JP2000160000A - Aromatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aromatic polycarbonate resin composition containing fibrous filler improved in stiffness, etc., by adding the fibrous filler while utilizing characteristics which a polycarbonate copolymer originally has and excellent in wet fatigue performance. SOLUTION: This aromatic polycarbonate resin composition comprises (A) 100 pts.wt. polycarbonate copolymer in which at least 80 mol% of whole aromatic dihydroxy component comprises 1,1-bis(4-hydroxyphenyl)-3,3,5- trimethylcyclohexane (component a) and 4,4'-(m-phenylenediisopropylidene) diphenol and/or 2,2-bis (4-hydroxy-3-methylphenyl)propane (component b) and the molar ratio of the component (a) to the component (b) is (99:1) to (20:80) and (B) 5-200 pts.wt. fibrous filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic polycarbonate resin composition containing a fibrous filler excellent in wet heat fatigue resistance and weld strength. More specifically, an aromatic polycarbonate resin containing a fibrous filler excellent in wet heat fatigue resistance, while improving properties such as rigidity by making use of the inherent properties of the aromatic polycarbonate resin and adding a fibrous filler. It relates to a resin composition.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are widely used because they have excellent mechanical properties such as impact resistance, and also have excellent heat resistance and transparency. As a method for producing such an aromatic polycarbonate resin, a method of directly reacting phosgene with a dihydric phenol such as bisphenol A (interfacial polymerization method) or a method of melting a dihydric phenol such as bisphenol and a diallyl carbonate such as diphenyl carbonate is used. There is known a method of performing a transesterification reaction in a state and performing polymerization (hereinafter, sometimes referred to as a melting method).

Various studies have been made on aromatic polycarbonate resin compositions using an aromatic polycarbonate resin and a glass filler as materials having excellent rigidity and the like.
It is widely used in various fields such as the automobile field and the OA field. As such an aromatic polycarbonate resin, a polycarbonate boat made of bisphenol A is generally put to practical use.

Japanese Patent No. 2683662 describes an aromatic polycarbonate resin composition using an aromatic polycarbonate resin and a glass filler. It is disclosed that the aromatic polycarbonate resin used in the patent is substantially an aromatic polycarbonate resin derived from bisphenol A and has excellent impact resistance. However, the aromatic polycarbonate resin from bisphenol A used in such a composition has a high water absorption rate and thus has a disadvantage of poor wet heat fatigue resistance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to make use of the inherent properties of a polycarbonate copolymer, to improve properties such as rigidity by adding a fibrous filler, and to have excellent wet heat fatigue resistance. To provide an aromatic polycarbonate resin composition containing a fibrous filler. As a result of intensive studies on such a resin composition, the present invention has been completed by using a specific polycarbonate copolymer.

[0006]

According to the present invention, (A) at least 80 mol% of the wholly aromatic dihydroxy component is (a)
1,1-bis (4-hydroxyphenyl) -3,3,5
Trimethylcyclohexane (components a) and (b)
Consisting of 4,4 ′-(m-phenylenediisopropylidene) diphenol and / or 2,2-bis (4-hydroxy-3-methylphenyl) propane (component b),
And the molar ratio of component a to component b is 99: 1 to 20:
Polycarbonate copolymer 10 composed of 80
The present invention relates to an aromatic polycarbonate resin composition comprising 0 parts by weight and (B) 5 to 200 parts by weight of a fibrous filler.

In the polycarbonate copolymer (A) used in the present invention, at least 80 mol% of the total aromatic dihydroxy component is (a) 1,1-bis (4-hydroxyphenyl) -3,3,5- Trimethylcyclohexane (abbreviated as bisphenol TMC) (components a) and (b) 4,
4 '-(m-phenylenediisopropylidene) diphenol (abbreviated as bisphenol M) and / or 2,2
-Bis (4-hydroxy-3-methylphenyl) propane (abbreviated as bisphenol C) (component b), and the ratio of component a to component b is 99: 1 to 20: 8 in molar ratio.
It is a polycarbonate copolymer constituted in the range of 0. In the polycarbonate copolymer of the present invention, it is necessary to use the bisphenol TMC at a certain ratio as the aromatic dihydroxy component.
In order to reduce the content to 0.18% by weight or less, a specific dihydroxy component is combined with the bisphenol TMC to form a polycarbonate copolymer, and a terminal modifier having a specific structure in a terminal group is used. May be introduced.

According to the study of the present inventor, an aromatic polycarbonate resin composition comprising a polycarbonate copolymer obtained by combining a specific dihydroxy component with the bisphenol TMC and a fibrous filler is:
In particular, it has been found that the composition has excellent wet heat fatigue properties. This is considered to be because the specific polycarbonate resin has a low water absorption and a high flexural modulus. One preferred embodiment of the polycarbonate copolymer is a combination wherein component a is bisphenol TMC and component b is bisphenol M, wherein component a:
Component b has a molar ratio of 20:80 to 80:20, preferably 30:70 to 80:20, particularly 40:60 to 7:
A range of 0:30 is more preferred. Another preferred embodiment is that component a is bisphenol TMC and component b
Is a combination of bisphenol C, in which case the ratio of component a: component b is from 20:80 to 80:20 in molar ratio,
Preferably 30: 70-80: 20, especially 40: 60-
More preferably, it is in the range of 70:30. In these preferred embodiments, the sum of components a and b is advantageously at least 80 mol%, preferably at least 90 mol%, of the total aromatic dihydroxy component. In other words, the content of the other dihydroxy component (component c) may be less than 20 mol%, preferably less than 10 mol%, based on the total aromatic dihydroxy component.

The component c may be any component other than the components a and b usually used as a dihydroxy component of an aromatic polycarbonate resin. Examples thereof include hydroquinone, resorcinol, 1,6-dihydroxynaphthalene, 6-dihydroxynaphthalene,
4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylmethane, bis {(4-hydroxy-3,5-dimethyl) phenyl} methane , 1,1-
Bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,1-bis (4
-Hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane,
2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 2- (4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, 2,
2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis} (3,5-dibromo-
4-hydroxy) phenyl {propane, 2,2-bis {(3,5-dichloro-4-hydroxy) phenyl} propane, 2,2-bis {(3-bromo-4-hydroxy) phenyl} propane, 2, 2-bis {(3-chloro-4-hydroxy) phenyl} propane, 4-bromoresorcinol, 2,2-bis} (3-isopropyl-4
-Hydroxy) phenyl {propane, 2,2-bis {(3-phenyl-4-hydroxy) phenyl} propane, 2,2-bis {(3-ethyl-4-hydroxy) phenyl} propane, 2,2-bis {(3-n-propyl-4-hydroxy) phenyl} propane, 2,2-bis {(3-sec-butyl-4-hydroxy) phenyl}
Propane, 2,2-bis} (3-tert-butyl-4
-Hydroxy) phenyl {propane, 2,2-bis {(3-cyclohexyl-4-hydroxy) phenyl}
Propane, 2,2-bis {(3-methoxy-4-hydroxy) phenyl} propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-dibromo-2,2-bis (4- (Hydroxyphenyl) ethylene, 1,1-dichloro-2,2-bis {(3-phenoxy-4-hydroxy) phenyl} ethylene, ethylene glycol bis (4-hydroxyphenyl) ether,
2,2-bis (4-hydroxyphenyl) butane, 2,
2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3
-Dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2- Bis (4-hydroxyphenyl) -4-methylpentane, 3,3-bis (4
-Hydroxyphenyl) pentane, 1,1-bis (4-
(Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 9,9-bis (4-hydroxyphenyl) fluorene, 9 , 9-Bis} (4-hydroxy-3
-Methyl) phenyl} fluorene, α, α'-bis (4
-Hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-
Diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,
4′-dihydroxydiphenyl sulfone, bis ｛(3,
5-dimethyl-4-hydroxy) phenyl} sulfone,
4,4′-dihydroxydiphenylsulfoxide, 4,
4'-dihydroxydiphenyl sulfide, 4,4'-
Examples thereof include dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenyl ether, and 4,4′-dihydroxydiphenyl ester, and these can be used alone or in combination of two or more.

The polycarbonate copolymer of the present invention is produced by 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 a carbonic acid diester. You. Next, basic means of these manufacturing methods will be briefly described.

In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and amine compounds such as pyridine. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. For promoting the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt may be used. At that time, the reaction temperature is usually 0 to 40 ° C, and the reaction time is several minutes to 5 hours.

The transesterification using a carbonic acid diester as a carbonate precursor is a method in which a predetermined ratio of an aromatic dihydroxy component is stirred with a carbonic acid diester while heating under an inert gas atmosphere to distill off the alcohol or phenol to be produced. It is performed by The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, and is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off alcohol or phenols generated under reduced pressure from the beginning. Further, a catalyst usually used in a transesterification reaction to promote the reaction can be used. As the carbonic acid diester used in the transesterification reaction, for example, a carbonate ester or a haloformate is used. Specifically, diphenyl carbonate, ditolyl carbonate,
Examples include, but are not limited to, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and the like. Preferably, diphenyl carbonate or dihaloformate of dihydric phenol is used, and more preferably, diphenyl carbonate is used. These carbonates may be used alone or in combination of two or more.

In the aromatic pocarbonate copolymer of the present invention, monofunctional phenols which are usually used as a terminal stopper in the polymerization reaction can be used. In particular, in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminal stopper for controlling the molecular weight, and the obtained polycarbonate copolymer has a terminal with monofunctional phenols. Since it is blocked by a base group, it has better thermal stability than that which is not.

The monofunctional phenol may be any one used as a terminal terminator for an aromatic polycarbonate resin, and is generally phenol or a lower alkyl-substituted phenol, and is a monofunctional phenol represented by the following general formula. Can be shown.

[0015]

Embedded image

Wherein A is a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms or a phenyl-substituted alkyl 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. It is desirable that these monofunctional phenols are introduced into at least 5 mol%, preferably at least 10 mol%, of the terminals of the obtained polycarbonate copolymer.

Further, phenols having a long-chain alkyl group or aliphatic polyester group as a substituent, benzoic acid chlorides or long-chain alkyl carboxylic acid chlorides (hereinafter, these are distinguished from the monofunctional phenols) Is sometimes abbreviated as a terminal modifier.) Is bonded to the terminal of the polycarbonate copolymer, thereby improving the melt fluidity of the resin and facilitating the molding process, as well as the water absorption of the resin. Also has the effect of lowering. Further, since the terminal modifier is a monofunctional compound as a matter of course, it also has a function as a terminal terminator or a molecular weight regulator. Such a terminal modifier is
Depending on the composition of the polycarbonate copolymer, the proportion is not fixed, but it is used so as to bond to at least 5 mol%, preferably at least 10 mol%, of the terminals. The terminal modifier can be used in combination with the monofunctional phenols.

The terminal modifier is represented by the following general formula [I-
a] to [Ih].

[0020]

Embedded image

In the above general formulas [Ia] to [Ih], X represents -RO-, -R-CO-O- or -RO-CO-.
It is. Here, R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms, T represents a single bond or a bond similar to the above X, and n represents 10 to 50.
Indicates an integer.

Q is a halogen atom or C 1-10,
It preferably represents a monovalent aliphatic hydrocarbon group of 1 to 5;
Represents 0 to 4 integer, Y 1 to 10 carbon atoms, preferably an 1-5 divalent aliphatic hydrocarbon group, W ¹ is a hydrogen ^{atom, -CO-R 1, -CO-} R 2 Or R ³ . Here, R ¹ , R ² and R ³ each represent a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms,
8, preferably a monovalent alicyclic hydrocarbon group having 5 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15, preferably 6 to 12 carbon atoms.

A represents an integer of 4 to 20, preferably 5 to 10, m represents an integer of 1 to 100, preferably 3 to 60, particularly preferably 4 to 50, and Z represents a single bond or one carbon atom. Represents a divalent aliphatic hydrocarbon group having 10 to 10, preferably 1 to 5; W ² represents a hydrogen atom; a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms; A monovalent alicyclic hydrocarbon group of 5 to 8, preferably 5 to 6, or a monovalent aromatic hydrocarbon group of 6 to 15, preferably 6 to 12 carbon atoms.

The above-mentioned terminal modifiers [Ia] to [I-
h] is preferably [Ia] and [Ib]
Are substituted phenols. As the substituted phenols of [Ia], those having n of 10 to 30, particularly 10 to 26 are preferable, and specific examples thereof include, for example, decylphenol, dodecylphenol, tridecylphenol, tetradecylphenol, and pentadecylphenol. , Octadecylphenol, nonadecylphenol, eicosylphenol, heneicosylphenol, docosylphenol, tricosylphenol, tetracosylphenol, pentacosylphenol, hexacosylphenol, heptacosylphenol, octacosylphenol, Nonacosyl phenol and triacontyl phenol can be exemplified.

As the substituted phenols of [Ib], a compound in which X is -R-CO-O- and R is a single bond is suitable, and n is 10 to 30, especially 10 to 26. Are preferred, and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Tridecyl hydroxybenzoate, tetradecyl hydroxybenzoate, pentadecyl hydroxybenzoate, hexadecyl hydroxybenzoate, heptadecyl hydroxybenzoate, octadecyl hydroxybenzoate, nonadecyl hydroxybenzoate, eicosyl hydroxybenzoate,
Henicosyl hydroxybenzoate, docosyl hydroxybenzoate, tricosyl hydroxybenzoate, tetracosyl hydroxybenzoate, pentacosyl hydroxybenzoate, hexacosyl hydroxybenzoate, heptacosyl hydroxybenzoate, octakosyl hydroxybenzoate, nonakosyl hydroxybenzoate, triacontyl hydroxybenzoate, etc. Can be mentioned.

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

The polycarbonate copolymer may be a branched polycarbonate copolymer obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a mixture of two or more of the obtained polycarbonate copolymers. It may be a mixture.

Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, and 4,6-
Dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2,4,6-trimethyl-2,4
6-tris (4-hydroxyphenyl) heptane, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) ) -4-Methylphenol, 4
-{4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) )
Ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, 2- (4-hydroxyphenyl) -2-
(3′-phenoxycarbonyl-4′-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2
-(3'-carboxy-4'-hydroxyphenyl) propane and the like, and among them, 1,1,1-tris (4-
Hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferred, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferred.

The molecular weight of the polycarbonate copolymer is preferably 12,000 to 30,000, more preferably 14,000 to 27,000 in terms of viscosity average molecular weight (M).
15,000 to 25,000 are particularly preferred. A polycarbonate copolymer having such a viscosity-average molecular weight is preferable because sufficient strength can be obtained as a composition, the melt fluidity during molding is good, and molding distortion does not occur. The viscosity average molecular weight referred to in the present invention is determined by inserting the specific viscosity (ηsp) obtained from a solution obtained by dissolving 0.7 g of a polycarbonate copolymer in 100 mL of methylene chloride at 20 ° C. into the following equation. ηsp / c = [η] + 0.45 × [η] ² c (where [η] is the intrinsic viscosity) [η] = 1.23 × 10 ^-4 M ^0.83 c = 0.7

Examples of the fibrous filler (B) used in the present invention include glass fibers, glass milled fibers, wollastonite, carbon fibers, metal-based conductive fibers, whiskers such as potassium whisker and aluminum borate whisker. Can be mentioned. Of these, glass fibers, metal-based conductive fibers, wollastonite, and carbon fibers are preferable, and glass fibers, wollastonite, and carbon fibers are most preferable.

The glass fiber used in the present invention does not particularly limit the glass composition such as A glass, C glass, and E glass. In some cases, TiO ₂ , Zr ₂ O, BeO, C
It may contain components such as eO ₂ , SO ₃ and P ₂ O ₅ . However, E glass (alkali-free glass) is more preferable because it does not adversely affect the polycarbonate copolymer. The same applies to the glass milled fiber described below for such a glass composition. The glass fiber of the present invention is obtained by quenching molten glass while stretching it by various methods to form a predetermined fiber. The quenching and stretching conditions in such a case are not particularly limited. The cross-sectional shape may be a general round shape, or a variety of irregular cross-sectional shapes typified by superimposing perfectly round fibers in parallel. Further, a glass fiber mixed with a perfect circular shape and an irregular cross-sectional shape may be used.
Such 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, molding processability 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 can be applied to the surface of the fiber. The diameter of the metal-coated glass fiber is particularly preferably from 6 to 20 μm. The metal-coated glass fiber is obtained by coating a glass fiber with a metal such as nickel, copper, cobalt, silver, aluminum, iron, or an alloy thereof by a known plating method, vapor deposition method, or the like. Such a metal is preferably one or more metals selected from nickel, copper and cobalt from the viewpoints of conductivity, corrosion resistance, productivity and economy.

These fibers are currently known epoxy type,
Focusing treatment can be performed with various compounds such as urethane-based and acrylic-based compounds, and those that have been surface-treated with a silane coupling agent described later or the like are preferable. The average fiber length of these fibers in a molded product is about 200 to 400 μm.

The glass milled fiber used in the present invention has an L / D ≦ 10, and is obtained by cutting a glass fiber roving or chopped strand by a ball mill or the like to a predetermined length. It can be preferably used when the appearance of a molded article obtained from the composition of the present invention is to be improved. Here, L represents the length of the milled fiber in the fiber axis direction, and D represents the fiber diameter in the cross-sectional direction. The same glass fibers as those described above can be used as the glass fibers. These powders are preferably surface-treated with a silane coupling agent or the like, similarly to glass fibers. The glass milled fiber has an average fiber diameter of 6 to 23 μm and an average fiber length of 0.02 to 0.1.
mm is preferred.

In the present invention, wollastonite is a natural white mineral having acicular crystals in which the fibrous inorganic filler mainly composed of calcium silicate has a chemical formula of CaSiO _3.
And usually contains about 50% by weight of SiO ₂ , about 47% by weight of CaO, Fe ₂ O ₃ , Al ₂ O _3, etc., and has a specific gravity of about 2.9. As the wollastonite used in the present invention, those having a particle size distribution of 75% or more in 3 μm or more and 5% or less in 10 μm or more and having an aspect ratio L / D of 3 or more, particularly preferably L / D of 8 or more are preferable. . When the particle size distribution is 3 μm or more and 75% or more, the reinforcing effect is sufficient, and the rigidity tends to be higher. When the thickness is 10 μm or more and 5% or less, while having good impact strength, the surface appearance of the obtained molded article tends to be more favorable. In particular, when the aspect ratio is 8 or more, the reinforcing effect is sufficient, and higher rigidity can be obtained. However, considering the working environment, those having an aspect ratio of 50 or less are more preferable. The wollastonite may be subjected to a surface treatment with a normal surface treatment agent, for example, a coupling agent such as a silane coupling agent or a titanate coupling agent described below.

The carbon fiber used in the present invention is not particularly limited, and may be various known carbon fibers, for example, carbonaceous fibers and graphite fibers produced using polyacrylonitrile, pitch, rayon, lignin, hydrocarbon gas and the like. In particular, a polyacrylonitrile-based carbon fiber having excellent fiber strength is preferable. The carbon fiber can be oxidized on the fiber surface by a currently known method represented by ozone, plasma, nitric acid, electrolysis and the like, and is preferably used to increase the adhesion to the resin component. The 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 the carbon fiber, a metal coat can be applied to the fiber surface. The diameter of the metal-coated carbon fiber is particularly preferably from 6 to 20 μm. The metal-coated carbon fiber is obtained by coating a carbon fiber with a metal such as nickel, copper, cobalt, silver, aluminum, iron, or an alloy thereof by a known plating method or vapor deposition method.
Such a metal is preferably one or more metals selected from nickel, copper, and cobalt from the viewpoints of conductivity, corrosion resistance, productivity, and economic efficiency, and particularly preferably nickel-coated carbon fibers.

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

The metal-based conductive fibers used in the present invention need not be particularly limited, and include metal fibers and metal-coated fibers, such as metal fibers such as stainless steel fibers, aluminum fibers, copper fibers, and brass fibers. Can be These may be used in combination of two or more. Metal fiber diameter is 4-8
0 μm is preferred, and 6 to 60 μm is particularly preferred. Such conductive fibers may be surface-treated with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like. In addition, the convergence treatment may be performed 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.

The fibrous filler preferably has been surface-treated with a silane coupling agent or the like. By this surface treatment, decomposition of the polycarbonate copolymer is suppressed, and the adhesiveness is further improved, so that the wet heat fatigue property and the surface impact property, which are the objects of the present invention, can be improved. The silane coupling agent referred to here is the following formula

[0041]

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[Where 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, and a halogen atom;
^1, R ^2, R ³ represents respectively a single bond or an alkylene group having 1 to 7 carbon atoms, in the alkylene molecular chain, an amide bond, an ester bond, may be an ether bond or an imino bond is interposed, 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 include 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, γ-chloropropyltrimethoxysilane and the like.

The mixing ratio of the fibrous filler in the present invention is based on 100 parts by weight of the polycarbonate copolymer.
It is 5 to 200 parts by weight, preferably 10 to 100 parts by weight. When the amount is less than 5 parts by weight, the rigidity of the composition is insufficient,
Exceeding 200 parts by weight makes it difficult to extrude the resulting composition, which is not practical.

The aromatic polycarbonate resin composition of the present invention may contain a heat stabilizer in order to prevent a decrease in molecular weight or deterioration of hue during molding or the like. Examples of such a heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2 , 4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl Phosphite, monodecyl diphenyl phosphite,
Monooctyldiphenyl phosphite, bis (2,6-
Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphate, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, tetrakis 4,4′-biphenylenediphosphonate (2 , 4-di-tert-butylphenyl), dimethyl benzenephosphonate, diethylbenzenebenzene, dipropylbenzenephosphonate and the like. Among them, tris nonylphenyl phosphite,
Trimethyl phosphate, tris (2,4-di-ter
(t-Butylphenyl) phosphite and dimethyl benzenephosphonate are preferably used. These heat stabilizers may be used alone or in combination of two or more.
The amount of the heat stabilizer is 0.0001 to 100 parts by weight of the aromatic polycarbonate resin composition of the present invention.
1 part by weight is preferable, 0.0005 to 0.5 part by weight is more preferable, and 0.001 to 0.1 part by weight is further preferable.

Further, the aromatic polycarbonate resin composition of the present invention may be blended with an antioxidant generally known for the purpose of preventing oxidation. Examples of such antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, and triethylene glycol-bis [3 -(3-tert-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, 4,4′-biphenylenediphosphosphinic acid tetrakis (2,4-di-
tert-butylphenyl), 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. The compounding amount of these antioxidants is preferably 0.0001 to 0.5 part by weight based on 100 parts by weight of the aromatic polycarbonate resin composition of the present invention.

Further, in order to further improve the releasability from the mold at the time of melt molding, a releasing agent is blended with the aromatic polycarbonate resin composition of the present invention within a range not to impair the object of the present invention. Is also possible. Such release agents include:
Examples include olefin wax, olefin wax containing a carboxyl group and / or carboxylic anhydride group, silicone oil, organopolysiloxane, higher fatty acid ester of monohydric or polyhydric alcohol, paraffin wax, beeswax and the like. The amount of the release agent is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin composition of the present invention.

As the olefin wax, use of a polyethylene wax and / or a 1-alkene polymer is particularly preferred, and a very good releasing effect can be obtained. As the polyethylene wax, those generally widely known at present can be used, and examples thereof include those obtained by polymerizing ethylene under high temperature and high pressure, those obtained by thermally decomposing polyethylene, and those obtained by separating and purifying a low molecular weight component from a polyethylene polymer. The molecular weight and the degree of branching are not particularly limited, but the number average molecular weight is preferably 1,000 or more.

The 1-alkene polymer may have 5 to 4 carbon atoms.
What polymerized 1-alkene of 0 can be used. The molecular weight of the 1-alkene polymer was 1,000 in number average molecular weight.
0 or more is preferable.

The olefin wax containing a carboxyl group and / or a carboxylic anhydride group is a compound containing a carboxyl group and / or a carboxylic anhydride group by post-treatment of an olefin wax, preferably maleic acid. And / or modified by post-treatment with maleic anhydride. Further, when polymerizing or copolymerizing ethylene and / or 1-alkene, a compound containing a carboxyl group and / or a carboxylic anhydride group copolymerizable with such monomers, preferably maleic acid and / or maleic anhydride is used. Copolymers may also be mentioned, and those obtained by copolymerization include carboxyl groups and / or
Alternatively, a carboxylic acid anhydride group is preferably stably contained at a high concentration. The carboxyl group or carboxylic anhydride group may be bonded to any part of the olefin wax, and the concentration thereof is not particularly limited, but is preferably in the range of 0.1 to 6 meq / g per gram of the olefin wax. . Such olefin-based olefin waxes containing a carboxyl group and / or a carboxylic anhydride group are commercially available, for example, Diacarna-PA30.
[Trade name of Mitsubishi Chemical Corporation], high wax acid treatment type 2203A, 1105A [Trade name of Mitsui Petrochemical Co., Ltd.], etc., and these can be used alone or as a mixture of two or more kinds.

As the higher fatty acid ester, monohydric or polyhydric alcohols having 1 to 20 carbon atoms and 10 to 20 carbon atoms can be used.
It is preferably a partial ester or a total ester with 30 saturated fatty acids. Examples of such partial or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride,
Stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetraperargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate , Methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate and the like,
Of these, stearic acid monoglyceride, stearic acid triglyceride, and pentaerythritol tetrastearate are preferably used.

A light stabilizer can be added to the aromatic polycarbonate resin composition of the present invention as long as the object of the present invention is not impaired. Such light stabilizers include, for example, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3-tert-
Butyl-5-methyl-2-hydroxyphenyl) -5
Chlorobenzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl)
Phenyl] -2H-benzotriazole, 2,2′-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis (1,3-benzoxazin-4-one) and the like. Can be The compounding amount of such a light stabilizer is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin composition of the present invention.

An antistatic agent can be added to the aromatic polycarbonate resin composition of the present invention as long as the object of the present invention is not impaired. As such an antistatic agent,
For example, polyetheresteramide, glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, sodium sulfonate, monoglyceride maleic anhydride, diglyceride maleic anhydride, and the like can be mentioned.

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, and a halogenated aromatic phosphate ester type flame retardant. The above can be blended. Specifically, the polycarbonate type flame retardant of halogenated bisphenol A is a polycarbonate type flame retardant of tetrachlorobisphenol A, tetrachlorobisphenol A and bisphenol A
And a polycarbonate-type flame retardant of tetrabromobisphenol A, a polycarbonate-type flame retardant of tetrabromobisphenol A and bisphenol A, and the like. Specifically, organic salt-based flame retardants include dipotassium diphenylsulfone-3,3'-disulfonate, potassium diphenylsulfon-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, 2,4,5-trisulfonate. Potassium chlorobenzenesulfonate, bis (2,6-dibromo-4-cumylphenyl)
Potassium 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, potassium perfluorobutanesulfonate, sodium or potassium lauryl sulfate, sodium hexadecyl sulfate Or potassium and the like. Specifically, halogenated aromatic phosphate ester type flame retardants include tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate and the like. is there. Specifically, aromatic phosphate ester-based flame retardants include triphenyl phosphate, tris (2,6-xylyl) phosphate, tetrakis (2,
6-xylyl) resorcinol diphosphate, tetrakis (2,6-xylyl) hydroquinone diphosphate, tetrakis (2,6-xylyl) -4,4′-biphenol diphosphate, tetraphenylresorcin diphosphate, tetraphenylhydroquinone diphosphate,
Tetraphenyl-4,4'-biphenol diphosphate, aromatic polyphosphate whose aromatic ring source is resorcinol and phenol and does not contain phenolic OH group, aromatic whose aromatic ring source is resorcinol and phenol and contains phenolic OH group Polyphosphate, aromatic polyphosphate whose aromatic ring source is hydroquinone and phenol and does not contain phenolic OH group, similar aromatic polyphosphate containing phenolic OH group, ("aromatic polyphosphate" shown below is phenolic (Aromatic polyphosphate containing an aromatic polyphosphate containing an acidic OH group and aromatic polyphosphate not containing an aromatic OH group) An aromatic polyphosphate in which the aromatic ring source is bisphenol A and phenol, and an aromatic ring source in the form of tetrabromobisphenol A
And phenol as an aromatic polyphosphate, as aromatic ring sources as resorcinol and 2,6-xylenol, as aromatic polyphosphate as hydroquinone and 2,
Aromatic polyphosphate which is 6-xylenol, aromatic polyphosphate whose aromatic ring source is bisphenol A and 2,6-xylenol, aromatic polyphosphate whose aromatic ring source is tetrabromobisphenol A and 2,6-xylenol, etc. It is.

Among these flame retardants, polycarbonate-type flame retardants of halogenated bisphenol A, polycarbonate-type 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. As organic salt-based flame retardants, diphenyl sulfone-3,
3'-dipotassium disulfonic acid, diphenyl sulfone-
Potassium 3-sulfonate and sodium 2,4,5-trichlorobenzenesulfonate are preferred. As aromatic phosphate ester flame retardants, 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, triphenyl phosphate, which is an aromatic phosphate ester flame retardant that does not destroy the ozone layer,
Most preferred are tricresyl phosphate and resulcinol bis (dixylenyl phosphate).

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

As such other resins, for example, 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, polyethylene, polyolefin resin such as polypropylene,
Resins such as polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, phenol resin, and epoxy resin.

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

For producing the aromatic polycarbonate resin composition of the present invention, any method is employed. For example, a method of mixing with a tumbler, a V-type blender, a super mixer, a Nauta mixer, a Banbury mixer, a kneading roll, an extruder or the like is appropriately used. The aromatic polycarbonate resin composition thus obtained may be pelletized as it is or once by a melt extruder, and then formed into a molded article by a generally known method such as an injection molding method, an extrusion molding method, or a compression molding method. it can. In order to enhance the miscibility of the aromatic polycarbonate resin composition of the present invention and obtain stable mold release properties and various 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 the extruder hopper opening or in the middle of the extruder, a method of previously mixing with the polycarbonate copolymer, and a method of previously mixing with some polycarbonate copolymer to prepare a master Either a charging method or a method of charging the master from the middle of the extruder can be adopted.

The thus obtained aromatic polycarbonate resin composition of the present invention can be used for housings and chassis of OA equipment such as personal computers, word processors, fax machines, copiers and printers, trays for CD-ROMs, chassis, turntables and pickup chassis. OA for various gears
Internal parts, TV, video, electric washing machine, electric dryer,
Housing and parts for household appliances such as vacuum cleaners, electric tools such as electric saws and electric drills, telescope barrels, microscope barrels, camera bodies, camera housings, optical equipment parts such as camera barrels, door handles, pillars , Bumpers, instrument panels, and other automotive parts. In particular, it is useful for automobile parts (outer door handles, inner door handles, etc.) and mechanical parts (power tool covers, etc.) that require dimensional stability, rigidity, wet heat fatigue resistance, and the like.

[0060]

EXAMPLES Examples will be further described below with reference to examples. "Parts" or "%" in the examples indicates parts by weight or% by weight,
The symbols for the evaluation items and each component in the composition mean the following.

(I) Evaluation Items (1) Water Absorption Rate Measured according to ASTM D-0570. (2) Wet heat fatigue property Using the so-called C-type measurement sample shown in FIG.
80 ° C, 90% RH atmosphere, sine wave, frequency 1H
Under the conditions of z and a maximum load of 2 kg, the following fatigue tester [Shimadzu Servo Pulser EHF- manufactured by Shimadzu Corporation]
EC5], the number of times until the measurement sample was broken was measured. (3) Rigidity The flexural modulus was measured according to ASTM D790. (4) Tensile strength According to ASTM D638, a tensile test was performed to measure a tensile breaking strength.

(II) Symbol of each component in the composition (a) Polycarbonate resin EX-PC (production of the polycarbonate copolymer of the present invention) 3022 parts of ion-exchanged water was placed in a reactor equipped with a thermometer, a stirrer and a reflux condenser. , 481.6 parts of an aqueous solution of caustic soda, 25 parts of an aqueous solution of caustic soda, 0.8 part of hydrosulfite, 171.1 parts of bisphenol TMC and 215.4 parts of bisphenol M were dissolved, and 136.5 parts of a 48% aqueous solution of caustic soda were added. 1762.6 parts of methylene chloride was added, and 150 parts of phosgene was blown in at 15 to 20 ° C for 60 minutes while stirring. After the injection of phosgene was completed, 5.28 parts of p-tert-butylphenol was dissolved in 40 parts of methylene chloride and added, and 48.6 parts of a 48% aqueous sodium hydroxide solution was added to emulsify. Then, 0.3 parts of triethylamine was added. 28-
The reaction was completed by stirring at 33 ° C. for about 1 hour. 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 to obtain a colorless polymer. 7 parts were obtained (98% yield). The viscosity average molecular weight of this polymer was 24,000. The composition of the dihydric phenol component of this polymer is bisphenol TMC
Component is 47 mol%, bisphenol M component is 53 mol%
Met. This had a water absorption of 0.15% and a flexural modulus of 28,700 kgf / cm ² . 0.003% by weight of trisnonylphenyl phosphite and 0.05% by weight of trimethyl phosphate were added to the polycarbonate copolymer, and the mixture was extruded at 280 ° C. using an extruder to obtain polycarbonate copolymer pellets.

CEX-PC (Production of aromatic polycarbonate resin for comparison) Same as EX-PC except that 267.8 parts of bisphenol A was used in place of bisphenol TMC and bisphenol M in the production of EX-PC. This gave 295.3 parts of a colorless polymer (yield: 99%). The viscosity average molecular weight of this polymer was 24,200. It has a water absorption of 0.3% and a flexural modulus of 24000 kgf / c.
m ² . This was obtained in the same manner as in the production of EX-PC to obtain aromatic polycarbonate resin pellets.

(B) Filler Glass fiber: chopped strand ECS-03T-
511: Nippon Electric Glass Co., Ltd., urethane convergence treatment, fiber diameter 13 microns. Carbon fiber: Vesfite HTA-C6-U; manufactured by Toho Rayon Co., Ltd., PAN system, epoxy convergence treatment, fiber diameter 7 microns. Wollastonite: Psychatec NN-4; manufactured by Tomoe Kogyo Co., Ltd., average particle diameter D = 4 microns, particle diameter distribution of 3 microns or more is 82.5%, particle diameter distribution of 10 microns or more is 0.7%, L / D = 20

[EXAMPLES 1-3, COMPARATIVE EXAMPLES 1-3] The EX-PC or CEX-PC obtained above and the components shown in Table 1 were uniformly mixed using a tumbler, and then 30 m
Twin screw extruder with mφ vent (KTX- manufactured by Kobe Steel Ltd.)
According to 30), the cylinder temperature is 270 ° C. and 10 mmHg
The pellets were dried at 120 ° C. for 5 hours while degassing at a degree of vacuum of 5 ° C., and then, using an injection molding machine (SG150U type manufactured by Sumitomo Heavy Industries, Ltd.), a cylinder temperature of 330 ° C. and gold were used. A molded piece for measurement was prepared at a mold temperature of 100 ° C.

As is clear from each comparison, the aromatic polycarbonate resin composition comprising the polycarbonate copolymer of the present invention and the fibrous filler has a higher wet heat fatigue resistance than the aromatic polycarbonate resin of the comparative example. It can be seen that the rigidity is particularly excellent.

[0067]

[Table 1]

[0068]

The aromatic polycarbonate resin composition of the present invention makes use of the inherent properties of the polycarbonate copolymer, improves the properties such as rigidity by adding a fibrous filler, and improves the wet heat fatigue resistance. It is possible to provide an aromatic polycarbonate resin composition containing an excellent fibrous filler.

[Brief description of the drawings]

FIG. 1 is a front view of a so-called C-type sample used for evaluating wet heat fatigue resistance. The thickness of the sample is 3 mm. The test is performed by passing a jig of a test machine through the hole indicated by reference numeral 6 and applying a predetermined load in the vertical direction indicated by reference numeral 7.

[Explanation of symbols]

1 Center of C-shaped double circle 2 Radius of inner circle of double circle (20 mm) 3 Radius of outer circle of double circle (30 mm) 4 Center angle (60 °) indicating position of jig mounting hole 5 Gap between sample end faces (13 mm) 6 Jig mounting hole (circle 4 mm in diameter, located at center of sample width) 7 Direction of load imposed on sample during fatigue test

Claims (2)

[Claims] (A) at least 80 mol% of the wholly aromatic dihydroxy component comprises (a) 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (component a) and (b) 4,4 '-(m-phenylenediisopropylidene) diphenol and / or 2,2
Polycarbonate copolymer 100 comprising -bis (4-hydroxy-3-methylphenyl) propane (component b) and having a molar ratio of component a to component b in the range of 99: 1 to 20:80 An aromatic polycarbonate resin composition comprising parts by weight and (B) 5 to 200 parts by weight of a fibrous filler. 2. The ratio of component a to component b is 80:
The aromatic polycarbonate resin composition according to claim 1, wherein the ratio is 20 to 20:80.