JP2003113300A - Reinforced aromatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reinforced aromatic polycarbonate resin composition having improved weld strength and wide colorability (especially good jet black) and suitable for a molding e.g. required compatibility of good externals of the molding with strength of the boss part. SOLUTION: This reinforced aromatic polycarbonate resin composition comprises (A) aromatic polycarbonate (A component), (B) a fibrous or flake inorganic filler (B component) and (C) a core-shell elastic polymer (C component), wherein (i) the resin composition comprises 50-97 wt.% A component, 3-50 wt.% B component and 0.5-20 wt.% C component based on 100 wt.% total of the A component and the B component and (ii) the C component comprises the core-shell elastic polymer obtained by graft-polymerization of at least one kind of alky (meth)acrylate monomer having 1-3C alkyl onto a core comprising two or more kinds of polyalkyl (meth)acrylate rubber-like polymers.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a reinforced aromatic polycarbonate resin composition. More specifically, it is a resin composition comprising an aromatic polycarbonate resin, a fibrous or plate-like inorganic filler, and a specific core-shell elastic polymer, which has improved weld strength and a wide range of coloring properties (especially good The present invention relates to a reinforced aromatic polycarbonate resin composition having a jet blackness) and suitable for a molded product which is required to have both a good molded product appearance and a boss strength.

[0002]

BACKGROUND OF THE INVENTION Aromatic polycarbonate resins are widely used industrially because they have excellent mechanical properties, thermal properties and flame resistance. Further, a reinforced aromatic polycarbonate resin composition obtained by reinforcing an aromatic polycarbonate resin with glass fiber or the like is also used in a wide range of fields. Such a reinforced aromatic polycarbonate resin composition has been
It was often used for internal parts such as electrical equipment. Of course, it was also used as a part exposed to the outside of the product, but the current situation was that its application was limited. This is because the appearance of the molded product of the reinforced aromatic polycarbonate resin composition is relatively inferior. That is, in order to achieve a good appearance of a molded product, it is necessary to use extremely advanced molding technology, etc., or it is necessary to perform sufficient coating at high cost, so it is not possible to use it for parts that require a high appearance. There were few.

However, due to the progress of molding technology in recent years, a good molded product appearance can be obtained even with such a reinforced aromatic polycarbonate resin composition. Examples of such a molding technique include a molding method using various rapid heating and cooling molds, a molding method using an adiabatic mold, and the like. These molding techniques enable extremely good transfer to a mold and can significantly reduce the so-called floating of glass fibers and the like. According to such a technique, a molded product made of the reinforced aromatic polycarbonate resin composition having a good molded product appearance can be obtained with relatively simple coating or without coating. As a result, it can be widely applied to molded products that require high appearance.

On the other hand, these external moldings are also often provided with a boss portion for the purpose of attaching to the main body or fixing other parts. You can press fit screws into this boss,
The screw is tightened to the boss by a self-tapping method. However, defects such as cracking and loosening may occur in such boss portions. This is because welds usually occur in the boss portion, but the strength of such welds is low in the aromatic polycarbonate resin composition reinforced with glass fiber or the like. The decrease in the strength of the weld portion is due to the low reinforcing effect in the weld portion because the orientation of the filler is different from the other portions. In particular, oil or the like is attached to a screw or the like fitted in the boss portion, which further adversely affects the polycarbonate resin. Further, the environmental resistance properties such as chemical resistance of the polycarbonate resin deteriorate as the molecular weight decreases. On the other hand, since the exterior parts are usually thin products requiring high fluidity, a polycarbonate resin having a low molecular weight is required. This is also one of the unfavorable factors. Therefore, it may be required to improve the weld strength of the reinforced aromatic polycarbonate resin composition.

On the other hand, since it is expected that the parts which are required to have such a high appearance as described above will be painted relatively easily or not painted, it is necessary that the resin composition has a wide range of coloring properties. There is.

JP-A-3-273052 discloses a reinforced resin composition composed of an aromatic polycarbonate resin, glass fibers and a styrene elastomer, which is excellent in rigidity, impact strength and fluidity. No mention is made of improvement in strength, and it cannot be said that such a resin composition has good weld strength.

Japanese Unexamined Patent Publication (Kokai) No. 7-238213 discloses an aromatic polycarbonate resin composition containing a reinforcing fiber, an olefinic wax having a carboxylic acid anhydride group, a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component. There is described a resin composition which is composed of a composite rubber having a structure in which two and one are intertwined with each other so that they cannot be separated from each other, and which has both rigidity and impact resistance at a high level. However, this publication also does not describe improvement of weld strength, and the composite rubber used in such a resin composition is slightly inferior in terms of change in hue.

Further, as an example of the reinforced aromatic polycarbonate resin, Japanese Patent Laid-Open No. 63-15843 discloses a resin composition comprising an aromatic polycarbonate resin, glass fibers, and a specific elastic polymer. This publication also does not describe improvement in weld strength.

Further, JP-A-2000-26552 discloses an acrylic rubber-based impact strength improvement obtained by grafting a vinyl-based monomer onto a polyalkyl (meth) acrylate-based rubber composed of a plurality of rubber components having different glass transition temperatures. Agents have been proposed and such modifiers show a good impact modifying effect in polyvinyl chloride resin systems. However, such a publication has an improved weld strength and a wide range of coloring properties (especially good jet blackness), and is a reinforced fragrance suitable for exterior molded products that are required to have both good appearance of the molded product and strength of the boss. It did not disclose a Group polycarbonate resin composition.

[0010]

The object of the present invention is to have improved weld strength and a wide range of colorability (particularly good jet blackness), and to achieve both good appearance of molded product and strength of boss. The present invention is to provide a reinforced aromatic polycarbonate resin composition suitable for a molded article for exterior packaging.

As a result of intensive studies to achieve the above object, the present inventor has found that a resin composition comprising an aromatic polycarbonate resin, a fibrous or plate-like inorganic filler, and a specific core-shell elastic polymer is used. The inventors have found that the above problems can be solved and completed the present invention.

[0012]

The present invention is directed to (A) an aromatic polycarbonate (component A), (B) a fibrous or plate-like inorganic filler (component B), and (C) a core-shell elastic polymer. A resin composition comprising a combination (component C),
(I) For 100 parts by weight of the total of the components A and B,
A component is 50 to 97 parts by weight, B component is 3 to 50 parts by weight, and C component is 0.5 to 20 parts by weight,
(Ii) In the rubber core in which the C component is composed of two or more kinds of polyalkyl (meth) acrylate rubber-like polymers, 1
The present invention relates to a reinforced aromatic polycarbonate resin composition which is a core-shell elastic polymer obtained by graft-polymerizing an alkyl (meth) acrylate monomer having one or more alkyl groups having 1 to 3 carbon atoms.

The aromatic polycarbonate of the component A of the present invention is usually obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, or a carbonate prepolymer as a solid phase ester. It is obtained by polymerization by an exchange method or by a ring-opening polymerization method of a cyclic carbonate compound.

Typical examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,
4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-
Dimethyl) phenyl} methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4
-Hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis {(4-hydroxy-3-methyl)
Phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dibromo) phenyl}
Propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(4-
Hydroxy-3-phenyl) phenyl} propane, 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, 2,2-bis (4-hydroxyphenyl) pentane, 2, 2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-
Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl)-
3,3,5-Trimethylcyclohexane, 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) -m-diisopropylbenzene, α,
α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy Examples thereof include diphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenyl ether and 4,4′-dihydroxydiphenyl ester, which may be used alone or in combination of two or more. It may be a mixture.

Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
-Hydroxyphenyl) -3,3,5-trimethylcyclohexane and a homopolymer obtained from at least one bisphenol selected from the group consisting of α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene or Copolymers are preferred, especially homopolymers of bisphenol A and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane with bisphenol A, 2,2-bis {(4-hydroxy- A copolymer with 3-methyl) phenyl} propane or α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene is preferably used.

Particularly, a homopolymer of bisphenol A is preferably used. Such an aromatic polycarbonate is preferable because it has excellent impact resistance.

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 dihydric phenol.

In the production of a polycarbonate resin by reacting the above dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, the catalyst, the terminal terminator, and the dihydric phenol are optionally oxidized. You may use antioxidant etc. for preventing that.
The aromatic polycarbonate may be a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, and the aromatic polycarbonate may be a branched copolymer obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. It may be a polycarbonate resin. Further, it may be a mixture of two or more kinds of the obtained aromatic polycarbonate.

Examples of the aliphatic bifunctional carboxylic acid include aliphatic bifunctional carboxylic acids having 8 to 20 carbon atoms, preferably 10 to 12 carbon atoms. The aliphatic difunctional carboxylic acid may be linear, branched or cyclic. Aliphatic difunctional carboxylic acids are α, ω
-Dicarboxylic acids are preferred.

Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucide, or 4,6-
Dimethyl-2,4,6-tris (4-hydrodiphenyl) 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) )
Examples thereof include ketones, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among which 1,1,1-tris. (4-hydroxyphenyl) ethane, 1,1,1-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Ethane is preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable.

When a polyfunctional compound which gives such a branched polycarbonate resin is contained, such a proportion is 0.001 to 1 mol%, preferably 0.005 to 0.5 mol%, and particularly preferably, the total amount of the aromatic polycarbonate. 0.01
Is about 0.3 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction, and the amount of the branched structure is 0.001 to 1 mol%, preferably 0.005 to 5 mol% in the total amount of the aromatic polycarbonate.
0.5 mol%, particularly preferably 0.01 to 0.3 mol%
Are preferred. The ratio is ¹ H
-It can be calculated by NMR measurement.

The reaction by the interfacial polycondensation 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.

Further, in such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such an end terminator. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, such monofunctional phenols typically being phenol or lower alkyl substituted phenols,
The monofunctional phenols represented by the following general formula (1) can be shown.

[0024]

[Chemical 1]

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

As other monofunctional phenols,
Phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic polyester group as a substituent, or long-chain alkylcarboxylic acid chlorides can also be shown. Among these, phenols having a long-chain alkyl group represented by the following general formulas (2) and (3) as a substituent are preferably used.

[0027]

[Chemical 2]

[0028]

[Chemical 3]

(In the formula, X is -R-CO-O- or -R
-O-CO-, where R is a single bond or 1 carbon atom
-10, preferably 1-5 divalent aliphatic hydrocarbon group is shown, and n shows the integer of 10-50. ) N is 1 as the substituted phenols of the general formula (2).
0 to 30, particularly 10 to 26 are preferable, and specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol,
Examples thereof include docosylphenol and triacontylphenol.

As the substituted phenols of the general formula (3), 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. Moreover, you may use a terminal terminator individually or in mixture of 2 or more types.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, which is produced by mixing the dihydric phenol and the carbonate ester while heating in the presence of an inert gas. It is carried out by a method of distilling alcohol or phenol. 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 system was set at 1.33 × 10 ³ -1.
The alcohol or phenol produced by reducing the pressure to about 3.3 Pa is easily distilled. Reaction time is usually 1 to 4
It's about time.

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, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like, with diphenyl carbonate being preferred.

A polymerization catalyst can be used to accelerate the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salt of dihydric phenol and potassium salt, and water. Alkaline earth metal compounds such as calcium oxide, barium hydroxide and magnesium hydroxide, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine, alkoxides of alkali metals and alkaline earth metals , 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 compounds manganese Compounds, titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. The catalyst may be used alone or in combination of two or more kinds. The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁸ to 1 × with ^respect to 1 mol of the dihydric phenol as a raw material.
It is selected in the range of 10 ⁻³ equivalent, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalent.

In the polymerization reaction, in order to reduce the number of phenolic end groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate may be added after or after the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenyl phenyl carbonate,
Compounds such as bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate and ethoxycarbonylphenylphenyl carbonate can be added. Among them, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferable,
In particular, 2-methoxycarbonylphenylphenyl carbonate is preferably used.

Further, it is preferable to use a deactivator which neutralizes the activity of the catalyst in the polymerization reaction. Specific examples of the quenching agent include benzene sulfonic acid, p-toluene sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, p-toluene sulfone. Sulfonic acid esters such as methyl acidate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate; and further, trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene. , Methyl acrylate-sulfonated styrene copolymer, dodecylbenzenesulfonic acid-2-phenyl-2-propyl, dodecylbenzenesulfonic acid-2-
Phenyl-2-butyl, octylsulfonic acid tetrabutylphosphonium salt, decylsulfonic acid tetrabutylphosphonium salt, benzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetraethylphosphonium salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfone Acid tetrahexylphosphonium salt, dodecylbenzenesulfonic acid tetraoctylphosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl Dimethyl ammonium Chill sulfate, tetramethylammonium hexyl sulfate, decyltrimethylammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, there may be mentioned compounds such as tetramethylammonium dodecylbenzyl sulfate, and the like. Two or more of these compounds may be used in combination.

Among the deactivators, phosphonium salt or ammonium salt type ones are preferable. The amount of such a catalyst is preferably 0.5 to 50 mol based on 1 mol of the remaining catalyst, and 0.01 to 500 ppm based on the polycarbonate resin after polymerization, and more preferably 0. 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm is used.

The viscosity average molecular weight of the aromatic polycarbonate as the component A is preferably 13,000 or more and 40,000 or less. The lower limit is more preferably 14,000, further preferably 15,000, particularly preferably 16,000.
Is. On the other hand, the upper limit is more preferably 35,000, further preferably 25,000, particularly preferably 23,000.
It is 0. Especially B component is glass fiber, glass milled fiber, glass flake, carbon fiber,
When at least one inorganic filler selected from metal-coated carbon fibers is required to have a better appearance, its upper limit is preferably 21,000,
20,000 is more preferable. The resin composition of the present invention has a good weld strength even when the viscosity average molecular weight is relatively low, and also has a high fluidity necessary for molding a thin molded product.

In the present invention, the viscosity average molecular weight is the specific viscosity (η
Seek _SP) from a solution of the aromatic polycarbonate 0.7g at 20 ° C. in methylene chloride 100ml using an Ostwald viscometer, the obtained specific viscosity (eta _SP) the inserted viscosity average molecular weight M by the following formula Ask for. η _SP /c=[η]+0.45×[η] ² c [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7 The component A of the present invention is different from dihydric phenol. ,
Those with and without end-capping agents, those with linear and branched, those with different manufacturing methods, those with different terminal-terminating agents, polycarbonate and polyester carbonate, those with different viscosity average molecular weight, etc. Two or more types of polycarbonate can be mixed.

As the fibrous and / or plate-like inorganic filler which is the component B of the present invention, various kinds can be used. This is because the filler has a weak weld strength due to its orientation. Such fibrous inorganic fillers include, for example, glass fiber, glass milled fiber, carbon fiber, carbon milled fiber, metal fiber, asbestos, rock wool,
Ceramic fiber, slag fiber, potassium titanate whiskers, boron whiskers, aluminum borate whiskers, calcium carbonate whiskers, titanium oxide whiskers, wollastonite, zonotolite, palygorskite (attapulgite), sepiolite, and graphite whiskers, and their fillers On the other hand, examples thereof include fibrous fillers whose surfaces are coated with different materials such as metals and metal oxides. Further, such plate-like fillers include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, and fibrous substances obtained by coating these fillers with different materials such as metals and metal oxides. Examples include fillers.

Among the above-mentioned inorganic fillers, the aspect ratio of the filler is large and the larger the filler is, the more easily it is influenced by the orientation. Therefore, as the component B, the aspect ratio is 3 or more and the average fiber length is Preferable examples include at least one kind of inorganic filler selected from fibrous inorganic filler having a size of 30 to 1000 μm and plate-like inorganic filler having an aspect ratio of 3 or more and an average particle size of 20 to 600 μm.

The aspect ratio of the fibrous inorganic filler is preferably 5 or more, more preferably 10 or more. On the other hand, the upper limit of the aspect ratio is preferably 100 or less from the viewpoint of moldability. The aspect ratio of the fibrous inorganic filler is a value obtained by dividing the average fiber length by the average fiber diameter. The average fiber length of the fibrous inorganic filler is preferably 60 to 500 μm, more preferably 100 to 400 μm, and 120
˜300 μm is more preferable.

Further, the aspect ratio of the plate-like inorganic filler is preferably 4 or more, more preferably 5 or more. On the other hand, the upper limit of the aspect ratio is preferably 100 or less from the viewpoint of moldability. The aspect ratio of the plate-like inorganic filler is a value obtained by dividing the average particle diameter by the average thickness. The average particle size of the plate-like inorganic filler is preferably 10 to 200 μm,
15-100 micrometers is more preferable and 20-80 micrometers is still more preferable. The shape and size of the above inorganic filler are those in the reinforced aromatic polycarbonate resin composition. Usually, in the process of producing a resin composition, the inorganic filler may be broken or cracked so that the shape and size of the raw material are not always maintained. Therefore, as the raw material for the fibrous inorganic filler or the plate-like filler, it is possible to use a material larger than the above range.

From this point of view, the preferred embodiment of the component B is glass fiber, glass milled fiber,
Examples thereof include glass flakes, carbon fibers, and fillers obtained by surface-coating these fillers with different materials such as metals and metal oxides. Examples of the filler having a surface coated with a different kind of material include metal-coated glass fibers, metal-coated glass flakes, titanium oxide-coated glass flakes, and metal-coated carbon fibers. The method for coating the surface of a different material is not particularly limited, and examples thereof include various known plating methods (eg, electrolytic plating, electroless plating, hot dip plating, etc.), vacuum deposition method, ion plating method, CV.
Examples thereof include D method (for example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, and sputtering method.

Component B of the present invention is more preferably at least one inorganic filler selected from glass fiber, glass milled fiber, glass flake, carbon fiber, and metal-coated carbon fiber.

The glass fiber is obtained by drawing molten glass by various methods and quenching it into a predetermined fiber. The quenching and stretching in such a case are also not particularly limited. The shape of the cross section may be a shape other than a perfect circle, such as an ellipse, an eyebrow shape, and a trilobal shape. Further, it may be a mixture of a perfect circular glass fiber and a glass fiber having a shape other than a perfect circle.

The average fiber diameter of the glass fibers is not particularly limited, but is preferably 1 to 25 μm,
3 to 17 μm is more preferable. When glass fibers having an average fiber diameter in this range are used, good mechanical strength can be exhibited without impairing the appearance of the molded product. Moreover, the fiber length of the glass fiber is preferably 60 to 500 μm, and preferably 100 to 400 μm, as the number average fiber length in the reinforced aromatic polycarbonate resin composition.
m is more preferable, and 120 to 300 μm is particularly preferable. The number average fiber length is a value calculated by an image analyzer from an image obtained by observing the residue of glass fiber collected by a process such as high temperature ashing of a molded product, dissolution with a solvent, decomposition with a chemical, etc. with an optical microscope. is there. Further, when calculating such a value, the value is based on the fiber diameter and is not counted if the length is shorter than that.

The glass milled fiber is usually produced by shortening the glass fiber using a crusher such as a ball mill. The aspect ratio can take various values according to the degree of pulverization, but as described above, 3 or more is preferable. The fiber length of the glass milled fiber is preferably 10 to 150 μm as the number average fiber length in the reinforced aromatic polycarbonate resin composition, and 15
˜100 μm is more preferred. The average fiber diameter of the glass milled fiber is preferably 1 to 15 μm, more preferably 3 to 13 μm.

The glass flakes are produced by a cylindrical blow method or a sol-
It is a plate-shaped glass filler manufactured by a method such as a gel method. As for the size of the raw material of such glass flakes, various ones can be selected depending on the degree of pulverization and classification. The average particle size of the glass flakes used as a raw material is 10 to 100.
0 μm is preferable, 20 to 500 μm is more preferable,
30 to 300 μm is more preferable. This is because those in the above range are excellent in both handling and molding processability. Usually, such a glass flake is cracked by melt-kneading with a resin, and its average particle size is reduced, but the particle size of the glass flake in the resin composition is preferably 10 to 200 μm, more preferably 15 to 100 μm, and 20 ~ 80 μm
Is more preferable. The number average particle size is a value calculated by an image analysis device from an image obtained by observing the residue of glass flakes collected by a process such as high temperature ashing of a molded product, dissolution with a solvent, decomposition with a chemical, etc. with an optical microscope. is there. Also,
In the calculation of such a value, the value is based on the thickness of the flake and is not counted if the length is less than that.

The thickness is preferably 0.5 to 10 μm, more preferably 1 to 8 μm, and even more preferably 1.5 to 6 μm. Glass flakes having the above number average particle size and thickness achieve good moldability, molded product appearance, strength, and rigidity.

The composition of each of the above glass fillers is not particularly limited to the glass composition such as A glass, C glass, E glass, etc. In some cases, Ti may be used.
It may contain components such as O ₂ , SO ₃ , and P ₂ O ₅ . However, E glass (non-alkali glass) is more preferable. In addition, various glass fillers are well-known surface treatment agents,
For example, those subjected to surface treatment with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent or the like are preferable from the viewpoint of improving the mechanical strength. Further, the glass fibers and glass flakes are preferably those which have been subjected to a focusing treatment or a granulation treatment with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, etc., and particularly an epoxy resin. Those treated with or a urethane resin are particularly preferable from the viewpoint of improving the mechanical strength.

Examples of the carbon filler of the present invention include carbon fiber, metal-coated carbon fiber, carbon milled fiber, vapor-grown carbon fiber and the like, and also for the purpose of improving mechanical strength and imparting conductivity. , Carbon fiber and metal-coated carbon fiber are preferable.

As the carbon fiber, any of cellulose type, polyacrylonitrile type, pitch type and the like can be used, and a raw material composition consisting of a polymer and a solvent due to a methylene type bond of an aromatic sulfonic acid or a salt thereof is prevented. Alternatively, a product obtained by a method of performing spinning without undergoing an infusibilizing step represented by a method of molding and then carbonizing can also be used. Further, any of a general-purpose type, a medium elastic modulus type, and a high elastic modulus type can be used, but a polyacrylonitrile-based high elastic modulus type is particularly preferable.

The average fiber diameter of the carbon fibers is not particularly limited, but is usually 3 to 15 μm.
m is used, and preferably 5 to 13 μm.
When carbon fibers having an average fiber diameter in this range are used, good mechanical strength can be exhibited without impairing the appearance of the molded product. The preferred fiber length of the carbon fiber is 60 to 60 as the number average fiber length in the reinforced aromatic polycarbonate resin composition of the present invention.
The thickness is 500 μm, preferably 80 to 400 μm, and particularly preferably 100 to 300 μm. The number average fiber length is a value calculated by an image analyzer from the residue of carbon fibers collected by treatment such as high temperature ashing of a molded product, dissolution with a solvent, decomposition with a chemical agent, etc. from an optical microscope observation. . Further, in calculating such a value, a value of a fiber length or less is a value not counted. Furthermore, the surface of the carbon fiber enhances the adhesion with the matrix resin, and gas-phase oxidation that heats the fiber in an oxidizing gas for the purpose of improving mechanical strength, liquid-phase oxidation using a solution of an oxidizing agent, and in an electrolytic bath. It is desirable that the carbon fiber is subjected to surface oxidation treatment by a method such as anodic oxidation.

As the metal-coated carbon fiber,
The carbon fiber is coated on its surface with a metal layer by the above-mentioned various methods such as plating. Examples of the metal include copper, nickel, and aluminum, and nickel is preferable from the viewpoint of corrosion resistance of the metal layer. Also in the case of such a metal-coated carbon fiber, the carbon fiber mentioned above can be used as the original carbon fiber.

Such carbon fibers and metal-coated carbon fibers are preferably those which have been subjected to a bundling treatment or a granulation treatment with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin or the like, In particular, those treated with an epoxy resin or a urethane resin are particularly preferable from the viewpoint of improving mechanical strength.

The C-component core-shell elastic polymer of the present invention comprises a rubber core composed of two or more polyalkyl (meth) acrylate rubber-like polymers, and one or more carbon atoms having 1 to 3 carbon atoms. It is obtained by graft-polymerizing an alkyl (meth) acrylate monomer having an alkyl group.

The method for producing a rubber core composed of two or more polyalkyl (meth) acrylate rubber-like polymers is not particularly limited here. When I did
In general, the following method can be used (in the following description, two kinds of acrylic rubber-like elastic bodies will be described as AR1 and AR2).

That is, (i) after obtaining a latex of AR1 by emulsion polymerization, such a latex particle is impregnated with a monomer constituting AR2, and then a radical polymerization initiator is usually allowed to act. As the polymerization progresses, a rubber latex composed of two polyalkyl (meth) acrylate rubbery polymers AR1 and AR2 is obtained. The order of AR1 and AR2 may be reversed.

As another method, (ii) a latex of AR1 and a latex of AR2 are separately obtained by emulsion polymerization, and then these latexes are mixed to obtain two polyalkyl (meth) acrylates AR1 and AR2. A rubber latex composed of a rubber-like polymer is obtained. As a method of mixing the latex, in addition to a usual screw-type stirring mixer, a homomixer that stirs with a shearing force by high-speed rotation, a homogenizer that stirs with a jet output of a high-pressure generator, and a mixer that uses a porous filter, etc. It can be used.

Of the above, the method (i) is particularly preferable. This is because the probability that the rubbers of AR1 and AR2 are entangled with each other is increased and a higher synergistic effect is exhibited.

Further, the rubber-like polymers of two or more kinds of the core in the component C preferably have different glass transition temperatures. Furthermore, it is more preferable that the glass transition behaviors of the two are bimodal in the DSC differential curve shown below. Here, when AR1 is an acrylic rubber-like polymer having a lower glass transition temperature than AR2 (conversely, AR2 is an acrylic rubber-like polymer having a higher glass transition temperature than AR1), A
The difference in glass transition temperature between R1 and AR2 (peak temperature of DSC differential curve) is preferably 10 ° C. or more, and 12 ° C.
The above is more preferable.

On the other hand, the peak temperature of the glass transition derived from each rubber-like polymer in the C component core is preferably -35 ° C. or less. That is, A
Also in R2, it is preferable that the DSC differential curve has a peak temperature of −35 ° C. or lower, and more preferably −4.
It is 0 ° C or lower. Considering this point, AR1 and AR2
The upper limit of the difference between the glass transition temperatures of and is preferably 20 ° C, more preferably 18 ° C.

The DSC differential curve is a normal DSC curve obtained by taking the input difference of the thermal energy per unit time applied to both the horizontal axis and the vertical axis so that the temperature of the sample and the reference material are equal. On the other hand, a curve obtained by differentiating the curve with respect to the temperature on the horizontal axis. Such a curve is a normal DSC
A program that can be processed by the measuring device is installed and can be easily obtained. Also, DSC measurement is JI
According to SK7121, the measurement is started in a nitrogen atmosphere under the conditions of a measurement start temperature of -120 ° C to a temperature rising rate of 20 ° C / min.

The alkyl (meth) acrylate monomer used for the core has an alkyl group having 2 to 20 carbon atoms.
Are preferred. Specifically, for example, an alkyl (meth) acrylate having an alkyl group having 2 to 5 carbon atoms (hereinafter simply referred to as “C ₂ -C ₅ acrylate”) includes ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 4-hydroxybutyl acrylate etc. can be mentioned. Further, for example, as an alkyl (meth) acrylate having 6 to 20 carbon atoms in the alkyl group (hereinafter simply referred to as "C _{6 to} C ₂₀ acrylate"),
2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate and the like can be mentioned.

In the C component, the C _{2 to} C ₅ acrylate is preferably 30 to 70% by weight in 100% by weight of the B component from the viewpoint of achieving both the weld strength improving effect and the heat resistance, and preferably 35 to 60. % Is more preferable, and 40 to
55% by weight is more preferred. Within such a range, C _{2 to} C ₅
The effect of improving the weld strength is better than when the amount of acrylate is larger, and the heat resistance is better than when the amount of acrylate is smaller.

Similarly, the C _{6 to} C ₂₀ acrylate is preferably 15 to 55% by weight in 100% by weight of the component B, more preferably 20 to 50% by weight, still more preferably 25 to 45% by weight. Within such a range, the heat resistance is good as compared with the case where the amount of C _{6 to} C ₂₀ acrylate is larger,
The effect of improving the weld strength is better than that when the amount is small.

As a preferred embodiment of the component C in the present invention,
It is composed of a rubbery polymer (c1 component) containing C _{6 to} C ₂₀ acrylate as a main component and a rubbery polymer (c2 component) containing C _{2 to} C ₅ acrylate as a main component, and contains a b1 component and a b2 component. The weight ratio (c1 / c2) is c1 / c2
= 20/80 to 50/50 polyalkyl (meth)
Mention is made of a core-shell elastic polymer obtained by graft-polymerizing an alkyl (meth) acrylate monomer having one or more alkyl groups having 1 to 3 carbon atoms into a rubber core composed of an acrylate rubber-like polymer. You can Such a core-shell polymer can relatively easily achieve the preferable glass transition temperature characteristics of the above-mentioned core polyalkyl (meth) acrylate rubber.

Weight ratio of the above-mentioned c1 component and c2 component (c
1 / c2) is more preferably c1 / c2 = 25/75
To 40/60, more preferably 25/75 to 35
/ 65. In such a range, the preferable glass transition temperature characteristics of the core described above are achieved. Further, by relatively increasing the c2 component, the heat resistance of the rubber component can be improved, the high temperature during molding of the reinforced aromatic polycarbonate resin can be endured, and the recyclability can be improved.

The main component in the above-mentioned components c1 and c2 means containing at least 60% by weight, preferably 70% by weight or more of each acrylate component. Therefore, in the c1 component, C _{2 to} C ₅
Copolymerizing acrylate, and it is possible in c2 component copolymerized C ₆ -C ₂₀ acrylate.

In particular, in order to set the peak temperature of the DSC differential curve to −35 ° C. or less in a rubber composed of two or more kinds of polyalkyl (meth) acrylate rubber-like polymers as the core of the component C as described above. Is usually C ₆ even in the c2 component whose glass transition temperature is higher than that of the c1 component.
Copolymerizing -C ₂₀ acrylate, it is preferable to lower the glass transition temperature. Here, the copolymerization ratio is c
In the two-component 100 wt%, C ₂ -C ₅ acrylate 60-9
5 wt% and C ₆ -C ₂₀ acrylate 5-40 wt%
Is preferable, and the former is 70 to 90% by weight,
The latter is more preferably 10 to 30% by weight, particularly preferably the former is 75 to 85% by weight and the latter is preferably 15 to 25% by weight.

Further, as the above C ₂ -C ₅ acrylate,
N-butyl acrylate is preferred. On the other hand, C _{6 to} C ₂₀
As the acrylate, 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, lauryl methacrylate, tridecyl methacrylate, and stearyl methacrylate are preferable, and 2-ethylhexyl acrylate is particularly preferable in terms of heat resistance.

Further, the C component core polyalkyl (meth)
The acrylate rubber-like polymer can obtain preferable rubber elasticity by polymerizing a polyfunctional alkyl (meth) acrylate together with the above alkyl (meth) acrylate monomer. Here, as the polyfunctional alkyl (meth) acrylate, for example, allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, divinylbenzene, triallyl sialic acid Nurate, triallyl isocyanurate, and the like. These can be used in combination of two or more. As the polyfunctional alkyl (meth) acrylate, allyl methacrylate, triallyl cyanurate and the like are preferable, and allyl methacrylate is more preferable. Further, such polyfunctional alkyl (meth) acrylate is preferably 0.1 to 20% by weight in each rubber-like polymer of the core, and 0.2 to
3% by weight is more preferable, and 0.3 to 2.5% by weight is further preferable.

It is composed of the c1 component and the c2 component, which are the preferred embodiments of the C component in the present invention, and c1 / c2 = 2.
An alkyl (meth) acrylate monomer having one or more alkyl groups having 1 to 3 carbon atoms is added to the core of a rubber composed of a polyalkyl (meth) acrylate rubbery polymer having a ratio of 0/80 to 50/50. Core formed by graft polymerization
The shell elastic polymer is manufactured as follows based on the manufacturing method (i) described above.

That is, first, an acrylate monomer (C _{6 to} C ₂₀ acrylate, a small amount of a polyfunctional alkyl (meth) acrylate) constituting the c1 component, and optionally a C
_{2 to} C ₅ acrylate) is emulsion-polymerized to obtain a latex of component c1.

Here, when 2-ethylhexyl acrylate, lauryl methacrylate, tridecyl methacrylate, or stearyl methacrylate is the main component as the acrylate monomer of the c1 component, these monomers have poor water solubility, so that the forced emulsification weight It is preferably manufactured legally. As means for atomizing the latex in such a production method, a homomixer for atomizing the latex by shearing force by high-speed rotation, a homogenizer for atomizing the latex by jetting power from a high-pressure generator, and an atomizing using a porous filter A device for doing so can be mentioned.

The latex particles of the c1 component are added with c2
After impregnating the component acrylate monomer (C _{2 to} C ₅ acrylate, a small amount of polyfunctional alkyl (meth) acrylate, and preferably C _{6 to} C ₂₀ acrylate in the above proportion), a conventional radical polymerization initiator Is applied to obtain a rubber latex composed of the c1 component and the c2 component. At least one carbon number of 1 for the core latex
A core-shell elastic polymer is obtained by adding an alkyl (meth) acrylate monomer having an alkyl group of 3 to 3 and performing graft polymerization in one step or in multiple steps by a radical polymerization technique. Sulfuric acid, acid such as hydrochloric acid, calcium chloride, calcium acetate, or a salt of such an elastic polymer is poured into hot water in which a metal salt such as magnesium sulfate is dissolved, and salting out, coagulation, separation, and recovery are carried out. A solid core-shell elastic polymer is obtained. It is also possible to apply a direct drying method such as a spray drying method to the latex to obtain a solid core-shell elastic polymer.

The number of carbon atoms to be graft-polymerized on the core is 1 to
The alkyl (meth) acrylate monomer having an alkyl group of 3 is preferably methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, and more preferably methyl methacrylate or a combination of methyl methacrylate and ethyl acrylate. Particularly preferred is methyl methacrylate.

The proportion of methyl methacrylate is preferably 15 to 30% by weight, more preferably 18 to 25% by weight, based on 100% by weight of the component C. If the amount of methyl methacrylate is less than the above range, good dispersion cannot be obtained in the aromatic polycarbonate, which may be disadvantageous in terms of improvement in weld strength and heat resistance. On the other hand, when the amount of methyl methacrylate is more than the above range, the rubber elasticity is lowered, which may be disadvantageous in improving the weld strength.

Further, in the component C of the present invention, a small amount of another vinyl-based monomer may be added to both the core component and the graft component. Other vinyl-based monomers include styrene, α-methylstyrene, aromatic alkenyl compounds such as vinyltoluene, acrylonitrile, vinyl cyanide compounds such as methacrylonitrile,
Examples thereof include methacryl group-modified silicone. However, it is more preferable that the other vinyl-based monomer component is not substantially contained.

The composition ratios of the components A, B and C of the present invention are as follows. That is, A component and B
The component A is 50 to 97 parts by weight, the component B is 3 to 50 parts by weight, and the component C is 0.5 to 20 parts by weight with respect to a total of 100 parts by weight of the components. A component is A component and B
60 to 95 parts by weight is preferable, and 65 to 90 parts by weight is more preferable, based on 100 parts by weight of the total of the components. B component is A
5 to 40 based on 100 parts by weight of the total of the component and the B component
Part by weight is preferable, and 10 to 35 parts by weight is more preferable.
The C component is more preferably 1 to 15 parts by weight,
0 weight part is more preferable, and 1.5-8 weight part is especially preferable. When the amount of the component A exceeds 97 parts by weight or the amount of the component B is less than 3 parts by weight with respect to 100 parts by weight of the total of the components A and B, the effect of rigidity and strength expected by blending the inorganic filler is sufficient. In some cases, the decrease in weld strength is relatively small. When the amount of the component A is less than 50 parts by weight or the amount of the component B exceeds 50 parts by weight, the strength may be reduced due to the component C. Also, the total of A component and B component is 10
If the amount of the C component is less than 0.5 parts by weight relative to 0 parts by weight, the effect of improving the weld strength is not sufficient, and if it exceeds 20 parts by weight, the effect of the improvement is saturated, while the strength decreases and the flame retardancy is reduced. A decline occurs.

A function can be imparted to the reinforced aromatic polycarbonate resin composition of the present invention, if necessary, by inhibiting the adhesion between the resin and the filler.
Such functions include, for example, improved impact resistance, improved electromagnetic wave shielding properties (for conductive fillers such as carbon fibers and metal coated fibers), and improved rigidity (particularly for plate-like fillers such as glass flakes). , And improvement of recycling characteristics.

As the component (D component) which inhibits the adhesion between the resin and the filler, specifically, (i) a method of directly coating the surface of the B component with a compound having a low affinity with the A component, and (Ii) Adhesion between components A and B by melt kneading a compound having a structure with low affinity with component A and having a functional group capable of reacting with the surface of component B with components A and B It inhibits sex.

As the compound having a low affinity with the component A, various lubricants can be typically mentioned. Examples of the lubricant include mineral oil, synthetic oil, higher fatty acid ester, higher fatty acid amide, polyorganosiloxane (silicone oil, silicone rubber, etc.), olefin wax (paraffin wax, polyolefin wax, etc.), polyalkylene glycol, fluorinated fatty acid. Fluorine oil such as ester, trifluorochloroethylene, polyhexafluoropropylene glycol, etc. may be mentioned.

Examples of the higher fatty acid ester include glycerin fatty acid ester, sorbitan fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, ethylene glycol fatty acid ester, polyoxyethylene fatty acid ester, and the like. preferable.

Of the above-mentioned lubricants, olefin wax or polyorganosiloxane is preferable. Of the olefin waxes, polyolefin waxes are preferable, and particularly polyethylene wax and / or 1-alkene polymers (including α-olefin polymers) are preferably used. The molecular weight and the degree of branching are not particularly limited, but the weight average molecular weight is preferably 500 to 20,000, and more preferably 1,000 to 15,000. As the polyethylene wax, those 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 low molecular weight components from a polyethylene polymer. The polyolefin wax may be modified with various functional groups.

On the other hand, in the polyorganosiloxane, silicone oil is preferable. As the silicone oil, dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, cyclic dimethyl silicone oil, methylphenyl silicone oil, polyether modified silicone oil,
Examples thereof include higher fatty acid ester-modified silicone oil. As such silicone oil, one having a kinematic viscosity at 20 ° C. of 1 × 10 ⁻² m ² / s or less is preferable from the viewpoint of handling. The polyorganosiloxane may be modified with various functional groups.

The method of directly coating the surface of the component B with the compound having a low affinity with the component A includes (1) a compound having a low affinity with the component A, a solution of the compound in a solvent, and an emulsification of the compound. A method in which the component B is immersed in a liquid or suspension, these liquid agents are adhered, and then dried,
(2) A method of passing the B component through the powder of the compound having a low affinity with the A component, and (3) the powder of the compound having a low affinity with the A component for the B component at high speed. Irradiation, (4) mechanochemical method of rubbing the fiber roving against the lubricant solid, and the like can be mentioned.

It has a structure with a low affinity for the component A, and B
Examples of the compound having a functional group capable of reacting with the surface of the component include the above-mentioned lubricants modified with various functional groups. Examples of such a functional group include a carboxyl group, a carboxylic acid anhydride group, an epoxy group, an oxazoline group, an isocyanate group, an ester group, an amino group, and an alkoxysilyl group.

It has a structure having a low affinity with the component A, and B
When the compound having a functional group capable of reacting with the surface of the component is melt-mixed with the components A and B, it does not bond or adhere to the component A, while it bonds or adheres to the component B, resulting in B. By the action of the structure that covers the periphery of the component and has a low affinity with the A component, it becomes possible to inhibit the adhesion between the A component and the B component. From this point, the functional group is A
It is preferable that the reactivity with the component is lower, while the reactivity with the component B is higher.

Since the component A is an aromatic polycarbonate, the functional group capable of reacting with the surface of the component B in the component D is at least one selected from a carboxyl group, a carboxylic acid anhydride group, an epoxy group and an oxazoline group. It is preferable to use one kind of functional group, more preferably at least one kind of functional group selected from a carboxyl group and a carboxylic acid anhydride group.

That is, as the preferred component D in the present invention, there may be mentioned (i) a lubricant obtained by coating the component B in advance. More preferred is a lubricant obtained by coating the component B with at least one lubricant selected from polyglycerin fatty acid ester, olefin wax, and polyorganosiloxane in advance. Of these, the olefin wax is preferably coated with the component B in advance.

The preferred component D in the present invention is (ii) a lubricant having at least one functional group selected from a carboxyl group, a carboxylic acid anhydride group, an epoxy group, and an oxazoline group. As the lubricant, at least one lubricant selected from polyglycerin fatty acid ester, olefin wax, and polyorganosiloxane is more preferable.

More preferably, the D component of the present invention is
Mention may be made of lubricants having at least one functional group selected from carboxyl groups and carboxylic acid anhydride groups.

As a method of binding these lubricants to various functional groups, (1) a method of reacting the lubricant with the above-mentioned functional group and a compound having a functional group reactive with the lubricant,
(2) A method of copolymerizing the compound having the above functional group during the synthesis of the lubricant, (3) A method of mixing and reacting the lubricant, the compound having the functional group and the radical generator under heating, and (4) Heat Examples thereof include a method of modifying by oxidation, and any method can be used.

Particularly preferred as component D in the present invention is
It is a polyolefin wax having at least one functional group selected from a carboxyl group and a carboxylic acid anhydride group. As a method for incorporating such a carboxyl group or a carboxylic acid anhydride group into the polyolefin wax, various methods can be appropriately adopted. For example,
Heating a compound such as maleic acid or maleic anhydride with a polymer such as polyethylene, a polymer of 1-alkene (including α-olefin), or a copolymer of 1-alkene (including α-olefin) and ethylene The method of mixing in the presence or absence of a radical generator is mentioned below. By such a method, these functional groups can be introduced along with the cleavage of the main chain, the side chain or the bonding atom.
An even more preferable method is to copolymerize maleic acid, preferably maleic anhydride, when polymerizing or copolymerizing ethylene, propylene, 1-alkene having a carbon number of 4 or more (including α-olefin) and the like. This is a method of introducing a functional group. This method is a more preferable method because it does not have an unnecessary heat load and the amount of such functional groups can be easily controlled.

In the component D, the amount of the carboxyl group and the carboxylic acid anhydride group is at least 1 selected from the carboxyl group and the carboxylic acid anhydride group.
0.05-10 meq per gram of lubricant having certain functional groups
/ G is preferable, and more preferably 0.1 to 6 me.
q / g, and more preferably 0.5 to 4 meq / g. Here, 1 eq (1 equivalent) means that 1 mol of the carboxyl group is present in the case of a carboxyl group, and 0.5 mol of the carboxylic acid anhydride group is present in the case of a carboxylic acid anhydride group. It exists. In the case of the other functional group in the component D of the present invention, it is preferable that the functional group contains the same amount as the carboxyl group.

In the lubricant having at least one functional group selected from a carboxyl group and a carboxylic acid anhydride group, which is a preferred component D, α is particularly preferable.
Mention may be made of copolymers of olefins with maleic anhydride. Such a copolymer can be produced by a melt polymerization method or a bulk polymerization method in the presence of a radical catalyst according to a conventional method. As the α-olefin, those having an average carbon number of 10 to 60 can be preferably mentioned. More preferably, the α-olefin has an average carbon number of 16 to 60, and further preferably 2
5-55 can be mentioned. The amount of the carboxyl group and the carboxylic acid anhydride group is 0.
It is preferably 1 to 6 meq / g, and more preferably 0.5 to 4 meq / g.

The composition ratio of the component D is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the total of the components A and B.
More preferably 0.08 to 1 part by weight, 0.1 to 0.8
Part by weight is especially preferred. Even when the resin composition of the present invention contains the D component, the inclusion of the C component can improve the weld strength.

The reinforced aromatic polycarbonate resin composition of the present invention may further contain various flame retardants, if necessary. As a flame retardant (E component), an organic phosphorus compound, an alkali (earth) metal salt of an inorganic acid, an alkali (earth) metal salt of an organic acid, an organic halogen compound, red phosphorus, an organic siloxane, an inorganic phosphate, an inorganic Examples thereof include hydrates of metal compounds. Among these, organophosphorus compounds are preferable in that they can obtain good molding processability, appearance of molded articles, and high flame retardancy, and are suitable for alkali (earth) metal salts of inorganic acids and alkali (earth) of organic acids. ) A metal salt is suitable in that the heat resistance is less deteriorated and the weld strength is less affected, and an organic halogen compound is suitable in that the heat resistance is less deteriorated and high flame retardancy is obtained. Among these, an organic phosphorus compound, particularly a phosphoric acid ester compound is preferable from the viewpoint of having good moldability, and an alkali (earth) metal salt of an organic acid is preferable from the viewpoint of little influence on weld strength.

Examples of the phosphoric acid ester compound include one or more phosphoric acid ester compounds represented by the following general formula (4).

[0101]

[Chemical 4]

(However, Y in the above formula is hydroquinone,
Derived from resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfide And j, k, l, m are each independently 0 or 1, and n is an integer of 0 to 5,
Or 0 in the case of a mixture of phosphates having different n numbers
Is an average value of 5 to 5, R ¹ , R ² , R ³ , and R ⁴ are each independently a phenol, cresol, xylenol, isopropylphenol, butylphenol substituted or unsubstituted with one or more halogen atoms, p-
It is derived from cumylphenol. Among these, preferably Y in the above formula includes those derived from hydroquinone, resorcinol and bisphenol A, and j, k, l and m are each 1,
n is an integer of 0 to 3 or an average value of 0 to 3 in the case of blending phosphoric acid esters having different n numbers,
R ¹ , R ² , R ³ , and R ⁴ are each independently derived from phenol, cresol, or xylenol substituted or unsubstituted with one or more halogen atoms.

Further preferably, Y is resorcinol.
Derived from bisphenol A, j,
k, l and m are each 1 and n is 0 or 1.
R ¹, R², R³, And R^FourEach independently
It is derived from nor or xylenol.

Among such phosphoric acid ester compounds, triphenyl phosphate is used as the monophosphate compound, and resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are used as the condensed phosphoric acid ester compound, which have good flame retardancy. It is more preferably used because of its good fluidity during molding, good hydrolyzability and little long-term decomposition. In particular, the phosphoric acid ester compound in the E component is preferably substantially at least one phosphate selected from resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate). This is because these have a high thermal decomposition temperature, and therefore, when they are repeatedly melt-kneaded, they are less likely to be separated and volatilized from the resin composition and have excellent recycling characteristics. Further, it is also preferable to use a phosphazene compound typified by a phenoxyphosphazene oligomer or a cyclic phenoxyphosphazene oligomer as the organic phosphorus flame retardant in that the thermal decomposition temperature is high and the recyclability is excellent.

In the above description, "substantially" means that the condensed phosphoric acid ester compound may contain a component having a different polymerization degree, which is a by-product during the production, or another component which is insufficiently reacted, which is usually contained in the condensed phosphoric acid ester compound. It also shows that other phosphoric acid ester compounds may be contained in small amounts. Further, in the condensed phosphoric acid ester compound containing such other components, resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are contained in an amount of 80% by weight or more based on 100% by weight of the phosphoric acid ester compound. The content is preferably 85% by weight or more, more preferably 88% by weight or more.

The composition ratio of the phosphoric acid ester compound is 1 with respect to 100 parts by weight of the total of the components A and B.
-30 parts by weight is preferable, and 5-15 parts by weight is particularly preferable. If it is less than 1 part by weight, the improvement of flame retardancy is little, and if it exceeds 30 parts by weight, the heat resistance is lowered.

Examples of the alkali metal in the alkali (earth) metal salt of an organic acid of the present invention include lithium, sodium, potassium and cesium, and examples of the alkali (earth) metal include calcium, magnesium and barium. To be On the other hand, examples of the organic acid include aliphatic sulfonic acid, aliphatic sulfuric acid ester, aromatic sulfonic acid, aromatic sulfonamide, aromatic carboxylic acid and aliphatic carboxylic acid. Specific examples include methylsulfonic acid, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, ethylene glycol, propylene glycol, butanediol, and other mono- or di-sulfates. Ester, pentaerythritol mono-, di-, tri- or tetrasulfate, stearic acid monoglyceride monosulfate, 1,3-bis (2-ethylhexyl) glycerin ether monosulfate, trifluoromethanesulfonic acid, perfluoroethanesulfonic acid, per Fluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptane Rufonic acid, perfluorooctanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, 2,4,6-trichlorobenzenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid, diphenylsulfone -3-sulfonic acid, diphenylsulfone-3,3'-disulfonic acid, naphthalenetrisulfonic acid, β-naphthalenesulfonic acid formalin condensate, N-
(P-tolylsulfonyl) -p-toluenesulfoimide, N- (N'-benzylaminocarbonyl) sulfanylimide, and N- (phenylcarboxyl) sulfanylimide, caprylic acid, lauric acid, benzoic acid,
Examples thereof include naphtholcarboxylic acid and 2,4,6-tribromobenzoic acid. Preferred organic alkali metal salts or organic alkaline earth metal salts include potassium perfluorobutane sulfonate, calcium perfluorobutane sulfonate, cesium perfluorobutane sulfonate,
Diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3,3′-disulfonate, β-
Sodium naphthalene sulfonate formalin condensate, N
Examples thereof include-(p-tolylsulfonyl) -p-toluenesulfoimide potassium, and among these, potassium perfluorobutanesulfonate is particularly preferable. The alkali (earth) metal salt of such organic acid has a total of 1 component A and 1 component.
0.0005 to 1 part by weight is preferable with respect to 00 parts by weight, and 0.001 to 0.5 part by weight is particularly preferable. 0.0
When the amount is less than 005 parts by weight, the flame retardancy is not improved, and when the amount exceeds 1 part by weight, the flame retardance is decreased.

The reinforced aromatic polycarbonate resin composition of the present invention may contain an anti-dripping agent as the F component. It is more preferable to use the F component together with the E component flame retardant, but it is also possible to use it alone. Examples of the F component include a fluorinated polymer having a fibril forming ability. Examples of the polymer include polytetrafluoroethylene and tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymer, Etc.), a partially fluorinated polymer as shown in US Pat. No. 4,379,910, a polycarbonate resin produced from a fluorinated diphenol, and the like, but preferably polytetrafluoroethylene (hereinafter referred to as P
It may be referred to as TFE).

The PTFE having fibril-forming ability has an extremely high molecular weight, and tends to form a fibrous form by bonding PTFEs to each other by an external action such as shearing force. Its molecular weight is 1,000,000 to 10,000,000, more preferably 2,000,000 to 9,000,000 in terms of number average molecular weight determined from standard specific gravity. In addition to the solid form, such PTFE may be in the form of an aqueous dispersion. In addition, PTFE having such a fibril-forming ability improves the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there.

PTFE having the ability to form fibrils
Examples of commercially available products include Teflon 6J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 manufactured by Daikin Chemical Co., Ltd., and F-201L. Commercially available aqueous dispersions of PTFE include Fluon AD-1, AD-936 manufactured by Asahi IC Polymers Co., Ltd., Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui DuPont Fluoro. Representative examples thereof include Teflon 30J manufactured by Chemical Co., Ltd.

The mixed form of PTFE includes (1) PT
A method in which an aqueous dispersion of FE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (JP-A-60-258263 and JP-A-63-15474).
No. 4, etc.), (2) a method of mixing an aqueous dispersion of PTFE with dried organic polymer particles (the method described in JP-A-4-272957),
(3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and respective media are simultaneously removed from the mixture (described in JP-A 06-220210 and JP-A 08-188653). Method),
(4) A method of polymerizing a monomer forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer. Those obtained by a method of uniformly mixing the combined dispersion, further polymerizing a vinyl-based monomer in the mixed dispersion, and then obtaining a mixture (method described in JP-A No. 11-29679, etc.). Can be used. P of these mixed forms
Commercially available products of TFE include "METABLEN A3000" (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and "BLENDEX B449" manufactured by GE Specialty Chemicals.
(Product name) etc. can be mentioned.

The proportion of PTFE in the mixed form is as follows: PTFE is 1 to 6 in 100% by weight of the PTFE mixture.
0% by weight is preferable, and more preferably 5 to 55% by weight. If the ratio of PTFE is in the range, PT
Good dispersibility of FE can be achieved.

The composition ratio in the case of containing the F component is 100 parts by weight of the total of the A component and the B component,
It is preferably 0.05 to 3 parts by weight. 0.05 ~
1 part by weight is more preferable, and 0.1 to 0.5 part by weight is further preferable. This is because if the blending amount of the anti-dripping agent is less than 0.05 part by weight, the desired drip prevention tends to be insufficient, and 3 parts by weight is sufficient as the upper limit for such purpose. Even when the F component is in the form of a mixture with an aqueous dispersion or another resin, it means the net amount of PTFE.

The reinforced aromatic polycarbonate resin composition of the present invention achieves improved weld strength and wide colorability (particularly good jet blackness) by containing the components A to C. Due to the characteristics of the composition of the present invention, the reinforced aromatic polycarbonate resin composition of the present invention may further include carbon black as a more preferable embodiment.

The carbon black used herein is not particularly limited in production method, raw material species and the like, and examples thereof include oil furnace black, channel black, thermal black, acetylene black, ketjen black, lamp black, roller black, disk black and the like. Can also be used. Further, the structure of carbon black, particle size, specific surface area, coloring power, DBP oil absorption, volatile matter,
The properties such as pH are not particularly limited, but those having a significantly developed structure may be disadvantageous in moldability and surface appearance of the molded product, and therefore are preferably used as colorants for resins. Oil furnace black and channel black. Also in such preferable carbon black, HCC, HCF, MCF, LF
Although any type such as F and RCF can be used, HCF, MCF, LFF and the like are more preferable. It is more preferable that the pH value is 7 or less, 2 to 6
Is more preferable. Carbon black can be used alone or in combination of two or more kinds.

The raw material form of carbon black is not only powder form but also granule form with binder resin,
Also, various forms such as a masterbatch obtained by melt-kneading a high concentration in another resin can be used. The amount of carbon black is preferably 0.0001 to 10 parts by weight based on 100 parts by weight of the total of the components A and B. It is preferably 0.01 to 3 parts by weight, more preferably 0.02 to 2 parts by weight, and particularly preferably 0.1 to 1.5 parts by weight.

The reinforced aromatic polycarbonate resin composition of the present invention further comprises A as long as the object of the present invention is not impaired.
Component and thermoplastic resin other than C component (for example, polyester resin, polyamide resin, polyacetal resin, modified polyphenylene ether resin, polymethylmethacrylate resin, polyolefin resin, polyphenylene sulfide resin, etc.), filler other than B component (for example, ,
Glass beads, glass balloons, clay, granular calcium carbonate, carbon beads, silica particles, ceramic particles, ceramic balloons, aramid particles, aramid fibers, polyarylate fibers, etc., flame retardant aids (eg sodium antimonate, and trioxide). Antimony etc.),
Char-forming compound (for example, novolac type phenol resin, condensate of pitches and formaldehyde, poly (2,6-dimethyl-1,4-phenylene ether),
Polyphenylene sulfide etc.), nucleating agent (eg sodium stearate, ethylene-sodium acrylate etc.), heat stabilizer, antioxidant (eg hindered phenol type antioxidant, sulfur type antioxidant etc.) ), Other impact modifiers, ultraviolet absorbers, light stabilizers, mold release agents, antistatic agents, flow modifiers, antibacterial agents, photocatalytic antifouling agents (particulate titanium oxide, particulate zinc oxide, etc.), lubricants, Colorants other than carbon black, optical brighteners, phosphorescent pigments,
A fluorescent dye, an infrared absorber, a photochromic agent, etc. can be added.

Examples of the heat stabilizer include phosphorus heat stabilizers, and phosphite compounds and phosphate compounds are preferably used. Examples of the phosphite compound include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, and dioctadecyl phosphite. Decyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4- Methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-ter
t-butylphenyl) octylphosphite, bis (nonylphenyl) pentaerythritol diphosphite,
Examples include phosphite compounds such as bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite. Of these, tris (2,4-di-tert-butylphenyl) phosphite is preferably used from the viewpoint of thermal stability.

On the other hand, examples of the phosphate compound used as the heat stabilizer include tributyl phosphate,
Trimethyl phosphate, tricresyl phosphate,
Examples thereof include triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like. Among them, triphenyl phosphate and trimethyl phosphate preferable.

As another phosphorus-based heat stabilizer, tetrakis (2,4-di-tert-butylphenyl)-
4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3 '
-Biphenylene diphosphonite, tetrakis (2,4-
Phosphonite compounds such as di-tert-butylphenyl) -3,3'-biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -4-biphenylenediphosphonite are also used from the viewpoint of thermal stability. It can be preferably used.

The phosphorus-based heat stabilizer may be used alone or in combination of two or more. The phosphorus-based heat stabilizer is used in 100% by weight of the reinforced aromatic polycarbonate resin composition of the present invention.
0.001-0.5% by weight, more preferably 0.005
It is preferable to blend in the range of 0.3 wt%.

Specific examples of the phenolic antioxidant include 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-ter
t-Butyl-4-hydroxybenzyl) isocyanurate, 3,9-bis {1,1-dimethyl-2- [β- (3
-Tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,1
0-tetraoxaspiro (5,5) undecane and the like can be mentioned. The preferred range of addition of these antioxidants is
Reinforced aromatic polycarbonate resin composition 100% by weight
Of these, 0.0001 to 0.5% by weight is preferable, and 0.001 to 0.3% by weight is more preferable.

Examples of the ultraviolet absorber include 2,2'-
A benzophenone-based ultraviolet absorber represented by dihydroxy-4-methoxybenzophenone, and, for example, 2-
(3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2-
(3,5-Di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H -Benzotriazol-2-yl) phenol], 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole and 2- (3,5-di-tert-). Examples thereof include benzotriazole-based UV absorbers represented by amyl-2-hydroxyphenyl) benzotriazole. Furthermore, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-bis (2,4-dimethylphenyl))
-1,3,5-triazin-2-yl) -5-hexyloxyphenol and other hydroxyphenyltriazine compounds, as well as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1 , 2, 2,
It is also possible to use a hindered amine-based light stabilizer such as 6,6-pentamethyl-4-piperidyl) sebacate. These can be used alone or in combination of two or more. The preferred range of addition of these ultraviolet absorbers and light stabilizers is 0.0001 to 1% by weight, preferably 0.001 to 0.5% by weight, based on 100% by weight of the reinforced aromatic polycarbonate resin composition.

Examples of the releasing agent include olefin wax, silicone oil, organopolysiloxane, higher fatty acid ester of monohydric or polyhydric alcohol, paraffin wax and beeswax.

Any method may be employed to produce the reinforced aromatic polycarbonate resin composition of the present invention. For example, A component to C component, and optionally other additives, V type blender, Henschel mixer, mechanochemical device,
After thoroughly mixing using a pre-mixing means such as an extrusion mixer, granulate with an extrusion granulator or a briquetting machine in some cases, and then melt with a melt-kneader typified by a vented twin-screw ruder. Examples of the method include kneading and pelletizing with a device such as a pelletizer.

In addition, a method of supplying each component independently to a melt-kneader represented by a vent type twin-screw ruder,
A method of pre-mixing a part of each component and then supplying the mixture to the melt-kneader independently of the remaining components may be used. In particular, for the component B, which is a fibrous or plate-like filler, a method of supplying it into the molten resin from the middle of the extruder is preferable in order to prevent the filler from breaking or cracking during melt-kneading. As a premixing method, for example, when a powder having a form of A is included as a component A, a method of blending a part of the powder with an additive to be blended to form a masterbatch of the additive diluted with the powder is used. Can be mentioned.

Further, a method of independently supplying one component from the middle of the melt extruder may be mentioned. When the components to be blended are liquid, a so-called liquid injection device or liquid addition device can be used for supplying to the melt extruder.
The position of such liquid injection can be set at an arbitrary block position of the extruder, but more preferable is a case where a side feeder is provided and the block is set thereafter. In other cases, the setting on the upstream side is preferable. The heating temperature during the melt kneading is usually 240 to 34.
It is selected in the range of 0 ° C.

The aromatic polycarbonate resin composition of the present invention can be manufactured into various products by injection molding such pellets to obtain molded products. In such injection molding, not only a normal cold runner molding method but also a hot runner molding method is possible. Also, in injection molding, not only ordinary molding methods but also gas-assisted injection molding, injection compression molding, injection press molding, insert molding, in-mold molding, local high temperature mold molding (including heat insulation mold molding), two-color molding , Sandwich molding, ultra high speed injection molding and the like can be used. These can be used not only as a single method but also as a combination of a plurality of methods.

One of the more preferable molding methods in the above is local high temperature mold forming (including heat insulating mold forming). Such a molding method locally raises the temperature of only the mold cavity surface portion of a portion where a good molded product appearance is required during the resin filling, whereby high transferability of the mold cavity surface and an appropriate molding cycle are achieved. This is a molding method that balances the above. By this molding method, even in a polycarbonate resin composition containing a filler such as glass fiber, the appearance of the molded article can be achieved to the same extent as in the case of not containing the filler, which enables it to be widely used for exterior parts and the like. Become.

Specific examples of the method for locally raising the temperature of the mold cavity surface include, for example, a conventionally proposed method in which the surface portion is directly irradiated with radiant heat from a halogen lamp or the like, and high-frequency induction heating is performed. Method, method of heating / cooling with thin film electric resistor, method of rapidly adjusting temperature by replacing high temperature heat medium and refrigerant in temperature control pipe near the mold cavity surface, method of using ultrasonic wave, etc. Other than the method of heating the surface part with an external heat source,
By forming a heat insulating layer having a low thermal conductivity on the surface of the mold cavity, a method of utilizing the heat of the molten resin to raise the temperature of the surface portion can be used.
These may be used alone or in combination.

Among the methods described above, the method utilizing the heat insulating layer can reach a high temperature state after the filling and can take a longer relaxation time of the molecular chains than the filling, so that the stress of the resin around the inorganic filler can be relaxed. Generation of microcracks and the like is easily suppressed. Therefore, it is considered to be advantageous in long-term characteristics. Further, unlike other methods, it is easy to make the heat history of the surface of the molded product more uniform regardless of the shape of the molded product. Therefore, the method of utilizing the heat insulating layer is mentioned as a preferable molding method of the present invention.

The heat insulating layer may be at least one layer selected from the group consisting of heat resistant plastics, plastic composite materials, glass and ceramics. These can be selected in the case of either a single layer or a laminated structure. As a more preferable heat insulating layer, various polyimide resins such as polyamino bismaleimide resin and polyamide imide resin, or modified epoxy resin containing an inorganic filler such as alumina can be mentioned. Examples of various polyimide resins include Vespel (manufactured by DuPont, trade name), PI2080 (manufactured by Upjohn, trade name), Torlon (trade name by Teijin Amoco Engineering Plastics Co., Ltd.), Ultem (Japan GE Plastics ( Co., Ltd.), AURUM (Mitsui Chemicals, Inc., trade name), Upilex-VT (Ube Industries, Ltd., trade name), and the like.

The thermal conductivity of the heat insulating layer is 0.05 to 1 W.
/ M · K is preferable, more preferably 0.1 to 0.8 W
/ M · K, and more preferably 0.1 to 0.7 W / m · K. On the other hand, the thickness of the heat insulating layer is 0.1 to 3 mm, preferably 0.2 to 2 mm, more preferably 0.5 to 1.5 mm, further preferably 0.5 to
A range of 1.4 mm, particularly preferably 0.6 to 1.4 mm can be mentioned.

Further, in order to improve the surface hardness, durability, and smoothness of the mold, 0.001 to 0.001 is formed on the surface of the heat insulating layer.
A metal layer having a thickness of 0.3 mm is preferable.
As such a metal layer, a layer made of nickel can be preferably mentioned. Further, it is preferable to provide a hard metal layer such as chromium on the outermost layer from the viewpoint of extending the life of the entire die.

The method of connecting the heat insulating layer to the metal mold block, or the method of connecting the metal layer and the heat insulating layer when the metal layer is provided on the surface of the heat insulating layer, includes metal and plastic, glass, Various methods of joining the ceramics can be used. For example, an adhesive having excellent adhesiveness with each layer and excellent heat resistance can be used. Examples of such an adhesive include a cyanoacrylate polymer and an epoxy polymer.

When the heat insulating layer is plastic, a method of directly bonding the plastic itself with a metal can be mentioned. For example, a method may be mentioned in which a reactive plastic such as epoxy is brought into close contact with a metal under high pressure and / or high temperature, and the plastic is cured in that state. In the case of a thermoplastic resin such as polyamide-imide, a method of bringing the resin into close contact with a metal under high pressure in a molten state can be mentioned. Further, there may be mentioned a method in which an organic electrolytic solution such as an electrolytic solution of a triazine thiol derivative is used to perform plating treatment on the metal surface with an organic compound such as the derivative, and then the plating treated surface and the plastic heat insulating layer are brought into close contact with each other. Examples of the adhesion method in that case include a method of adhering the molten resin and the plated surface, and a method of adhering and curing a plastic reactive with the plated surface.

From the above, as a preferred embodiment of the present invention, the mold cavity has a thermal conductivity of at least 0.05 to 1 W / m · K and a thickness of 0.5 to 1.5 m in at least the uneven portion thereof.
m heat insulating layer, and 0.001 to 0.001 on the surface of the heat insulating layer.
The case where the metal layer of 0.3 mm is formed can be mentioned.

As a method for providing the metal layer on the heat insulating layer, there may be mentioned a method by plating, vapor deposition and sputtering, as well as a combination thereof, that is, a method in which electrolytic plating is carried out after vapor deposition and sputtering. Further, a method of applying a conductive polymer and then electroplating can be mentioned. Other methods include a method of adhering a metal layer to such a heat insulating layer via an adhesive.

As another method, a metal layer is formed by electroplating on a brass mother die (electroforming method), a resin and a metal material as a mother material are overlaid on the metal layer and integrated (packing), A preferable method is a method in which the metal layer is peeled off from the brass mother die by pressure bonding and bonding. The details of this method are described in JP-A-6-2187.
No. 69 publication.

As described above, according to the present invention, the appearance of the molded product is good in terms of hue and surface smoothness, and further, the weld strength is excellent and the boss portion is also excellent in strength. Provided is a molded article formed from the aromatic polycarbonate resin composition. As such a molded product, an exterior molded product is particularly suitable. That is, according to the present invention, there is provided a molded article having a boss portion formed from the reinforced aromatic polycarbonate resin composition of the present invention,
More preferably, an exterior molded article having a boss portion formed from the composition is provided.

Specific examples of such a molded article for exterior use include a center panel, an instrumental panel, and
Vehicle interior parts such as dashboards, door handles, rear boards, display housings for car navigation and TVs, fender panels, door panels, spoilers, garnishes, pillar covers, front grilles, rear body panels, motorbike cowls, truck bed covers. Exterior parts for vehicles such as VTRs, TVs, irons, hair dryers, rice cookers, microwave ovens, housings and external parts for electrical equipment such as audio equipment, cameras, digital cameras, video movies, telescopes, binoculars, mobile phones, mobile phones. Information terminals, portable notebook computers, portable tape recorders, portable optical disk players, portable navigation devices, housings and external parts of portable precision instruments such as wristwatches, notebook computers, desktop computers. Emissions, CRT display, printer, copier, a recording medium (CD, DVD, etc.) drive device, a scanner, and the like OA equipment housing or external components such as a facsimile. Further, it is also suitable for a cartridge used for a recording medium such as FD, MD, PD, DVD-RAM, DV-R, and video tape.

[0142]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be further described below with reference to examples. The evaluation was based on the following method. In the following description, the reference numerals of the raw materials shown below are used when expressing the raw materials. (1) Evaluation item (a) Bending elastic modulus: IS is applied to a test piece obtained by continuous molding without being forced to stay in the cylinder of the molding machine.
It was measured at O178. (B) Weld strength: TY described in ASTM D638
Using a test piece for measuring the tensile strength of PEI, a test piece having gates at both ends in the length direction of the test piece and a weld formed in the center was prepared by an injection molding method, and ASTM D of the test piece was prepared. The tensile strength according to -638 was measured. (C) Chemical resistance of weld part: As shown in FIG. 1, the test piece is bent by supporting three points so that the weld part has maximum strain (simply referred to as “strain amount” in the table). Oil in the weld part (Moresco High Lube B manufactured by Matsumura Oil Co., Ltd.
S-100) impregnated with four folded medical gauze,
The test piece containing no phosphate oligomer (FR-1) as a flame retardant was heat-treated at 80 ° C. for 24 hours, and the one containing a phosphate oligomer was heated at 70 ° C. for 24 hours to observe the presence or absence of breakage of the test piece. The test was carried out on five test pieces, and the breaking variable n among them was shown in the table as "n / 5". In addition, the strain amount (ε) is L (100 mm) for the span of two points at both ends of the three points, h (3.2 mm) for the thickness of the test piece, and the height of the test piece lifted from the horizontal state. When y (mm), ε = (6hy) / L
It is a value calculated from the formula of ² . (D) Hue L value: A flat plate having a side of 50 mm and a thickness of 2 mm was placed on a color analyzer [TC-1800M manufactured by Nippon Denshoku Co., Ltd.].
KII], and the L value of the Hunter color coordinate was evaluated by the reflection method. The lower the L value is, the stronger the black tint is and the more excellent the jet blackness is. (E) Flame retardancy: A combustion test was carried out using a test piece having a thickness of 1.6 mm according to UL standard 94V.

The size of the filler of each sample was measured by the following method and listed in the table. Part of the above test piece is C
Samples not containing F and Ni-CF are C at 600 ° C.
The sample containing F and Ni—CF was burned at 500 ° C. for 3 hours in an electric furnace to obtain ash. The obtained ash was observed at about 250 times using an optical microscope, the observed image was taken into a PIAS-III system manufactured by Pierce Co., Ltd., and image analysis was performed to calculate the number average fiber length and the number average particle diameter. . In the measurement of the number average fiber length, a method in which a length of 10 μm or less was not counted as a length substantially less than the fiber diameter was used. On the other hand, if the number average particle size is an area of 5 μm × 5 μm or less, the number average area is calculated from the areas of the individual fillers by a method that is not counted because the length is almost equal to or less than the flake thickness. And In all cases, the number of measurements was 200.

The various raw materials used in this example shown in the table are as follows. (A component: aromatic polycarbonate) PC: Aromatic polycarbonate resin powder in which the divalent phenol component is bisphenol A [Teijin Kasei Co., Ltd.
Made; L-1225WP, viscosity average molecular weight 19,700]

(Component B: Inorganic Filler) GF: Glass Fiber [Nippon Electric Glass Co., Ltd .; EC
S-03T-511, diameter 13 μm, cut length 3 mm] MF: glass milled fiber [manufactured by Nittobo Co., Ltd .; PE
F-301S, diameter 9 μm, number average fiber length 30 μm] GFL: Granular glass flake [FLEACA REFG-301 manufactured by Nippon Sheet Glass Co., Ltd., median average particle size 140 μm by standard sieving method, thickness 5 μm]] CF: Carbon fiber [ Toho Tenax Co., Ltd .;
Vesphite HTA-C6-U, diameter 7 μm, cut length 6 mm] Ni-CF: Nickel coated carbon fiber [Vesphite MCHTA-C6- manufactured by Toho Tenax Co., Ltd.
US (I), diameter 7.5 μm, cut length 6 mm]

(Component C: Core-shell elastic polymer) MD-1: Mitsubishi Rayon Co., Ltd. "Metabrene W-45"
0A "(a rubber-like polymer having a core composed of a 2-ethylhexyl acrylate polymer, and n-butyl acrylate and 2-
It is composed of two rubber components of a rubber-like polymer composed of a copolymer with ethylhexyl acrylate, and contains 35% by weight of 2-ethylhexyl acrylate and 45% by weight of n-butyl acrylate, and the shell has methyl methacrylate 2
0% by weight of core-shell elastic polymer. (See Figure 2 for the behavior of the glass transition temperature.)

(Other than C component: elastic polymer) MD-2: "Septon 2007" manufactured by Kuraray Co., Ltd. Styrenic thermoplastic elastomer MD-3 composed of hydrogenated (styrene-isoprene-styrene) block copolymer: Mitsubishi Rayon ( "METABLEN S-20"
01 ”(80% by weight of a composite rubber having a structure in which a dimethyl siloxane polymer and a (n-butyl acrylate) polymer are intertwined with each other, and a shell is methyl methacrylate 20
(Weight% elastic polymer)

(Component D: Adhesion inhibiting component) DC: Copolymer of maleic anhydride and α-olefin (manufactured by Mitsubishi Kagaku Co., Ltd. Diakarna PA30M, maleic anhydride ratio of about 1 meq / g, GPC method) Weight average molecular weight calculated by standard polystyrene conversion and calculated to be about 8,400)

(E component: Phosphate ester flame retardant) FR-1: Phosphate flame retardant consisting essentially of bisphenol A bis (diphenyl phosphate) [CR-741 manufactured by Daihachi Chemical Industry Co., Ltd.]

(Component E: Metal salt flame retardant) FR-2: Potassium perfluorobutane sulfonate [manufactured by Dainippon Ink and Chemicals, Inc .; Megafac F-1]
14P]

(F component: anti-drip agent) PTFE: Polytetrafluoroethylene having fibril forming ability [Polyflon MPA manufactured by Daikin Industries, Ltd.]
FA-500]

(Carbon Black) CBM-1: Carbon Black Master Pellet Carbon Black [manufactured by Mitsubishi Chemical Co., Ltd .; Furnace Black MA-100, pH = 3.5] 20% by weight and polyethylene wax [manufactured by Mitsui Chemicals Co., Ltd.] : High wax 405MP] 10% by weight of viscosity average molecular weight 16,000
No. 0 bisphenol A type aromatic polycarbonate resin and master pellet CBM-2 obtained by melt-kneading with an extruder: carbon black Master pellet CBM-1 was replaced with carbon black, and carbon black was manufactured by Mitsubishi Chemical Corporation. Furnace Black # 9
70, pH = 3.5] except that the master pellet was obtained in the same manner as CBM-1.

(Others) TMP: trimethyl phosphate (Dahachi Chemical Industry Co., Ltd.)
(Made by TMP)

[Examples 1 to 10 and Comparative Examples 1 to 9] Mixtures having the compositions shown in Tables 1 and 2 in which all the components other than FR-1 of the B component and the E component were mixed were first fed to the extruder. Supplied by mouth. In such a mixture, (i) components A and F except components are mixed with a super mixer, and (ii) components A and F are 2.5 wt% of F component.
And (iii) these mixtures were obtained by uniformly mixing the remaining A component with a tumbler.
On the other hand, the component B was charged from the second charging port in the middle of the cylinder using a side feeder. FR-1 of E component was used in the block between the side feeder and the vent exhaust port using a liquid injection device (HYM-JS-08 manufactured by Fuji Techno Industry Co., Ltd.).
It was supplied while being heated to 0 ° C. The liquid injecting device was set to supply a fixed amount, and the amounts of the other raw materials charged were precisely measured by a measuring instrument [CWF manufactured by Kubota Corporation]. As the extruder, a bent type twin-screw extruder with a diameter of 30 mmφ (TEX30XSSS, Japan Steel Works, Ltd.) was used.
The screw structure was such that the first-stage kneading zone was provided before the side feeder position, and the second-stage kneading zone was provided between the supply block by the liquid injection device and the vent exhaust port. Cylinder temperature and die temperature 290 ° C, screw rotation speed 180 rpm, vent suction degree 3000P
and a discharge rate of 15 kg / h were melt-kneaded to obtain pellets. The obtained pellets are 120 containing FR-1.
Those that did not contain FR-1 were dried at 100 ° C. for 5 hours at 100 ° C. for 5 hours using a hot air dryer. Then, using an injection molding machine (Sumitomo Heavy Industries, Ltd .; SG-150U), F
A sample containing R-1 was obtained at a cylinder temperature of 290 ° C. and a mold temperature of 70 ° C., and a sample not containing FR-1 was obtained at a cylinder temperature of 320 ° C. and a mold temperature of 100 ° C. to obtain a predetermined evaluation test piece. It was The evaluation results are shown in Tables 1 and 2.

[0155]

[Table 1]

[0156]

[Table 2]

As is apparent from the above table, the reinforced aromatic polycarbonate resin composition of the present invention has improved weld strength and can withstand higher deformation even when oil or the like is attached. I know there is. Further, its hue is as good as that in the case where the core-shell elastic polymer is not contained. On the other hand, it can be seen that other elastic polymers have a low effect of improving the weld strength or do not satisfy the hue.

Further, the resin composition of Example 10 was used to mold a housing molding of a notebook computer shown in FIG. 3 as an exterior molding using a heat insulating mold nest having the following construction. That is, the insert is nickel-plated (thickness: about 100 μm) on a brass base material in the cavity on the front surface of the housing, and the post-cured plate of Torlon 4203L manufactured by Teijin Amoco Engineering Plastics Co., Ltd. is formed on the plated layer. A molded product (thermal conductivity of about 0.25 W / mK) cut to a thickness of 1 mm and mirror-polished, and an HPM50 plate manufactured by Hitachi Metals, Ltd. as a die base material on the upper layer of the molded product (epoxy adhesive) Using a chemical agent (thickness: 10 μm), and then releasing the nickel layer from the brass base material, the area shown in FIG. 3 is made into a matte surface by sand blasting with respect to the obtained nickel mirror surface, and such matte It is a mold nest in which the surface and mirror surface are mixed. Molding was performed by using an injection molding machine (Sumitomo Heavy Industries, Ltd .; SG-150U) under the conditions of a cylinder temperature of 310 ° C. and a mold temperature of 100 ° C.
The obtained molded housing of the laptop computer is a molded product with a good appearance in which a mirror surface part with extremely strong blackness and a good matte part coexist, and its rigidity is extremely high and its strength is also strong. Met.

[0159]

EFFECTS OF THE INVENTION The reinforced aromatic polycarbonate resin composition of the present invention has good weld strength and a wide range of coloring properties (especially good jet blackness), so that it can be used in electric / electronic devices and OA.
It can be widely applied to the field of equipment, automobiles, etc., and is particularly suitable for a molded product that is required to have both a good appearance of the molded product and the strength of the boss portion, and its industrial effect is exceptional.

[Brief description of drawings]

FIG. 1 is a perspective view showing an outline of a jig for performing a three-point bending in a chemical resistance test of a weld portion carried out in the above embodiment.

FIG. 2 shows a DSC curve derived from the rubber component of the core of the component C sample MD-1 in Example C and a derivative curve thereof. The horizontal axis represents temperature, the left side of the vertical axis represents the heat flow rate (mW), and the right side of the vertical axis represents the differential heat flow rate (the amount obtained by differentiating the heat flow rate by the temperature of the horizontal axis) (mW / ° C). The downward arrow indicates the peak temperature of the glass transition temperature in the differential curve of the DSC curve of each of the two rubber components (low temperature side: about -56 ° C, high temperature side: about -41 ° C). The measurement was carried out using a DSC2910 model manufactured by TA Instruments Co., Ltd. under a nitrogen atmosphere (flow rate 50 ml / min), and the temperature rising rate was 20 ° C. from −120 ° C.
It was measured in minutes.

FIG. 3 is a schematic front perspective view of a molded housing product of a notebook computer used in an example (vertical 178 mm ×).
Width 245 mm x edge height 10 mm).

FIG. 4 is a schematic front view of the back surface side of the molded product used in the examples, showing a state in which there are ribbed bosses (the matte surface portion is a boss with ribs on the upper and lower sides).

FIG. 5 shows a side view of the ribbed boss (reference numeral 14).

FIG. 6 shows a front view of a boss with ribs (reference numeral 14).

FIG. 7 shows a front view of a ribbed boss (reference numeral 13) (the shape is obtained by removing one rib from the ribbed boss of reference numeral 9).

[Explanation of symbols]

1 First fixing rod (made of stainless steel with a diameter of 3.9 mmφ) 2 Weld part of the test piece (installed so as to be located at the top of the arc drawn by the test piece. Place oil-impregnated gauze on this part) 3 Strain-loading moving rod (made of stainless steel with a diameter of 3.9 mmφ) 4 Strain-loading screw screw (through the back surface of the pedestal 7. Turn the screw screw from the position in contact with the unloaded test piece , A predetermined amount of strain is applied to the test piece based on the screw pitch) 5 Test piece (shape conforming to ASTM D638 TYPE I) 6 Second fixing rod (made of stainless steel with a diameter of 3.9 mmφ) 7 Pedestal 8 2 Horizontal distance between fixed rod and moving rod for strain load (50.0 mm) 9 Horizontal distance between 1st fixed rod and moving rod for strain load (50.0 mm) 11 Molded housing for laptop computer Body 12 Matte surface portion 13 Mirror surface portion 14 Rib boss (corresponding to the mirror surface back side) 15 Rib boss (corresponding to the mirror surface back side) 20 Boss outer diameter (die size 6.0 mmφ) 21 Boss trimming portion outer diameter ( Mold size 4.4 mmφ) 22 Boss inner diameter (mold size 3.4 mmφ) 23 Boss trimming depth (mold size 0.5 mm) 24 Boss and rib height (mold size 6.0 mm) 25 Stepped rib Height (die size 4.0 mm) 26 Rib length (die size 3.0 mm) 27 Rib length (die size 3.0 mm) 28 Cutting rib length (die size 20.0 mm) 29 Rib Width (die size 2.0 mm)

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F071 AA33 AA50 AA77 AB03 AB28                       AD01 AD02 AD05 AE17 AF14                       AH00 AH17 BB05 BC07                 4J002 BN112 BN212 CG001 DA016                       DA026 DE136 DE186 DE236                       DJ006 DJ026 DJ036 DJ046                       DJ056 DK006 DL006 DM006                       FA016 FA046 FA066 FB076                       FD016 GM00

Claims (8)

[Claims] 1. (A) Aromatic polycarbonate (component A), (B) fibrous and / or plate-like inorganic filler (component B), and (C) core-shell elastic polymer (C).
Component), wherein the component (A) is 50 to 9 with respect to 100 parts by weight of the total of component (A) and component (B).
7 parts by weight and B component is 3 to 50 parts by weight, and C
The component is 0.5 to 20 parts by weight, and (ii) the C component is a rubber core composed of two or more polyalkyl (meth) acrylate rubbery polymers, and one or more carbon atoms of 1 to 1
A reinforced aromatic polycarbonate resin composition which is a core-shell elastic polymer obtained by graft-polymerizing an alkyl (meth) acrylate monomer having an alkyl group of 3. 2. The aromatic polycarbonate resin composition according to claim 1, wherein each of the components derived from the core of the C component has a glass transition peak temperature of −35 ° C. or lower. 3. The C component has a ratio of an alkyl (meth) acrylate component having an alkyl group having 2 to 5 carbon atoms (hereinafter simply referred to as C _{2 to} C ₅ acrylate) in 100% by weight of 30 to 70. The aromatic polycarbonate resin composition according to any one of claims 1 and 2, which is contained in a weight percentage. 4. The component C has an alkyl (meth) acrylate component having an alkyl group having 6 to 20 carbon atoms (hereinafter simply referred to as C _{6 to} C ₂₀ acrylate) in 100% by weight of 15 to 55. % By weight
The aromatic polycarbonate resin composition according to any one of 1 to 3. 5. The aromatic polycarbonate resin composition according to any one of claims 1 to 4, wherein the proportion of methyl methacrylate in 100% by weight of the component C is 15 to 30% by weight. 6. The component B is a fibrous inorganic filler having an aspect ratio of 3 or more and an average fiber length of 30 to 1000 μm, and an aspect ratio of 3 or more and an average particle size of 20 to 600.
at least 1 selected from plate-like inorganic fillers having a size of μm
The reinforced aromatic polycarbonate resin composition according to any one of claims 1 to 5, which is a kind of inorganic filler. 7. The component B is at least one inorganic filler selected from glass fiber, glass milled fiber, glass flake, carbon fiber and metal-coated carbon fiber. The reinforced aromatic polycarbonate resin composition described. 8. A molded article having a boss portion formed from the reinforced aromatic polycarbonate resin composition according to any one of claims 1 to 7.