JP3228309B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition having excellent heat resistance and impact resistance and suitably used for mechanical parts, electric / electronic parts, automobile parts, optical parts and the like.

[0002]

2. Description of the Related Art
It is known that a polycarbonate copolymer containing -bis (4-hydroxyphenyl) fluorene has high heat resistance (US Pat. No. 3,546,165).
However, polycarbonate containing 9,9-bis (4-hydroxyphenyl) fluorene has low impact resistance, and its improvement is strongly desired. As a method for improving the impact resistance, for example, a method such as block copolymerization with siloxane is known (J. Appl. Polym. Sci. Vol. 20, P-
3275,1976). However, the polycarbonate copolymer with siloxane obtained by this method is expensive, is not very useful industrially, and its improvement effect is not so great.

[0003]

Means for Solving the Problems Accordingly, the present inventors have:
In view of the above, intensive studies have been made to solve the conventional problems described above and to obtain a polycarbonate resin composition having excellent heat resistance and impact resistance. As a result, the main chain is composed of a carbonate structural unit I derived from bisphenols and a carbonate structural unit II derived from fluorenes, and the proportion of the carbonate structural unit II is adjusted to a specific range. Has been found to have the desired properties. The present invention has been completed based on such findings. That is, in the present invention, (A) the main chain is represented by the general formula (I):

[0004]

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[Wherein R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different. And (b) a carbonate structural unit represented by the general formula (II):

[0006]

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[Wherein X is a halogen atom or a group having 1 to 1 carbon atoms.
8 represents an organic group, and when there are a plurality of Xs, each X may be the same or different. m and n are each an integer of 0-4. A polycarbonate copolymer comprising a carbonate structural unit II represented by the formula (1), wherein the proportion of the carbonate structural unit II is 15 to 100 mol% based on the total amount of the carbonate structural unit I and the carbonate structural unit II; B) General formula (III)

[0008]

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Wherein Y is a halogen atom, having 1 to 8 carbon atoms.
Represents an alkyl group or an aryl group having 6 to 15 carbon atoms,
When there are a plurality of Ys, each Y may be the same or different. p and q are each an integer of 0-4. A is a single bond, -O-, -S
—, —SO ₂ —, 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, a cycloalkylene group having 5 to 15 carbon atoms, and a carbon atom having 6 to 6 carbon atoms. 15 represents an arylene group or an arylalkylene group having 7 to 15 carbon atoms. And a polycarbonate polymer having a carbonate structural unit III represented by the formula (I), and based on the total amount of the components (A) and (B):
The carbonate structural unit II represented by the general formula (II) has 2 to 2
An object of the present invention is to provide a polycarbonate resin composition characterized by being 15 mol%.

First, the polycarbonate copolymer (PC copolymer) of the component (A) constituting the polycarbonate resin composition of the present invention has a main chain represented by the general formula (I) in which the component (a) is used. And a carbonate structural unit II represented by the general formula (II) as the component (b). Here, R ¹ and R ² in the carbonate structural unit I represented by the general formula (I) each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, butyl group). And may be the same or different. X in the carbonate structural unit II represented by the general formula (II) is
A halogen atom (eg, chlorine, bromine, fluorine, iodine) or an organic group having 1 to 8 carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl,
Alkyl groups such as heptyl group and octyl group, methoxy group, ethoxy group, propyloxy group, butyloxy group,
A pentyloxy group, a hexyloxy group, a heptyloxy group, an alkoxy group such as an octyloxy group), and when there are a plurality of X, each X may be the same or different; And n are each an integer of 0 to 4.

In the present invention, the PC copolymer as the component (A) is produced from the following bisphenols as raw materials. That is, the bisphenol (i) corresponding to the carbonate structural unit I of the component (a) constituting the main chain of the PC copolymer has the general formula (IV)

[0012]

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Wherein R ¹ and R ² are the same as above. ] Is used. The bisphenol (ii) corresponding to the carbonate structural unit II of the component (b) constituting the main chain of the PC copolymer is represented by the general formula (V)

[0014]

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Wherein X, m and n are the same as above. ] Is used. Here, there are various bisphenols (i) represented by the general formula (IV). Specifically, bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A]; 2,2-bis (4-hydroxyphenyl) butane; 2,2-bis (4
-Hydroxyphenyl) pentane; 3,3-bis (4-
2,2-bis (4-hydroxyphenyl) octane; 2,2-bis (4-hydroxyphenyl) hexane; 3,3-bis (4-hydroxyphenyl) hexane and the like. Among these bisphenols (i), 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A] is preferably used. These bisphenols may be used alone or in combination of two or more.

There are various bisphenols (ii) represented by the general formula (V). Specific examples include 9,9-bis (4-hydroxyphenyl) fluorene; and 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene. Among these bisphenols (ii), 9,9-bis (4-hydroxyphenyl) fluorene is preferably used. These bisphenols may be used alone or in combination of two or more.

In the present invention, the PC copolymer is
The polycarbonate can be produced by a method commonly used in the production of ordinary polycarbonate, for example, an interfacial polycondensation method using phosgene or a phosgene derivative or a transesterification method (melting method). Among these, it is preferable to produce by the interfacial polycondensation method. As an interfacial polycondensation method using phosgene or a phosgene derivative, for example, a bisphenol (i) polycarbonate oligomer (PC oligomer I) or bisphenol (ii) is prepared in advance from bisphenol (i) or (ii) and phosgene or a phosgene derivative. Polycarbonate oligomer (P
C Oligomers II) have been synthesized, and a solution of these oligomers in an inert organic solvent, bisphenols (i) and (ii)
A phosgene or phosgene derivative in a mixed solution of an alkaline aqueous solution containing bisphenols (i) and (ii) in a predetermined ratio and an inert organic solvent. And a reaction method. Among these, the former oligomer method is preferred. Examples of the phosgene or phosgene derivative include phosgene, triphosgene, bromophosgene, bis (2,4,6-trichlorophenyl).
Carbonate, bis (2,4-dichlorophenyl) carbonate, bis (2-cyanophenyl) carbonate,
Trichloromethyl chloroformate and the like.

Here, PC of component (A) in the present invention
A method for producing a copolymer by an oligomer method will be described. First, the bisphenol (i) or bisphenol (ii) is dissolved in an aqueous solution of an alkali metal hydroxide to prepare an alkaline aqueous solution of bisphenol. Next, phosgene or a phosgene derivative is introduced into the mixture of the alkaline aqueous solution and the inert organic solvent to synthesize PC oligomer I or PC oligomer II. At this time, the alkali concentration of the aqueous alkali solution is preferably in the range of 1 to 15% by weight, and the volume ratio of the organic phase to the aqueous phase is 5: 1 to 1%.
It is desirably in the range of 1: 7, preferably 2: 1 to 1: 4. The reaction temperature is cooled in a water bath and is usually selected in the range of 0 to 50 ° C, preferably 5 to 40 ° C, and the reaction time is about 15 minutes to 4 hours, preferably about 30 minutes to 2 hours. The degree of polymerization of the PC oligomer thus obtained is usually 20 or less, preferably about 2 to 10.

Subsequently, if necessary, an inert organic solvent is added to the organic phase containing the PC oligomer obtained as described above, and an aqueous alkaline solution containing bisphenols (i) and (ii) at a predetermined ratio is added thereto. , Usually 0 to 50
C., preferably at a temperature in the range of 5 to 40.degree.
Interfacial polycondensation is carried out for about minutes to 6 hours. At this time, the alkali concentration of the aqueous alkali solution is preferably 1 to 15% by weight, and the volume ratio of the organic phase to the aqueous phase is in the range of 7: 1 to 1: 2, preferably 4: 1 to 1: 1. It is desirable. And the ratio of bisphenol and the PC oligomer is
The molar ratio of the chloroformate group of the bisphenol / PC oligomer is usually from 0.4 to 0.55, preferably from 0.45 to 0.5.
Is chosen to be The alkali metal hydroxide / oligomer ratio is such that the alkali metal hydroxide / oligomer chloroformate group molar ratio is usually 1.0 to 2.0,
Preferably, it is selected to be 1.2 to 1.7. further,
In this reaction, a terminal terminator or a catalyst can be used as desired. The amount of the terminating agent used is the terminating agent /
The chloroformate group molar ratio of the oligomer is usually 0.02
00.20, preferably 0.04〜0.17. The amount of the catalyst used is such that the molar ratio of the chloroformate group of the catalyst / oligomer is usually 1.0 × 10 ^{−3 to} 10.0.
× 10 ⁻³ , preferably 1.0 × 10 ^{−3 to} 5.0 × 10 ⁻³ .

The alkali metal hydroxide used in the production of the PC copolymer includes, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide and the like. Of these, sodium hydroxide and potassium hydroxide are preferred. Particularly, in the case of fluorene of bisphenol (ii), potassium hydroxide is most suitable. There are various kinds of inert organic solvents. For example, dichloromethane (methylene chloride); chloroform; 1,1-dichloroethane;
-Dichloroethane; 1,1,1-trichloroethane;
1,1,2-Trichloroethane; 1,1,1,2-tetrachloroethane; 1,1,2,2-tetrachloroethane; chlorinated hydrocarbons such as pentachloroethane and chlorobenzene, and acetophenone. These organic solvents may be used alone or in combination of two or more. Of these, methylene chloride is particularly preferred.

As the terminal terminator, various types can be used. Specifically, examples of the monohydric phenol include phenol, p-cresol, pt-
Butylphenol, p-cumylphenol, tribromophenol, nonylphenol, pt-octylphenol and the like can be mentioned. Also, various catalysts can be used. Specifically, it is a quaternary ammonium salt, a quaternary phosphonium salt, a tertiary amine, or the like. , Tetrabutylammonium chloride, tetrabutylammonium bromide and the like. Examples of the quaternary phosphonium salt include tetrabutylphosphonium chloride and tetrabutylphosphonium bromide, and examples of the tertiary amine include triethylamine, tributylamine, N, N-dimethylcyclohexylamine, pyridine and dimethylaniline. And the like.

The PC copolymer of the present invention can be obtained by subjecting the thus produced polymer to a recovery operation according to a usual method. This PC copolymer is a polycarbonate copolymer having a main chain of a carbonate structural unit I represented by the general formula (I) and a carbonate structural unit II represented by the general formula (II). In the PC copolymer, the proportion of the carbonate structural unit II represented by the general formula (II) is 15 to 15 with respect to the total amount of the carbonate structural unit I and the carbonate structural unit II.
100 mol%. This PC copolymer has a viscosity average molecular weight of 10,000 to 50,000, preferably 1 to 50,000.
It is 2,000 to 40,000, and is excellent in heat resistance and impact resistance.

Next, the polycarbonate polymer (P) of the component (B) constituting the polycarbonate resin composition of the present invention.
C) has a carbonate structural unit III represented by the general formula (III), and includes various types. For the production of this PC, bisphenol is represented by the general formula (VI)

[0024]

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The compound represented by the following formula is used. here,
In the above general formula (VI), Y is a halogen atom (for example, a salt
, Bromine, fluorine, iodine) or alkyl having 1 to 8 carbon atoms
Groups (eg, methyl, ethyl, propyl, butyl
Group, pentyl group, hexyl group, heptyl group, octyl group
Or an aryl group having 6 to 15 carbon atoms (for example,
Nyl, hydroxyphenyl, methylphenyl, na
And a plurality of Y's.
Y may be the same or different. Ma
Here, p and q are each an integer of 0 to 4. Soshi
A is a single bond, an alkylene group having 1 to 8 carbon atoms or a carbon
An alkylidene group having a prime number of 2 to 8 (for example, a methylene group,
Tylene group, propylene group, butylene group, pentylene group,
Hexylene, ethylidene, isopropylidene
Etc.), a cycloalkylene group having 5 to 15 carbon atoms or carbon number
5 to 15 cycloalkylidene groups (for example, cyclopen
Tylene group, cyclohexylene group, cyclopentylidene
Group, cyclohexylidene group, etc.)
A arylene group or an arylalkylene group having 7 to 15 carbon atoms
(For example, phenylene group, naphthylene group, xylylene
Group, phenylethylidene group, etc.), or -S-, -SO
−, −SO _Two-, -O-, -CO- bond or general formula
(VII)

[0026]

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The bond represented by In the present invention,
The PC as the component (B) can be easily prepared by reacting the bisphenol represented by the general formula (VI) with phosgene or a carbonic acid diester compound by an interfacial polycondensation method or transesterification method commonly used in the production of ordinary PC. Can be manufactured. That is, for example, in the interfacial polycondensation method, in a solvent such as methylene chloride, in the presence of a known acid acceptor or terminal terminator, the bisphenol represented by the general formula (VI) and the phosgene or the phosgene derivative described above are used. It is produced by a reaction with a suitable carbonate precursor or, in the transesterification method, by a transesterification reaction of the bisphenol with a carbonate precursor such as diphenyl carbonate.

Here, there are various bisphenols represented by the general formula (VI). Specifically, for example, bis (4-hydroxyphenyl) methane; 1,1
-Bis (4-hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A); 2,2-bis (4-hydroxyphenyl)
Butane; 2,2-bis (4-hydroxyphenyl) octane; 2,2-bis (4-hydroxyphenyl) phenylmethane; 2,2-bis (4-hydroxy-1-methylphenyl) propane; 1,1- Bis (4-hydroxy-
t-butylphenyl) propane; 2,2-bis (4-hydroxy-3-bromophenyl) propane; 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane; 2,2-bis (4 -Hydroxy-3-chlorophenyl) propane; 2,2-bis (4-hydroxy-3,
5-dichlorophenyl) propane; 2,2-bis (4-
Bis (hydroxyaryl) alkanes such as hydroxy-3,5-dibromophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane; 1,1
-Bis (4-hydroxyphenyl) cyclohexane;
1,1-bis (4-hydroxyphenyl) -3,5,5
Bis (hydroxyaryl) cycloalkanes such as -trimethylcyclohexane, 4,4-dihydroxydiphenyl ether; 4,4'-dihydroxy-3,3'-
Dihydroxyaryl ethers such as dimethylphenyl ether; 4,4'-dihydroxydiphenylsulfide; dihydroxydiarylsulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide;4,4'-dihydroxydiphenylsulfoxide; Dihydroxyarylsulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide;4,4'-dihydroxydiphenylsulfone; dihydroxydiaryl such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone Sulfones and the like. Among these, bisphenol A is particularly preferred. These bisphenols may be used alone or in combination of two or more.

In the production of PC as the component (B), bisphenol represented by the general formula (VI) can be used including a compound having three or more functional groups (branching agent). Here, the compound having three or more functional groups includes a compound having three or more functional groups such as a hydroxyl group, a carboxyl group, an amino group, an imino group, a formyl group, an acid halide group, and a haloformate group in one compound. It is. For example, phloroglucin, melitic acid, trimellitic acid, trimellitic chloride, trimellitic anhydride, gallic acid, n-propyl gallate, protocatechuic acid, pyromellitic acid, pyromellitic dianhydride, α-resorcinic acid, β-resorcinic acid
-Resorcinic acid, resorcinaldehyde, trimethyl chloride, trimethyltri-4-chloroformylphthalic anhydride, benzophenonetetracarboxylic acid; 4,6-dimethyl-2,4,6-tri (4'-hydroxyphenyl)
-Heptene-2; 4,6-dimethyl-2,4,6-tri (4'-hydroxyphenyl) -heptane-2; 1,
3,5-tri (4'-hydroxyphenyl) -benzene; 1,1,1-tri- (4'-hydroxyphenyl)
-Ethane; 2,2-bis- [4,4-bis (4'-hydroxyphenyl) cyclohexyl] -propane; 2,6
-Bis- (2'-hydroxy-5'-methylbenzyl)
4-methylphenol; 2,6-bis- (2'-hydroxy-5'-isopropylbenzyl) -4-isopropylphenol; bis- [2-hydroxy-3- (2 '
-Hydroxy-5'-methylbenzyl) -5-methylphenyl] methane; tetra- (4-hydroxyphenyl)
Methane; tri- (4-hydroxyphenyl) phenylmethane; tris (4'-hydroxyaryl) -amyl-
s-triazine; α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl-4- [Α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; 1- [α-methyl-α
-(4'-hydroxyphenyl) ethyl] -3-
[Α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene and the like.
1,1-Tri- (4'-hydroxyphenyl) -ethane is preferred.

Various types of terminal terminators can be used. Usually, it is used for polymerization of polycarbonate, and monohydric phenol is used. For example, phenol, p-cresol, p-tert-
Butylphenol, p-tert-octylphenol, p
-Cumylphenol, p-bromophenol, tribromophenol, nonylphenol and the like. The viscosity average molecular weight of the PC thus obtained is 100,000
It is from 0 to 50,000, preferably from 12,000 to 40,000. When the viscosity average molecular weight is less than 10,000, mechanical strength such as impact resistance is reduced. On the other hand, when it exceeds 50,000, the fluidity is lowered and the moldability is deteriorated, which is not preferable. As the PC of the component (B), a commercially available PC can be used.

The resin composition of the present invention comprises the PC copolymer of the component (A) and PC of the component (B), and the components (A) and (B) comprise the components (A) and (B). The carbonate structural unit II represented by the general formula (II) is 2 to 15 mol%, preferably 5 to 1 mol%, based on the total amount of the component (B).
It is blended to be 5 mol%. When the amount of the carbonate structural unit II represented by the general formula (II) in the resin composition is less than 2 mol%, the heat resistance decreases. On the other hand, if it exceeds 15 mol%, the mechanical strength is undesirably reduced.

The resin composition of the present invention may optionally contain various additives as the component (C) as long as the object of the present invention is not impaired. For example,
Various additives include antioxidants such as hindered phenols, phosphites and phosphates, ultraviolet absorbers such as benzotriazoles and benzophenones, light stabilizers such as hindered amines, and aliphatics. Examples include internal lubricants such as carboxylic acid esters, paraffin, silicone oil, and polyethylene wax, flame retardants, flame retardant assistants, antistatic agents, coloring agents, and the like.

The resin composition of the present invention comprises the above component (A)
And component (B) and, if necessary, component (C),
It can be obtained by kneading. For the compounding and kneading, a method generally used, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a co-kneader, a multi-screw extruder, etc. Can be performed. In addition, the heating temperature at the time of kneading is usually selected in the range of 250 to 300 ° C. The polycarbonate resin composition thus obtained can be applied to various known molding methods, for example, injection molding, hollow molding, extrusion molding, compression molding, calendar molding, rotational molding, etc., to produce various molded products. Can be used for

[0034]

The present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples. Synthesis Example 1 [Synthesis of PC oligomer I] 5% by weight of 400 liters
60 kg of bisphenol A in aqueous sodium hydroxide solution
After dissolution, an aqueous sodium hydroxide solution of bisphenol A was prepared. Then, the sodium hydroxide aqueous solution of bisphenol A kept at room temperature was passed through an orifice plate at a flow rate of 138 liters / hour and methylene chloride at a flow rate of 69 liters / hour through a tubular reactor having an inner diameter of 10 mm and a length of 10 m. And phosgene was co-currently added to the mixture.
Blowing was performed at a flow rate of 7 kg / hour, and the reaction was continuously performed for 3 hours. The tubular reactor used here is a double tube,
The outlet temperature of the reaction solution was maintained at 25 ° C. through cooling water through the jacket portion. The pH of the discharged liquid is 10 to 11
Was adjusted as shown. The reaction solution thus obtained was allowed to stand, and the aqueous phase was separated and removed. 220 l of a methylene chloride phase was collected, and 170 l of methylene chloride was further added thereto. Oligomer I (concentration 317 g / l)
And The degree of polymerization of the PC oligomer I obtained here was 3
-4.

Synthesis Example 2 [Synthesis of PC Oligomer II] The sodium hydroxide aqueous solution of Synthesis Example 1 was changed to a 9% by weight aqueous solution of potassium hydroxide, and 9,9-bis (4-hydroxyphenyl) fluorene was used instead of bisphenol A. Synthesis Example 1 except that the weight was 55 kg
It carried out similarly to. PC oligomer obtained here
The polymerization degree of II was 3-4.

[0036] Production Example 1 [Production of PC copolymer A _1] A solution prepared PC oligomer I 7 liters of methylene chloride 7.5 liters and p- tert-butylphenol (PTB
Solution A was prepared by adding 64.4 g (0.43 mol) of P). Preparation of solution B 9,9-bis (4-hydroxyphenyl) fluorene 7
82 g (2.24 mol) of KOH aqueous solution (448 g of KOH)
Was dissolved in 9 liters of water. ) To prepare solution B. To the solution A, 3 ml of triethylamine was added, and the solution B was quickly added with stirring, followed by stirring for 60 minutes. 6
After stirring for 0 minutes, 7 liters of methylene chloride was added, diluted, and centrifuged. The methylene chloride phase was washed with a 0.03 NKOH aqueous solution, 0.1 N hydrochloric acid and water in this order. The washed methylene chloride phase was gradually added into vigorously stirred methanol to obtain a polymer powder. The polymer powder is then:
After drying at 20 ° C. for 12 hours under a stream of N ₂ ,
Vacuum drying was performed at 0 ° C. for 48 hours to obtain a flaky polymer.

[0037] Production Example 2 [Production of PC copolymer A _2] A solution prepared polycarbonate oligomer II 7 liters of methylene chloride 7.5 liters and p- tert-butylphenol (PTBP) 43.6g (0.29 mol ) Was added to prepare solution A. Preparation of Liquid B Liquid B was prepared by dissolving 510 g (2.24 mol) of bisphenol A in an aqueous NaOH solution (320 g of NaOH was dissolved in 4.7 liters of water). Hereinafter, in the same manner as in Production Example 1, a flaky polymer was obtained.

The PC copolymer A ₁ obtained in Production Examples 1 and 2
And for PC copolymer A _2, and measuring the composition analysis and the viscosity-average molecular weight of the monomer. The analysis and measurement results are shown in Table 1. The analysis and measurement methods are as follows. 1) Analysis of monomer composition Analysis was performed using a high-resolution nuclear magnetic resonance apparatus (NMR). 2) Viscosity average molecular weight (Mv) The intrinsic viscosity [η] was measured in methylene chloride at 20 ° C. using an Ubbelohde viscosity tube, and the molecular weight was determined by the following relational expression. [Η] = 1.23 × 10 ^-5 · Mv ^0.83

[0039]

[Table 1]

Examples 1 to 5 and Comparative Examples 1 to 3 The PC copolymers A ₁ and A 2 obtained in Production Examples ₁ and ₂ and commercially available polycarbonates B _{1 to} B ₃ are shown in Table 2. Dry blending was performed at the mixing ratio shown, and 800 ppm of tris (2,4-di-t-butylphenyl) phosphite (Irgafos 168, manufactured by Ciba Geigy) was added as an antioxidant, and the mixture was kneaded using an extruder to form pellets. did. Each of the obtained pellets was dried at 120 ° C. for 8 hours, and then injection molded to prepare a test piece. About the obtained test piece, impact resistance and heat resistance were measured as quality evaluation. In addition, flame retardancy and melt tension were measured for a part. Table 3 shows the measurement results. In addition, the measuring method of quality evaluation is as follows. 1) Impact resistance Izod impact strength test (based on JIS K-7110)
Fracture behavior at time (thickness 1/8 inch, with notch) Ductile fracture number / test number 2) Heat resistance High load thermal deformation temperature (based on JIS K-7207 Load deflection temperature test method A) 3) Flame retardancy Flame Retardancy Test UL-94 1/16 inch (thickness) A vertical flammability test was performed according to Underwriters Laboratory Subject 94. 4) Melt tension 300 ° C., take-up speed 60 rpm Orifice L / D = 8 / 2.1 Tension generated at 8 / 2.1 (g) The commercially available polycarbonate is as follows. B ₁ : Toughlon A-2200 [manufactured by Idemitsu Petrochemical Co., Ltd.
Polycarbonate whose carbonate structural unit is derived from bisphenol A] B ₂ : Tafflon NB-2500 [Idemitsu Petrochemical Co., Ltd.]
Ltd., carbonate structural units, bisphenol A and polycarbonate derived from tetrabromobisphenol A] B _3: TARFLON IB-2500 [manufactured by Idemitsu Petrochemical Co.,
, A branched polycarbonate having a carbonate structural unit derived from bisphenol A]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

As described above, the polycarbonate resin composition of the present invention has excellent heat resistance and impact resistance. Therefore, the polycarbonate resin composition of the present invention can be used for mechanical parts,
It can be suitably used for electronic parts, automobile parts, optical parts and the like.

──────────────────────────────────────────────────続 き Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 64/00-64/42 C08L 69/00

Claims (2)

(57) [Claims] (A) the main chain is (a) a compound represented by the following general formula (I): [Wherein, R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different. And (b) a carbonate structural unit represented by the general formula (II): [In the formula, X represents a halogen atom or an organic group having 1 to 8 carbon atoms, and when there are a plurality of Xs, each X may be the same or different. m and n are each an integer of 0-4. And the proportion of the carbonate structural unit II is the same as that of the carbonate structural unit I and the carbonate structural unit II.
15 to 100 mol% of a polycarbonate copolymer with respect to the total amount of II, and (B) a general formula (III) [In the formula, Y represents a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms. When there are a plurality of Y, even if each Y is the same, they are different. You may. p and q are each an integer of 0-4. A is a single bond, —O—, —S—, —SO ₂ —, 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, and 5 carbon atoms.
A cycloalkylidene group having 1 to 15 carbon atoms, an arylene group having 6 to 15 carbon atoms or an arylalkylene group having 7 to 15 carbon atoms. Wherein the carbonate structural unit II represented by the general formula (II) is composed of a polycarbonate polymer having a carbonate structural unit III represented by the following general formula (II) with respect to the total amount of the components (A) and (B): 2 to 15 mol% of the polycarbonate resin composition. 2. The polycarbonate resin composition according to claim 1, wherein the carbonate structural unit II represented by the general formula (II) is derived from 9,9-bis (4-hydroxyphenyl) fluorene.