JP2010083983A - Flame retardant aromatic polycarbonate resin composition and electrical and electronic parts composed thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition which excels in flame retardancy and drip-proofness during burning and has high mechanical strengths. <P>SOLUTION: The resin composition includes, based on 100 pts.wt. polycarbonate resin (A), 5-100 pts.wt. fibrous reinforming material (B), 0.01-1 pt.wt. metal salt compound (C) selected from the group consisting of alkali metal salts and alkaline earth metal salts, 0.01-1 pt.wt. fluoropolymer (D), and 0.1-7.5 pts.wt. polyorganosiloxane (E), provided that the polyorganosiloxane (E) has a siloxane unit (T unit) of formula (3) in an amount of not less than 50 mol% of all siloxane units constituting the polysiloxane skeletal chain and an aryl group among the organic groups directly bonded to the silicon atom or bonded to the silicon atom through an oxygen atom in an amount of not less than 80 mol%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to an aromatic polycarbonate resin composition, and more particularly to an aromatic polycarbonate resin composition having excellent flame retardancy and flame extinguishing properties during combustion, and excellent mechanical strength such as rigidity and impact resistance.

Aromatic polycarbonate resins are resins with excellent heat resistance, mechanical properties, and electrical characteristics, and are widely used in automobile materials, electricity, electronic equipment materials, housing materials, and the like. In particular, the flame retardant polycarbonate resin composition is preferably used as a member of office equipment and information equipment such as computers, notebook computers, mobile phones, printers, and copying machines. In addition, when used for internal structural members of electrical, electronic equipment, OA, information equipment, etc., in order to increase rigidity and heat resistance, a material containing a reinforcing material is often used.

As means for imparting flame retardancy to the aromatic polycarbonate resin, attempts have been made to blend various flame retardants and flame retardant aids such as silicones, inorganics, and metal salts. Conventionally, halogen-based flame retardants have been widely used, but aromatic polycarbonate resin compositions containing this flame retardant corrode molding dies and generate harmful gases when incinerated for used products. Can be contaminated and its use has been avoided.

Phosphorus flame retardants are also used, but this improves the flame retardancy of the aromatic polycarbonate resin, but has the disadvantage of significantly reducing the mechanical properties such as heat resistance and impact resistance of the molded product, Its range of use is limited. In particular, when a reinforcing material is blended, the use of a phosphorus flame retardant is avoided, and a metal salt flame retardant is exclusively used.

Under such circumstances, in recent years, it has been actively studied to use a silicone-based flame retardant as a flame retardant that does not generate harmful gas at the time of fire or incineration and has a low environmental load.

Silicone (polyorganosiloxane) is represented by the following formulas (2) to (4), and an organic group bonded to a silicon atom by a silicon-carbon bond has two D units, one T unit, and zero It is a polymer having a polysiloxane skeleton chain composed of units selected from three types of siloxane units of Q units. In addition, the organic group couple | bonded with a silicon atom by the silicon-carbon bond shown by following formula (1) at the terminal may be sealed by three M units.

In these formulas, R represents an organic group. In general, R is a hydrocarbon group, usually an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or the like, but a methyl group or a phenyl group Often.

Patent Document 1 discloses a polyorganosiloxane having a T unit of 80 mol% or more, in particular, a polyorganosiloxane having a molecular weight of 2000 to 6000, 80 mol% or more of the organic group is a phenyl group, and the remainder is a methyl group. It is described to be used as a flame retardant.
Patent Document 2 describes that a polyorganosiloxane containing a D unit and a T unit, having an average molecular weight of 10,000 to 270,000 and having an organic group of a methyl group and a phenyl group as a silicone flame retardant.

Patent Document 3 describes that a polyorganosiloxane containing a phenyl group and an alkoxy group as an organic group is used as a flame retardant for a resin having an aromatic ring.
In Patent Document 4, a polyorganosiloxane composed of M units and Q units and a Group 2 metal salt are used in combination in order to impart a high degree of flame retardancy that cannot be obtained with silicone flame retardants alone to thermoplastic resins. Is described.

Patent Document 5 contains a branched polyorganosiloxane containing T units and M units, having a hydroxyl group content of 3% by weight or less, an average molecular weight of 300 to 50000, and a softening point of 100 ° C. or higher, and an alkali of an organic acid or an ester thereof. (Earth) It is described that an aromatic polycarbonate resin is made flame retardant in combination with a metal salt.
Patent Document 6 contains a polyorganosiloxane having an organic group composed of an aromatic hydrocarbon group and an aliphatic hydrocarbon group and an aromatic hydrocarbon group of 40 mol% or more, and an impact modifier such as a rubber component. It describes use as a flame retardant for aromatic polycarbonate resins.

Japanese Examined Patent Publication No. 62-60421 Japanese Patent No. 3240972 JP-A-11-222559 Japanese Patent Publication No. 3-48947 Japanese Patent No. 3439710 JP 2001-200152 A

However, the conventionally known flame retarding methods still have a problem that sufficient flame retardancy cannot be obtained yet or the mechanical properties inherent to the aromatic polycarbonate resin are impaired. Moreover, the aromatic polycarbonate resin which mix | blended the fibrous reinforcement material in order to improve mechanical strength is generally difficult to flame-retardant compared with the thing which does not mix | blend a reinforcement material. For example, fibrous reinforcements have a candle effect and therefore tend to significantly increase the burning time, making it difficult to impart stable flame retardancy.

The present invention intends to provide an aromatic polycarbonate resin composition having excellent mechanical properties and further flame retardancy, particularly remarkable flame-retarding properties, by flame retarding with a specific flame retardant. .

The aromatic polycarbonate resin composition according to the present invention is composed of 5 to 100 parts by weight of a fibrous reinforcing material (B), an alkali metal salt and an alkaline earth metal salt with respect to 100 parts by weight of the aromatic polycarbonate resin (A). Metal salt compound (C) selected from 0.01 to 1 part by weight, fluoropolymer (D) 0.01 to 1 part by weight, and polyorganosiloxane (E) 0.1 to 7.5 parts by weight (provided that In this, the siloxane unit (T unit) represented by the following formula (3) occupies 50 mol% or more of the total siloxane units forming the polysiloxane skeleton chain, and directly or through an oxygen atom to the silicon atom. The proportion of the aryl group in the organic group bonded is 80 mol% or more.).

In the formula, R is an organic group, and is preferably selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

The flame-retardant aromatic polycarbonate resin composition according to the present invention has sufficient flame resistance even when it is a thin-walled resin molded product without impairing the excellent mechanical, thermal, and electrical properties of the aromatic polycarbonate resin. In particular, it has anti-inflammatory properties. Therefore, this resin composition can be suitably used for a wide range of applications.

Hereinafter, the present invention will be described in detail. In the present specification, “to” includes numerical values described before and after the lower limit value and the upper limit value. Further, the “group” may further have a substituent without departing from the gist of the present invention.

Aromatic polycarbonate resin (A)
The aromatic polycarbonate resin is a thermoplastic resin that is industrially manufactured in large quantities as is well known. This is generally produced by an interfacial polymerization method in which an aromatic dihydroxy compound is used as a raw material and phosgene is reacted with this, or a transesterification method in which a carbonate is reacted. In the present invention, any of the production methods is used. be able to.

The viscosity average molecular weight [Mv] of the aromatic polycarbonate resin may be usually 10,000 or more, but preferably 16,000 or more, particularly 18000 or more. In general, a high molecular weight is used for applications requiring high mechanical strength. The upper limit of the molecular weight is preferably 40000 or less, particularly 30000 or less from the viewpoint of ensuring the fluidity of the resin composition so that the molding process can be easily performed. When several aromatic polycarbonate resins are used in combination, the molecular weight of each resin may be outside the above range.

For the viscosity average molecular weight, methylene chloride was used as a solvent, an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. was obtained using an Ubbelohde viscometer, and Schnell's viscosity formula η = 1.23 × 10 ^−4. It is a value calculated from M ^0.83 .

2,2-bis (4-hydroxyphenyl) propane (= bisphenol A) is most commonly used as an aromatic dihydroxy compound as a raw material for the aromatic polycarbonate resin, but bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) Propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4-dihydroxyphenyl sulfide, hydroquinone, resorcin, 4,4-dihydroxydiphenyl, etc. Used.

In the present invention, it is preferable to use an aromatic polycarbonate resin using a bis (4-hydroxyphenyl) compound as a raw material. Particularly preferred from the viewpoint of impact resistance is an aromatic polycarbonate resin produced by using a small amount of bisphenol A or another dihydroxy compound in combination therewith.

In the production of an aromatic polycarbonate resin, as is well known, a molecular weight regulator is added to adjust the molecular weight to a desired range, a polyfunctional compound is added to form a branched structure, or a terminal blocking agent is used. The terminal hydroxyl group concentration may be adjusted, but those obtained by these methods can also be used in the present invention. Examples of the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group such as m-methylphenol, p-methylphenol, pt-butylphenol, and p-long chain alkylphenol. Examples of the end capping agent include monovalent phenols and carboxylic acids. In this case, the terminal hydroxyl group concentration should not be lower than 10 ppm, and is preferably not lower than 30 ppm, particularly 40 ppm. The terminal hydroxyl group concentration is determined by a colorimetric method (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.

Polyfunctional compounds include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol) and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferably used.

The aromatic polycarbonate resin having a branched structure generally has a structural viscosity index N of 1.2 or more, and this resin has an effect of improving a dripping prevention effect (an effect of preventing dripping of a molten resin during combustion). The structural viscosity index N is a numerical value described on pages 15 to 16 of “Rheology for chemists” by Shigeharu Onoki.

The terminal hydroxyl group concentration of the aromatic polycarbonate resin used in the present invention is 1000 ppm or less, preferably 800 ppm or less, particularly preferably 600 ppm or less. When the terminal hydroxyl group concentration is high, the residence heat stability and color tone of the finally obtained resin composition tend to be lowered.

The aromatic polycarbonate resin may be a single resin or a mixture of several resins having different compositions, molecular weights, structures, and the like. For example, an oligomer may be used as part of the aromatic polycarbonate in order to improve the fluidity of the resin composition and the appearance of the molded product obtained therefrom. In this case, the viscosity average molecular weight [Mv] of the oligomer is preferably 1500 to 9500, and particularly preferably 2000 to 9000. The oligomer is preferably used in an amount of 30% by weight or less of the aromatic polycarbonate resin.

As the aromatic polycarbonate resin, a so-called material recycled recycled resin can also be used. Examples of the recycled material include optical recording media such as optical disks, light guide plates, vehicle window glass and headlamp lenses, vehicle transparent members such as windshields, and building materials such as beverage containers, eyeglass lenses, and corrugated plates. Furthermore, defective products, sprues, runners and the like at the time of molding are also included. Since the recycled resin is highly likely to have undergone deterioration such as heat deterioration and aging deterioration, if the amount used is large, the color tone and mechanical properties of the resin composition may decrease. Therefore, the amount used is preferably 80% by weight or less, particularly preferably 50% by weight or less of the whole aromatic polycarbonate resin.

Fibrous reinforcement (B)
Examples of the fibrous reinforcing material include glass fiber, carbon fiber, various metal fibers, whiskers, and the like that are used as a reinforcing material for thermoplastic resins, and it is preferable to use glass fiber or carbon fiber. By blending the fibrous reinforcing material, it is possible to obtain a resin composition that gives a molded product having high mechanical strength required for electrical, electronic equipment, OA equipment and the like. The diameter of the fibrous reinforcing material is 1 to 100 μm, preferably 2 to 50 μm, since it is not flexible when it is thick and it is difficult to obtain a thin one less than 1 μm. Usually, those having an average diameter of 3 to 30 μm, particularly 5 to 20 μm are used because they are easily available and have a great effect as a reinforcing material.

The length of the fibrous reinforcing material is preferably 0.1 mm or more from the viewpoint of the reinforcing effect. The upper limit of the length is usually 20 mm, and even when a length longer than this is used, it is usually broken and shortened when preparing a resin composition by melt-kneading. Preferably, an average length of 0.3 to 5 mm is used. A fibrous reinforcing material is usually used as a chopped strand obtained by cutting a number of these fibers into a predetermined length. In addition, since mixing | blending of carbon fiber provides electroconductivity to a resin composition, a glass fiber is used when a high resistance resin composition is desired.

The fibrous reinforcing material is blended in an amount of 5 to 100 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A). If the blending amount is less than 5 parts by weight, the reinforcing effect is small. Conversely, if it exceeds 100 parts by weight, mechanical properties such as impact resistance of the resin composition are lowered. A preferable blending amount of the fibrous reinforcing material is 10 to 70 parts by weight, particularly 15 to 50 parts by weight.

Metal salt compound (C) selected from the group consisting of alkali metal salts and alkaline earth metal salts
The compounding of the metal salt compound (C) has an effect of improving the flame retardancy of the resin composition. The metal salt compound may be an organic metal salt compound or an inorganic metal salt compound, but an organic metal salt compound is preferred in terms of good dispersibility in an aromatic polycarbonate resin. For example, metal salt compounds such as organic sulfonic acid metal salt compounds, carboxylic acid metal salt compounds, organic borate metal salt compounds, and organic phosphate metal salt compounds are used. Among these, an organic sulfonic acid metal salt compound is preferable from the viewpoint of the thermal stability of the finally obtained resin composition.

As the organic sulfonic acid metal salt compound, any of lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt, magnesium salt, calcium salt, strontium salt and barium salt of organic sulfonic acid can be used. A salt or a cesium salt is preferably used.

Such as diphenyl sulfone-3,3 ^'- disulfonic acid dipotassium, potassium diphenylsulfone-3-sulfonate, sodium benzene sulfonate, (branched) sodium dodecylbenzenesulfonate, sodium trichlorobenzene sulfonate, potassium trichlorobenzene sulfonate, benzenesulfonate Potassium acetate, cesium benzenesulfonate, potassium styrenesulfonate, cesium styrenesulfonate, potassium polystyrenesulfonate, sodium polystyrenesulfonate, cesium polystyrenesulfonate, sodium paratoluenesulfonate, potassium paratoluenesulfonate, cesium paratoluenesulfonate , (Branched) potassium dodecylbenzenesulfonate, (branched) cesium dodecylbenzenesulfonate, trichlorobe Such Zensuruhon cesium, alkali metal salts of aromatic sulfonic acids having at least one aromatic group is used in the molecule.

Further, at least in the molecule, such as magnesium paratoluenesulfonate, calcium paratoluenesulfonate, strontium paratoluenesulfonate, barium paratoluenesulfonate, magnesium (branched) dodecylbenzenesulfonate, calcium (branched) dodecylbenzenesulfonate Alkaline earth salts of aromatic sulfonic acids having one aromatic group are also used.

Further, it is preferable to use a fluorine-containing sulfonate other than the aromatic sulfonate, that is, one having at least one C—F bond. For example, potassium perfluorobutane sulfonate, lithium perfluorobutane sulfonate, sodium perfluorobutane sulfonate, cesium perfluorobutane sulfonate, magnesium perfluorobutane sulfonate, calcium perfluorobutane sulfonate, barium perfluorobutane sulfonate, Alkali metal salts and alkaline earth metal salts of fluoroalkylsulfonic acids having 1 to 4 carbon atoms such as calcium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, and barium trifluoromethanesulfonate are used.

These, diphenyl sulfone-3,3 ^'- disulfonic acid dipotassium, potassium diphenylsulfone-3-sulfonate, sodium paratoluene sulfonate, potassium p-toluenesulfonic acid, to use potassium perfluorobutane sulfonic acid. Some metal salt compounds may be used in combination.

The compounding quantity of a metal salt compound (C) is 0.01-1 weight part with respect to 100 weight part of aromatic polycarbonate resin, Preferably it is 0.05-0.5 weight part. If the blending amount is small, the flame retardancy of the resin composition becomes insufficient. On the other hand, if the amount is too large, the thermal stability may be deteriorated, the appearance of a molded product obtained from the resin composition may be poor, and the mechanical strength may be decreased. The most preferable blending amount is 0.05 to 0.4 parts by weight, particularly 0.07 to 0.35 parts by weight.

Fluoropolymer (D)
The blending of the fluoropolymer (D) improves the flame retardancy and particularly improves the dripping prevention property during combustion. In addition, the ignition resistance is improved, and the fire extinguishing property is also improved by a synergistic action with the metal salt compound (C). As fluoropolymers, those conventionally used for this purpose can be used. Fluoroethylene resins such as difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, etc. It is preferred to use (co) polymerization of Most preferred is a tetrafluoroethylene resin, and among these, those having fibril-forming ability are preferred.

Examples of commercially available fluoroethylene resins having fibril forming ability include Teflon (registered trademark) 6J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Polyflon F201L and Polyflon F103 manufactured by Daikin Chemical Industries. Examples of the aqueous dispersion of fluoroethylene resin include Teflon (registered trademark) 30J manufactured by Mitsui DuPont Fluorochemical Co., Ltd. and Fullon D-1 manufactured by Daikin Chemical Industries. As the fluoropolymer, a fluoroethylene resin having a multilayer structure formed by polymerizing a vinyl monomer such as METABRENE A-3800 manufactured by Mitsubishi Rayon Co., Ltd. may be used.

The compounding quantity of a fluoropolymer (D) is 0.01-1 weight part with respect to 100 weight part of polycarbonate resin (A), Preferably it is 0.05-0.7 weight part. If the blending amount is small, the flame retardancy of the resin composition becomes insufficient. On the other hand, if the amount is too large, the appearance of the molded product obtained from the resin composition is deteriorated and the mechanical strength is lowered. The most preferred amount is 0.1 to 0.7 parts by weight, particularly 0.15 to 0.5 parts by weight.

Polyorganosiloxane (E)
The polyorganosiloxane used in the present invention is a polysiloxane skeleton composed of one or more siloxane units selected from the group consisting of D units, T units and Q units represented by the following formulas (2) to (4). A polymer having a chain. The terminal may be sealed with an M unit in which three organic groups are bonded to a silicon atom represented by the following formula (1) by a carbon-silicon bond.

In each of the above formulas, R is an organic group bonded to a silicon atom through a silicon-carbon bond. R is usually an alkyl group having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms such as a methyl group, an ethyl group or a butyl group; an alkenyl group having 2 to 12 carbon atoms, preferably 2 to 4 carbon atoms such as a vinyl group or an allyl group; A hydrocarbon group such as an aryl group having 6 to 12 carbon atoms such as a group, a tolyl group and a naphthyl group. The alkyl group or alkenyl group may be linear or branched. R is preferably an alkyl group or an aryl group, particularly a phenyl group.

The polyorganosiloxane used in the present invention is one in which 50 mol% or more, preferably 60 mol% or more of all siloxane units constituting the polyorganosiloxane skeleton are T units. Those having a small proportion of T units are easily decomposed during melt-kneading, and the flame retardancy of the resin composition is significantly reduced. The most preferable polyorganosiloxane used in the present invention is one having a T unit of 70 mol% or more, particularly 85 mol% or more.

The polyorganosiloxane used in the present invention has at least 80 mol% of organic groups bonded directly or through oxygen atoms (that is, forming Si—O—C bonds) to the silicon atoms of the siloxane units constituting the polyorganosiloxane. An aryl group, preferably a phenyl group. When the proportion of the aryl group is small, it is easily decomposed during kneading and is not compatible with the aromatic polycarbonate resin (A), so that the dispersibility in the resin composition is poor and the resin composition is difficult. Flammability becomes insufficient. The organic group other than the aryl group is preferably a methyl group. Among the polyorganosiloxanes, those in which the proportion of the aryl group in the organic group in which the T unit is bonded to Si directly or through an oxygen atom are 50 mol% or more, particularly 80 mol% or more are preferable. Most preferred as the polyorganosiloxane is one in which all of the organic groups bonded directly to the silicon atom or through the oxygen atom are aryl groups, particularly phenyl groups.

As the polyorganosiloxane (E), those having a weight average molecular weight of 500 or more and 300,000 or less are usually used. Preferably, those having a weight average molecular weight of 1000 or more, further 1500 or more and 100,000 or less are used. Those having a small weight average molecular weight are difficult to obtain, and the heat resistance of the resin composition is significantly reduced. On the contrary, if the weight average molecular weight is too large, the flame retardancy of the resin composition tends to be insufficient due to poor dispersibility in the resin composition, and the mechanical properties tend to decrease. The weight average molecular weight of the polyorganosiloxane (E) is most preferably 1700-20000, particularly 2000-15000. The weight average molecular weight is measured by GPC (gel permeation chromatography).

The oxygen atom bonded to the silicon atom of each siloxane unit forming the polyorganosiloxane forms an Si-O-Si bond or bonds with an alkyl group, alkenyl group, aryl group, hydrogen atom, etc. Group, alkenyloxy group, aryloxy group, hydroxyl group and the like are formed. As the alkyl group, those having 1 to 12 carbon atoms, particularly 1 to 4 carbon atoms such as methyl group, ethyl group, butyl group, and octyl group are preferable. As the alkenyl group, those having 2 to 12 carbon atoms, particularly 2 to 4 carbon atoms such as vinyl group, allyl group and 7-octenyl group are preferable. Of these, the most preferred is a methyl group. As the aryl group, those having 6 to 16 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group, particularly a phenyl group is preferable. The content of alkoxy groups, alkenyloxy groups and aryloxy groups in the polyorganosiloxane is preferably 10% by weight or less. When there are many these, a resin composition tends to gelatinize and there exists a possibility of causing the fall of the mechanical physical property of a resin composition.

The polyorganosiloxane preferably contains a silanol group. The content is usually 0.25% by weight or more, preferably 0.5% by weight or more, and particularly preferably 1% by weight or more. Although the exact action of the silanol group is unknown, it combines with polycarbonate resin during combustion to exhibit flame retardancy, and reacts with the fibrous reinforcement to improve adhesion, thereby improving the mechanical properties of the resin composition. It is thought to improve. However, if the silanol group content is too large, the mechanical properties such as impact resistance of the resin composition are unexpectedly lowered, so the content should be 10% by weight or less. Preferably, the silanol group content should be 7.5% by weight or less, in particular 5% by weight or less. From the viewpoint of achieving both flame retardancy and mechanical properties, the silanol group content is preferably 1.5 to 5% by weight, particularly preferably 1.5 to 4% by weight.

The compounding quantity of polyorganosiloxane (E) is 0.1-7.5 weight part with respect to 100 weight part of aromatic polycarbonate resin. If the blending amount is small, the flame retardancy of the resin composition becomes insufficient. On the contrary, when the blending amount is increased, appearance defects of the molded product obtained from the resin composition are likely to occur, and the mechanical strength and thermal stability may be lowered. The compounding amount of the polyorganosiloxane (E) is preferably 0.3 to 7.0 parts by weight, particularly preferably 0.5 to 6.0 parts by weight.

You may mix | blend another thermoplastic resin with the resin composition of this invention in the range which does not impair the physical property further. For example, polyester resin such as polyethylene terephthalate resin, polytetramethylene terephthalate resin, polybutylene terephthalate resin, polystyrene resin, high impact polystyrene resin, acrylonitrile-styrene copolymer, styrene resin such as acrylonitrile-butadiene-styrene copolymer can do. The blending of these resins generally improves the fluidity of the resin composition and the chemical resistance of the molded product obtained therefrom. The amount is 2 to 30 parts by weight, particularly 3 to 15 parts by weight, based on 100 parts by weight of the aromatic polycarbonate resin (A). When the blending amount is large, the heat resistance and mechanical strength of the molded product obtained from the resin composition tend to be lowered.

Moreover, you may mix | blend various conventional additives. For example, a heat stabilizer, an antioxidant, a release agent, an ultraviolet absorber, a dye / pigment, and the like can be blended. As the heat stabilizer, an organic phosphate compound or an organic phosphite compound is usually used. A hindered phenol compound is used as the antioxidant. As the mold release agent, aliphatic carboxylic acid, its ester, aliphatic hydrocarbon compound or the like is used. As the ultraviolet absorber, a benzotriazole compound, a benzophenone compound, a triazine compound, or the like is used.

The resin composition of the present invention can be prepared according to a conventional method for preparing a resin composition. Usually, the components (A) to (E) and various auxiliary agents blended as desired are mixed together and then melt-kneaded in a single or twin screw extruder. Also, the aromatic polycarbonate resin composition of the present invention can be prepared without mixing each component in advance or by mixing only a part of the components in advance and supplying the mixture to an extruder using a feeder and melt-kneading. it can. If desired, a master batch is prepared by melt-kneading a part of the polycarbonate resin (A) and a part of the other ingredients, and then the remaining polycarbonate resin (A) and other ingredients are added thereto. And may be melt-kneaded. For example, when a metal salt compound or polyorganosiloxane is previously melt-kneaded with an aromatic polycarbonate resin and other components are blended and melt-kneaded, a resin composition excellent in extrusion workability can be obtained. Moreover, in order to improve the dispersibility of a metal salt compound, it is also preferable to dissolve this in a solvent.

Manufacture of the molded article from the flame-retardant aromatic polycarbonate resin composition according to the present invention can be carried out by any method generally employed for molding thermoplastic resins. For example, an injection molding method, an ultra-high speed injection molding method, an injection compression molding method, a two-color molding method, a hollow molding method, a molding method using a heat insulating mold, an extrusion molding method, a foam molding method, a rotational molding method and the like can be mentioned. In addition, the molded product obtained by these methods is used as a part of an electric, electronic device, OA device, information terminal device, home appliance or the like. For example, display devices such as personal computers, game machines, TVs, mobile phones, battery packs, electronic notebooks and PDAs, electronic dictionaries, calculators, CD players, MD players, recording media drives and reading devices, liquid crystal projectors, printers, copiers It is suitably used for scanners, fax machines, etc. Particularly, it is suitably used for a camera or a lens barrel of a projector. Further, it is also suitably used for machine parts, vehicle parts, building parts, lighting equipment, containers, daily goods, and the like.

The present invention will be described more specifically with reference to the following examples. In the following description, “parts” is parts by weight.

<Preparation of resin pellet>
Among the components shown in Table 2, each component except the fibrous reinforcing material (B) was blended in the amounts shown in Tables 3 to 4, and mixed for 20 minutes with a tumbler. This mixture is supplied to a Nippon Steel Works extruder (TEX30HSST), and the fibrous reinforcing material (B) is side fed in the amounts shown in the table, under the conditions of a screw speed of 200 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 290 ° C. Kneaded and extruded into strands. This was cooled with water and pelletized using a pelletizer.

<Preparation of UL test specimen>
After the pellets obtained above were dried at 120 ° C. for 5 hours, using a J50-EP type injection molding machine manufactured by Nippon Steel Tsunasho, conditions of cylinder temperature 290 ° C., mold temperature 80 ° C., molding cycle 30 seconds And a test piece having a length of 125 mm, a width of 13 mm, and a thickness of 1 mm was molded.

<Preparation of ISO test piece>
After drying the pellets obtained above at 120 ° C for 5 hours, using SG-75MIII type injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. under the conditions of cylinder temperature 290 ° C and mold temperature 80 ° C, conform to ISO An ISO test piece was molded.

<Evaluation of flame retardancy>
The UL test piece prepared above is conditioned for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity, and then flame retardant according to the UL 94 test (combustion test of plastic materials for equipment parts). evaluated. The results are shown in Tables 3-4. This test is a method for evaluating the flame retardancy according to the following criteria from the after-flame time and drip property after the burner flame is brought into contact with the test piece held vertically for 10 seconds.

The after-flame time is the length of time that the specimen continues to burn in flame after releasing the burner. The cotton ignition by the drip is a test for examining whether or not the marking cotton located at about 300 mm from the lower end of the test piece is ignited by the dripping from the test piece. If any of the five samples did not satisfy the above criteria, NR (not rated) was determined as not satisfying V-2.

<Charpy impact strength test>
Using the ISO test piece prepared above, the Charpy impact strength with notch was measured according to ISO179. The results are shown in Tables 3-4. The unit is KJ / m ² .

<Bending modulus test>
It measured according to ISO178 using the ISO test piece produced above. The results are shown in Tables 3-4. The unit is MPa.

Claims (9)

0.1 to 100 parts by weight of the aromatic polycarbonate resin (A), 5 to 100 parts by weight of the fibrous reinforcing material (B), a metal salt compound (C) selected from the group consisting of an alkali metal salt and an alkaline earth metal salt; Flame retardancy characterized by containing 01 to 1.0 part by weight, fluoropolymer (D) 0.01 to 1.0 part by weight, and polyorganosiloxane (E) 0.1 to 7.5 part by weight Aromatic polycarbonate resin composition (however, in polyorganosiloxane (E), the siloxane unit (T unit) represented by the following formula (3) accounts for 50 mol% or more of the total siloxane units forming the polysiloxane skeleton chain) And the proportion of the aryl group in the total organic group bonded to the silicon atom directly or through the oxygen atom is 80 mol% or more).

(In the formula, R represents an organic group.) The flame retardant aromatic polycarbonate resin composition according to claim 1, wherein the fibrous reinforcing material (B) is a glass fiber. The flame retardant aromatic according to claim 1 or 2, wherein the metal salt compound (C) is an alkali metal salt of a sulfonic acid selected from the group consisting of a fluorine-containing alkylsulfonic acid and an aromatic sulfonic acid. Polycarbonate resin composition. The polyorganosiloxane (E) is one in which the proportion of T units in all siloxane units forming the polysiloxane skeleton chain is 85 mol% or more. Flame retardant aromatic polycarbonate resin composition. The flame-retardant aromatic polycarbonate resin according to any one of claims 1 to 4, wherein the polyorganosiloxane (E) has a silanol group (Si-OH) content of 5 wt% or less. Composition. 6. The difficulty according to claim 1, wherein in the polyorganosiloxane (E), 80 mol% or more of the organic groups bonded to silicon directly or through an oxygen atom are phenyl groups. Flammable aromatic polycarbonate resin composition. The content of the metal salt compound (C) is 0.05 to 0.5 parts by weight, and the content of the fluoropolymer (D) is 0.1 to 0.7 parts by weight. 6. The flame-retardant aromatic polycarbonate resin composition according to any one of 6 above. The flame retardancy according to any one of claims 1 to 7, wherein a flexural modulus by an ISO 178 test is 5000 MPa or more, and a flame retardancy by a UL94 vertical combustion test at a thickness of 1 mm is V-0. Aromatic polycarbonate resin composition. 9. An electric / electronic component obtained by injection-molding the flame-retardant aromatic polycarbonate resin composition according to any one of claims 1 to 8.