JP2016141722A - Polycarbonate resin composition and polycarbonate resin molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition having high hardness and excellent in balance of heat resistance and transparency and a molded body thereof.SOLUTION: There is provided a polycarbonate resin composition containing a polycarbonate resin (A) containing at least a structural unit represented by the following formula (1) and a polycarbonate resin (B), where the polycarbonate resin (B) is a polycarbonate copolymer containing a structural unit (B-1) represented by the formula (2) and a structural unit (B-2) represented by the formula (3) and the content of the polycarbonate resin (B) is 5 to 200 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. More specifically, the present invention relates to a polycarbonate resin composition excellent in hardness, heat resistance and transparency.

  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 copiers. Since the polycarbonate resin of a mold is easily damaged, improvement in hardness is required in a field where design properties are required.

Under such circumstances, Patent Document 1 proposes a 2,2-bis (3-methyl-4-hydroxyphenyl) propane type polycarbonate resin and a polycarbonate resin composition. Such a polycarbonate resin and a polycarbonate resin composition are proposed. In the case of a product, since the heat resistance is lowered, it cannot be applied to a member requiring high heat resistance.
In contrast, in Patent Document 2, a polycarbonate resin composition comprising a 2,2-bis (3-methyl-4-hydroxyphenyl) propane type polycarbonate resin and a polycarbonate resin made of bisphenol having a specific alicyclic structure. Things have been proposed. However, in the above polycarbonate resin composition, since transparency is actually sacrificed, there is a problem that it cannot be applied to a member requiring transparency.

  Patent Document 3 discloses a polycarbonate resin composition excellent in heat resistance, which is composed of a specific polycarbonate resin having a spirobiindane skeleton and a bisphenol A-type polycarbonate resin. However, there is a disadvantage that transparency is not obtained.

Japanese Examined Patent Publication No. 64-69625 JP 2011-148988 A JP-A-8-73729

However, in the above polycarbonate resin composition, since transparency is actually sacrificed, there is a problem that it cannot be applied to a member requiring transparency.
The present invention has been made in view of the above problems, and an object thereof is to provide a polycarbonate resin composition excellent in the balance between high hardness, heat resistance and transparency, and a molded product thereof.

The inventor of the present invention has intensively studied to solve the above problems, and as a result, by combining a polycarbonate resin containing a specific structure with a polycarbonate resin copolymer having a specific structure, the hardness, heat resistance, and transparency are improved. The inventors have found that both can be improved and completed the present invention.
That is, the gist of the present invention resides in the following [1] to [5].
[1] A polycarbonate resin composition comprising at least a polycarbonate resin (A) having a structural unit represented by the following formula (1) and a polycarbonate resin (B),
The polycarbonate resin (B) is a polycarbonate copolymer containing a structural unit (B-1) represented by the following formula (2) and a structural unit (B-2) represented by the following formula (3): And the content of this polycarbonate resin (B) is 5-200 mass parts with respect to 100 mass parts of this polycarbonate resin (A), The polycarbonate resin composition characterized by the above-mentioned.

(In the above formula (2), 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 molded article having a thickness of 3 mm has a haze of 3 or less.
[3] The proportion of the structural unit (B-1) represented by the formula (2) in the polycarbonate resin (B) is 5 to 70 mol%, and the structural unit represented by the formula (3) ( B-2) The polycarbonate resin composition according to [1] or [2], which is 30 to 95 mol%.
[4] The polycarbonate resin composition according to any one of [1] to [3], wherein the structural unit (B-1) is represented by the following formula (4).

[5] A polycarbonate resin molded article obtained by molding the polycarbonate resin composition according to any one of [1] to [4].

  According to the polycarbonate resin composition of the present invention, higher hardness, heat resistance, and transparency 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
[1. Overview]
The polycarbonate resin composition of the present invention contains at least a polycarbonate resin having a specific structure and a polycarbonate resin copolymer having a specific structure. Moreover, the polycarbonate resin composition of this invention may contain the other component as needed.

[2. Polycarbonate resin (A)]
The polycarbonate resin (A) used in the polycarbonate resin composition of the present invention is a polymer (polymer) having at least a structural unit represented by the following formula (1).

  Such a polycarbonate resin (A) can be obtained by polymerizing a dihydroxy compound containing 2,2-bis (3-methyl-4-hydroxyphenyl) propane as an essential component and a carbonate-forming compound. As a dihydroxy compound which forms resin, dihydroxy compounds other than the said 2, 2-bis (3-methyl-4-hydroxyphenyl) propane may also be included.

  Examples of dihydroxy compounds other than 2,2-bis (3-methyl-4-hydroxyphenyl) propane include aromatic dihydroxy compounds represented by the following formula (5).

In said formula (5), R <^9> , R < ¹⁰ > shows a hydrogen atom, a C1-C20 alkyl group, or an aryl group each independently. Each of the alkyl group and the aryl group may have a substituent. The linking group X represents a single bond, a carbonyl group, an alkylidene group, a sulfur atom, or an oxygen atom, and n represents an integer of 0 to 4. The alkylidene group, sulfur atom or oxygen atom may have a substituent.

In the above formula (5), when R ⁹ and R ¹⁰ are alkyl groups having 1 to 20 carbon atoms, 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. Among these, a methyl group, an ethyl group, and an n-propyl group are preferable, and a methyl group is more preferable.

In the above formula (5), when the linking group X is an alkylidene group, preferable examples include those represented by the following formula (6) or the following formula (7). Furthermore, the linking group X is a sulfur atom, as a suitable, for example, -S -, - SO ₂ - and the like.

Here, R ¹¹ and R ¹² in the above formula (6) each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group. In addition, this alkyl group or aryl group may each have a substituent. Z represents an alkylene group having 4 to 20 carbon atoms. n represents an integer of 1 to 10. In addition, this alkylene group may have a substituent.

When R ¹¹ and R ¹² are alkyl groups having 1 to 20 carbon atoms, preferred examples thereof include a 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. Moreover, in the case of an aryl group, as a suitable thing, a phenyl group, a benzyl group, a tolyl group, 4-methylphenyl group, a naphthyl group etc. are mentioned, for example. Among these, 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, and in particular, both R ¹¹ and R ¹² are methyl groups, It is preferable that n is 1, that is, the linking group X in the above formula (5) is an isopropylidene group. Z in the above formula (7) is bonded to carbon bonding two phenyl groups in the above formula (5) to form a substituted or unsubstituted divalent carbocycle. Examples of the divalent carbocycle include a cycloalkylidene group such as a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group (preferably a carbon number of 5 To 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.

Examples of other dihydroxy compounds represented by formula (5) include dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, and 4,4′-dihydroxybiphenyl; -Dihydroxydiphenyl ether, 3,3
'-Dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) benzene, 1,3-bis (4-hydroxy) Dihydroxydiaryl ethers such as phenoxy) benzene; 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes abbreviated as bisphenol A or “BPA”), 1,1-bis (4-hydroxyphenyl) Propane, 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-hydride) Loxy-3,5-dimethylphenyl) propane, 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) naphthyl Methane, 1,1-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) Tan, 2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) 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 (hydroxyaryl) such as bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) nonane, 10-bis (4-hydroxyphenyl) decane, 1-bis (4-hydroxyphenyl) dodecane, etc. ) Alkanes; 1-bis (4-hydroxyphenyl) cyclopentane, 1-bis (4-hydroxy) Phenyl) 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, 1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3-t Bis (hydroxyaryl) cycloalkanes such as ert-butyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane, 1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl);
Cardiostructure-containing bisphenols such as fluorene; dihydroxydiaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide; 4,4′-dihydroxydiphenyl sulfoxide, 4 Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone And the like.

  Among these, bis (hydroxyaryl) alkanes are preferable among these dihydroxy compounds, and bis (4-hydroxyphenyl) alkanes are preferable among them, and in particular, from the viewpoint of impact resistance and heat resistance, 2,2- Bis (4-hydroxyphenyl) propane (BPA) is preferred. In addition, 1 type may be used for a dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

  Among the components in which the structural unit constituting the polycarbonate resin (A) is a dihydroxy compound, 2,2-bis (3-methyl-4-hydroxyphenyl) propane is usually 30 to 100 mol% in all dihydroxy compounds. It is preferably 40 to 100 mol%, more preferably 50 to 100 mol%, and particularly preferably 100 mol%. By containing 2,2-bis (3-methyl-4-hydroxyphenyl) propane in the above range, the hardness of the polycarbonate resin composition of the present invention can be effectively improved.

[3. Polycarbonate resin (B)]
The polycarbonate resin (B) used in the polycarbonate resin composition of the present invention has a structural unit (B-1) represented by the following formula (2) and a structural unit (B-2) represented by the following formula (3). A polycarbonate copolymer.

In the above formula (2), 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 is , 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.

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

Examples of the alkoxy group having 1 to 6 carbon atoms of R ¹ and R ^{2 in} the above formula (2) include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.
As a halogen atom of R < ¹ >, R < ² > in the said Formula (2), a chlorine atom, a bromine atom, a fluorine atom, etc. are mentioned.
In the above formula (2), R ¹ and R ² are preferably at least one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and are preferably a hydrogen atom or a methyl group. More preferably, it is a hydrogen atom.

In the above formula (2), R ³ , R ⁴ , R ⁵ and R ⁶ are preferably at least one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. More preferred is an atom or a methyl group, and most preferred is a methyl group.
In the above formula (2), R ⁷ and R ⁸ are preferably at least one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and are a hydrogen atom or a methyl group. It is more preferable that it is a hydrogen atom.

  Preferable specific examples of the structural unit represented by the above formula (2) include the following formulas (4), (8), (9), and (10), and the heat resistance of the polycarbonate resin composition of the present invention. It is preferable that the following formula (4) is used because flame retardancy is effectively enhanced and foreign matter tends to be reduced.

  Specific preferred examples of the structural unit represented by the above formula (4) include the following formulas (11), (12), and (13). Among them, dihydroxy of the following formula (11) Compounds are preferred.

The dihydroxy compound as a component derived from the constituents represented by the above formulas (2), (3), (4), (8) to (13) can be obtained by a known method (for example, JP-A-2014-114281). (Synthesis method described in the publication). The dihydroxy compound obtained by these methods is purified as necessary and applied to the dihydroxy compound contained as a structural unit in the polycarbonate resin (B) contained in the polycarbonate resin composition of the present invention.

  The polycarbonate resin (B) used in the polycarbonate resin composition of the present invention is a polycarbonate copolymer containing the structural unit (B-1) and the structural unit (B-2), and the proportion of the structural unit is as follows. The structural unit (B-1) is preferably 5 to 70 mol%, and the structural unit (B-2) is preferably 30 to 95 mol%. By including the structural unit (B-1) and the structural unit (B-2) in such a range, the compatibility with the polycarbonate resin (A) is enhanced, and the transparency of the polycarbonate resin composition of the present invention is enhanced. In addition, heat resistance is increased and mechanical properties such as impact resistance are improved.

  From such a viewpoint, the polycarbonate resin (B) used in the polycarbonate resin composition of the present invention is a polycarbonate copolymer containing the structural unit (B-1) and the structural unit (B-2). The proportion of the structural unit is more preferably composed of 10 to 65 mol% of the structural unit (B-1) and 45 to 90 mol% of the structural unit (B-2). It is still more preferable that it consists of 60 mol% and a structural unit (B-2) 40-80 mol%, a structural unit (B-1) 25-58 mol%, and a structural unit (B-2) 42-75. It is particularly preferred that it consists of mol%.

Moreover, the polycarbonate resin (B) used for the polycarbonate resin composition of this invention of this invention is the range which does not impair the objective of this invention, and the said structural unit (B-1) and structural unit (B-2).
1) or 2 or more types of structural units may be included, but these structural units are usually 30 moles in the total structural units including the structural unit (B-1) and the structural unit (B-2). % Or less, more preferably 20 mol% or less, still more preferably 10 mol% or less.
In addition, examples of the structural unit other than the structural unit (B-1) and the structural unit (B-2) include structures derived from monomers exemplified as other dihydroxy compounds represented by the formula (3). .

[4. Carbonate-forming compound]
Of the monomers used as the raw materials for the polycarbonate resin (A) and the polycarbonate resin (B) used in the polycarbonate resin composition of the present invention, examples of carbonate-forming compounds include carbonyl halides and carbonate esters. In addition, a carbonate forming compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

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 (14), R ¹³ and R ¹⁴ each independently represent 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 (15).

In formula (15), 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 to 20 carbon atoms. And an aryl group having 6 to 20 carbon atoms, p and q each independently represent an integer of 0 to 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. 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.

[5. Production method of polycarbonate resin]
The manufacturing method of polycarbonate resin (A) and polycarbonate resin (B) used for this invention 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.
The polycarbonate resin (A) and the polycarbonate resin (B) may be simply referred to as “polycarbonate resin”.

<Interfacial polymerization method>
First, the case where a polycarbonate resin is produced 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 the carbonate precursor are as described above. Of the carbonate precursors, phosgene is preferably used, and the method using phosgene is particularly called a 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 bisphenol 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 o-oxinebenzoic 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 usage-amount of a molecular weight regulator is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of a polycarbonate resin composition can be improved.
In the reaction, the order of mixing the reaction substrate, reaction solvent, catalyst, 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 precursor, the molecular weight regulator can be mixed at any time as long as it is between the reaction (phosgenation) of the dihydroxy compound and phosgene and 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 a polycarbonate resin is produced by a 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.
The dihydroxy compound and carbonate ester are as described above, 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, the amount of terminal hydroxyl groups tends to have a great influence on 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, a polycarbonate resin in which the amount of terminal hydroxyl groups is adjusted can be usually obtained by adjusting the mixing ratio of carbonate ester and aromatic dihydroxy compound; the degree of pressure reduction during the transesterification reaction. In addition, the molecular weight of the polycarbonate resin 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 producing a polycarbonate resin 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. In the case of a batch method, the order of mixing the reaction substrate, reaction solvent, catalyst, additive, etc. is arbitrary as long as the desired aromatic polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. However, in view of the stability of the polycarbonate resin 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.

<Other matters concerning polycarbonate resin>
The molecular weight of the polycarbonate resin is arbitrary and may be appropriately selected and determined. The viscosity average molecular weight [Mv] converted from the solution viscosity is usually 8000 or more, preferably 10,000 or more, more preferably 15000 or more, Usually, it is 40000 or less, preferably 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 is arbitrary and may be appropriately selected and determined, but is usually 2000 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. In addition, the lower limit is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, particularly for polycarbonate resins 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.

The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the polycarbonate resin. The measurement method is colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.
The polycarbonate resin composition according to the present invention is characterized in that the content of the polycarbonate resin (B) is 5 to 200 parts by mass of the polycarbonate resin (B) with respect to 100 parts by mass of the polycarbonate resin (A). To do. When content of a polycarbonate resin (B) is below the minimum of the said range, there exists a possibility that the heat resistance of the polycarbonate resin composition of this invention may become inadequate. Moreover, when content of polycarbonate resin (B) exceeds the upper limit of the said range, not only the fall of the hardness of the polycarbonate resin composition of this invention will be caused, but there exists a possibility that transparency and a moldability may be impaired. From such a viewpoint, the polycarbonate resin (B) is more preferably contained in an amount of 10 to 180 parts by mass, more preferably 20 to 150 parts by mass, with respect to 100 parts by mass of the polycarbonate resin (A). The content is particularly preferably 120 parts by mass, and most preferably 50 to 110 parts by mass.

[6. 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.

<Other resins>
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, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.

<Resin additive>
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.

[7. Transparency of polycarbonate resin composition]
The polycarbonate resin composition of the present invention preferably has a haze of 3 or less when formed into a molded product having a thickness of 3 mm. Such a resin composition is particularly excellent in transparency, and since such a resin composition is particularly excellent in the balance of hardness, heat resistance, and transparency, various electrical / OA equipment casings and displays , Panels, covers, lighting members, window members, signboards, display devices, and the like. Such a resin composition includes the structural unit (B-1) constituting the polycarbonate resin copolymer (B), the composition ratio of the structural unit (B-2), and the polycarbonate resin (A) as described above. It can be obtained by controlling the blending ratio with the polycarbonate resin copolymer (B).
The haze may be appropriately selected and used according to the member used and purpose, but is preferably 2.5 or less, more preferably 2.2 or less, and 2 or less. Particularly preferred.

[8. 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.
To give specific examples, the polycarbonate resin (A) and the polycarbonate resin copolymer (B) according to the present invention and other components to be blended as required are used, for example, by using various mixers such as a tumbler and a Henschel mixer. Examples of the method include 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 after mixing in advance.

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.

[9. 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. 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 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) 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter sometimes abbreviated as “BPC”) (Honshu Chemical Co., Ltd.) 6 5.7 kg (26.14 mol) and diphenyl carbonate (hereinafter sometimes abbreviated as “DPC”) 5.77 kg (26.92 mol), an aqueous solution of cesium carbonate, and 1.5 μmol of cesium carbonate per mol of dihydroxy compound Was added to prepare a mixture. Next, the mixture was charged into a first reactor having an internal volume of 200 L equipped with a stirrer, a heat medium jacket, a vacuum pump, and a reflux condenser.

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 55 rpm, the temperature in the heating medium jacket was controlled, and the internal temperature of the first reactor was kept at 220 ° C. The pressure in the first reactor was 101.3 kPa (760 Torr) in absolute pressure over 40 minutes while distilling off phenol produced as a by-product by the oligomerization reaction of BPC and DPC performed in the first reactor. To 13.3 kPa (100 Torr).

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.
Thereafter, the inside of the system was restored to the 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. Was pumped to the second reactor. 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 16 rpm, the internal temperature was raised with a heat 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 295 ° C. The polycondensation reaction was completed when the stirrer of the second reactor reached a predetermined stirring power.

Next, the inside of the second reactor is restored to 101.3 kPa in absolute pressure with nitrogen, and the gauge pressure is increased to 0.2 MPa, and the polycarbonate resin is extracted in a strand form from the bottom of the second reactor, The mixture was pelletized by using a rotary cutter while being cooled at the same time.
Blending the obtained pellets and 4-fold molar amount of butyl p-toluenesulfonate with respect to cesium carbonate, feeding to a twin-screw extruder, extruding onto a strand through an extruder die, and cutting with a cutter The pellet of the polycarbonate resin (A) which deactivated the polymerization catalyst was obtained.

Production Example 2 Production of Polycarbonate Resin (B) As a dihydroxy compound, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane (hereinafter abbreviated as “SBI”) May be abbreviated to 3.85 kg (about 12.5 mol) and 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as “BPA”) represented by the above formula (4). ) 2.85 kg (about 12.5 mol) and diphenyl carbonate (hereinafter sometimes abbreviated as “DPC”) 5.54 kg (about 25.85 mol), an aqueous solution of cesium carbonate, cesium carbonate containing 1 mol of dihydroxy compound The mixture was adjusted by adding 0.5 μmol per unit. 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.
Then, it superposed | polymerized similarly to manufacture example 1 (The polymerization reaction time in the 2nd reactor was 260 minutes), and the pellet of the polycarbonate resin copolymer (B) was obtained by deactivating a catalyst.

Production Example 3 Production of Polycarbonate Resin (C) As a dihydroxy compound, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane (hereinafter abbreviated as “SBI”) 3.66 kg (about 11.87 mol) and 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter referred to as “BPC”) represented by the above formula (4). 3.04)
kg (about 11.87 mol) and diphenyl carbonate (hereinafter may be abbreviated as “DPC”) 5.21 kg (about 24.33 mol), an aqueous solution of cesium carbonate, and cesium carbonate per 1 mol of dihydroxy compound. The mixture was adjusted by adding 5 μmol. 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.

Then, it superposed | polymerized similarly to manufacture example 1 (The polymerization reaction time in the 2nd reactor was 365 minutes), and the pellet of the polycarbonate resin copolymer (C) was obtained by deactivating a catalyst.
In addition, the SDI which is the raw material for producing the polycarbonate resin in Production Examples 1 to 3 was obtained by producing according to the method described in JP-A-2014-114281. BPA,
A DPC manufactured by Mitsubishi Chemical Corporation was used.

The components used in Examples and Comparative Examples are as follows.
Polycarbonate resin (A) (BPC homopolycarbonate resin obtained in Production Example 1 above, viscosity average molecular weight 26,100, terminal hydroxyl group concentration 540 ppm, abbreviated as “PC (A)”),
Polycarbonate resin (B) (copolymerized polycarbonate resin of SBI / BPA = 56/44 (mass ratio) obtained in Production Example 2 above, viscosity average molecular weight 16,400, terminal hydroxyl group concentration is 400 ppm, “PC (B) ”),
Polycarbonate resin (C) (copolymerized polycarbonate resin of SBI / BPC = 54/46 (mass ratio) obtained in Production Example 3 above, viscosity average molecular weight 17,900, terminal hydroxyl group concentration is 520 ppm, “PC (C) ”),
Polycarbonate resin (D) (bisphenol A type polycarbonate resin obtained by the melt ester method, viscosity average molecular weight 27,000, NOVAREX (registered trademark) 7027BF, manufactured by Mitsubishi Engineering Plastics Co., Ltd.)
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
The terminal hydroxyl group concentration was calculated according to the method described above (the 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.

[Preparation of test piece]
The pellets obtained by the above production method were dried at 120 ° C. for 5 hours, and then injection molded by an injection molding machine (J55AD manufactured by Nippon Steel Works, Ltd.) under conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. A flat test piece having a length of 60 mm, a width of 60 mm, and a thickness of 3 mm was formed.
[Hardness evaluation]
The plate pencil hardness measured with a 750 g load using a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd.) in accordance with ISO15184 was determined.

[Heat resistance evaluation]
Using a differential operation calorimeter (DSC 6220, manufactured by SII), about 10 mg of a polycarbonate resin sample is heated at a rate of temperature increase of 20 ° C./min to measure the amount of heat. In accordance with JIS-K7121, a baseline on the low temperature side is measured. The extrapolated glass transition start temperature, which is the temperature of the intersection of the straight line extending to the high temperature side and the tangent drawn at the point where the slope of the step-change part of the glass transition is maximized, is obtained, and this compensation is obtained. The outer glass transition temperature was defined as the glass transition temperature (Tg).

[Transparency evaluation]
In accordance with JIS K-7105, the above-mentioned flat test piece (3 mm thickness) was used as a test piece, and the haze value (unit: “%”) was measured with an NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd. The haze is a value used as a measure of the turbidity of the resin, and the smaller the numerical value, the higher the transparency.

As can be seen from Table 2, the polycarbonate resin compositions of Examples 1 and 2 are excellent in the balance of hardness, heat resistance, and transparency. On the other hand, Comparative Examples 1 and 2 have insufficient heat resistance, Comparative Example 3 has insufficient transparency, and Comparative Example 4 has both insufficient hardness and transparency.
Therefore, from the above Examples and Comparative Examples, it was confirmed that the effect of enhancing the hardness, 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 (5)

A polycarbonate resin composition comprising at least a polycarbonate resin (A) having a structural unit represented by the following formula (1) and a polycarbonate resin (B),
The polycarbonate resin (B) is a polycarbonate copolymer containing a structural unit (B-1) represented by the following formula (2) and a structural unit (B-2) represented by the following formula (3): And the content of this polycarbonate resin (B) is 5-200 mass parts with respect to 100 mass parts of this polycarbonate resin (A), The polycarbonate resin composition characterized by the above-mentioned.

(In the above formula (2), 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 claim 1, wherein the molded article having a thickness of 3 mm has a haze of 3 or less. The proportion of the structural unit (B-1) represented by the formula (2) in the polycarbonate resin (B) is 5 to 70 mol%, and the structural unit (B-2) represented by the formula (3) 3) The polycarbonate resin composition according to claim 1 or 2, which is 30 to 95 mol%. A structural unit (B-1) is represented by following formula (4), The polycarbonate resin composition of any one of Claim 1 thru | or 3 characterized by the above-mentioned.

  The polycarbonate resin molded object formed by shape | molding the polycarbonate resin composition of any one of Claims 1 thru | or 4.