JP3334732B2 - Polycarbonate resin, method for producing the same, and resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin, a method for producing the same, and a resin composition. More specifically, the present invention relates to a polycarbonate resin excellent in mold release, impact resistance, fluidity and rigidity, a method for producing the same, and a resin composition.

[0002]

2. Description of the Related Art Polycarbonate resin (hereinafter sometimes abbreviated as PC) is a type of polycarbonate resin.
It is excellent in mechanical strength, electrical properties, transparency, etc., and is widely used as an engineering plastic in various fields such as electric / electronic devices and automobiles.
As a polycarbonate resin having such characteristics, a glass fiber reinforced polycarbonate resin to which glass fibers are added as an inorganic filler in order to improve rigidity and dimensional stability is known. However, the polycarbonate resin has a problem that the releasability at the time of molding is significantly reduced by adding glass fiber. Conventionally, as a method of improving the releasability at the time of molding, which is reduced by adding the glass fiber to a polycarbonate resin, a technique of adding a small amount of polyorganosiloxane (silicone oil) has been developed. However, although the releasability is improved by this method, it is still not satisfactory. When a large amount of silicone oil is added, there is a problem that kneading of the resin becomes difficult. Also, for example, Japanese Patent Application Laid-Open No. Hei 2-173601 discloses a technique of blending a copolymer of a polyorganosiloxane and a polycarbonate resin with glass fiber, and the releasability is improved. There is a strong demand for the development of technology with improved moldability.

[0003]

In view of the above circumstances, the present inventor has solved the drawbacks of the conventional method and provided a polycarbonate resin excellent in mold release, impact resistance, fluidity and rigidity. Intensive research was conducted to develop a production method and a resin composition. As a result, an AB diblock polymer and an ABA triblock which are polycarbonate-polyorganosiloxane copolymers obtained by copolymerizing the polycarbonate (A) and the polyorganosiloxane (B). It has been found that the use of a polycarbonate resin containing a polymer further improves the intended releasability. The present invention has been completed based on such findings.

That is, the present invention provides a compound represented by the general formula (I)

[0005]

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[Wherein R ¹ and R ² each represent a halogen atom, an alkyl group having 1 to 8 carbon atoms or a C 6 to 20
Which may be the same or different, and p and q are integers of 0 to 4,
m is 1 to 150. R ³ is a halogen atom, carbon number 1
Represents an alkyl group having from 20 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, or an arylalkyl group having from 7 to 20 carbon atoms;
It is an integer of 5. And Z is a single bond, carbon number 1-2.
0 alkylene group or alkylidene group, 5-20 carbon atoms
A cycloalkylene or cycloalkylidene group of —O
—, —S—, —SO ₂ — bond or general formula (II) or (II ′)

[0007]

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[0008] The bond represented by Also, R ^{4 to} R ⁷
Is an alkyl group having 1 to 8 carbon atoms or 6 to 8 carbon atoms, respectively.
And represents 20 aryl groups, which may be the same or different, and n is 1 to 500. R ⁸ represents a divalent organic residue containing an aliphatic and / or aromatic group;
R ⁹ is an alkyl group having 1 to 8 carbon atoms or 6 to 2 carbon atoms.
And 0 represents an aryl group. A represents a single bond, -O- or -NH-. A polycarbonate-polyorganosiloxane diblock copolymer represented by the general formula:
(III)

[0009]

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Wherein R ¹ and R ² are each a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a C 6 to 20
Which may be the same or different, and p and q are integers of 0 to 4,
m is 1 to 150. R ³ is a halogen atom, carbon number 1
Represents an alkyl group having from 20 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, or an arylalkyl group having from 7 to 20 carbon atoms;
It is an integer of 5. And Z is a single bond, carbon number 1-2.
0 alkylene group or alkylidene group, 5-20 carbon atoms
A cycloalkylene or cycloalkylidene group of —O
—, —S—, —SO ₂ — bond or general formula (II) or (II ′)

[0011]

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The bond represented by Also, R ^{4 to} R ⁷
Is an alkyl group having 1 to 8 carbon atoms or 6 to 8 carbon atoms, respectively.
And represents 20 aryl groups, which may be the same or different, and n is 1 to 500. R ⁸ represents a divalent organic residue containing an aliphatic and / or aromatic group.
A represents a single bond, -O- or -NH-. A polycarbonate-based resin comprising a polycarbonate-polyorganosiloxane triblock copolymer represented by the formula: wherein the viscosity-average molecular weight of the polycarbonate-based resin is from 10,000 to 50,000, and Polyorganosiloxane content in resin
An object of the present invention is to provide a polycarbonate-based resin having a content of 0.1 to 20% by weight. Further, the present invention, in the presence of dihydric phenol and monohydric phenol, a polycarbonate oligomer, a general formula (IV)

[0013]

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[Wherein R^Four~ R⁷Has 1 to 1 carbon atoms
8 represents an alkyl group or an aryl group having 6 to 20 carbon atoms.
And whether they are the same or differentYo
And n is 1 to 500. R⁸Is aliphatic and / or aromatic
A divalent organic residue containing an aromatic group;⁹Is 1 carbon
Represents an alkyl group having from 8 to 8 or an aryl group having from 6 to 20 carbon atoms.
You. And A represents a single bond, -O- or -NH-.
You. And a one-terminal reactive polyorganosiloxane represented by the formula:
General formula (V)

[0015]

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[Wherein R^Four~ R⁷Has 1 to 1 carbon atoms
8 represents an alkyl group or an aryl group having 6 to 20 carbon atoms.
And whether they are the same or differentYo
And n is 1 to 500. R⁸Is aliphatic and / or aromatic
Shows a divalent organic residue containing an aromatic. And A is simple
In the case, it represents -O- or -NH-. Reacts the polyorganosiloxane having both ends reactive represented by
And a monohydric phenol represented by the general formula (IV)
5 times the amount of one-end reactive polyorganosiloxane
(Molar ratio) or more and polycarbonate oligomer
-Formula (IV) and Formula (V) for 100 parts by weight
One- and both-end reactive polyorganosilates represented by
Characterized by using a total of 0.12 to 35 parts by weight of sun
the aboveProviding a method for producing a polycarbonate resin
It is. Further, the present invention provides (A) the above polycarbonate
(B) polycarbonate resin
0-80% by weight of fat and (C) 5-60% by weight of inorganic filler
Polycarbonate resin composition characterized by comprising
It provides things.

First, the polycarbonate resin of the present invention has the general formula (I)

[0018]

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The polycarbonate-polyorganosiloxane diblock copolymer represented by the following formula (hereinafter referred to as PC-PDM)
It may be abbreviated as S copolymer I. ) And the general formula (III)

[0020]

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The polycarbonate-polyorganosiloxane triblock copolymer represented by the following formula (hereinafter referred to as PC-PD)
It may be abbreviated as MS copolymer II. ). Here, PC-P represented by the general formula (I)
In the DMS copolymer, R ¹ and R ² each represent a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, an iodine atom) and an alkyl group having 1 to 8 carbon atoms (for example, a methyl group,
Ethyl group, propyl group, n-butyl group, isobutyl group,
Amyl group, isoamyl group, hexyl group and the like or an aryl group having 6 to 20 carbon atoms, preferably 6 to 18 carbon atoms (for example,
A phenyl group, a tolyl group, a xylyl group, and a naphthyl group), which may be the same or different, p and q are integers of 0 to 4, and m is 1 to 15
0, preferably 3 to 140, particularly preferably 5 to 130
It is. Z represents a single bond, an alkylene group having 1 to 20, preferably 2 to 18 carbon atoms or an alkyldene group (for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an ethylidene group,
An isopropylidene group, a cycloalkylene group having 5 to 20 carbon atoms or a cycloalkylidene group (eg, a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group, a cyclohexylidene group, etc.), -O-, -S- ,
—SO ₂ —, —CO— bond or general formula (II) or
(II ')

[0022]

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The bond represented by

R ^{4 to} R ⁷ each have 1 to 1 carbon atoms.
8 alkyl groups (for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, an amyl group, an isoamyl group, a hexyl group and the like) or an aryl group having 6 to 20, preferably 6 to 18 carbon atoms. For example, a phenyl group, a tolyl group, a xylyl group, and a naphthyl group) may be the same or different. And n is 1 to
500, preferably 51-500, more preferably 10
1 to 500. R ⁸ is a divalent organic residue containing an aliphatic and / or aromatic group (for example, a methylene group, an ethylene group, a propylene group, a butylene group, a penterylene group,
Hexylene group, ethylidene group, isopropylidene group, cyclopentylene group, cyclohexylene group, cyclopentylidene group, cyclohexylidene group, etc.)
(VI), (VI ') or (VI ")

[0025]

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[Wherein (A) and (Si) represent bonding to A and Si in the general formulas (I) and (III), respectively. O-allylphenol residue, p-vinylphenol residue, eugenol residue and the like. Further, R ⁹ is an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, an amyl group, an isoamyl group, a hexyl group) or a C ⁶ to C 20 group. And an aryl group (for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc.). A represents a single bond, -O- or -NH-.

PC-PDM represented by the general formula (I)
The S copolymer I has a main chain represented by the general formula (VII)

[0028]

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Wherein R ¹ , R ² , Z, p and q are the same as above. And a polycarbonate (PC) part (A) of the repeating unit I represented by the following general formula (VIII):

[0030]

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[Wherein R ^{4 to} R ⁷ , R ⁸ , R ⁹ , A and n are the same as above. A polyorganosiloxane (PDMS) in which one end of the structural unit II is blocked
A / B type diblock polymer composed of a part (B). One end of the PC portion of the repeating unit I represented by the general formula (VII) is represented by the general formula (IX)

[0032]

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The terminal group derived from the monohydric phenol represented by the formula is bonded and sealed. Here, in the terminal group represented by the general formula (IX), R ³ is a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, an iodine atom) and has 1 to 1 carbon atoms.
20 alkyl groups (e.g., methyl, ethyl, propyl, n-butyl, tert-butyl, isobutyl, tert-amyl, isoamyl, n-hexyl,
tert-octyl group, nonyl group, etc.), having 6 to 20 carbon atoms,
It preferably represents an aryl group having 6 to 18 (for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group) or an arylalkyl group having 7 to 20 carbon atoms (for example, an α, α-dimethylbenzyl group), and r is 0. -5.

On the other hand, PC-PD represented by the general formula (III)
In MS copolymer II, R ^{1 to} R ⁸ , m, n, p, q and r
Is the same as in the case of the PC-PDMS copolymer I. This PC-PDMS copolymer II has a general formula (X) in which the main chain constitutes the PDMS part (B).

[0035]

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Wherein R ^{4 to} R ⁸ , A and n are the same as described above. Structural unit III represented by the general formula (VII)

[0037]

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Wherein R ¹ , R ² , Z, p and q are the same as above. ] The A / B / A type triblock polymer to which the PC portion (A) of the repeating unit I represented by the formula (1) is bonded.

The PC-PDMS copolymers I and II are as follows:
Usually, homo PC (that is, a homopolymer having only the repeating unit I as a main chain) is produced in the production process. Therefore, the polycarbonate-based resin of the present invention is a blend with Homo PC, and contains PC-PDMS copolymers I and II.
Is contained. The viscosity average molecular weight of the polycarbonate resin is from 10,000 to 50,000, preferably from 12,000 to 40,000. If the viscosity average molecular weight is less than 10,000, the mechanical strength decreases. Also,
If it exceeds 50,000, the solution viscosity at the time of polymerization becomes high,
It is not preferable in production. In addition, injection molding becomes difficult. Further, the content of polyorganosiloxane in the polycarbonate resin is 0.1 to 20% by weight, preferably 0.2 to 18% by weight. If the content is less than 0.1% by weight, no releasability is improved. On the other hand, if it exceeds 20% by weight, heat resistance is undesirably reduced.

Such a PC-PDMS copolymer I and
II can be manufactured by various techniques. Preferred production methods include the following methods. In this preferred method, in the presence of a dihydric phenol and a monohydric phenol, a polycarbonate oligomer (hereinafter sometimes abbreviated as a PC oligomer) and a compound represented by the general formula (I)
V)

[0041]

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Wherein R ^{4 to} R ⁷ , R ⁸ , R ⁹ , A and n are the same as described above. ] (Hereinafter sometimes abbreviated as one-terminal-reactive PDMS) represented by the formula (V):

[0043]

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Wherein R ^{4 to} R ⁷ , R ⁸ , A and n are
Same as above. And a monohydric phenol is reacted with a single-terminal-reactive PDMS represented by the general formula (IV). 5 times (mole ratio) or more, preferably 10 times or more, more preferably 20 times or more with respect to 100 parts by weight of the PC oligomer, and the above-mentioned one-terminal-reactive PDMS and both-terminal-reactive PDMS are used. 0.12 to 35 parts by weight, preferably 0.2
By using ＭＳ33 parts by weight, PC-PDMS copolymers I and II can be produced. According to the above method, the above-mentioned polycarbonate resin of the present invention can be efficiently produced, and by appropriately selecting a PC oligomer, a monohydric phenol and a dihydric phenol, another type of PC-PDMS copolymer can be obtained. Coalescence can also be manufactured. One-terminal-reactive PDMS used in the present invention
And the proportion of PDMS reactive at both ends is determined by
DMS 1 to 99% by weight, preferably 5 to 99% by weight, more preferably 10 to 99% by weight, and a PDM having both ends reactive
S99-1% by weight, preferably 95-1% by weight, more preferably 90-1% by weight. If the one-terminal-reactive PDMS is less than 1% by weight, the effect of improving the releasability is undesirably small.

Here, PC-PDMS copolymers I and II
The PC oligomer used for the production of the compound (I) has a repeating unit I represented by the general formula (VII), and is prepared by a solvent method (interfacial polycondensation method), that is, a known acid acceptor in an organic solvent such as methylene chloride. Formula (XI) in the presence of a polyhydric phenol (terminal terminator)

[0046]

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[Wherein R ¹ , R ² , Z, p and q are the same as above. Or a transesterification reaction between a dihydric phenol and a carbonate diester (for example, a carbonate precursor such as diphenyl carbonate). There are various dihydric phenols represented by the general formula (XI). Specifically, as bis (4-hydroxyphenyl) alkane, for example, bis (4-hydroxyphenyl) alkane
Methane [bisphenol F]; 2,2-bis (4-hydroxyphenyl) phenylmethane; bis (4-hydroxyphenyl) naphthylmethane; bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane; bis (3 5-dichloro-4-hydroxyphenyl) methane; bis (3,5-dimethyl-4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl)
Ethane; 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane; 1-phenyl-1,1-bis (4-
1,2-bis (4-hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A];
-Methyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl-1-
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1-ethyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (3,5 -Dichloro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane; 2,2-bis (3-chloro-4-hydroxyphenyl) propane;
2,2-bis (3-methyl-4-hydroxyphenyl)
Propane; 2,2-bis (3-fluoro-4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) butane; 1,1-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) butane [bisphenol B]; 1,4-bis (4-
2,2-bis (4-hydroxyphenyl) pentane; 3,3-bis (4-hydroxyphenyl) pentane; 4-methyl-2,2-bis (4-hydroxyphenyl) pentane; 2-bis (4-hydroxyphenyl) hexane; 3,3-bis (4-hydroxyphenyl) hexane; 4,4-bis (4-hydroxyphenyl) heptane; 2,2-bis (4-hydroxyphenyl) octane; 2,2-bis (4-hydroxyphenyl) nonane; 1,10-bis (4-hydroxyphenyl) decane and the like.

Examples of the bis (4-hydroxyphenyl) cycloalkane include 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane A 1,1-bis (4-hydroxyphenyl) cyclodecane and the like; And bis (4-hydroxyphenyl) sulfone; bis (3,5-dimethyl-
4-hydroxyphenyl) sulfone; dihydroxydiaryl sulfones such as bis (3-chloro-4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) ether; bis (3,5-dimethyl-4-hydroxyphenyl) ether and the like 4,4′-dihydroxybenzophenone;
Dihydroxydiaryl ketones such as 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide;
Bis (3-methyl-4-hydroxyphenyl) sulfide; dihydroxydiaryl sulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide;
Dihydroxydiarylsulfoxides such as bis (3-methyl-4-hydroxyphenyl) sulfoxide;
Examples include dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl, bisphenolfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene, and thiobisphenols. Further, examples of the tetrahalogenobisphenols include tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, tetraiodobisphenol A, tetrabromobisphenol F, tetrachlorobisphenol F, tetrachlorobisphenol B, and the like. Among these, bisphenol A is particularly preferably used. These dihydric phenols may be used alone or in combination of two or more.

As the diester carbonate, a diaryl carbonate compound, a dialkyl carbonate compound or an alkylaryl carbonate compound can be used. Here, examples of the diaryl carbonate compound include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, and bisphenol A bisphenyl carbonate. Examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and bisphenol A bismethyl carbonate. And as the alkylaryl carbonate compound, for example,
Methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, bisphenol A methyl phenyl carbonate and the like can be mentioned.

When the PC oligomer is produced by a solvent method, that is, an interfacial polycondensation method, the PC oligomer can be obtained by reacting the dihydric phenol with phosgene and reacting substantially all of the phosgene in the reaction system. it can. This PC oligomer has a repeating unit I represented by the general formula (IV) constituted by a reaction between dihydric phenol and phosgene in the above polycondensation reaction. That is, the PC oligomer is reacted with 100 of dihydric phenol at a molar ratio of phosgene of 110 to 150.
Usually, in this reaction, dihydric phenol is added in an aqueous alkali solution, and a solvent such as methylene chloride, chlorobenzene, chloroform, carbon tetrachloride and, if necessary, a catalyst such as triethylamine or trimethylbenzylammonium chloride are mixed at a predetermined ratio. It can be produced by stirring, blowing phosgene into the mixture, and allowing the interfacial polycondensation reaction to proceed at a reaction temperature of 30 to 70 ° C for 1 to 3 hours. At this time, since the reaction system generates heat, it is preferable to cool with water or ice. Since the reaction system shifts to the acidic side as the reaction proceeds, it is preferable to maintain the pH at 10 or more by adding an alkali compound while measuring with a pH meter. The PC oligomer thus obtained has a number average molecular weight of 2,000 or less and is a 1- to 10-mer. In addition, at the time of the above-mentioned polycondensation reaction, a terminal terminator usually used for the production of PC may be added.

Here, there are various organic solvents. For example, dichloromethane (methylene chloride); chloroform; 1,1-dichloroethane; 1,2-dichloroethane; 1,1,1-trichloroethane;
Trichloroethane; 1,1,1,2-tetrachloroethane; 1,1,2,2-tetrachloroethane; chlorinated hydrocarbons such as pentachloroethane and chlorobenzene; and acetophenone. These organic solvents are
They may be used alone or in combination of two or more. Of these, methylene chloride is particularly preferred. Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide. Of these, sodium hydroxide and potassium hydroxide are preferred.
Various catalysts can be used. Specifically, it is a quaternary ammonium salt, a quaternary phosphonium salt or a tertiary amine. Examples of the quaternary ammonium salt include trimethylbenzylammonium chloride, triethylbenzylammonium chloride, and the like.
Tributyl benzyl ammonium chloride, trioctyl methyl ammonium chloride, tetrabutyl ammonium chloride, tetrabutyl ammonium bromide and the like can be mentioned. Examples of the quaternary phosphonium salt include, for example, tetrabutyl phosphonium chloride,
Such as tetrabutylphosphonium bromide, and
Examples of the tertiary amine include triethylamine, tributylamine, N, N-dimethylcyclohexylamine, pyridine, dimethylaniline and the like.

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-amylphenol, p-
tert-octylphenol, p-cumylphenol, p
-Bromophenol, tribromophenol, nonylphenol and the like. The PC-PDM of the present invention
In order to prepare the S copolymer I, the compound represented by the general formula (XII)

[0053]

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Wherein R ³ and r are the same as above. ] Is preferably used.

Next, in the present invention, the one-terminal-reactive PDMS represented by the general formula (IV) used for the production of the PC-PDMS copolymer I has a reactive group at one terminal, Are sealed at the ends. In particular, those having a phenolic OH group as the reactive group are preferably used. This one-terminal-reactive PDMS can be produced by various techniques. Preferred production methods include the following methods. That is, first, an alkyl lithium reagent (eg, n-butyl lithium, tert.
-Butyllithium, lithium trimethylsilylate, etc.) and a cyclic dimethylsiloxane (eg, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, etc.) are reacted in an organic solvent, and one end is sealed with a dimethylalkylsiloxane unit. The other end is made to be a living terminal by a dimethyl lithium siloxane unit. Then, it is reacted with a dialkyl silicon halide such as dimethylchlorosilane or dimethylbromosilane to obtain polydimethylsiloxane having one terminal hydrogen. Next, this is reacted with an aliphatic unsaturated phenol (for example, 2-allylphenol, 4-hydroxystyrene, eugenol (2-methoxy-4-allylphenol), etc.) to give a one-terminal reactive compound having one-terminal phenolic OH. P
DMS can be obtained.

On the other hand, in the present invention, the terminal-reactive PDMS represented by the general formula (V) used for the production of the PC-PDMS copolymer II has a reactive group at both terminals. In particular, those having a phenolic OH group as the reactive group are preferably used. This two-terminal reactive P
DMS can be manufactured by various methods.
Preferred production methods include the following methods.
That is, first, a cyclic dimethylsiloxane (eg, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, etc.) is reacted with disiloxane to produce a hydrogen-terminated polydisiloxane. Then, the terminal phenolic OH is reacted by reacting a hydrogen-terminated polydisiloxane with an aliphatic unsaturated phenol (eg, 2-allylphenol, 4-hydroxystyrene, eugenol (2-methoxy-4-allylphenol), etc.). Can be easily obtained.

In the present invention, the PC-PDMS copolymers I and II are preferably prepared in advance from the PC oligomer, the one-terminal reactive PDMS and the both-terminal reactive PMS.
It can be produced by dissolving DMS in an organic solvent, adding an aqueous solution of an alkali metal hydroxide of a dihydric phenol or a monohydric phenol (terminal terminator), and performing an interfacial polycondensation reaction using various catalysts. . Here, as the dihydric phenol, various types can be used,
Preferably, the same dihydric phenol as used in producing the PC oligomer is used. Similarly, the monohydric phenol may be the same as that used in producing the PC oligomer. The total amount of these monohydric phenols must be 5 or more in a molar ratio with the reactive polyorganosiloxane (monohydric phenol / reactive polyorganosiloxane).
Preferably it is 10 or more, more preferably 20 or more.
In the present invention, if necessary, as a branching agent, for example, phloroglucin; trimellitic acid; 1,1,1-
Tris (4-hydroxyphenyl) ethane; 1- [α-
Methyl-α- (4′-hydroxyphenyl) ethyl]-
4- [α ′, α′-bis (4 ″ -hydroxyphenyl)
Ethyl] benzene; α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; a compound having three or more functional groups such as isatin bis (o-cresol) may be used. it can.

The PC-PD of the present invention is obtained by the interfacial polycondensation method.
FIG. 1 shows a flow chart of an example of a method for producing a polycarbonate-based resin containing MS copolymers I and II. That is, for example, in the case of the interfacial polycondensation method, first, a dihydric phenol and phosgene are reacted in an organic solvent to produce a PC oligomer in advance. Then, in an organic solvent, the PC oligomer, preliminarily prepared one-end reactive PDMS, and both-end reactive PDM
S, monohydric phenol (terminal terminator) and dihydric phenol are reacted. In this reaction, the PDMS reactive at one end and at both ends is added as it is or in a methylene chloride solution. The monohydric phenol is added as a methylene chloride solution or an aqueous alkali solution. And the dihydric phenol is
Add with an aqueous alkali solution. The order of addition is not particularly limited, but it is preferable to add the dihydric phenol last. The reaction time ranges from 30 minutes to 2 hours, and the reaction temperature ranges from 20 to 40 ° C. The PC-PDMS copolymers I and II are produced as described above as an example, but in this production process, homo-PC is also produced, and the reaction product is essentially a PC-PDMS copolymer. I and
Obtained as a mixture of II and Homo PC. The polycarbonate resin of the present invention is a PC-PDMS copolymer I and
It contains II. And PC-PDMS
As described above, the copolymers I and II may be mixed after the PC-PDMS copolymer I and the PC-PDMS copolymer are produced independently.

Next, the polycarbonate resin composition of the present invention comprises: (A) the polycarbonate resin described above;
Consisting of polycarbonate resin and (C) inorganic filler,
And 10 to 95% by weight of the component (A) and 0% of the component (B).
-80% by weight and 5-60% by weight of component (C), preferably 10-50% by weight. Here, the polycarbonate resin (PC) as the component (B) constituting the resin composition of the present invention can be easily prepared by reacting a dihydric phenol with phosgene or a carbonic acid diester compound in the same manner as in the case of the PC oligomer. Can be manufactured. That is, for example, by reacting a dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor or molecular weight regulator, or by reacting a dihydric phenol with a carbonate diester (diphenyl It is produced by transesterification with a carbonate precursor such as carbonate). Here, the dihydric phenol may be the same as or different from the compound represented by the general formula (VII). Examples of the carbonic acid diester include diaryl carbonate such as diphenyl carbonate and dialkyl carbonate such as dimethyl carbonate and diethyl carbonate. Of course, a commercially available polycarbonate resin can be used.

As the inorganic filler of the component (C) constituting the resin composition of the present invention, there are various inorganic fillers.
It is used for the purpose of improving the mechanical strength or dimensional stability of the polycarbonate resin composition and for increasing the amount. As described above, the inorganic filler is blended in the resin composition at a ratio of 5 to 60% by weight, preferably 10 to 50% by weight. If the compounding ratio is less than 5% by weight, the rigidity is insufficient and the dimensional stability decreases. If it exceeds 60% by weight, kneading becomes difficult or impossible, which is not preferable. Here, as the inorganic filler, for example, potassium titanate whisker, mineral fiber (eg, rock wool), glass fiber, carbon fiber, metal fiber (eg, stainless steel fiber), aluminum borate whisker, silicon nitride whisker, boron Fiber, tetrapotted zinc oxide whisker, talc, clay, mica, pearl mica, aluminum foil, alumina, glass flake, glass beads, glass balloon, carbon black, graphite, calcium carbonate,
Examples include calcium sulfate, calcium silicate, titanium oxide, zinc sulfide, zinc oxide, silica, asbestos, quartz powder and the like. These inorganic fillers may be subjected to a surface treatment in advance, or may be untreated. Examples of the surface treatment agent include chemical treatments using various treatment agents such as a silane coupling agent system, a higher fatty acid system, a fatty acid metal salt system, an unsaturated organic acid system, an organic titanate system, a resin acid system, and a polyethylene glycol system. Or physical surface treatment can be mentioned.

Among them, as the glass fiber as the fibrous filler, any of alkali glass, low alkali glass, alkali-free glass and the like can be suitably used. The length of this glass fiber is preferably in the range of 0.1 to 8 mm, more preferably 0.3 to 6 mm, and the fiber diameter is 0.1 to 30 μm, preferably 0.5 to 25 μm. is there. The form of these glass fibers is not particularly limited, and any form such as roving, milled fiber, and chopped strand can be used. These glass fibers can be used alone or in combination of two or more. Further, these glass fibers are desirably subjected to a surface treatment with a surface treatment agent and then subjected to a sizing treatment with an appropriate sizing agent for the purpose of improving the adhesiveness with the polycarbonate resin. Here, as the surface treatment agent,
For example, silane-based such as aminosilane-based, epoxysilane-based, vinylsilane-based, and acrylsilane-based, titanate-based, aluminum-based, chromium-based, zirconium-based, and boron-based coupling agents can be used. Among these, silane coupling agents and titanate coupling agents, particularly silane coupling agents, are preferred. The method for treating the glass fiber with the surface treatment agent is not particularly limited, and any method conventionally used, for example, an aqueous solution method, an organic solvent method, a spray method, or the like can be used. Examples of the sizing agent include, for example, urethane-based, acrylic-based, acrylonitrile-styrene-based copolymer-based, epoxy-based, and the like, and any of them can be used. There is no particular limitation on the method of sizing the glass fibers using these sizing agents, and any conventionally used method such as dip coating, roller coating, spray coating, flow coating, or spray coating may be used. be able to.

[0062] The carbon fiber is generally produced by firing using cellulose fiber, acrylic fiber, lignin, petroleum or coal-based special pitch as a raw material, and is made of various materials such as flame-resistant, carbonaceous or graphite. There are types. The length of the carbon fiber is usually in the range of 0.01 to 10 mm in the pellet, and the fiber diameter is 5 to 15 μm.
m. The form of the carbon fiber is not particularly limited, and examples thereof include various types such as roving, milled fiber, chopped strand, and strand. In addition, the surface of the carbon fiber may be surface-treated with an epoxy resin, a urethane resin, or the like in order to increase the affinity with the copolymer.

In addition to the components (A), (B) and (C), the resin composition of the present invention may optionally contain
As far as the object of the present invention is not impaired, component (D)
Various additives or other synthetic resins, elastomers and the like can be blended. First, as an additive, for example, an antioxidant such as a hindered phenol type, a phosphite ester type, a phosphate ester type or an amine type, for example, an ultraviolet absorber such as a benzotriazole type or a benzophenone type, for example, a hindered amine -Based light stabilizers, for example, aliphatic carboxylic acid ester-based, paraffin-based, internal lubricants such as silicone oil, polyethylene wax, release agents, common flame retardants, flame retardant assistants, antistatic agents, coloring agents, etc. Is mentioned.

Examples of other synthetic resins include, for example, polyester (polyethylene terephthalate, polybutyrene terephthalate, etc.), polyamide, polyarylate, polyethylene, polypropylene, polymethyl methacrylate, polystyrene, AS resin, ABS resin and the above (A). Examples of each resin such as polycarbonate other than the polycarbonate as a component can be given. And
Examples of the elastomer include isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and core shell type elastomers such as MBS and MAS.

The resin composition of the present invention can be obtained by blending and kneading the components (A), (B) and (C) with (D) as required. For the compounding and kneading, a method usually 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 resin composition thus obtained can be applied to various known molding methods, for example, injection molding, hollow molding, extrusion molding, compression molding, calender molding, rotational molding, and the like. Can be offered.

[0066]

EXAMPLES The present invention will be described in further detail with reference to Production Examples, Examples and Comparative Examples. Production Example 1 [Production of PC oligomer] 60 kg of bisphenol A was added to 400 liters of a 5% by weight aqueous sodium hydroxide solution.
Was dissolved to prepare an aqueous sodium hydroxide solution of bisphenol A. 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. Phosgene was introduced into this
Blowing was performed at a flow rate of 0.7 kg / hour, and the reaction was continuously performed for 3 hours. The tubular reactor used here was a double tube, and the outlet temperature of the reaction solution was kept at 25 ° C. by passing 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, whereby the aqueous phase was separated and removed, and the methylene chloride phase (220 liters) was collected to obtain a PC oligomer (concentration: 317 g / liter). P obtained here
The polymerization degree of the C oligomer was 2 to 4, and the concentration of the chloroformate group was 0.7N.

Production Example 2-1 [Synthesis of Reactive PDMS-A (One Terminal Type)] 1.73 g (0.027 mol) of butyllithium was dissolved in 350 ml of tetrahydrofuran (THF) and kept at 0 ° C. or lower. . In addition, hexamethylcyclotrisiloxane 30
0 g (1.35 mol) was dissolved in 170 ml of THF and kept at 0 ° C. or lower. Both were mixed and kept at 0 ° C. or lower and stirred for 10 hours. Then dimethylchlorosilane
2.55 g (0.027 mol) and 320 ml of cyclohexane were added, and the mixture was further stirred for 10 hours. The solvent was removed by evaporation to obtain an oily precipitate. After the obtained precipitate was filtered, it was evaporated in vacuo at 150 ° C. and 3 torr to remove low-boiling substances to obtain an oil. Then, a mixture of 60 g of 2-allylphenol and 0.0014 g of platinum as a platinum chloride-alcoholate complex was added to the oil 2 obtained above.
94 g were added at a temperature of 90 ° C. 90-
The mixture was stirred for 3 hours while maintaining the temperature at 115 ° C. The product was extracted with methylene chloride and washed three times with 80% aqueous methanol to remove excess 2-allylphenol. The product is dried over anhydrous sodium sulphate and 115 ° C. in vacuo
The solvent was distilled off to a temperature of. The obtained phenol PDMS at one end had a repeating number of dimethylsilanooxy units of 150 as measured by NMR.

Production Example 2-2 [Synthesis of Reactive PDMS-B (One Terminal Type)] In Production Example 2-1, 1.73 g of butyllithium was added to 3.26 g (0.034 mol) of lithium trimethylsilylate. Further, 3.21 g (0.03 g) of 2.55 g of dimethylchlorosilane was used.
4 mol), and carried out in the same manner as in Production Example 2-1. The obtained one-terminal phenol PDMS showed that the number of repeating dimethylsilanooxy units was 1 by NMR measurement.
20.

Production Example 2-3 Synthesis of Reactive PDMS-C (Single Terminal Type) In Production Example 2-1, 3.20 g of 1.73 g of butyllithium was used.
(0.05 mol) and dimethylchlorosilane 2.55
Production Example 2 except that g was changed to 4.73 g (0.05 mol).
-1 was performed. Obtained phenol PD at one end
The MS showed that the number of repeating dimethylsilanooxy units was 80 by NMR measurement.

Production Example 2-4 [Synthesis of Reactive PDMS-D (both terminal type)] 1,483 g of octamethylcyclotetrasiloxane, 1,1,
18.1 g of 3,3-tetramethyldisiloxane and 86%
35 g of sulfuric acid was mixed and stirred at room temperature for 17 hours. Thereafter, the oil phase was separated, 25 g of sodium hydrogen carbonate was added, and the mixture was stirred for 1 hour. After filtration, 150 ℃, 3torr
Vacuum distillation was performed at r to remove low-boiling substances. Then, 294 g of the oil obtained above was added at a temperature of 90 ° C. to a mixture of 60 g of 2-allylphenol and 0.0014 g of platinum as a platinum chloride-alcoholate complex. The mixture was stirred for 3 hours while maintaining the temperature at 90-115 ° C. The product was extracted with methylene chloride and washed three times with 80% aqueous methanol to remove excess 2-allylphenol. The product was dried over anhydrous sodium sulfate and evaporated in vacuo to a temperature of 115 ° C. The number of repeating dimethylsilanooxy units in the obtained phenol PDMS at both ends was 150 as determined by NMR.

Production Example 2-5 [Synthesis of reactive PDMS-E (both terminal type)] Except that in Example 2-4, both 1,1,3,3-tetramethyldisiloxane were changed to 96 g. It carried out similarly to manufacture example 2-4. The resulting phenol PDMS at both ends is
As a result of NMR measurement, the number of repeating dimethylsilanooxy units was 30.

Example 1 [Polycarbonate resin (PC-PDMS copolymer A)
Called. Synthesis of)] Reactive PDMS obtained in Production Example 2-1
-A 45 g (0.0040 mol) and reactive PDMS-D
45 g (0.0040 mol) was dissolved in 2 liters of methylene chloride and mixed with 10 liters of the PC oligomer obtained in Production Example 1. Then, sodium hydroxide (56 g) dissolved in water (1 liter) and triethylamine (5.7 cc) were added.
And stirred at 500 rpm for 1 hour at room temperature. Then, 4 liters of methylene chloride and 119 g (0.793 mol) of p-tert-butylphenol were added to an alkaline solution of bisphenol A (650 g of bisphenol A, 378 g of sodium hydroxide, and 4.5 liters of water), and added 50
The mixture was stirred at 0 rpm at room temperature for 1 hour. Then, add 8 liters of methylene chloride and wash with 5 liters of water.
Wash alkaline with 5 liters of 0.01N sodium hydroxide aqueous solution, acid wash with 5 liters of 0.1N hydrochloric acid, and water wash (twice) with 5 liters of water in order. Finally, methylene chloride is removed, and flake PC -PDMS copolymer A was obtained.

Example 2 [Polycarbonate resin (PC-PDMS copolymer B)
Called. Synthesis of Example 1)
As reactive PDMS-C 191 g (0.0228 mol) and reactive PDMS-D 46 g (0.0040 mol)
Was carried out in the same manner as in Example 1 except for using, to obtain a flake-shaped PC-PDMS copolymer B. Example 3 [Polycarbonate resin (PC-PDMS copolymer C
Called. Synthesis of Example 1)
As reactive PDMS-A 95 g (0.0084 mol)
And 285 g (0.115 mol) of reactive PDMS-E were used.
C-PDMS copolymer C was obtained.

Example 4 [Polycarbonate resin (PC-PDMS copolymer D)
Called. Synthesis of Example 1)
370 g (0.041 mol) of reactive PDMS-B
The reaction was carried out in the same manner as in Example 1 except that 370 g (0.022 mol) of reactive PDMS-D and 199 g of p-tert-butylphenol were changed to 103 g (0.485 mol) of p-cumylphenol. PC-PD
MS copolymer D was obtained.

Example 5 [Polycarbonate resin (PC-PDMS copolymer E)
Called. Synthesis of Example 1)
As reactive PDMS-A 37 g (0.0033 mol)
And 148 g (0.013 mol) of reactive PDMS-D were used.
C-PDMS copolymer E was obtained. Example 6 [Polycarbonate resin (PC-PDMS copolymer F
Called. Synthesis of Example 1)
As reactive PDMS-A 6 g (0.00053 mol)
And flaky PMS-D was prepared in the same manner as in Example 1 except that 17 g (0.0015 mol) of reactive PDMS-D was used.
C-PDMS copolymer F was obtained.

Comparative Example 1 [Polycarbonate resin (PC-PDMS copolymer G
Called. Synthesis of Example 1)
Flake PC-PD in the same manner as in Example 1 except that only 185 g of reactive PDMS-D was used.
MS copolymer G was obtained. PC-PDMS copolymers A to F and PC-PDM obtained in Examples 1 to 6 and Comparative Example 1
For S copolymer G, the PDMS content, viscosity average molecular weight and flow value were measured. Table 1 shows the results.

[0077]

[Table 1]

The measurement of the PDMS content, viscosity average molecular weight and flow value was carried out according to the following. 1: PDMS content It was determined from the intensity ratio of the peak of the isopropyl methyl group of bisphenol A found at 1.7 ppm in ¹ HNMR and the peak of the methyl group of dimethylsiloxane found at 0.2 ppm. 2: Viscosity average molecular weight (Mv) The viscosity of the methylene chloride solution at 20 ° C. was measured using an Ubbelohde type viscosity tube, and the intrinsic viscosity [η] was determined from this. [Η] = 1.23 × 10 ⁻⁵ × Mv ^0.83 3: Flow value Measured according to JIS K-7210.

Examples 7 to 14 and Comparative Examples 2 to 7 PC-PDMS copolymers A to E, G, polycarbonate resin (PC resin) [Teflon A1 manufactured by Idemitsu Petrochemical Co., Ltd.]
500] and an inorganic filler in the proportions shown in Table 2,
Pelletized by extruder with 30 mm vent. As the inorganic filler, GF [MA-409C manufactured by Asahi Fiberglass Co., Ltd.] and CF [HTA-C6-CS manufactured by Toho Rayon Co., Ltd.] were used. Supplied from the downstream side. Then, to Example 2 and Comparative Example 3, 200 ppm of trisnonylphenyl phosphite was added as an antioxidant,
Pelletized. Comparative Example 3 includes silicone oil [SH2 manufactured by Dow Corning Toray Silicone Co., Ltd.]
[00-350] was added and the mixture was pelletized. The obtained pellets were processed for 280 using an injection molding machine.
A test piece was prepared by molding at a molding temperature of ３００300 ° C. For each pellet, the flow value and release pressure were measured, and for the test piece, the breaking strength was measured. Table 3 shows the results.

[0080]

[Table 2]

[0081]

[Table 3]

The measurement of the flow value, the releasing pressure and the breaking strength was carried out according to the following. 1: Flow value Measured according to JIS K-7210. 2: Release pressure Using a cylindrical mold, release resistance at the time of protrusion (release) was measured. 3: Breaking strength Measured according to JIS K-7113.

[0083]

As described above, the polycarbonate resin of the present invention has a sufficient molecular weight of the PC-PDMS copolymer contained therein, has excellent fluidity, can be produced efficiently, and has a resin composition of It has excellent releasability, impact resistance, fluidity and rigidity. Therefore, the polycarbonate resin composition of the present invention is effectively used as a material for various molded articles, for example, various molded articles widely used in the fields of electric / electronic devices, automobiles, and the like.

[Brief description of the drawings]

FIG. 1 is a diagram showing a flow of an example of a method for producing a resin composition of the present invention by an interfacial polycondensation method.

Claims (3)

(57) [Claims] 1. A compound of the general formula (I) [Wherein, R ¹ and R ² each represent a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may be the same or different; And q are integers of 0 to 4, and m is 1 to 150
It is. R ³ represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms.
And r is an integer of 0-5. And Z is a single bond, an alkylene group or alkylidene group having 1 to 20 carbon atoms, a cycloalkylene group or cycloalkylidene group having 5 to 20 carbon atoms, -O-, -S-,
—SO ₂ — bond or general formula (II) or (II ′) The bond represented by is shown. R ^{4 to} R ⁷ each represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may be the same or different, and n is 1 to 500. is there. R ⁸ represents a divalent organic residue containing an aliphatic and / or aromatic group, and R ⁹ represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms. A represents a single bond, -O- or -NH-. And a polycarbonate-polyorganosiloxane diblock copolymer represented by the general formula (III): [Wherein, R ¹ and R ² each represent a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may be the same or different; And q are integers of 0 to 4, and m is 1 to 150
It is. R ³ represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms.
And r is an integer of 0-5. And Z is a single bond, an alkylene group or alkylidene group having 1 to 20 carbon atoms, a cycloalkylene group or cycloalkylidene group having 5 to 20 carbon atoms, -O-, -S-,
—SO 2 — bond or general formula (II) or (II ′) The bond represented by is shown. R ^{4 to} R ⁷ each represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may be the same or different, and n is 1 to 500. is there. R ⁸ represents a divalent organic residue containing an aliphatic and / or aromatic group. A represents a single bond, -O- or -NH-. ] The polycarbonate resin which contains the polycarbonate-polyorganosiloxane triblock copolymer represented by these, The viscosity average molecular weight of this polycarbonate resin is 10,000-50,000, and the said polycarbonate resin A polycarbonate resin, wherein the content of the polyorganosiloxane in the resin is 0.1 to 20% by weight. 2. In the presence of a dihydric phenol and a monohydric phenol, a polycarbonate oligomer is reacted with a compound represented by the general formula (IV): Wherein, R ⁴ to R ⁷ are each an alkyl group or an aryl group having 6 to 20 carbon atoms having 1 to 8 carbon atoms, rather it may also be those different even for the same, n represents 1 ~ 50
0. R ⁸ represents a divalent organic residue containing an aliphatic and / or aromatic group, and R ⁹ represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms. A represents a single bond, -O- or -NH-. And a one-terminal-reactive polyorganosiloxane represented by the general formula (V): Wherein, R ⁴ to R ⁷ are each an alkyl group or an aryl group having 6 to 20 carbon atoms having 1 to 8 carbon atoms, rather it may also be those different even for the same, n represents 1 ~ 50
0. R ⁸ represents a divalent organic residue containing an aliphatic and / or aromatic group. And A is a single bond, -O- or -N
H- is shown. And the monofunctional phenol is used in an amount of 5 times or more (molar ratio) with respect to the one-terminal reactive polyorganosiloxane represented by the general formula (IV). And formula (V) and formula (V) based on 100 parts by weight of the polycarbonate oligomer
The method for producing a polycarbonate resin according to claim 1 , wherein a total of 0.12 to 35 parts by weight of a polyorganosiloxane reactive at one end and at both ends represented by formula (1) is used. 3. The composition according to claim 1, comprising (A) 10 to 95% by weight of the polycarbonate resin according to claim 1, (B) 0 to 80% by weight of the polycarbonate resin and (C) 5 to 60% by weight of an inorganic filler. Polycarbonate resin composition.