassium paratoluenesulfonate, potassium (branched) dodecylbenzenesulfonate, potassium trichlorobenzenesulfonate, cesium benzenesulfonate, (poly ) Cesium styrene sulfonate, cesium p-toluenesulfonate, cesium (branched) dodecylbenzene sulfonate, cesium trichlorobenzene sulfonate, etc. An alkali metal salt of an aromatic sulfonic acid having at least one aromatic group; magnesium paratoluenesulfonate, calcium paratoluenesulfonate, strontium paratoluenesulfonate, barium paratoluenesulfonate, (branched) dodecylbenzenesulfonic acid Alkaline earth metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule, such as magnesium and calcium (branched) dodecylbenzene sulfonate; Metal salts of aromatic sulfonic acid such as bis (trifluoro) L-methane) sulfonylimide lithium, bis (trifluoromethane) sulfonylimide sodium, bis (trifluoromethane) sulfonylimide potassium, bis (nonafluorobutane) sulfonylimide lithium, bis (nonafluorobutane) sulfonylimide Sodium, bis (nonafluorobutane) sulfonylimide potassium, trifluoromethane (pentafluoroethane) sulfonylimide potassium, trifluoromethane (nonafluorobutane) sulfonylimide sodium, trifluoromethane (nonafluorobutane) sulfonylimide potassium, trifluoromethane, etc. , Alkali metal salts of linear fluorine-containing aliphatic sulfonamides; cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide lithium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide sodium, cyclo- A metal salt of a fluorinated aliphatic sulfonamide, such as an alkali metal salt of a cyclic fluorinated aliphatic sulfonamide, such as hexafluoropropane-1,3-bis (sulfonyl) imide potassium; Sodium salt of saccharin, potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfimide, potassium salt of N- (N′-benzylaminocarbonyl) sulfanilimide, potassium of N- (phenylcarboxyl) -sulfanilimide Examples thereof include metal salts of aromatic sulfonamides such as alkali metal salts of aromatic sulfonamides having at least one aromatic group in the molecule, such as salts.

  Among the examples described above, fluorine-containing aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts are more preferable, and fluorine-containing aliphatic sulfonic acid metal salts are particularly preferably alkali metal salts of fluorine-containing aliphatic sulfonic acids. Further, an alkali metal salt of perfluoroalkanesulfonic acid is more preferable, and specifically, potassium perfluorobutanesulfonate is preferable. From the viewpoint of excellent balance between transparency and flame retardancy, the aromatic sulfonic acid metal salt is particularly preferably an alkali metal salt of aromatic sulfonic acid, specifically, diphenylsulfone-3,3′-disulfonic acid. Dipotassium, potassium diphenylsulfone-3-sulfonate, sodium paratoluenesulfonate, potassium paratoluenesulfonate, cesium paratoluenesulfonate, and the like are particularly preferable.

In addition, a metal salt compound (B) may use only a single compound, and may use together 2 or more types of different compounds by arbitrary combinations and a ratio.
Content of the metal salt compound (B) in the polycarbonate resin composition of this invention is 0.01 mass part or more and 1 mass part or less with respect to 100 mass parts of polycarbonate resin (A). Preferably it is 0.02 parts by mass or more, more preferably 0.03 parts by mass or more, particularly preferably 0.05 parts by mass or more, preferably 0.75 parts by mass or less, more preferably 0.5 parts by mass. Hereinafter, it is particularly preferably 0.3 parts by mass or less. If the content of the metal salt compound is too small, the flame retardancy of the obtained polycarbonate resin composition may be insufficient. Conversely, if the content is too large, the thermal stability of the polycarbonate resin may decrease, Poor appearance and reduced mechanical strength can occur.

[5. Other ingredients]
The polycarbonate resin composition of the present invention may contain other components in addition to those described above as necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resins and various resin additives. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), and polybutylene terephthalate resin (PBT resin);
Polystyrene resin (PS resin), high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA) Resin), styrene resin such as acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin); polyethylene resin (PE resin), polypropylene resin (PP resin), cyclic cycloolefin resin (COP resin), cyclic cycloolefin Polyolefin resin such as copolymer (COP) resin; Polyamide resin (PA resin); Polyimide resin (PI resin); Polyetherimide resin (PEI resin); Polyurethane resin (PU resin); Polyphenylene ether resin (PPE resin) Polyphenylene sulfide resin (PPS resin); polysulfone resins (PSU resin); polymethacrylate resin (PMMA resin) and the like.

In addition, even if other resin is only 1 type among these, two or more different types may be contained by arbitrary combinations and ratios.
Examples of resin additives include heat stabilizers, antioxidants, mold release agents, ultraviolet absorbers, dyes and pigments, flame retardants, anti-dripping agents, antistatic agents, antifogging agents, lubricants, antiblocking agents, and fluidity. Examples include improvers, plasticizers, dispersants, and antibacterial agents. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.

[6. Production method of polycarbonate resin composition]
There is no restriction | limiting in the manufacturing method of the polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely.
For example, the polycarbonate resin (A) and the metal salt compound (B) according to the present invention and other components to be blended as necessary are premixed using various mixers such as a tumbler or a Henschel mixer. Then, a method of melt kneading with a mixer such as a Banbury mixer, a roll, a Brabender, a single screw kneading extruder, a twin screw kneading extruder, or a kneader can be mentioned.

In addition, for example, without mixing each component in advance, or only a part of the components is mixed in advance, and fed to an extruder using a feeder and melt-kneaded to produce the polycarbonate resin composition of the present invention. You can also.
Also, for example, by mixing a part of the components in advance and supplying the resulting mixture to an extruder and melt-kneading it as a master batch, this master batch is again mixed with the remaining components and melt-kneaded. The polycarbonate resin composition of the present invention can also be produced.
In addition, for example, when mixing a component that is difficult to disperse, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance, and kneaded with the solution or the dispersion. It can also improve sex.

[7. Polycarbonate resin molded body]
The polycarbonate resin composition of the present invention is usually molded into an arbitrary shape and used as a polycarbonate resin molded body (resin composition molded body). There is no restriction | limiting in the shape, pattern, color, dimension, etc. of this molded object, What is necessary is just to set arbitrarily according to the use of the molded object.
Examples of the molded body include parts such as electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods / miscellaneous goods, and lighting equipment. Among these, it is particularly suitable for use in parts such as electrical and electronic equipment, OA equipment, information terminal equipment, and home appliances, and is particularly suitable for use in parts of electrical and electronic equipment.

  Examples of the electric and electronic devices include display devices such as personal computers, game machines, and televisions, printers, copiers, scanners, fax machines, electronic notebooks and PDAs, electronic desk calculators, electronic dictionaries, cameras, video cameras, and mobile phones. Battery pack, recording medium drive and reader, mouse, numeric keypad, CD player, MD player, portable radio / audio player, and the like.

  The manufacturing method of a molded object is not specifically limited, The molding method generally employ | adopted about the polycarbonate resin composition can be employ | adopted arbitrarily. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, etc. Is mentioned. A molding method using a hot runner method can also be used.

  The obtained polycarbonate resin molded article of the present invention can be used as a practical molded article having high scratch resistance without impairing the excellent properties of the polycarbonate resin as described above.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In the following description, “parts” means “parts by mass” based on mass standards unless otherwise specified.

Production Example 1 Production of Polycarbonate Resin (A-1-1) As the dihydroxy compound (a), 6,6′-dihydroxy-3,3,3 ′, 3′-tetra represented by the above formula (10) 3.85 kg (12.5 mol) of methyl-1,1′-spirobiindane (hereinafter sometimes abbreviated as “SBI”) and a dihydroxy compound represented by the above formula (4) as a dihydroxy compound (b) ( BPA) 2.85 kg (12.5 mol) and diphenyl carbonate (hereinafter sometimes abbreviated as “DPC”) 5.54 kg (25.85 mol) added to an aqueous solution of cesium carbonate Was added such that cesium carbonate was 0.5 μmol per 1 mol of all dihydroxy compounds. Next, the mixture was charged into a first reactor having an internal volume of 200 L equipped with a stirrer, a heating medium jacket, a vacuum pump, and a reflux condenser.
The SBI that is a raw material for producing the polycarbonate resin in Production Example 1 was obtained by producing according to the method described in JP-A-2014-114281. BPA, DPC
The one manufactured by Mitsubishi Chemical Corporation was used.

Next, the operation of depressurizing the inside of the first reactor to 1.33 kPa (10 Torr) and then restoring the pressure to the atmospheric pressure with nitrogen was repeated five times to replace the inside of the first reactor with nitrogen. After nitrogen substitution, the internal temperature of the first reactor was gradually raised through a heat medium having a temperature of 230 ° C. through the heat medium jacket to dissolve the mixture. Then, the stirrer was rotated at 300 rpm, the temperature in the heating medium jacket was controlled, and the internal temperature of the first reactor was kept at 220 ° C. And while distilling off the phenol by-produced by the oligomerization reaction of BPA and DPC performed in the first reactor, 40
The pressure in the first reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) in absolute pressure over a period of minutes.

  Subsequently, a transesterification reaction was performed for 80 minutes while maintaining the pressure in the first reactor at 13.3 kPa and further distilling off the phenol. The inside of the system was restored to absolute pressure of 101.3 kPa with nitrogen, the gauge pressure was increased to 0.2 MPa, and the oligomer in the first reactor was passed through a transfer pipe heated to 200 ° C. or higher in advance. Two reactors were pumped. The second reactor had an internal volume of 200 L, was equipped with a stirrer, a heat medium jacket, a vacuum pump and a reflux condenser, and the internal pressure was controlled to atmospheric pressure and the internal temperature was controlled to 240 ° C.

  Next, the oligomer fed into the second reactor was stirred at 38 rpm, the internal temperature was raised with a heating medium jacket, and the inside of the second reactor was absolute pressure from 101.3 kPa to 13.3 kPa over 40 minutes. The pressure was reduced to. Thereafter, the temperature increase was continued, and the internal pressure was reduced from 13.3 kPa to 399 Pa (3 Torr) as an absolute pressure over an additional 40 minutes, and phenol distilled out was removed out of the system. Further, the temperature was continuously raised, and after the absolute pressure in the second reactor reached 70 Pa (about 0.5 Torr), the pressure was maintained at 70 Pa, and a polycondensation reaction was performed. The final internal temperature in the second reactor was 285 ° C. The polycondensation reaction was completed when the stirrer of the second reactor reached a predetermined stirring power. The polymerization reaction time in the second reactor was 260 minutes.

Production Example 2 Production of Polycarbonate Resin (A-1-2) Production was performed under the same conditions as in Production Example 1 except that the polymerization reaction time in the second reactor was 340 minutes.
(Production Example 3) Production of Polycarbonate Resin (A-1-3) In Production Example 1, 3.66 kg (about 11.87 mol) of SBI as a dihydroxy compound and a dihydroxy compound represented by the above formula (5) ( The mixture was adjusted by adding an aqueous solution of cesium carbonate to 3.04 kg (about 11.87 mol) of BPC) and 5.21 kg (about 22.33 mol) of DPC so that the cesium carbonate was 1.5 μmol per mol of dihydroxy compound. The polymerization was conducted under the same conditions as in Production Example 1 except that the polymerization reaction time in the second reactor was 365 minutes.

  Table 1 shows components of the polycarbonate resin (A) used in Examples and Comparative Examples.

Polycarbonate resin [A-1-1] (copolymerized polycarbonate resin of SBI / BPA = 56/44 (mass ratio) obtained in Production Example 1 above, viscosity average molecular weight 12500, terminal hydroxyl group concentration is 530 ppm),
Polycarbonate resin [A-1-2] (copolymerized polycarbonate resin of SBI / BPA = 56/44 (mass ratio) obtained in Production Example 2 above, viscosity average molecular weight 15500, terminal hydroxyl group concentration is 490 ppm),
Polycarbonate resin [A-1-3] (SBI / BPC = 54/46 (mass ratio) copolymer polycarbonate resin obtained in Production Example 3 above, viscosity average molecular weight 18000, terminal hydroxyl group concentration is 520 ppm),
Polycarbonate resin [A-2-1] (bisphenol A type polycarbonate resin obtained by interfacial polymerization, viscosity average molecular weight 17000, structural viscosity index 1.0, manufactured by Mitsubishi Engineering Plastics),
Polycarbonate resin [A-3] (bisphenol A type polycarbonate resin obtained by the melt ester method, Novalex (registered trademark) M7027BF, viscosity average molecular weight 27000, structural viscosity index 1.3, manufactured by Mitsubishi Engineering Plastics),
Metal salt compound [B] (potassium perfluorobutanesulfonate, manufactured by LANXESS, Bayowet C4),
In addition, the viscosity average molecular weight (Mv) and structural viscosity index (N value) of said polycarbonate resin were measured with the following method.

<Viscosity average molecular weight (Mv)>
A polycarbonate resin was dissolved in methylene chloride (concentration 6.0 g / L) to obtain a solution. Using this solution, the specific viscosity (η _sp ) at 20 ° C. was measured with an Ubbelohde viscosity tube, and the viscosity average molecular weight (Mv) was calculated by the following formula.
η _sp /C=[η](1+0.28η _sp)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83

<Structural viscosity index (N value)>
Using the capillary rheometer measures the melt viscoelasticity at a temperature 260 ° C., the terminal hydroxyl groups from formula described above, the calculation of the N values from eta _a at γ = 12.16sec ^-1 and γ = 24.32sec ^-1 The concentration was calculated according to the method described above (Method described in Macromol. Chem. 88 215 (1965)).

[Production of resin pellets]
The components shown above were blended in the proportions (mass ratio) shown in Table 2, mixed for 20 minutes with a tumbler, then supplied to Nippon Steel Works (TEX30α) equipped with 1 vent, and the screw rotation speed The molten resin, which was kneaded under the conditions of 200 rpm, discharge rate 15 kg / hour, barrel temperature 280 ° C. and extruded into a strand, was quenched in a water tank and pelletized using a pelletizer to obtain a pellet of a polycarbonate resin composition.

[Glass transition temperature measurement]
Using a differential operation calorimeter (DSC 6220, manufactured by SII), about 10 mg of the above pelletized polycarbonate resin composition was heated at a heating rate of 20 ° C./min to measure the calorie, and in accordance with JIS-K7121. The extrapolated glass transition, which is the temperature at the intersection of the straight line obtained by extending the base line on the low temperature side to the high temperature side and the tangent line drawn at the point where the slope of the step change part of the glass transition is maximized The starting temperature was determined. The extrapolated glass transition temperature was defined as the glass transition temperature (Tg).

[Preparation of UL test specimen]
After the pellets obtained by the above-described production method were dried at 120 ° C. for 5 hours, a cylinder temperature of 260 ° C., a mold temperature of 80 ° C., a molding cycle of 30 was used using a J50-EP type injection molding machine manufactured by Nippon Steel. Test specimens having a length of 125 mm, a width of 13 mm, a thickness of 1.5 mm, and a thickness of 1 mm were molded under the conditions of seconds. The obtained molded body was evaluated for flame retardancy as a UL test sample in the manner described below.

[Flame retardance evaluation]
The flame resistance of each polycarbonate resin composition was evaluated by conditioning the test specimen for UL test obtained by the above method for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity. The test was conducted in accordance with UL94 test (combustion test of plastic materials for equipment parts) defined by Laboratories (UL). UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in Table 2 below.

  Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied. The composition of the polycarbonate resin composition and the measurement results are summarized in Table 3. In addition, the ratio of the dihydroxy compound (a) in all the hydroxy compounds was computed from the preparation amount of the dihydroxy compound of a raw material.

  As can be seen from Table 3, the polycarbonate resin compositions of Examples 1 to 5 have high heat resistance and flame retardancy, and do not contain the dihydroxy compound (a). It can be seen that the polycarbonate resin composition of Comparative Example 2 with less dihydroxy compound (a) is inferior in heat resistance and flame retardancy. Moreover, it turns out that the comparative example 3 which does not contain a metal salt compound also has inadequate flame retardance. Furthermore, in Example 5 including the polycarbonate resin composed of the dihydroxy compound (a) and the dihydroxy compound represented by the formula (5), it is clear that high flame retardancy can be imparted even with a molded article as thin as 1 mm. .

  Therefore, from the above Examples and Comparative Examples, it was confirmed that the effect of improving heat resistance and flame retardancy was obtained for the first time by the configuration of the present invention.

  According to the polycarbonate resin composition of the present invention, it becomes a polycarbonate resin having high heat resistance and flame retardancy, so that the application field of the polycarbonate resin can be expanded.

Claims (12)

A polycarbonate resin composition comprising at least a polycarbonate resin (A) containing a structural unit derived from a dihydroxy compound (a) and a metal salt compound (B),
The dihydroxy compound (a) is a dihydroxy compound represented by the following formula (1), and is derived from the dihydroxy compound (a) among structural units derived from all the dihydroxy compounds in the polycarbonate resin (A). The proportion of the structural unit is 10 to 50% by mass, and the metal salt compound (B) is 0.01 to 1.00 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). A polycarbonate resin composition.
(In the above formula (1), R ¹ and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom, and n Represents an integer of 0 to 2. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 6 carbon atoms, and R ⁷ and R ⁸ each independently represents a hydrogen atom. And represents an alkyl group having 1 to 6 carbon atoms.) The polycarbonate resin composition according to claim 1, wherein the dihydroxy compound (a) is a dihydroxy compound represented by the following formula (2).
The polycarbonate resin (A) is
A structural unit derived from the dihydroxy compound (a) represented by the formula (1) and a structural unit derived from the dihydroxy compound (b) represented by the following formula (3), and the dihydroxy compound (a) And the dihydroxy compound (b) are present in a molar ratio of 100/0 to 10/90 in polycarbonate resin (A-1) and other polycarbonate resin (A-) different from the polycarbonate resin (A-1). The polycarbonate resin composition according to claim 1, which is a polycarbonate resin comprising 2).
(In said formula (3), R <^9> , R < ¹⁰ > shows a hydrogen atom, a C1-C20 alkyl group, or an aryl group each independently. The coupling group X is a single bond, a carbonyl group, an alkylidene group,
Represents a sulfur atom or an oxygen atom. n represents an integer of 0 to 4. )   The polycarbonate resin composition according to claim 3, wherein the dihydroxy compound (a) is a dihydroxy compound represented by the formula (2). The polycarbonate resin composition according to claim 3 or 4, wherein the dihydroxy compound (b) is a dihydroxy compound represented by the following formula (4).
The polycarbonate resin composition according to claim 3 or 4, wherein the dihydroxy compound (b) is a dihydroxy compound represented by the following formula (5).
  The polycarbonate resin composition according to any one of claims 3 to 6, wherein the polycarbonate resin (A-2) contains 20 to 100 mass% of a polycarbonate resin (A-3) having a structural viscosity index N of 1.2 or more. object.   The polycarbonate resin composition according to claim 3, wherein the polycarbonate resin (A-2) is a polycarbonate resin containing a structural unit derived from the dihydroxy compound represented by the formula (4).   The polycarbonate resin composition according to any one of claims 1 to 8, wherein the metal salt compound (B) is an alkali metal salt of an organic sulfonic acid.   The polycarbonate resin composition according to claim 9, wherein the alkali metal salt of the organic sulfonic acid is an alkali metal salt of a fluorine-containing aliphatic sulfonic acid.   The polycarbonate resin composition according to claim 10, wherein the alkali metal salt of the fluorinated aliphatic sulfonic acid is an alkali metal salt of perfluoroalkanesulfonic acid.   The polycarbonate resin molding formed by shape | molding the polycarbonate resin composition of any one of Claims 1 thru | or 11.