WO2011024659A1 - Flame-retardant polycarbonate resin composition and moldings thereof - Google Patents

Abstract

Disclosed is a flame-retardant polycarbonate resin composition capable of providing moldings which exhibit excellent flame retardance, thermal conductivity, heat stability, mechanical characteristics, impact resistance, flow characteristics, and wettability even when the moldings have thicknesses of about 1.2 to 1.0mm and contain no silicone compound. Also disclosed are moldings of the same. A silicone-free flame-retardant polycarbonate resin composition which comprises (A) 100 parts by mass of a polycarbonate resin, (B) 30 to 70 parts by mass of artificial graphite, (C) 1 to 5 parts by mass of a fluorine-containing anti-drip agent, and (D) a flame retardant consisting of 0.15 to 0.73 part by mass of sodium p-toluenesulfonate and 0.15 to 0.25 part by mass of at least one compound selected from between potassium perfluorobutanesulfonate and potassium trifluoromethanesulfonate; and moldings of the composition.

Description

Flame retardant polycarbonate resin composition and molded body thereof

The present invention relates to a flame retardant polycarbonate resin composition and a molded body thereof. Specifically, a molded article having good flame retardancy even at a thickness of about 1.2 to 1.0 mm and excellent in thermal conductivity, thermal stability, mechanical characteristics, impact resistance, flow characteristics and wettability. The present invention relates to a flame retardant polycarbonate resin composition suitable for the electric / electronic field and the like, and a molded product thereof.

In product development in the electric and electronic fields, high-pixel processing and high-speed processing in digital cameras and digital video cameras, miniaturization of projectors, high-speed processing in personal computers and mobile devices, and use of LEDs for various light sources as countermeasures against heat Emphasis is placed.
Measures using heat dissipation circuits for metal parts have also been taken, but since the heat dissipation circuit becomes complicated in devices that are downsized, the resin housing and heat dissipation circuit can be integrated, and it has excellent thermal conductivity. In addition, a resin material having excellent mechanical strength as a housing is required.
Further, in a small electronic device, the casing and the chassis are required to be thin, and accordingly, the flame resistance is also required.

In order to obtain a resin composition excellent in thermal conductivity, it is known to contain specific graphite (see, for example, Patent Document 1). Further, for example, in Patent Document 2, in order to achieve good flame retardancy in addition to antistatic performance and the like, (A) 100 parts by mass of a thermoplastic resin, (B) 5 to 100 parts by mass of graphite having a specific particle size, (C) A flame-retardant resin composition comprising 0.001 to 1 part by mass of an alkali (earth) metal salt of an organic sulfonate is disclosed.
However, in Patent Document 2, evaluation is made only at a thickness of 2.5 mm in the flame retardancy evaluation. Further, in such a resin composition, even when natural graphite (flaky graphite) was used as graphite, UL94 vertical combustion (V test) at a thickness of 1.5 mm could not be obtained.
For example, in Patent Document 3, in order to achieve improvement in thermal stability, (A) 60 to 90 parts by mass of an aromatic polycarbonate resin and (B) 10 to 40 parts by mass of graphite, C) An aromatic polycarbonate resin composition comprising 0.001 to 5 parts by mass of a silane compound and / or a silicone compound having an amino group and / or an epoxy group is disclosed.
However, Patent Document 3 does not describe flame retardancy, and even such a resin composition does not provide sufficient flame retardancy at a thickness of about 1.5 mm required for a casing of an electronic device or the like. It is done.
For example, in Patent Document 4, a heat dissipating case in which a heating element is accommodated, which is composed of a thermoplastic resin [A] and a specific heat conductive filler [B], and heat conduction to 100 parts by mass of the thermoplastic resin [A]. A heat dissipating case made of a heat conductive resin composition having a filler [B] content of 10 to 1,000 parts by mass is disclosed.
However, in Patent Document 4, there is no description relating to flame retardancy required for a housing such as an electronic device, and since there is no addition of a flame retardant or an anti-drip agent, it does not have sufficient flame retardancy. Conceivable.
On the other hand, the prior art using polytetrafluoroethylene (PTFE) as an anti-drip agent is often intended for non-halogen flame retardant materials stipulated by various regulations and standards. Even if the addition amount of PTFE is widely taken, in the examples, the addition amount is almost 0.5% by mass or less of the whole resin composition (for example, see Patent Document 2).

JP 2007-31611 A JP 2006-273931 A JP 2007-126499 A JP 2008-31358 A

As described above, in the development of products in the electric / electronic field, there is a demand for a resin composition that gives a molded article excellent in flame retardancy, thermal conductivity, thermal stability, mechanical properties, impact resistance, etc. in a thin wall. Yes.
Moreover, when applying to a housing | casing etc. with the heat conductive resin composition which added the silicone compound, although coating is required, a coating property will fall by the influence of silicone.
Therefore, in the present invention, even if a silicone compound is not added, even if the thickness is about 1.2 to 1.0 mm, it has good flame retardancy, thermal conductivity, thermal stability, mechanical properties, impact resistance It aims at providing the flame-retardant polycarbonate resin composition which gives the molded object excellent in the property, the flow characteristic, and the wettability, and the molded object.

As a result of diligent investigations, the present inventors have found that a polycarbonate resin, artificial graphite, a fluorine-containing anti-dripping agent, and a flame retardant containing a specific organic sulfonic acid alkali metal salt in a specific ratio and not containing a silicone compound The present invention was completed with the resin composition.
That is, this invention provides the following flame-retardant polycarbonate resin composition and its molded object.

1. (A) 30 to 70 parts by mass of (B) artificial graphite, (C) 1 to 5 parts by mass of a fluorine-containing anti-dripping agent, and (D) sodium paratoluenesulfonate as a flame retardant with respect to 100 parts by mass of the polycarbonate resin. A flame-retardant polycarbonate resin composition containing 0.15 to 0.73 parts by mass and containing no silicone compound.
2. (A) 30 to 70 parts by mass of (B) artificial graphite, (C) 1 to 5 parts by mass of a fluorine-containing anti-dripping agent and (D) potassium perfluorobutanesulfonate as a flame retardant with respect to 100 parts by mass of the polycarbonate resin And a flame retardant polycarbonate resin composition containing 0.15 to 0.25 parts by mass of at least one selected from potassium trifluoromethanesulfonate and containing no silicone compound.
3. 3. The flame retardant polycarbonate resin composition according to 1 or 2 above, further comprising 0.001 to 1 part by mass of (E) an antioxidant with respect to 100 parts by mass of the polycarbonate resin.
4). 4. The flame retardant polycarbonate resin composition according to any one of the above 1 to 3, further comprising 0.3 to 2 parts by mass of (F) a release agent with respect to 100 parts by mass of the polycarbonate resin (A).
5. 5. A molded article using the flame retardant polycarbonate resin composition according to any one of 1 to 4 above.
6). 6. The molded product according to 5 above, which is a part for electrical / electronic equipment.
7). 6. The molded product according to 5 above, which is a chassis for electrical / electronic equipment.
8). 6. The molded product according to 5 above, which is a heat radiating component or a heat transfer component.

According to the present invention, even if it does not contain a silicone compound, it has a thickness of 1.2 to 1.V depending on the polycarbonate resin composition containing artificial graphite, a fluorine-containing anti-dripping agent, and a specific organic sulfonic acid alkali metal salt. Flame retardant polycarbonate resin composition which has good flame retardancy even at about 0 mm, and gives a molded article excellent in thermal conductivity, thermal stability, mechanical properties, impact resistance, flow properties and wettability, and molding thereof The body can be provided.

[Flame-retardant polycarbonate resin composition]
((A) Polycarbonate resin)
In the present invention, the polycarbonate resin as the component (A) preferably has a viscosity average molecular weight of 19,000 to 30,000 in order to obtain excellent impact resistance. From the viewpoint of moldability, the viscosity average molecular weight Is more preferably 19,000-27,000. Moreover, when mixing and using two or more types of polycarbonate resin, it is desirable to adjust and use the viscosity average molecular weight in the said range as (A) component whole.
The viscosity average molecular weight was determined by measuring the viscosity of the methylene chloride solution at 20 ° C. using an Ubbelohde viscometer, and determining the intrinsic viscosity [η] from this, [η] = 1.23 × 10 ⁻⁵ Mv ^0.83 It is a value calculated by the formula of

Moreover, it is preferable that it is an aromatic polycarbonate resin as (A) component, Usually, the various aromatic polycarbonate resin manufactured by reaction of bivalent phenol and a carbonate precursor can be used.
Various divalent phenols can be mentioned, and in particular, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 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) ether Bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide and bis (4-hydroxyphenyl) ketone. These dihydric phenols may be used alone or in combination of two or more.
Particularly preferred dihydric phenols are those based on bis (hydroxyphenyl) alkanes, especially bisphenol A or bisphenol A.

Examples of the carbonate precursor include carbonyl halide, carbonyl ester and haloformate, specifically phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate and diethyl carbonate.
The aromatic polycarbonate may have a branched structure, and 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, and isatin bis (o-cresol).

In the present invention, as the component (A), for example, a commercially available aromatic polycarbonate resin such as Teflon FN3000A, FN2600A, FN2500A, FN2200A, FN1900A, FN1700A, FN1500A (trade name, manufactured by Idemitsu Kosan Co., Ltd.) is used. be able to. These aromatic polycarbonate resins may be used alone or in admixture of two or more.

((B) Artificial graphite)
In the present invention, the resin composition can obtain thermal conductivity by containing artificial graphite as the component (B). Artificial graphite is obtained by molding and firing petroleum coke, etc., and further highly graphitized at ultra-high temperatures. Since artificial graphite is difficult to orient during molding, it is easy to obtain strength and has excellent mechanical strength. It can be a composition.
On the other hand, the object of the present invention is to obtain flame retardancy with a thin wall, and in addition to natural graphite, expanded graphite, spherical graphite, flake graphite obtained by pulverizing natural graphite, and the like, the above object of the present invention. Therefore, artificial graphite is used in the present invention.

The component (B) is not particularly limited as long as it is artificial graphite, but the average particle diameter (50% cumulative diameter) is preferably in the range of about 20 to 180 μm, more preferably in the range of 30 to 170 μm. . If the average particle size of the artificial graphite is in the range of about 20 to 180 μm, the impact strength of the molded product obtained from the composition containing the artificial graphite will not decrease. The average particle diameter of artificial graphite can be measured by a laser diffraction scattering method according to JIS R 1629.
Further, those having a fixed carbon content of 99.0% by mass or more are preferable, those having an ash content of 0.5% by mass or less are preferable, and those having a volatile content of 0.4% by mass or less are preferable. If the volatile content is large, gas winding may occur during molding, which may impair the appearance.

In the present invention, as the component (B), commercially available products such as PAG series and HAG series manufactured by Nippon Graphite Industry Co., Ltd. can be used. These artificial graphites may be used alone or in combination of two or more.
The content of the component (B) is 30 to 70 parts by mass with respect to 100 parts by mass of the component (A). If it is less than 30 parts by mass, sufficient thermal conductivity cannot be obtained, and if it exceeds 70 parts by mass, flame retardancy with a thin wall cannot be obtained, impact strength is lowered, and molecular weight of polycarbonate resin is reduced during granulation. cause. The amount is preferably 40 to 50 parts by mass.

((C) Fluorine-containing anti-dripping agent)
In this invention, it is preferable that the fluorine-containing dripping inhibitor which is (C) component is polytetrafluoroethylene which has fibril formation ability. Here, the fibril forming ability refers to a tendency of the resins to be bonded and become fibrous due to an external action such as shearing force.
Polytetrafluoroethylene having fibril-forming ability imparts an effect of preventing melt dripping to the polycarbonate resin composition of the present invention, and exhibits excellent flame retardancy. Specific examples include polytetrafluoroethylene, tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymers) and the like. Among these, polytetrafluoroethylene (hereinafter sometimes referred to as “PTFE”) is preferable.

PTFE having the ability to form fibrils has a very high molecular weight, and the number average molecular weight determined from the standard specific gravity is usually 500,000 or more, preferably 500,000 to 15 million, more preferably 1,000,000 to 10 million. For example, such PTFE is obtained by polymerizing tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium or ammonium peroxydisulfide at a pressure of 7 to 700 kPa at a temperature of 0 to 200 ° C., preferably 20 to 100 ° C. Can be obtained by: Such PTFE can be used in solid form or in the form of an aqueous dispersion.

Examples of PTFE having such fibril-forming ability include those classified as type 3 in the ASTM standard. Specific examples thereof include, for example, Teflon 6-J (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), Polyflon D-1, Polyflon F-103, Polyflon F201 (manufactured by Daikin Industries, Ltd.), CD076 (Asahi Glass Fluoro) Polymers Co., Ltd.] and the like.
Other than those classified as type 3 above, for example, Algoflon F5 (manufactured by Solvay Solexis Co., Ltd.), polyflon MPA, polyflon FA-100 (manufactured by Daikin Industries, Ltd.) and the like can be mentioned. These PTFE may be used independently and may combine 2 or more types.

The content of component (C) is 1 to 5 parts by mass with respect to 100 parts by mass of component (A). If it is less than 1 part by mass, the effect of preventing dripping cannot be obtained, and if it exceeds 5 parts by mass, the impact strength is reduced. The amount is preferably 1 to 4 parts by mass.

((D) Flame retardant)
In the present invention, an organic sulfonic acid alkali metal salt selected from sodium paratoluenesulfonate, potassium perfluorobutanesulfonate, and potassium trifluoromethanesulfonate is used as the flame retardant as the component (D), and these are specified. Include in proportions.

When sodium paratoluenesulfonate is used as the component (D), the content thereof is 0.15 to 0.73 parts by mass with respect to 100 parts by mass of the component (A). If it is less than 0.15 parts by mass, the effect as a flame retardant is not exhibited, and if it exceeds 0.73 parts by mass, the thermal stability is lowered. The amount is preferably 0.15 to 0.4 parts by mass.
In addition, when potassium perfluorobutanesulfonate and / or potassium trifluoromethanesulfonate is used as the component (D), the content thereof is 0.15 to 0.25 parts by mass with respect to 100 parts by mass of the component (A). It is. If it is less than 0.15 parts by mass, the effect as a flame retardant will not be exhibited, and even if it exceeds 0.25 parts by mass, not only an excellent flame retardant effect can be obtained, but also the flame retardancy is lowered. Further, if it exceeds 0.5 parts by mass, the thermal stability and impact strength are lowered.

((E) Antioxidant)
The resin composition of the present invention can contain an antioxidant as the component (E). (E) As antioxidant, phosphorus antioxidant, a phenolic antioxidant, etc. are used suitably. These may be used alone or in combination of two or more.
Examples of phosphorus antioxidants include triphenyl phosphite, diphenyl nonyl phosphite, diphenyl (2-ethylhexyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, trisnonyl phenyl phosphite. , Diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, diphenylisodecyl phosphite, diphenylmono (tridecyl) phosphite, phenyldiisodecyl phosphite, phenyldi ( Tridecyl) phosphite, Tris (2-ethylhexyl) phosphite, Tris (isodecyl) phosphite, Tris (tridecyl) phosphite, Dibutyl hydrogen phosphite, Trilauryl trithiophosphite, Te Trakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite, 4,4′-isopropylidene diphenol dodecyl phosphite, 4,4′-isopropylidene diphenol tridecyl phosphite 4,4′-isopropylidene diphenol tetradecyl phosphite, 4,4′-isopropylidene diphenol pentadecyl phosphite, 4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) ditridecyl phosphite Phyto, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) penta Erythritol diphosphite, distearyl-pentaerythritol di Sulphite, phenylbisphenol A pentaerythritol diphosphite, tetraphenyldipropylene glycol diphosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, 3,4,5,6-dibenzo-1,2-oxaphosphane, triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, tris- (p-tolyl) phosphine, tris- (p-nonylphenyl) phosphine, tris -(Naphthyl) phosphine, diphenyl- (hydroxymethyl) -phosphine, diphenyl- (acetoxymethyl) -phosphine, diphenyl- (β-ethylcarboxyethyl) -phosphine, tris- (p-chlorophenyl) phosphine, tris- ( p-fluorophenyl) phosphine, diphenylbenzylphosphine, diphenyl-β-cyanoethylphosphine, diphenyl- (p-hydroxyphenyl) -phosphine, diphenyl-1,4-dihydroxyphenyl-2-phosphine, phenylnaphthylbenzylphosphine, etc. .

Examples of phosphorus antioxidants include Irgafos 168 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irgafos 12 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irgafos 38 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) ), ADKSTAB C (trademark), ADKSTAB 株式会社 329K (trademark, ADEKA Corp.), ADKSTAB PEP36 (trademark, ADEKA Corp.), ADKSTAB PEP-8 (trademark, ADEKA Corporation), JC263 (trademark) Johoku Chemical Industry Co., Ltd., Trademark), Sardstab P-EPQ (Clariant, Trademark), Weston 618 (GE, Trademark), Weston 619G (GE, Trademark) and West n 624 (GE Co., trademark) can be exemplified commercially available products such as.

Examples of phenolic antioxidants include n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4-methylphenol, 2, Hindered phenols such as 2'-methylenebis (4-methyl-6-tert-butylphenol), pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] It is done. Among these antioxidants, bis (2,6-di-tert-butyl 4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, etc. Those having a pentaerythritol diphosphite structure and triphenylphosphine are preferred.

Examples of phenolic antioxidants include Irganox 1010 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irganox 1076 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irganox 1330 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) Irganox 3114 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irganox 3125 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), BHT (trade name, manufactured by Takeda Pharmaceutical Company Limited), Cyanox 1790 (trade name, manufactured by Cyanamid Co., Ltd.), and Examples include commercial products such as Sumilizer GA-80 (trademark, manufactured by Sumitomo Chemical Co., Ltd.).

The content of the component (E) is preferably about 0.001 to 1 part by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the component (A). If it is 0.001 part by mass or more, thermal stability does not decrease during granulation and molding, and if it is 1 part by mass or less, there is no possibility of causing a decrease in molecular weight.

((F) mold release agent)
The resin composition of the present invention may contain a release agent as the component (F) for the purpose of improving productivity during molding and improving dimensional accuracy of the molded body. (F) There is no restriction | limiting in particular as a component, For example, a well-known mold release agent, for example, fatty acid ester, polyolefin wax, fluorine oil, paraffin wax, etc. can be used.
Of these, fatty acid esters are preferred, for example, stearic acid monoglyceride, stearic acid diglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol distearate, propylene glycol monostearate, sorbitan monostearate, etc. Partial esters are preferable, and stearic acid monoglyceride, stearic acid monosorbate, pentaerythritol monostearate, and pentaerythritol distearate are more preferable. These release agents may be used alone or in combination of two or more.

The content of component (F) is preferably about 0.3 to 2 parts by mass with respect to 100 parts by mass of component (A). When the content of the component (F) is within the above range, the physical properties are not greatly lowered, and the sustainability during continuous molding and the residual distortion and yield of the molded body are improved.

(Other additives)
In addition to the components (A) to (F) described above, the resin composition of the present invention may contain various additives as long as the object of the present invention is not impaired. Various additives include, for example, ultraviolet absorbers such as benzotriazoles and benzophenones, light stabilizers such as hindered amines, talc, mica, kaolin, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, glass fiber, and carbon fiber. And inorganic fillers such as potassium titanate.
On the other hand, it is known to add a silicone compound such as a silicone-based flame retardant for the purpose of improving the flame retardancy as an additive. It is not always preferable to apply a resin composition containing a silicone compound to the production of a molded article rich in design. Therefore, the resin composition of the present invention is excellent in paintability by not containing a silicone compound, and is further made into a resin composition that gives a molded article having good flame retardancy and the like by containing each of the aforementioned components. Can do.

(Production of flame retardant polycarbonate resin composition)
The flame-retardant polycarbonate resin composition of the present invention can be obtained by blending the above-described components (A) to (F) and various additives by a conventional method and melt-kneading. For example, some (C) fluorine-containing anti-dripping agents and the like may aggregate when blended as they are, and may be blended after (A) masterbatch with a polycarbonate resin. However, when a high-speed mixer or the like is used, it may not always be necessary to make a master batch.
The melt kneading can be performed using, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a kneader, a multi-screw extruder, or the like. The heating temperature in melt kneading is usually about 250 to 330 ° C.

[Molded body]
The flame-retardant polycarbonate resin composition of the present invention is applied to a known molding method such as hollow molding, injection molding, extrusion molding, vacuum molding, pressure forming, hot bending molding, compression molding, calendar molding, rotational molding, and the like. Thus, a thin molded article excellent in flame retardancy, thermal conductivity, thermal stability, mechanical properties, impact resistance, flow properties and wettability can be obtained.
In particular, the flame-retardant polycarbonate resin composition of the present invention is a molded product that is used in a part that requires a thin wall thickness (about 1.2 to 1.0 mm) and flame resistance when used, for example, for electrical and electronic use. It is suitably used for manufacturing parts, chassis for electric / electronic devices, heat dissipation components, heat transfer components, communication device components, and the like.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In addition, the physical-property measurement and evaluation of the sample obtained by the below-mentioned Example and comparative example were performed with the following method.
(1) Flame retardance A test piece having a width of 12.7 mm, a length of 127 mm, a thickness of 1.2 mm or 1.0 mm was molded by injection molding. Using this test piece, a combustion test was performed by a method based on UL94 vertical combustion (V test), and the flame retardance rank was determined. Note that the test result that did not satisfy the criteria of V-0 to V-2 was defined as NOT.
(2) Thermal conductivity (thermal conductivity)
Measurement was performed by the hot disk method.
(3) Tensile strength at break Measured according to ASTM D638.
(4) Flexural strength and flexural modulus Measured according to ASTM D790.
(5) Impact resistance-IZOD impact strength (with notch) / (without notch): Measured according to ASTM D256.
Charpy impact strength (flatwise, no notch): Measured according to JIS K7111.
(6) Flow characteristics Measured according to JIS K7199 at a temperature of 320 ° C / temperature of 360 ° C and a load of 980N.
(7) Wettability (surface tension)
The surface tension was measured according to JIS K6768.

The following were used as raw materials.
(A) Polycarbonate resin FN1900A [made by Idemitsu Kosan Co., Ltd., viscosity average molecular weight: 19500]
・ FN2200A [manufactured by Idemitsu Kosan Co., Ltd., viscosity average molecular weight: 22500]
・ FN2500A [manufactured by Idemitsu Kosan Co., Ltd., viscosity average molecular weight: 25000]
・ FN2600A [Idemitsu Kosan Co., Ltd., viscosity average molecular weight: 26500]
The polycarbonate resin was used and mixed while being prepared so that the viscosity average molecular weight (prepared molecular weight) was 19,000 to 30,000.

(B) Artificial graphite ・ Artificial graphite PAG-420 [manufactured by Nippon Graphite Industry Co., Ltd.]
Fixed carbon content: 99.4% or more, volatile content: 0.3% or less, ash content: 0.3% or less,
Amorphous, 50% cumulative diameter: 30-40μm (50μm or more, 50% or less),
Apparent density: 0.29-0.37 g / cm ³
・ Artificial graphite PAG-120 [Nippon Graphite Industry Co., Ltd.]
Fixed carbon content: 99.6% or more, volatile content: 0.2% or less, ash content: 0.2% or less,
Particle size distribution 150-250 μm: 10% or less, 75-150 μm: 60% or more,
75 μm or less: 10% or less ・ Natural graphite CB-150 (manufactured by Nippon Graphite Industry Co., Ltd.)
Fixed carbon content: 98% or more, ash content: 1% or less, volatile content: 1% or less, scaly, particle size distribution 63 μm or less: 77-87%, 106 μm or more: 5% or less,
50% cumulative diameter: 31-48 μm, apparent density: 0.2-0.3 g / cm ³
・ Expanded graphite EXP-P [Nippon Graphite Industry Co., Ltd.]
Fixed carbon content: 98.48% (standard 93.00% or more),
Volatile content: 1.14% (standard 5.00% or less),
Ash content 0.38% (standard 2.00% or less),
Apparent density: 0.07 g / cm ³ (standard 0.03-0.08 g / cm ³ )
・ Flame graphite UP-35N [Nippon Graphite Industry Co., Ltd.]
Fixed carbon content: 99.61%, ash content: 0.19%, volatile content: 0.2%,
50% cumulative diameter: 33.38 μm, apparent density 0.11 g / cm ³

(C) Fluorine-containing anti-dripping agent PTFE [manufactured by Solvay Solexis, Algoflon F5]
(D) Flame retardant-Perfluorobutane sulfonate potassium [Mitsubishi Materials, Ftop KFBS]
・ Potassium trifluoromethanesulfonate [Mitsubishi Materials, F-Top EF-12]
・ Sodium paratoluenesulfonate (DAH DIING CHEMICAL INDUSTRY, purity 93% or more, sodium sulfate 3% by mass or less, impurities 5% by mass or less)
(E) Antioxidant ・ JC263 [manufactured by Johoku Chemical Industry Co., Ltd., triphenylphosphine]
Irgafos 168 [Ciba Specialty Chemicals, Tris (2,4-di-t-butylphenyl) phosphite]
ADK Stab C [made by ADEKA Corporation, diphenyl (2-ethylhexyl) phosphite]
Irganox 1076 (Ciba Specialty Chemicals, Inc., octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate)
(F) Mold release agent S-100A [manufactured by Riken Vitamin Co., Ltd., glycerol monostearate]
EW-440A (Riken Vitamin Co., Ltd., pentaerythritol tetrastearate)
(Other)
Silicone compound [manufactured by Shin-Etsu Chemical Co., Ltd., KR-511 (organopolysiloxane having a phenyl group, a methoxy group and a vinyl group)]

[Examples and Comparative Examples]
The composition shown in each table is blended in a twin screw extruder (manufactured by Toshiba Machine Co., Ltd., model name TEM35), and melt kneaded at a barrel temperature of 300 to 320 ° C., a screw rotation speed of 100 to 600 rotations, and a discharge of 10 to 30 kg / hr. Thus, a sample for evaluation was obtained.
The physical properties of the obtained evaluation samples were measured and evaluated according to the above methods, and the results are shown in the table.

The flame-retardant polycarbonate resin composition of the present invention has good flame retardancy even with a thickness of about 1.2 to 1.0 mm, and has thermal conductivity, thermal stability, mechanical properties, impact resistance, flow Because it can give molded products with excellent characteristics and wettability, it can be used in the electric and electronic fields, and in particular, projectors, digital equipment (CCD, etc.), personal computers, LED lighting, digital that require countermeasures against heat It is suitable for heat dissipation parts around a heat source such as a camera, a chassis, a case, and the like. In addition, the flame retardant polycarbonate resin composition of the present invention does not contain a silicone compound, so it has excellent wettability, and from the viewpoint of paintability, a mobile that requires a metal-like tactile feel as a part of the design. It is suitable for uses such as equipment casings.

Claims (8)

1. (A) 30 to 70 parts by mass of (B) artificial graphite, (C) 1 to 5 parts by mass of a fluorine-containing anti-dripping agent, and (D) sodium paratoluenesulfonate as a flame retardant with respect to 100 parts by mass of the polycarbonate resin. A flame-retardant polycarbonate resin composition containing 0.15 to 0.73 parts by mass and containing no silicone compound.
2. (A) 30 to 70 parts by mass of (B) artificial graphite, (C) 1 to 5 parts by mass of a fluorine-containing anti-dripping agent and (D) potassium perfluorobutanesulfonate as a flame retardant with respect to 100 parts by mass of the polycarbonate resin And a flame retardant polycarbonate resin composition containing 0.15 to 0.25 parts by mass of at least one selected from potassium trifluoromethanesulfonate and containing no silicone compound.
3. The flame-retardant polycarbonate resin composition according to claim 1 or 2, further comprising 0.001 to 1 part by mass of (E) an antioxidant with respect to 100 parts by mass of the (A) polycarbonate resin.
4. The flame-retardant polycarbonate resin composition according to any one of claims 1 to 3, further comprising 0.3 to 2 parts by mass of (F) a release agent with respect to 100 parts by mass of (A) the polycarbonate resin.
5. A molded article using the flame retardant polycarbonate resin composition according to any one of claims 1 to 4.
6. The molded article according to claim 5, which is a part for an electric / electronic device.
7. The molded article according to claim 5, which is a chassis for electrical and electronic equipment.
8. The molded body according to claim 5, which is a heat radiating part or a heat transfer part.