JP2003327819A - Highly heat-resistant conductive polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly heat-resistant conductive polycarbonate resin composition having high heat-resistance and excellent electrical conductivity and free from stimulation to the skin. <P>SOLUTION: The polycarbonate resin composition is composed of (A) a polycarbonate copolymer composed of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene of formula (1) accounting for 5-95 mol% of the total aromatic dihydroxy component and an aromatic dihydroxy component expressed by general formula (2) (R<SP>1</SP>to R<SP>4</SP>are each independently H, a halogen atom or a 1-9C hydrocarbon group which may contain an aromatic group; and W is a single bond, a 1-20C hydrocarbon group which may contain an aromatic group, O, S, SO, SO<SB>2</SB>, CO or COO) accounting for 95-5 mol% of the total aromatic dihydroxy component and (B) a carbonaneous filler. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate resin composition. More specifically, it has good heat resistance, excellent electrical conductivity, no irritation to the skin, and low water absorption, such as OA equipment parts for PCs and mobile phones, automobile parts, electric / electronic parts, mechanical parts, etc. In particular, the present invention relates to a highly heat-resistant conductive polycarbonate resin composition that can be suitably used for a semiconductor, memory, or hard disk transport tray.

[0002]

2. Description of the Related Art Polycarbonate resins obtained by reacting a carbonate precursor substance with 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes referred to as "bisphenol A") are transparent, heat resistant, Due to its excellent mechanical properties and dimensional stability, it is widely used in many fields as an engineering plastic, or as a resin composition containing a single thermoplastic resin, glass fiber, carbon fiber, or the like. However, in recent years, materials having excellent heat resistance and conductivity have been desired.

Various types of polycarbonate having improved heat resistance are known (for example, JP-A-6-2).
5401, JP-A-7-52270, JP-A-6-192411, JP-A-11-306823, JP-A-11-35815). However, since these polycarbonates do not have sufficient conductivity, they are unsuitable for use in the field of electric / electronic equipment.

As an improvement on this point, Japanese Patent Laid-Open No. 7-
JP-A-268197 discloses a resin composition comprising a polycarbonate copolymer having a structure of 9,9-bis (4-hydroxyphenyl) fluorene and an inorganic filler. Some of these include those having heat resistance as well as conductivity, but 9,9-bis (4-
(Hydroxyphenyl) fluorene has low reactivity at the time of polymerization, it is difficult to obtain an aromatic polycarbonate copolymer, and it is generated by decomposition during melt extrusion or molding.
Vapors derived from 9-bis (4-hydroxyphenyl) fluorene are highly irritating and have been problematic in attacking the skin. In particular, when compounding various additives with the resin, some of the additives accelerate the decomposition of the polycarbonate resin, which is a particular problem when handling a resin composition containing these additives. Furthermore, 9,9-bis (4
-Hydroxyphenyl) fluorene aromatic polycarbonate copolymer has a high water absorption rate, and when a molded product made of the polycarbonate copolymer is repeatedly treated at high temperature, mechanical properties are deteriorated and cracks are generated. there were.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate resin composition which has heat resistance and conductivity, is non-irritating to the skin, and has a low water absorption rate. The present inventor has conducted extensive studies to achieve this object, and as a result, 9,9-bis (4-hydroxy-
It has been found that the above object can be achieved by blending a conductive filler with an aromatic polycarbonate copolymer obtained by using 3-methylphenyl) fluorene and a specific aromatic dihydroxy component, Reached

[0006]

That is, according to the present invention, in the present polycarbonate resin composition, 5 to 95 mol% of the total aromatic dihydroxy component (A) is represented by the following formula [1]: 9,9 -Bis (4-hydroxy-3-methylphenyl) fluorene

[0007]

[Chemical 3]

95 to 5 mol% is represented by the following general formula [2].

[0009]

[Chemical 4]

[Wherein, R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms or a halogen atom, and W is a single bond or a carbon atom. A hydrocarbon group which may contain an aromatic group of the number 1 to 20,
Is an O, S, SO, SO ₂ , CO, or COO group]
It is composed of a polycarbonate copolymer composed of a dihydroxy component represented by and (B) a carbon-based filler.

The aromatic polycarbonate copolymer (A) of the present invention contains 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter, referred to as "biscresolfluorene" as an aromatic dihydroxy component constituting the aromatic polycarbonate copolymer (A). ”
5) of wholly aromatic dihydroxy component
~ 95 mol%, preferably 7-90 mol%, and further 1
It is preferably contained in an amount of 0 to 85 mol%. When the content of biscresolfluorene is less than 5 mol%, it is difficult to sufficiently improve heat resistance. On the other hand, if the content of biscresolfluorene is more than 95 mol%, the melt fluidity of the resin composition is lowered and molding becomes difficult, which is not preferable.

The dihydroxy component as a copolymerization component with biscresolfluorene in the aromatic polycarbonate copolymer (A) of the present invention has the following general formula [2].

[0013]

[Chemical 5]

[In the formula, R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms or a halogen atom, and W is a single bond or a carbon atom. A hydrocarbon group which may contain an aromatic group of the number 1 to 20,
Is an O, S, SO, SO ₂ , CO, or COO group]
It is preferably an aromatic dihydroxy component represented by

Such an aromatic dihydroxy component may be one that is usually used as a dihydroxy component of polycarbonate, and for example, 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1- Bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (“bisphenol A”), 2,2-bis (4-
Hydroxy-3-methylphenyl) propane (“bisphenol C”), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2
-Bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-t-butyl-4-hydroxyphenyl) Propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4
-Hydroxyphenyl) octane, 2,2-bis (3-
Bromo-4-hydroxyphenyl) propane, 2,2-
Bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) ) Propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 1,1- Bis (4-hydroxyphenyl) cyclohexane (“bisphenol Z”), 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3 '-Dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihi B carboxymethyl diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide,
4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxy-
3,3'-Dimethyldiphenyl sulfoxide, 4,4 '
-Dihydroxy-3,3'-diphenyldiphenyl sulfone, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 4,4'-dihydroxy-3,
3'-diphenyldiphenyl sulfoxide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene ("bisphenol M"), 1,4-bis {2- (4
-Hydroxyphenyl) propyl} benzene and the like. Among them, bisphenol A, bisphenol C,
Bisphenol M and bisphenol Z are preferable, and bisphenol A is particularly preferable. These may be used alone or in combination of two or more.

The aromatic dihydroxy component represented by the above general formula [2] used in the aromatic polycarbonate copolymer (A) of the present invention is 95 to 5 mol%, preferably 93 to 10% of the total aromatic dihydroxy component. Mol%, more preferably 90 to 15 mol%. When the content of the aromatic dihydroxy component represented by the general formula [2] is more than 95 mol%, heat resistance becomes insufficient, which is not preferable. On the other hand, if it is less than 5 mol%, melt flowability becomes insufficient and molding becomes difficult, which is not preferable.

The aromatic polycarbonate copolymer of the present invention is a reaction means known per se for producing an ordinary aromatic polycarbonate resin, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or carbonic acid diester. Manufactured by. Next, the basic means of these manufacturing methods will be briefly described.

As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples thereof include phosgene, diphenyl carbonate or dihaloformate of aromatic dihydroxy component.

In the case of producing a polycarbonate resin by reacting the aromatic dihydroxy component with the carbonate precursor by an interfacial polymerization method or a melting method, a catalyst, a terminal stopper, an antioxidant of a dihydric phenol may be added, if necessary. Etc. may be used.

The reaction by the interfacial polymerization method is usually a reaction between a dihydric phenol and phosgene, which is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. It is also possible to use a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound for accelerating the reaction. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably 10 minutes to 5 hours, and the pH during the reaction is preferably 9 or more.

The reaction by the melting method is usually a transesterification reaction between a dihydric phenol and a carbonate ester,
It is carried out by a method in which a dihydric phenol and a carbonate ester are heated and mixed in the presence of an inert gas to distill off the alcohol or phenol produced. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, but is usually in the range of 120 to 350 ° C.
In the latter stage of the reaction, the pressure of the system is reduced to about 1.3 × 10 ^{3 to} 1.3 × 10 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group or an alkyl group having 1 to 4 carbon atoms. Specific examples include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and among them, diphenyl carbonate. Is preferred.

In the melting method, a polymerization catalyst can be used to accelerate the polymerization rate. Examples of the polymerization catalyst include alkali metal such as sodium hydroxide, potassium hydroxide, sodium salt of dihydric phenol, potassium salt and the like. Compounds, alkaline earth metal compounds such as calcium hydroxide, barium hydroxide and magnesium hydroxide, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine, alkali metals and alkaline earth metals Alkoxides, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony Conversion Object class, manganese compounds, titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. The catalysts may be used alone or in combination of two or more. The amount of these polymerization catalysts used is
1 x 10 ^-8 to 1 x per mol of dihydric phenol as a raw material
10 ⁻³ equivalent, preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻³ equivalent,
More preferably, it is selected in the range of 1 × 10 ^{−6 to} 5 × 10 ⁻⁴ equivalents.

For the aromatic polycarbonate resin, in the polymerization reaction, monofunctional phenols which are usually used as an end terminating agent can be used. Especially in the case of reactions using phosgene as carbonate precursor, monofunctional phenols are commonly used as molecular terminators for molecular weight control, and the polymers obtained are also based on monofunctional phenol-based groups. Because it is blocked by, it has better thermal stability than those that do not.

The monofunctional phenols may be any one used as an end terminating agent for aromatic polycarbonate resins, and are generally phenols or lower alkyl-substituted phenols, which are represented by the following general formula. It can indicate phenols.

[0026]

[Chemical 6]

[In the formula, A is a hydrogen atom or 1 to 9 carbon atoms.
Is a linear or branched alkyl group or arylalkyl group, and r is an integer of 1 to 5, preferably 1 to 3. ] Specific examples of the monofunctional phenols include, for example, phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

Further, as other monofunctional phenols,
Phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic ester group as a substituent, or long-chain alkylcarboxylic acid chlorides can be used, and the aromatic polycarbonate copolymer of When the ends are blocked, these not only function as a terminal terminator or a molecular weight modifier, but also improve the melt fluidity of the resin and facilitate the molding process, and also improve the physical properties of the substrate. In particular, it has the effect of lowering the water absorption of the resin and is preferably used. These are represented by the following general formulas [Ia] to [Ih].

[0029]

[Chemical 7]

[0030]

[Chemical 8]

[0031]

[Chemical 9]

[0032]

[Chemical 10]

[0033]

[Chemical 11]

[0034]

[Chemical 12]

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[In each formula, X is -R-O-, -R-CO-
O- or -R-O-CO-, wherein R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and T represents a single bond or the above X. And a bond similar to the above, and n is an integer of 10 to 50.

Q is a halogen atom or 1 to 10 carbon atoms,
Preferably, it represents a monovalent aliphatic hydrocarbon group of 1 to 5, and p
Represents an integer of 0 to 4, Y represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5, W ¹ represents a hydrogen atom, —CO—R ¹³ , —CO—O. -R ¹⁴ or R ¹⁵ , wherein R ¹³ , R ¹⁴ and R ¹⁵ each have 1 carbon atom.
-10, preferably 1-5 monovalent aliphatic hydrocarbon groups,
A monovalent alicyclic hydrocarbon group having 4 to 8 carbon atoms, preferably 5 to 6 or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, preferably 6 to 12 carbon atoms is shown.

L is an integer of 4 to 20, preferably 5 to 10, m is an integer of 1 to 100, preferably 3 to 60, particularly preferably 4 to 50, and Z is a single bond or 1 carbon atom. -10, preferably 1 to 5 divalent aliphatic hydrocarbon group, W ² is a hydrogen atom, 1 to 10 carbon atoms, preferably 1 to 5 monovalent aliphatic hydrocarbon group, 4 carbon atoms ~ 8, preferably 5-6 monovalent alicyclic hydrocarbon groups or C6-15, preferably 6-12 monovalent aromatic hydrocarbon groups are shown. ] Of these, preferred are [Ia] and [I-
b] Substituted phenols. As the substituted phenols of [Ia], n is 10 to 30, particularly 10 to 2
No. 6 is preferred, and specific examples thereof include decylphenol, dodecylphenol, tetratetodecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol.

As the substituted phenols of [Ib], compounds in which X is —R—CO—O— and R is a single bond are suitable, and n is 10 to 30, particularly 10 to 26. Are preferred, and specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Mention may be made of tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

In the substituted phenols or substituted benzoyl chlorides represented by the above general formulas [Ia] to [Ig], the position of the substituent is generally preferably p-position or o-position, and a mixture of the two. Is preferred.

It is desirable that the monofunctional phenols are introduced into at least 5 mol%, preferably at least 10 mol% of the ends of the obtained aromatic polycarbonate copolymer, and the monofunctional phenols are also introduced. These may be used alone or in combination of two or more.

In addition, in the aromatic polycarbonate copolymer of the present invention, 9,9-bis (4-hydroxy-3-)
When the content of methylphenyl) fluorene is 80 mol% or more of the total dihydric phenol component, the fluidity of the resin may decrease, and therefore, the above general formulas [Ia] to [I-].
It is preferable to use substituted phenols or substituted benzoic acid chlorides represented by g] as the terminal terminating agent.

The aromatic polycarbonate copolymer of the present invention has 0.7 g of the polymer dissolved in 100 ml of methylene chloride and has a specific viscosity of 0.17 to 20 measured at 20 ° C.
The range of 0.55 is preferable, and 0.21 to 0.45
The range of is more preferable. If the specific viscosity is less than 0.17, the molded product becomes brittle, and if it exceeds 0.55, the melt viscosity and the solution viscosity become high, which makes handling difficult, which is not preferable.

The aromatic polycarbonate copolymer of the present invention preferably has a glass transition temperature (Tg) of 150 ° C. or higher measured at a heating rate of 20 ° C./min. Further, it is preferably 155 ° C. Tg is 1
If the temperature is 50 ° C. or lower, the heat resistance is insufficient and it becomes difficult to use it for heat resistance, which is not preferable.

On the other hand, examples of the component (B) carbonaceous filler constituting the polycarbonate resin composition of the present invention include carbon fibers, carbon black, graphite, carbon nanotubes, fullerenes and the like. From the viewpoint of the effect of improving conductivity and cost, carbon fiber and carbon black are particularly preferable. First, the carbon fiber is not particularly limited, and various known carbon fibers such as polyacrylonitrile, cellulose, pitch, rayon, lignin, and carbonaceous fiber or graphite fiber produced by using hydrocarbon gas, etc., A polyacrylonitrile-based carbon fiber having excellent fiber strength is preferable. Further, the carbon fiber can be subjected to an oxidation treatment on the surface of the fiber by a known method represented by ozone, plasma, nitric acid, electrolysis and the like, which is preferably performed because the adhesion with the resin component is increased. Carbon fibers are usually in the form of chopped strands, roving strands, milled fibers and the like.

In order to impart conductivity or the like to such carbon fiber, the surface of the fiber may be coated with a metal. The diameter of the metal-coated carbon fiber is particularly preferably 6 to 20 μm. The metal-coated carbon fiber is a carbon fiber coated with a metal such as nickel, copper, cobalt, silver, aluminum, iron, or an alloy thereof by a known plating method or vapor deposition method.
The metal is preferably one or more metals selected from nickel, copper and cobalt from the viewpoints of conductivity, corrosion resistance, productivity and economy, and nickel-coated carbon fiber is particularly preferable.

These carbon fibers are epoxy resin,
Those bundled with various sizing agents such as urethane resin and acrylic resin can be preferably used, and epoxy resin and / or urethane resin are preferable.

As the component (B) carbon black constituting the polycarbonate resin composition of the present invention, conventionally known Ketjen black, acetylene black, furnace black, lamp black, thermal black, channel black, roll black, disk black. Etc. can be mentioned. Among these carbon blacks, Ketjen black, acetylene black and furnace black are particularly preferable.

The resin composition of the present invention comprises the above-mentioned (A) polycarbonate copolymer and (B) carbon-based filler, and the blending ratio of each component thereof varies depending on the situation, and may be various. However, generally, the polycarbonate copolymer (A) is 40 to 99% by weight, preferably 50 to 99% by weight.
90% by weight and (B) the carbon-based filler are 60 to 1% by weight, preferably 50 to 10% by weight.
Here, if the content of (B) is less than 1% by weight, the effect of improving conductivity tends to be small. On the other hand, if it exceeds 60% by weight, the fluidity is lowered, and it may be difficult to knead and mold the resin, which is not preferable.

In the present invention, in addition to the above carbon-based filler, various inorganic fillers can be added as the component (C) in order to improve the rigidity or conductivity of the resin.
Examples of these inorganic fillers include glass materials, metallic fillers, and various inorganic fillers.

As the glass material used as the inorganic filler, for example, glass fiber, glass milled fiber,
Glass beads, glass flakes, glass powder and the like can be used. Here, the glass material used is not particularly limited to glass compositions such as A glass, C glass, and E glass, and may be TiO ₂ , Zr ₂ O,
It may contain components such as BeO, CeO ₂ , SO ₃ , P ₂ O _{5 and the} like. However, E-glass (non-alkali glass) is more preferable because it does not adversely affect the polycarbonate copolymer. The glass fiber is obtained by drawing molten glass by various methods and quenching it into a predetermined fiber. The quenching and stretching conditions in such a case are also not particularly limited. Further, the cross-sectional shape may be, in addition to the general round shape, various types of modified cross-sectional shapes, which are typified by overlapping of round fibers in parallel. Further, it may be a glass fiber having a mixture of a perfect circle and an irregular cross section. The glass fibers have an average fiber diameter of 1 to 25 μm, preferably 5 to 17 μm. If glass fibers having an average fiber diameter of less than 1 μm are used, the moldability is impaired, and if glass fibers having an average fiber diameter of more than 25 μm are used, the appearance is impaired and the reinforcing effect is not sufficient.

In order to impart conductivity or the like to the glass fiber, a metal coat may be applied to the fiber surface. The diameter of the metal-coated glass fiber is particularly preferably 6 to 20 μm. The metal-coated glass fiber is a glass fiber coated with a metal such as nickel, copper, cobalt, silver, aluminum, iron, or an alloy thereof by a known plating method or vapor deposition method. The metal is preferably one or more metals selected from nickel, copper and cobalt from the viewpoints of conductivity, corrosion resistance, productivity and economy.

The metal-based filler used in the present invention is not particularly limited, and refers to metal fibers, metal-coated fibers, and metal flakes. Examples of the material include metals such as stainless steel, aluminum, copper, and brass. To be Two or more of these may be used in combination. Diameter of metal fiber is 4-8
0 μm is preferable, and 6 to 60 μm is particularly preferable.

The glass flakes and metal flakes used in the present invention preferably have an average particle size of 10 to 1000 μm, and when the average particle size is (a) and the thickness is (c), ( The a) / (c) ratio is preferably 5 to 500, more preferably 6 to 450, and 7
Those of up to 400 are more preferable. If the average particle size is less than 10 microns or the (a) / (c) ratio is less than 5, the rigidity is insufficient and the average particle size exceeds 1000 microns or the (a) / (c) ratio exceeds 500. And the appearance and weld strength of the molded product deteriorate, which is not preferable. The average particle diameter of the glass flakes and the metal flakes as used herein is calculated as the median diameter of the weight distribution of the particle diameter obtained by the standard sieving method.

Other various inorganic fillers include, for example, potassium titanate whiskers, aluminum borate whiskers, silicon carbide whiskers, silicon nitride whiskers and the like, calcium carbonate, magnesium carbonate,
Dolomite, silica, diatomaceous earth, alumina, iron oxide, zinc oxide, magnesium oxide, calcium sulfate, magnesium sulfate, calcium sulfite, talc, clay, mica,
Kaolin, asbestos, calcium silicate, montmorillonite, bentonite, wollastonite, graphite,
Iron powder, lead powder, aluminum powder and the like can also be used.

The inorganic filler is preferably surface-treated with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent or the like. A silane coupling agent is particularly preferable. By this surface treatment, the decomposition of the polycarbonate copolymer is suppressed, and the adhesion is further improved, whereby the mechanical properties, which are the object of the present invention, can be improved. The silane coupling agent here is the following formula

[0058]

[Chemical 15]

[Wherein Y is a group having reactivity or affinity with the resin matrix such as an amino group, an epoxy group, a carboxylic acid group, a vinyl group, a mercapto group or a halogen atom, R
¹ , R ² and R ³ each represent a single bond or an alkylene group having 1 to 7 carbon atoms, and an amide bond, an ester bond, an ether bond or an imino bond may be present in the alkylene molecular chain, and X ¹ , X ² , and X ³ each represent an alkoxy group, preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom], and specifically, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane. , Γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ−
Aminopropyltriethoxysilane, N-phenyl-γ
-Aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and γ-chloropropyltrimethoxysilane. Further, these metal-based fillers may be subjected to a focusing treatment with an olefin resin, a styrene resin, a polyester resin, an epoxy resin, a urethane resin, or the like. These fibrous fillers may be used alone or in combination of two or more kinds.

In the present invention, the aromatic polycarbonate copolymer contains at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid and esters thereof. It can be added in a proportion of 0.0001 to 0.05% by weight with respect to the polymer. By blending this phosphorus compound, the thermal stability of such an aromatic polycarbonate copolymer is improved, and a decrease in molecular weight and deterioration of hue during molding are prevented.

The phosphorus compound is at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid and esters thereof, preferably the following general formula (1) To (4) are at least one phosphorus compound selected from the group consisting of:

[0062]

[Chemical 16]

[0063]

[Chemical 17]

[0064]

[Chemical 18]

[0065]

[Chemical 19]

Here, R ^{1 to} R ¹² are each independently a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
1 carbon atom such as dodecyl, hexadecyl, octadecyl
It represents an alkyl group having 20 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms such as phenyl, tolyl, and naphthyl, or an aralkyl group having 7 to 18 carbon atoms such as benzyl and phenethyl. Further, when two alkyl groups are present in one compound, the two alkyl groups may be bonded to each other to form a ring.

Examples of the phosphorus compound represented by the above formula (1) include triphenylphosphite, trisnonylphenylphosphite and tris (2,4-di-tert-phosphite).
Butylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite Fight, monooctyl diphenyl phosphite, bis (2,6-di-tert
-Butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-t
ert-Butylphenyl) octylphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) penta Examples thereof include erythritol diphosphite and distearyl pentaerythritol diphosphite. Examples of the phosphorus compound represented by the above formula (2) include tributyl phosphate, trimethyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl monoorthoxenyl phosphate. , Dibutyl phosphate, dioctyl phosphate,
Examples of the phosphorus compound represented by the above formula (3) include tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite, and the above ( Examples of the compound represented by the formula 4) include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Among them, distearyl pentaerythritol diphosphite, triethyl phosphate, dimethyl benzenephosphonate and bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferably used.

The amount of the phosphorus compound blended is 0.0001 to 0.05 with respect to the aromatic polycarbonate copolymer.
%, Preferably 0.0005 to 0.02% by weight, particularly preferably 0.001 to 0.01% by weight. If the blending amount is less than 0.0001% by weight, it is difficult to obtain the above effect,
If it exceeds 0.05% by weight, the heat stability of the aromatic polycarbonate copolymer is adversely affected and the hydrolysis resistance is also deteriorated, which is not preferable.

To the aromatic polycarbonate copolymer of the present invention, a generally known antioxidant can be added for the purpose of preventing oxidation. Examples thereof include phenolic antioxidants and benzofuranone antioxidants. Specific examples of the phenolic antioxidant include triethylene glycol-bis (3- (3-ter).
t-butyl-5-methyl-4-hydroxyphenyl) propionate), 1,6-hexanediol-bis (3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol-tetrakis (3- (3,5-di-tert-butyl-4-)
Hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-
2,4,6-Tris (3,5-di-tert-butyl-4)
-Hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-
Butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 3.9
-Bis {1,1-dimethyl-2- [β- (3-tert
-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane and the like. Specific examples of the benzofuranone-based antioxidant include 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one and 5,7.
-Di-t-butyl-3- (2,3-dimethylphenyl)
-3H-benzofuran-2-one and the like. The preferred range of addition of these antioxidants is 0.0001 to 0.05% by weight based on the aromatic polycarbonate copolymer.

Further, a higher fatty acid ester of a monohydric or polyhydric alcohol may be added to the aromatic polycarbonate copolymer of the present invention, if necessary. By blending the higher fatty acid ester of the monohydric or polyhydric alcohol, the mold releasability from the mold at the time of molding the aromatic polycarbonate copolymer is improved, and in the molding of optical parts, the mold release load is increased. It is possible to prevent deformation of the molded product due to poor release. There is also an advantage that the melt fluidity of the aromatic polycarbonate copolymer is improved.

The higher fatty acid ester is preferably a partial ester or whole ester of a monohydric or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.

Further, as the partial ester or total ester of the monohydric or polyhydric alcohol and the saturated fatty acid, stearic acid monoglyceride, stearic acid monosorbitate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate. , Propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, 2-ethylhexyl stearate and the like. Among them, stearic acid monoglyceride, pentaerythritol tetrastearate. Is preferably used.

The amount of the ester of the alcohol and the higher fatty acid to be blended is 0.01 to 2% by weight, preferably 0.015 to 0.5% by weight, and preferably 0.05 to 0.5% by weight based on the aromatic polycarbonate copolymer. It is more preferably from 02 to 0.2% by weight.
If the blending amount is less than 0.01% by weight, the above effect cannot be obtained,
If it exceeds 2% by weight, it may cause stains on the mold surface.

Additives such as a light stabilizer, a colorant, an antistatic agent and a lubricant can be added to the aromatic polycarbonate copolymer of the present invention within a range that does not impair heat resistance and mechanical properties.

The aromatic polycarbonate resin composition of the present invention may contain a flame retardant in an amount that does not impair the object of the present invention. Examples of the flame retardant include a halogenated bisphenol A polycarbonate type flame retardant, an organic salt type flame retardant, an aromatic phosphate ester type flame retardant, or a halogenated aromatic phosphate ester type flame retardant. The above can be blended. Specifically, the polycarbonate flame retardant of halogenated bisphenol A is a polycarbonate flame retardant of tetrachlorobisphenol A, tetrachlorobisphenol A and bisphenol A.
And a copolycarbonate flame retardant of tetrabromobisphenol A, a copolycarbonate flame retardant of tetrabromobisphenol A and bisphenol A, and the like. Specifically, organic salt-based flame retardants include diphenylsulfone-3,3′-dipotassium disulfonate, potassium diphenylsulfone-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, 2,4,5-trisulfate. Potassium chlorobenzene sulfonate, potassium bis (2,6-dibromo-4-cumylphenyl) phosphate, sodium bis (4-cumylphenyl) phosphate, potassium bis (p-toluenesulfone) imide, potassium bis (diphenylphosphate) imide, Potassium bis (2,4,6-tribromophenyl) phosphate, potassium bis (2,4-dibromophenyl) phosphate, potassium bis (4-bromophenyl) phosphate, potassium diphenylphosphate, sodium diphenylphosphate,
Examples include potassium perfluorobutane sulfonate, sodium or potassium lauryl sulfate, and sodium or potassium hexadecyl sulfate. Specifically, halogenated aromatic phosphoric acid ester type flame retardants are tris (2,4,6-
Tribromophenyl) phosphate, tris (2,4-
Dibromophenyl) phosphate, tris (4-bromophenyl) phosphate and the like. Specifically, aromatic phosphate ester flame retardants include triphenyl phosphate, tris (2,6-xylyl) phosphate, tetrakis (2,6-xylyl) resorcin diphosphate, tetrakis (2,6-xylyl) hydroquinone diphosphate. , Tetrakis (2,6-xylyl) -4,4'-biphenol diphosphate, tetraphenyl resorcin diphosphate, tetraphenylhydroquinone diphosphate, tetraphenyl-4,4'-biphenol diphosphate, aromatic ring sources resorcin and phenol Aromatic polyphosphate containing no phenolic OH group, aromatic ring source is resorcin and phenol, aromatic polyphosphate containing phenolic OH group, aromatic ring source is hydroquinone and phenol containing phenolic O Aromatic polyphosphates containing no group, similar aromatic polyphosphate containing a phenolic OH group, (shown below "aromatic polyphosphates" include a phenolic O
Both aromatic polyphosphates containing H groups and aromatic polyphosphates not containing H groups are meant) aromatic polyphosphates whose aromatic ring source is bisphenol A and phenol, and aromatic ring sources are tetrabromobisphenol A and phenol An aromatic polyphosphate, an aromatic polyphosphate in which the aromatic ring source is resorcin and 2,6-xylenol, an aromatic polyphosphate in which the aromatic ring source is hydroquinone and 2,6-xylenol, and an aromatic ring source is bisphenol A and 2 , 6-xylenol is an aromatic polyphosphate, and the aromatic ring source is tetrabromobisphenol A and 2,6-xylenol.

Among these flame retardants, polycarbonate flame retardants of halogenated bisphenol A, polycarbonate flame retardants of tetrabromobisphenol A,
A copolymerized polycarbonate of tetrabromobisphenol A and bisphenol A is preferable, and a polycarbonate type flame retardant of tetrabromobisphenol A is more preferable. Diphenylsulfone-3 as an organic salt flame retardant,
3'-dipotassium disulfonate, diphenyl sulfone-
Preference is given to potassium 3-sulfonate and sodium 2,4,5-trichlorobenzenesulfonate. As the aromatic phosphate ester flame retardant, triphenyl phosphate,
Tricresyl phosphate, cresyl diphenyl phosphate, resulcinol bis (dixylenyl phosphate), bis (2,3 dibromopropyl) phosphate,
Tris (2,3 dibromopropyl) phosphate is preferred. Among these, aromatic phosphate ester-based flame retardants that do not destroy the ozone layer, such as triphenyl phosphate, tricresyl sulfate, and resulcinol bis (dixylenyl phosphate), are most preferable.

Other resins may be added to the aromatic polycarbonate resin composition of the present invention as long as the object of the present invention is not impaired.

Examples of such other resins include polyethylene terephthalate, polybutylene terephthalate,
Polyester resin such as polyethylene naphthalate, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, polyphenylene ether resin,
Polyphenylene sulfide resin, polysulfone resin, polyolefin resin such as polyethylene and polypropylene,
Resins such as polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, phenol resin, epoxy resin and the like can be mentioned.

As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber,
Ethylene / propylene rubber, acrylic elastomer,
Examples thereof include silicone rubber, polyester-based elastomer, polyamide-based elastomer, MBS rubber, MAS rubber and the like.

Any method may be employed to produce the aromatic polycarbonate resin composition of the present invention. For example, a method of mixing with a tumbler, a V-type blender, a super mixer, a Nauter mixer, a Banbury mixer, a kneading roll, an extruder or the like is appropriately used. The aromatic polycarbonate resin composition thus obtained can be molded into a molded product by a commonly known method such as an injection molding method, an extrusion molding method, or a compression molding method, after being pelletized as it is or with a melt extruder. it can. In addition, in order to improve the miscibility of the aromatic polycarbonate resin composition of the present invention and to obtain stable mold release properties and physical properties, it is preferable to use a twin-screw extruder in melt extrusion. Furthermore, when compounding an inorganic filler, a method of directly charging from an extruder hopper port or the middle of the extruder, a method of premixing with a polycarbonate copolymer, and a method of premixing with a part of a polycarbonate copolymer to prepare a master are prepared. Either of the method of charging and the method of charging such a master in the middle of the extruder can be used.

The polycarbonate resin composition of the present invention preferably has a surface specific resistance value of 1 × 10 ¹² or less as measured according to ASTM D257, and 1 × 1.
It is more preferably 0 ¹⁰ or less, and most preferably 1 × 10 ⁸ or less. When the surface resistivity is more than 1 × 10 ¹² , the conductivity becomes insufficient, and when the resin composition is used for a carrying tray of electronic equipment, the electronic equipment may be short-circuited, which is not preferable.

The polycarbonate resin composition of the present invention is not irritating to the vapor of the polycarbonate copolymer generated during melt extrusion or molding, and therefore does not damage the skin, and therefore can be safely handled.

The aromatic polycarbonate resin composition of the present invention thus obtained is transported during the production of housings and chassis for office automation equipment such as personal computers, word processors, fax machines, copiers, printers, semiconductors, memories, hard disks, etc. Transport tray and CD used when
, CD-ROM, CD-R, CD-RW, MO, DV
D, DVD-ROM, DVD-R, optical disc, magneto-optical disc tray, chassis, turntable,
OA internal parts such as pickup chassis, various gears, TVs, videos, DVD players, game machines, electric washing machines, electric dryers, vacuum cleaners, and other home electric appliances housings and parts, electric saws, electric drills, etc. Tools, telescope lens barrel, microscope lens barrel, camera body, camera housing,
It is useful for optical equipment parts such as camera barrels and instrument panels for automobiles.

[0084]

The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the examples, "part" means "part by weight". The evaluation was carried out by the following method.

(I) Evaluation item (1) Specific viscosity: 0.7 g of the polymer was dissolved in 100 ml of methylene chloride and measured at a temperature of 20 ° C. (2) Glass transition point (Tg) It was measured at a temperature rising rate of 20 ° C./min using a 2910 type DSC manufactured by TA Instruments Japan Co., Ltd. (3) Heat resistance Based on ASTM D648, the deflection temperature under load was measured with a load of 18.5 kg. (4) Conductivity According to ASTM D257, the surface specific resistance value was measured. (5) Water absorption rate Based on ASTM D-0570, the water absorption rate after immersion in water at 23 ° C for 24 hours was measured. (6) Irritation When molding a molded piece for measurement by the following method, "I" indicates irritation or skin irritation, "Non irritation or skin irritation" ○ ”.

(II) Synthesis of Each Component in Composition (a) Polycarbonate Resin ◎ Production of Polycarbonate Copolymer of the Present Invention-Part 1 Thermometer, stirrer, 21538 parts of ion-exchanged water in a reactor equipped with a reflux condenser, 48% sodium hydroxide aqueous solution 4229
Parts, bisphenol A 1949 parts, biscresol fluorene 3231 parts and hydrosulfite 1
After dissolving 0.9 parts, 14530 parts of methylene chloride was added, and phosgene 2200 was added at 16 to 20 ° C. with stirring.
The part was blown in in 60 minutes. After the completion of phosgene blowing, p-tert-butylphenol 115.4 parts and 4
705 parts of 8% sodium hydroxide aqueous solution was added, and 2.6 parts of triethylamine was further added to the mixture at 40 to 20 ° C.
The reaction was completed by stirring for a minute. After completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, methylene chloride was evaporated with a kneader, 5520 parts of a yellowish white polymer having a molar ratio of bisphenol A to biscresolfluorene of 50:50 of 0.272 and a Tg of 197 ° C. were obtained (96% yield).
Tris (2,4-di-
tert-butylphenyl) phosphite 0.050
%, Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate to 0.0.
10% and 0.030% of pentaerythritol tetrastearate were added and extruded with an extruder at a cylinder temperature of 300 ° C. Polycarbonate copolymer pellets (EX-P
C1) was obtained.

Preparation of Polycarbonate Copolymer of the Present Invention-Part 2 19580 Parts of Deionized Water and 3845 Aqueous Sodium Hydroxide Solution 3845 in a reactor equipped with a thermometer, a stirrer and a reflux condenser.
Bisphenol A 2835 parts, biscresol fluorene 1175 parts and hydrosulfite 8.4 parts were dissolved, methylene chloride 13209 parts were added, and then phosgene 2000 at 18 to 20 ° C. with stirring.
The part was blown in in 60 minutes. After the completion of phosgene blowing, p-tert-butylphenol 93.2 parts and 48
% Aqueous sodium hydroxide solution (641 parts) and triethylamine (2.0 parts) were added, and the mixture was stirred at 20 to 27 ° C. for 40 minutes to complete the reaction. After completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, methylene chloride was evaporated with a kneader, As a result, 4230 parts of a yellowish white polymer having a molar ratio of bisphenol A and biscresolfluorene of 80:20, a specific viscosity of 0.374 and a Tg of 173 ° C. was obtained (yield 94%).
Tris (2,4-di-
tert-butylphenyl) phosphite 0.050
%, Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate to 0.0.
10% and 0.030% of pentaerythritol tetrastearate were added and extruded at a cylinder temperature of 280 ° C. with an extruder to obtain polycarbonate copolymer pellets (EX-P
C2) was obtained.

Preparation of Aromatic Polycarbonate Resin for Comparison-Part 1 20980 parts of ion-exchanged water and 1523 parts of potassium hydroxide were placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and bisphenol A 886 parts, 9,9. 1360 parts of bis (4-hydroxyphenyl) fluorene (hereinafter "bisphenolfluorene") and hydrosulfite 4.7
After dissolving 1 part, 13210 parts of methylene chloride was added, and 1000 parts of phosgene was blown thereinto at 18 to 20 ° C. over 60 minutes while stirring. After finishing blowing phosgene,
52.4 parts of p-tert-butylphenol and 218 parts of potassium hydroxide were added, and triethylamine 2.7 was further added.
Parts were added and stirred at 20 to 27 ° C. for 40 minutes to complete the reaction. After completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, methylene chloride was evaporated with a kneader, A yellowish white polymer 2 having a molar ratio of bisphenol A to bisphenolfluorene of 50:50 of 0.272 and a Tg of 205 ° C.
250 parts were obtained (yield 90%). Tris (2,4-di-tert-butylphenyl) phosphite 0.050%, octadecyl-3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (0.010%) and pentaerythritol tetrastearate (0.030%) were added and extruded at a cylinder temperature of 300 ° C. with an extruder to form a polycarbonate copolymer pellet. (CEX-PC1) was obtained.

Production of Aromatic Polycarbonate Resin for Comparison-Part 2 Bisphenol A3907 was produced during the production of EX-PC1.
Parts, E except that 59 parts of biscresolfluorene was used
3870 parts of a yellowish white polymer having a molar ratio of bisphenol A to biscresolfluorene of 99: 1, a specific viscosity of 0.390 and a Tg of 148 ° C. were obtained in the same manner as in the production of X-PC1 (yield: 95%). This is EX-P
Aromatic polycarbonate resin pellets (CEX-PC2) were obtained in the same manner as in the production of C1.

(B) Carbon-based filler ◎ Carbon fiber: Vesphite HTA-C6-U; manufactured by Toho Rayon Co., Ltd., PAN-based, epoxy converging treatment, fiber diameter 7
Micron ◎ Carbon Black: Ketjen Black EC600J
D: manufactured by Lion Corporation (referred to as "CB")

Examples 1 to 5 and Comparative Examples 1 to 4 EX-PC1 and EX-PC2 or CEX obtained above.
-PC1 and CEX-PC2, and Tables 1 and 2
After uniformly mixing the listed components using a tumbler, a twin-screw extruder with a 30 mmφ vent (Kobe Steel Co., Ltd.)
Cylinder temperature 300 ° C, 1
Pelletizing while degassing with a vacuum degree of 0 mmHg, drying the obtained pellets at 120 ° C. for 5 hours, and then using an injection molding machine (Sumitomo Heavy Industries, Ltd. SG150U type), a cylinder temperature of 330 ° C., A molded piece for measurement was prepared under the condition that the mold temperature was 100 ° C. The evaluation results are shown in Tables 1 and 2.

As is clear from each comparison, the aromatic polycarbonate resin composition comprising the polycarbonate copolymer of the present invention and the carbon fiber has a heat resistance and a conductivity higher than those using the aromatic polycarbonate resin of Comparative Example. Is excellent and there is no irritation.

[0093]

[Table 1]

[0094]

[Table 2]

[0095]

EFFECT OF THE INVENTION The highly heat-resistant conductive polycarbonate resin composition of the present invention has good heat resistance, excellent conductivity, no irritation to the skin, and low water absorption rate. It is particularly preferably used for a housing, a chassis, a semiconductor, a memory, a transport tray used for transporting these during production of a hard disk, and the like.

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[Procedure amendment]

[Submission date] September 18, 2002 (2002.9.1)
8)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Chemical 1]

[Chemical 2] [In the formula, R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms or a halogen atom, and W is a single bond, 1 to 1 carbon atoms. 20
A hydrocarbon group which may contain an aromatic group, O, S, SO,
SO _2, CO or polycarbonate copolymer composed of an aromatic dihydroxy component represented by a is] COO group, and (B) a polycarbonate resin composition characterized by comprising a carbon-based filler.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

[0009]

[Chemical 4]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

[0013]

[Chemical 5]

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 3E096 BA08 BA17 CA06 CC02 DA14                       EA02X EA02Y EA06X EA06Y                       EA10X EA10Y EA11X EA11Y                       FA07 FA20 FA40                 4F071 AA50 AF37 AF45 BB05 BC04                 4J002 CG001 DA016 DA026 DA036                       EA026 FA046 FD116 GQ00                 4J029 AA09 AE01 BB09A BB12A

Claims (5)

[Claims] 1. A total aromatic dihydroxy component (A) of 5
95 mol% of 9,9-bis (4 represented by the following formula [1]
-Hydroxy-3-methylphenyl) fluorene, 95
~ 5 mol% is represented by the following general formula [2] [Chemical 2] [Wherein, R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group which may include an aromatic group having 1 to 9 carbon atoms or a halogen atom, and W is a single bond, 1 to 1 carbon atoms. 20
A hydrocarbon group which may contain an aromatic group, O, S, SO,
SO _2, CO or polycarbonate copolymer composed of an aromatic dihydroxy component represented by a is] COO group, and (B) a polycarbonate resin composition characterized by comprising a carbon-based filler. 2. The (A) polycarbonate copolymer is 40
% To 99% by weight, and 60% to 1% by weight of the (B) carbon-based filler are contained, The polycarbonate resin composition of Claim 1 characterized by the above-mentioned. 3. The polycarbonate resin composition according to claim 1, wherein the aromatic dihydroxy component represented by the general formula [2] is 2,2-bis (4-hydroxyphenyl) propane. 4. A high heat resistant conductive part molded using the composition according to claim 1. 5. The high heat resistant conductive part according to claim 4, wherein the high heat resistant conductive part is a carrier tray of a semiconductor, a memory or a hard disk.