JP2001055500A - Flame retardant polycarbonate resin composition and molding thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition having satisfactory, impact resistance and rigidity while maintaining excellent flame retardancy and capable of molding moldings excellent in thermostability in flameproofing a polycarbonate with a non-halogen, non-phosphorus compound, and also to provide moldings using the same composition. SOLUTION: This flame retardant polycarbonate resin composition comprises 100 pts.wt. of a resin consisting of (A) 1-99 wt.% polycarbonate resin and (B) 1-99 wt.% styrene-based resin, (C) 0.01-5 pts.wt. of a polyfluoroolefin resin, (D) 1-100 pts.wt. of an inorganic filler, (E) 1-500 pts.wt. of a polycarbonate- polyorganosiloxane copolymer and/or (F) 0.1-10 pts.wt. of a functional group- containing silicone compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polycarbonate resin composition, and more particularly to a flame-retardant polycarbonate resin composition containing no halogen or phosphorus and containing a small amount of an additive. The present invention relates to a flame-retardant polycarbonate resin composition having excellent impact resistance, rigidity and thermal stability, and a molded article.

[0002]

2. Description of the Related Art Polycarbonate resins have excellent impact resistance, heat resistance, electrical characteristics, etc., and are used in electrical and electronic equipment such as OA (office automation) equipment, information and communication equipment, home electric equipment, automotive fields, and construction. It is widely used in various fields such as fields. Polycarbonate resins are generally self-extinguishing resins, but OA
There are fields that require a high degree of flame retardancy, mainly in the field of electrical and electronic devices such as devices, information and communication devices, and home appliances, and improvements have been made by adding various flame retardants.

As a method for improving the flame retardancy of a polycarbonate resin, halogen-based flame retardants such as halogenated bisphenol A and halogenated polycarbonate oligomer have been used together with a flame retardant auxiliary such as antimony oxide from the viewpoint of flame retardant efficiency. . However, from the viewpoints of recent safety and impact on the environment at the time of disposal and incineration, a flame retardant method using a halogen-free flame retardant is required from the market. As a non-halogen flame retardant, an organic phosphorus flame retardant, in particular, a polycarbonate resin composition containing an organic phosphate compound exhibits excellent flame retardancy and also acts as a plasticizer, and many methods have been proposed. I have.

[0004] In order to make a polycarbonate resin flame-retardant with a phosphate ester compound, it is necessary to add a relatively large amount of the phosphate ester compound. Further, polycarbonate resins have high molding temperatures and high melt viscosities, so that molding temperatures tend to be higher and higher in order to cope with thinner and larger moldings. For this reason, the phosphoric ester compound generally contributes to the flame retardancy, but may not always be sufficient in terms of the molding environment and the appearance of the molded product, such as mold corrosion and gas generation during molding. In addition, it has been pointed out that problems such as a decrease in impact strength and the occurrence of discoloration when the molded article is placed under heating or under high temperature and high humidity.
Furthermore, there remains a problem that it is difficult to attain recyclability in recent resource saving due to insufficient heat stability.

[0005] On the other hand, it is also known that a flame retardancy can be imparted to a polycarbonate resin by adding a silicone compound thereto without generating harmful gas during combustion. For example, (1) JP-A-10-139964 discloses a flame retardant comprising a silicone resin having a specific structure and a specific molecular weight. Also, (2) JP-A-51-45160, JP-A-1-318069, JP-A-6-306265, and JP-A-8-12
868, JP-A-8-295796, and JP-B-3-48947 also disclose flame-retardant polycarbonate resins using silicones. In the former (1), the level of flame retardancy is excellent to some extent. In the latter (2), silicones are not used alone as a flame retardant, but are used as exemplary compounds for the purpose of improving dripping resistance, or as other flame retardant additives. Is different from the former in that a flame retardant such as a phosphate ester compound or a Group 2 metal salt is essential.

Further, a flame-retardant resin composition comprising a polycarbonate-polyorganosiloxane copolymer-containing resin and a polycarbonate resin composition comprising polytetrafluoroethylene having fibril-forming ability is also known as the polycarbonate resin. (JP-A-8-81
620). This composition is an excellent composition exhibiting excellent flame retardancy in a specific range where the content of polyorganosiloxane is small. However, said (1)
With Japanese Patent Application Laid-Open No. Hei 10-139964, the flame retardancy is excellent, but the impact resistance and the moldability, which are characteristics of the polycarbonate resin, may be insufficient. It has been demanded.

[0007]

SUMMARY OF THE INVENTION Under the above-mentioned circumstances, the present invention provides a method for improving the moldability, impact resistance, and rigidity while maintaining excellent flame retardancy in flame retardation of a polycarbonate resin with a non-halogen / non-phosphorus compound. An object of the present invention is to provide a polycarbonate resin composition capable of forming a molded product that is satisfactory and has excellent thermal stability, and a molded product using the composition.

[0008]

Means for Solving the Problems In order to achieve the object of the present invention, the present inventors have studied the flame retardancy of a flame-retardant polycarbonate resin by using a silicone compound, and have investigated the impact resistance, thermal stability, moldability, etc. The improvement was seriously studied. As a result, the purpose of the present invention can be effectively achieved by selectively using a styrene-based resin, a specific fluorine-based resin, an inorganic filler, and a polycarbonate-polyorganosiloxane copolymer and / or a specific silicone compound. It has been found that the present invention can be achieved and the present invention has been completed.

That is, the gist of the present invention is as follows. 1. Resin 10 comprising (A) 1 to 99% by weight of a polycarbonate resin and (B) 1 to 99% by weight of a styrene resin.
(C) 0.01 to 5 parts by weight of a polyfluoroolefin resin, (D) 1 to 100 parts by weight of an inorganic filler, and (E) 1 to 500 parts by weight of a polycarbonate-polyorganosiloxane copolymer with respect to 0 parts by weight. And / or (F) a functional group-containing silicone compound in an amount of 0.1 to 10 parts by weight. 2. 2. The flame-retardant polycarbonate resin composition according to the above 1, wherein the silicone content derived from the component (E) and / or (F) is 0.3 to 10% by weight of the flame-retardant polycarbonate composition. 3. (D) The inorganic filler of the component has an average particle size of 0.2 to 20.
3. The flame-retardant polycarbonate resin composition according to the above 1 or 2, which is a talc of μm. 4. The functional group-containing silicone compound of the component (F) is represented by the following general formula (1): R ¹ aR ² bSiO _{(4-ab) / 2} (1) (wherein R ¹ is a functional group and R ² is carbon The hydrocarbon groups of Formulas 1 to 12, a and b are 0 <a ≦ 3, 0 ≦ b <3, 0 <a +
The numbers satisfy the relationship of b ≦ 3. The flame-retardant polycarbonate resin composition according to any one of the above items 1 to 3, which is an organopolysiloxane having a basic structure represented by the following formula: 5. (F) The flame-retardant polycarbonate resin composition according to any one of (1) to (4) above, wherein in the functional group-containing silicone compound of the component, the functional group is selected from an alkoxy group, a vinyl group, a hydrogen group, and an epoxy group. 6. (F) The functional group-containing silicone compound of the component, wherein the functional group is a methoxy group or a vinyl group.
The flame-retardant polycarbonate resin composition according to any one of the above. 7. The flame-retardant polycarbonate resin composition according to any one of the above items 1 to 6, wherein the polyfluoroolefin resin as the component (C) is polytetrafluoroethylene having a fibril-forming ability and an average molecular weight of 500,000 or more. 8. (A) The flame-retardant polycarbonate resin composition according to any one of the above items 1 to 7, wherein the viscosity average molecular weight of the polycarbonate resin as the component is 15,000 to 20,000. 9. A molded article comprising the flame-retardant polycarbonate resin composition according to any one of the above 1 to 8. 10. An injection-molded product which is a housing or a part of an electric / electronic device comprising the flame-retardant polycarbonate resin according to any one of the above items 1 to 8.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (A) Polycarbonate resin The polycarbonate resin (PC) as the component (A) constituting the flame-retardant polycarbonate resin composition of the present invention is not particularly limited, and various ones can be mentioned.
Usually, an aromatic polycarbonate produced by reacting a dihydric phenol with a carbonate precursor can be used. That is, a solution prepared by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method, that is, a reaction of a dihydric phenol with phosgene, or a transesterification method of a dihydric phenol with diphenyl carbonate is used. be able to.

As the dihydric phenol, various ones can be mentioned. In particular, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] and bis (4
-Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4 ′
-Dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, Screw (4-
(Hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone, and the like.

Particularly preferred dihydric phenols are those based on bis (hydroxyphenyl) alkanes, especially bisphenol A. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate. Specific examples include phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, and diethyl carbonate. In addition, examples of the dihydric phenol include hydroquinone, resorcin, and catechol. These dihydric phenols may be used alone or as a mixture of two or more.

The polycarbonate resin may have a branched structure. Examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′,
α "-tris (4-bidroxyphenyl) -1,3,5
-Triisopropylbenzene, phloroglysin, trimellitic acid, isatin bis (o-cresol) and the like. In order to control the molecular weight, phenol and p-
t-butylphenol, pt-octylphenol,
For example, p-cumylphenol is used.

The polycarbonate resin used in the present invention includes a bifunctional carboxylic acid such as terephthalic acid and the like.
Alternatively, a copolymer such as a polyester-polycarbonate resin obtained by polymerizing a polycarbonate in the presence of an ester precursor such as an ester-forming derivative thereof, or a mixture of various polycarbonate resins can be used.

The viscosity average molecular weight of the polycarbonate resin used in the present invention is usually from 10,000 to 50,000.
0, preferably 13,000 to 35,000, more preferably 15,000 to 20,000. This viscosity average molecular weight (Mv) was determined using an Ubbelohde viscometer.
The viscosity of the methylene chloride solution at 20 ° C. is measured, and the intrinsic viscosity [η] is determined from this, and is calculated by the following equation. [η] = 1.23 × 10 ⁻⁵ Mv ^0.83

(B) Styrene resin As the styrene resin, 20 to 100% by weight of a monovinyl aromatic monomer such as styrene and α-methylstyrene, and a vinyl cyanide monomer such as acrylonitrile and methacrylonitrile 0-60% by weight, and a monomer or monomer mixture comprising 0-50% by weight of another vinyl monomer such as maleimide and methyl (meth) acrylate copolymerizable therewith. Polymer. Examples of these polymers include polystyrene (GPPS) and acrylonitrile-styrene copolymer (AS resin).

As the styrene resin, a rubber-modified styrene resin can be preferably used. The rubber-modified styrene resin is preferably an impact-resistant styrene resin obtained by graft-polymerizing at least a styrene monomer onto rubber. Examples of the rubber-modified styrene-based resin include impact-resistant polystyrene (HIPS) in which styrene is polymerized in rubber such as polybutadiene, ABS resin in which acrylonitrile and styrene are polymerized in polybutadiene, and MBS in which methyl methacrylate and styrene are polymerized in polybutadiene. Resin, rubber-modified styrenic resin,
Two or more of them can be used in combination, and can also be used as a mixture with the above-mentioned rubber-unmodified styrene resin.

The content of rubber in the rubber-modified styrenic resin is, for example, 2 to 50% by weight, preferably 5 to 30% by weight, particularly 5 to 15% by weight. 2% by weight of rubber
When the amount is less than 50%, the impact resistance becomes insufficient. When the amount exceeds 50% by weight, problems such as a decrease in thermal stability, a decrease in melt fluidity, generation of a gel, and coloring may occur.
Specific examples of the rubber include a rubber polymer containing polybutadiene, acrylate and / or methacrylate, styrene-butadiene-styrene rubber (SB
S), styrene / butadiene rubber (SBR), butadiene / acryl rubber, isoprene / rubber, isoprene / styrene rubber, isoprene / acryl rubber, ethylene / propylene rubber, and the like. Among them, particularly preferred is polybutadiene. The polybutadiene used here is a low cis polybutadiene (eg, 1,2
1 to 30 mol% of vinyl bonds and 3 to 1,4-cis bonds
0-42 mol%), high cis polybutadiene (for example, 20 mol% or less of 1,2-vinyl bond, 1,4
-Containing at least 78 mol% of a cis bond), or a mixture thereof.
The flame retardant polycarbonate resin composition of the present invention improves the melt fluidity of the resin composition by blending a styrene resin with the polycarbonate resin. Here, the compounding ratio of both resins is (A) 1 to 99% by weight of polycarbonate resin, preferably 50 to 90% by weight, and (B)
1 to 99% by weight of styrene resin, preferably 10 to 5%
0% by weight.

(C) Polyfluoroolefin Resin The flame-retardant polycarbonate resin composition of the present invention further uses a polyfluoroolefin resin for the purpose of preventing dripping during melting in a flame retardancy test or the like.
Here, the polyfluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure, for example, a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, or a tetrafluoroethylene copolymer. It is a copolymer of ethylene and an ethylene monomer containing no fluorine. Preferably, it is polytetrafluoroethylene (PTFE), and its average molecular weight is preferably 500,000 or more, and particularly preferably 500,000 to 10,000.
1,000,000. As the polytetrafluoroethylene that can be used in the present invention, all types currently known can be used.

When polytetrafluoroethylene having fibril-forming ability is used, higher anti-dripping property can be imparted. Polytetrafluoroethylene (PTF) having fibril-forming ability
E) is not particularly limited, and includes, for example, those classified into type 3 in the ASTM standard. Specific examples thereof include Teflon 6-J (manufactured by DuPont Fluorochemicals, Mitsui), polyflon D-1, polyflon F-103, polyflon F201 (manufactured by Daikin Industries, Ltd.), and CD076 (manufactured by Asahi Glass Fluoropolymers). Can be mentioned.

Other than those classified into the above-mentioned type 3, for example, Algoflon F5 (manufactured by Montefluos), polyflon MPA, polyflon FA-100 (manufactured by Daikin Industries, Ltd.) and the like can be mentioned. These polytetrafluoroethylene (PTFE) may be used alone or in combination of two or more. Polytetrafluoroethylene (PTFE) having a fibril-forming ability as described above is prepared by, for example, adding tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium, or ammonium peroxydisulfide under a pressure of 1 to 100 psi, at a temperature of 0 ° C. To 200 ° C, preferably 20 to 100 ° C
And polymerized by

Here, the content of the polyfluoroolefin resin is 0.01 to 5 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the resin composed of the above (A) and (B).
05 to 3 parts by weight. Here, if this amount is too small, the effect of preventing the molten dripping in the intended flame retardancy is not enough, if too large, there is no improvement in the effect corresponding to this.
It has an adverse effect on impact resistance and appearance of molded products. Therefore,
Depending on the degree of flame retardancy required for each molded article, for example, V-0, V-1, V-2 of UL-94, etc., it can be appropriately determined in consideration of the amount of other components used. it can.

(D) Inorganic Filler In the present invention, the inorganic filler of the component (D) is necessary for improving the rigidity and flame retardancy of the molded article. Here, as the inorganic filler, talc, mica, kaolin,
Diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, glass fiber, carbon fiber, potassium titanate fiber and the like can be mentioned. Above all, plate-like talc,
Mica and the like and fibrous fillers are preferred. As the talc, a hydrated silicate of magnesium, which is generally commercially available, can be used. The average particle size of the inorganic filler such as talc is 0.1 to 50 μm, preferably 0.2 to 20 μm. These inorganic fillers,
In particular, by adding talc, the addition amount of the silicone compound can be sometimes reduced in addition to the effect of improving the rigidity.

Here, the content of the inorganic filler is 1 to 100 parts by weight of the resin composed of the components (A) and (B).
100 parts by weight, preferably 2 to 70 parts by weight. Here, if the amount is too small, the desired rigidity, the effect of improving the flame retardancy is not sufficient, if too large, the impact resistance, the melt fluidity is reduced, the thickness of the molded product, the resin flow length, etc. It can be appropriately determined in consideration of the required properties and moldability of the molded article. In the present invention, the components (E) and / or (F) are contained in the components (A) to (D).

(E) Polycarbonate-polyorganosiloxane copolymer The polycarbonate-polyorganosiloxane copolymer (hereinafter sometimes abbreviated as PC-polyorganosiloxane copolymer) as the component (E) of the present invention is as follows. It is composed of a polycarbonate part and a polyorganosiloxane part. For example, a polyorganosiloxane (polydimethylsiloxane, polydiethylenesiloxane, polymethylphenylsiloxane, etc.) having a reactive group at the terminal constituting the polycarbonate oligomer and the polyorganosiloxane part Is dissolved in a solvent such as methylene chloride, an aqueous sodium hydroxide solution of bisphenol A is added, and an interfacial polycondensation reaction is performed using a catalyst such as triethylamine.

The degree of polymerization of the polycarbonate part of the PC-polyorganosiloxane copolymer is preferably 3 to 100, and the degree of polymerization of the polydimethylsiloxane part is preferably about 2 to 500. The content of polydimethylsiloxane in the PC-polyorganosiloxane copolymer is usually in the range of 0.5 to 30% by weight, preferably 1 to 20% by weight. The viscosity average molecular weight of the polycarbonate resin, PC-polyorganosiloxane copolymer and the like used in the present invention is usually 5,000 to 100,000, preferably 10,000 to 30,000, particularly preferably 1 to 30,000.
It is 2,000-30,000. Here, these viscosity average molecular weights (Mv) can be determined in the same manner as the above-mentioned polycarbonate resin. PC- of this (E) component
The content of the polyorganosiloxane copolymer is 1 to 100 parts by weight of the resin composed of the components (A) and (B).
500 parts by weight, preferably 5 to 450 parts by weight. If the amount is too small, the effect of improving the flame retardancy may not be obtained, and if it is too large, the effect corresponding to the amount may not be obtained.

(F) Functional Group-Containing Silicone Compound The functional group-containing silicone compound which is the component (F) of the present invention is a (poly) organosiloxane having a functional group and has a skeleton represented by the formula R ¹ aR ² bSiO
_{(4-ab ) / 2} [R ¹ is a functional group, R ² is a hydrocarbon group having 1 to 12 carbon atoms, 0 <a ≦ 3, 0 ≦ b <3, 0 <a + b ≦ 3]
And a polymer having a basic structure represented by
The functional group contains an alkoxy group, an aryloxy, a polyoxyalkylene group, a hydrogen group, a hydroxyl group, a carboxyl group, a silanol group, an amino group, a mercapto group, an epoxy group, a vinyl group, and the like. Among them, an alkoxy group, a hydrogen group, a hydroxyl group, and an epoxy group are preferable, and a methoxy group and a vinyl group are particularly preferable.

As these functional groups, a silicone compound having a plurality of functional groups and a silicone compound having different functional groups can be used in combination. The silicone compound having this functional group has a functional group (R ¹ ) / hydrocarbon group (R ² ) of usually about 0.1 to 3, preferably about 0.3 to ² . These silicone compounds are liquids, powders and the like, but those having good dispersibility in melt kneading are preferred. For example, the viscosity at room temperature is 10 to 50.
A liquid of about 000 cst can be exemplified. The polycarbonate resin composition of the present invention is characterized in that even when the silicone compound is in a liquid state, it is uniformly dispersed in the composition and bleeds less during molding or on the surface of the molded article.

The content of the functional group-containing silicone compound of the component (F) is the same as that of the resin 1 comprising the components (A) and (B).
The amount is 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on 00 parts by weight. If the amount is too small, the effect of improving the flame retardancy may not be obtained, and if it is too large, the effect corresponding to the amount may not be obtained. In the present invention, the content of the silicone derived from the component (E) and / or the component (F) is from 0.3 to 1 in the flame-retardant polycarbonate resin composition.
It is preferable to adjust so as to be 0% by weight. further,
Preferably it is 0.5 to 5% by weight. If it is less than 0.3% by weight, the effect of improving the flame retardancy may be small, and
If the content exceeds the weight percentage, impact resistance and heat resistance may be reduced.

The flame-retardant polycarbonate resin composition of the present invention contains the following components (A) to (F) for the purpose of improving moldability, impact resistance, appearance, weather resistance and rigidity. Other synthetic resins and elastomers can be contained. Further, an additive component commonly used in a thermoplastic resin can be contained as necessary. For example, phenol-based, phosphorus-based, sulfur-based antioxidants, antistatic agents, polyamide polyether block copolymers (providing permanent antistatic properties), benzotriazole-based and benzophenone-based ultraviolet absorbers, hindered amine-based light stabilizers (Weathering agent), plasticizer, antibacterial agent, compatibilizer, coloring agent (dye, pigment) and the like. The amount of the optional component is not particularly limited as long as the properties of the flame-retardant polycarbonate resin composition of the present invention are maintained.

Next, a method for producing the flame-retardant polycarbonate resin composition of the present invention will be described. The flame-retardant polycarbonate resin composition of the present invention comprises the above components (A) to
It is obtained by blending (F) at the above ratio and various optional components used as needed at an appropriate ratio and kneading. The compounding and kneading at this time are preliminarily mixed with a commonly used device, for example, a ribbon blender, a drum tumbler, etc., and a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi-screw extrusion. Can be carried out by using a machine, a kneader or the like. The heating temperature during kneading is usually 24
It is appropriately selected in the range of 0 to 300 ° C. As the melt-kneading molding, it is preferable to use an extruder, particularly a vent-type extruder. The components other than the polycarbonate resin may be previously melt-kneaded with the polycarbonate resin or another thermoplastic resin, that is, added as a master batch.

The flame-retardant polycarbonate resin composition of the present invention can be prepared by injection molding, injection compression molding, extrusion molding, blow molding, press molding using the above-mentioned melt-kneading molding machine or the obtained pellet as a raw material. Various molded products can be manufactured by a molding method, a vacuum molding method, a foam molding method, or the like. However, a pellet-shaped molding raw material is produced by the above-mentioned melt-kneading method, and then the pellets can be used particularly suitably for production of an injection molded product by injection molding or injection compression molding. In addition, as the injection molding method,
Gas injection molding may be employed to prevent sink marks on the appearance or to reduce the weight.

Molded articles obtained from the flame-retardant polycarbonate resin composition of the present invention include copying machines, fax machines,
It is also used in other fields such as housings or parts of electric and electronic devices such as televisions, radios, tape recorders, video decks, personal computers, printers, telephones, information terminals, refrigerators, microwave ovens, and automobile parts.

[0034]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited thereto. Examples 1 to 5 and Comparative Examples 1 to 4 The components were blended at the ratios shown in Table 1 (the components (A) and (B) are in weight%, and the other components are resins composed of (A) and (B). 1
Shown in parts by weight relative to 00 parts by weight. And supplied to a vent-type twin-screw extruder (model: TEM35, manufactured by Toshiba Machine Co., Ltd.), melt-kneaded at 260 ° C., and pelletized. In addition,
In all Examples and Comparative Examples, 0.2 parts by weight of Irganox 1076 (manufactured by Ciba Specialty Chemicals) and 0.1 parts by weight of ADK STAB C (manufactured by Asahi Denka Kogyo) were added as antioxidants. . The obtained pellet was dried at 120 ° C. for 12 hours, and then injection molded at a molding temperature of 260 ° C. and a mold temperature of 80 ° C. to obtain a test piece. The performance was evaluated by various tests using the obtained test pieces, and the results are shown in Table 1.

The molding materials used and the performance evaluation methods are as follows. (A) Polycarbonate resin PC: Toughlon A1900 (manufactured by Idemitsu Petrochemical Co., Ltd.): bisphenol A polycarbonate resin, MI = 20 g /
10 minutes (300 ° C., 1.2 kg load), viscosity average molecular weight = 19,000 (B) Styrene resin HIPS: High impact polystyrene (HIPS): IDE
MITSU PS IT44 (manufactured by Idemitsu Petrochemical Co., Ltd.) Polybutadiene grafted with styrene, rubber content = 10% by weight, MI = 8 g / 10 min (200 ° C., 5
ABS: acrylonitrile butadiene styrene copolymer (ABS): DP-611 (manufactured by TECRIPOLYMER), M
(I = 2 g / 10 min) (C) Fluoroolefin resin PTFE: CD076 (manufactured by Asahi Glass Fluoropolymers)

(D) Inorganic filler Talc: FFR (manufactured by Asada Flour Milling Co., Ltd.), average particle size = 0.7 μm
m GF: 03MA419 (manufactured by Asahi Fiber Glass Co., Ltd.), diameter = 13 μm, length = 3 mm (E) PC-polyorganosiloxane copolymer PC-PDMS: bisphenol A-polydimethylsiloxane (PDMS) copolymer, MI = 45 g / 10 min (300 ° C., 1.2 kg load), PDMS chain length (n = 3
0, PDMS content = 4% by weight, viscosity average molecular weight = 2
000 [Production Example 3-1 of JP-A-8-81620]
(Copolymer produced by (A1)) (F) Functional group-containing silicone compound Silicone-1: Vinyl group methoxy group-containing methylphenylsilicone, KR219 (manufactured by Shin-Etsu Chemical Co., Ltd.), viscosity = 18 cst Silicone-2: Methoxy group Containing dimethyl silicone,
KC-89 (Shin-Etsu Chemical Co., Ltd.), viscosity = 20 cst Silicone-3: dimethyl silicone, SH200 (Toray Dow Corning), viscosity = 350 cst

[Performance Evaluation Method] (1) Melt fluidity MI (melt index): based on JIS K7210. 260 ° C, 2.16 kg load (2) IZOD (Izod impact strength) According to ASTM D256, 23 ° C (1/8 inch wall thickness), unit: kJ / m ² (3) Flexural modulus According to ASTM D-790 (Test conditions: 23 ° C, 4
mm), unit: MPa (4) Retention heat stability The injection molding machine IS-45P is used to set the molding temperature to 300 ° C., and is retained in a cylinder for 20 minutes and then molded to a thickness of 3 mm (80 mm × 40 mm × 3 mm). ) Was prepared. The change in color tone of the prepared test piece was measured. JI
According to SH7103 (Yellowing degree test method), the hue (L, a, b) of the test piece before and after recycling was measured by a color difference meter and calculated as a color difference (ΔE). (5) Flame retardancy Complies with UL94 combustion test (test piece thickness: 1.5 mm,
2.5mm)

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

Table 1 shows the following. In Comparative Examples 1 and 4 having no component (D), the rigidity and the flame retardancy are poor. In Comparative Example 2 having no component (E) and no component (F),
Poor impact resistance, thermal stability and flame retardancy. Comparative Example 3 using a general silicone compound as the component (F) is inferior in rigidity, thermal stability and flame retardancy.

[0042]

Industrial Applicability The flame-retardant polycarbonate resin composition of the present invention is non-halogen / non-phosphorous, and has excellent flame-retardant properties by containing a small amount of additives.
Excellent impact resistance and thermal stability. Therefore, OA equipment,
It is expected that electric and electronic devices such as information devices and home electric appliances, and application fields such as automobile parts will be expanded.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C08L 27/12 C08L 27/12 27/18 27/18 83/04 83/04 83/10 83/10 / / B29K 25:00 69:00 83:00 105: 16 B29L 31:34 F term (reference) 4F071 AA22 AA26 AA27 AA50 AA67 AB16 AB24 AB26 AE07 AE17 AH12 BA01 BB05 4F206 AA13 AA16 AA28 AA28E AA33E AB11 AB16 AE10 A002 BC BC04X BC06X BC07X BC09X BD12Y BD15Y BD16Y BN14X BN15X CG00W CP03U CP06U CP09U CP10U CP12U CP17Z DE236 DG056 DJ036 DJ046 DJ056 FD016

Claims (10)

[Claims] 1. A polyfluoroolefin resin (C) in an amount of 0.01 to 5 parts by weight per 100 parts by weight of a resin composed of (A) 1 to 99% by weight of a polycarbonate resin and (B) 1 to 99% by weight of a styrene resin. Part, (D) inorganic filler 1 to 1
A flame-retardant polycarbonate resin composition containing 00 parts by weight and (E) 1 to 500 parts by weight of a polycarbonate-polyorganosiloxane copolymer and / or (F) 0.1 to 10 parts by weight of a functional group-containing silicone compound. 2. The flame retardant polycarbonate composition according to claim 2, wherein the silicone content derived from the component (E) and / or the component (F) is less than 0.1%.
The flame-retardant polycarbonate resin composition according to claim 1, wherein the content is 3 to 10% by weight. 3. The flame-retardant polycarbonate resin composition according to claim 1, wherein the inorganic filler as the component (D) is talc having an average particle size of 0.2 to 20 μm. 4. The functional group-containing silicone compound of the component (F) is represented by the following general formula (1): R ¹ aR ² bSiO _{(4-ab) / 2} (1) wherein R ¹ is a functional group , R ² is a hydrocarbon group having 1 to 12 carbon atoms, and a and b are 0 <a ≦ 3, 0 ≦ b <3, 0 <a +
The numbers satisfy the relationship of b ≦ 3. The flame-retardant polycarbonate resin composition according to any one of claims 1 to 3, which is an organopolysiloxane having a basic structure represented by the formula: 5. The flame-retardant polycarbonate according to claim 1, wherein the functional group in the functional group-containing silicone compound (F) is selected from an alkoxy group, a vinyl group, a hydrogen group, and an epoxy group. Resin composition. 6. The flame-retardant polycarbonate resin composition according to claim 1, wherein the functional group in the functional group-containing silicone compound (F) is a methoxy group or a vinyl group. 7. The polyfluoroolefin resin as component (C) has an average molecular weight of 500,0 having a fibril-forming ability.
2. A polytetrafluoroethylene having a molecular weight of at least 00.
7. The flame-retardant polycarbonate resin composition according to any one of items 1 to 6. 8. The flame-retardant polycarbonate resin composition according to claim 1, wherein the viscosity average molecular weight of the polycarbonate resin (A) is 15,000 to 20,000. 9. A molded article comprising the flame-retardant polycarbonate resin composition according to claim 1. 10. An injection-molded article which is a housing or a part of an electric / electronic device made of the flame-retardant polycarbonate resin according to claim 1.