JP2003089749A - Flame-retardant polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a flame-retardant polycarbonate resin that has a proper balance between flame retardancy, impact strength and fabrication quality by using non-halogen and non-phosphorus flame retardants. SOLUTION: The polycarbonate resin composition comprises (A) 100 pts.wt. polycarbonate resin with a specific viscosity-average molecular weight, (B) (B-1) a polyorganosiloxane-including graft copolymer, preferably a graft copolymer produced by polymerizing 60-10 wt.% of a vinyl monomer in the presence of 40-90 wt.% of a polyorganosiloxane having an average particle size of 0.008-0.6 μm or (B-2) 1-20 pts.wt. of an aromatic group-bearing polyorganosiloxane, (C) 0.05-1 pt.wt. of a fluororesin and (D) 0-2 pts.wt. of an antioxidant.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant polycarbonate resin composition.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used as electric / electronic parts, OA equipment, household products or building materials because of their excellent impact resistance, heat resistance and electrical characteristics. Polycarbonate-based resins have higher flame retardancy than polystyrene-based resins, but there are fields where high flame-retardancy is required, mainly in the fields of electrical and electronic parts and office automation equipment. By adding flame retardant,
The improvement is aimed at. For example, organic halogen compounds and organic phosphorus compounds have been widely added in the past. However, many of the organic halogen-based compounds and organic phosphorus-based compounds have a problem in terms of toxicity, and in particular, the organic halogen-based compound has a problem that a corrosive gas is generated during combustion. For these reasons, in recent years, there has been an increasing demand for flame retardancy using non-halogen / non-phosphorus flame retardants.

As the non-halogen / non-phosphorus flame retardant, a polyorganosiloxane compound (also called silicone) is used.
The use of is proposed. For example, JP-A-54-36
Japanese Patent Publication No. 365 describes that a flame-retardant resin can be obtained by kneading a silicone resin composed of monoorganopolysiloxane with a non-silicone polymer.

JP-A-8-113712 discloses that 100 parts by weight of polyorganosiloxane and 10 to 10 parts of silica filler are used.
A method for obtaining a flame-retardant resin composition by dispersing a silicone resin prepared by mixing with 150 parts by weight in a thermoplastic resin is described.

JP-A-10-139964 discloses a flame-retardant resin composition obtained by adding a silicone resin soluble in a solvent having a weight average molecular weight of 10,000 to 270,000 to a non-silicone resin containing an aromatic ring. It is stated that you can get things.

However, when the silicone resin described in the above publication is added to the polycarbonate resin, flame retardancy is recognized to some extent, but the flame retardance-impact resistance-molding processability balance is insufficient. .

In JP-A-2000-17029, a composite rubber flame retardant obtained by graft-polymerizing a vinyl monomer to a composite rubber composed of a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber is blended with a polycarbonate resin. It is described that a flame-retardant polycarbonate resin composition can be obtained by doing so.

Japanese Patent Laid-Open No. 2000-226420 discloses that
A flame-retardant polycarbonate resin composition can be obtained by compounding a polycarbonate resin with a polyorganosiloxane-based flame retardant obtained by grafting a vinyl-based monomer onto composite particles of a polyorganosiloxane having an aromatic group and a vinyl-based polymer. Is described.

Japanese Patent Laid-Open No. 2000-264935 discloses that
It is described that a flame-retardant polycarbonate resin composition can be obtained by blending a polycarbonate resin with a polyorganosiloxane-containing graft copolymer obtained by graft-polymerizing a vinyl-based monomer onto polyorganosiloxane particles of 0.2 μm or less. There is.

The above-mentioned JP-A-2000-17029, JP-A-2000-226420 and JP-A-2000-26.
All of the flame-retardant polycarbonate resin compositions described in Japanese Patent No. 4935 have satisfactory impact resistance, but have insufficient flame retardancy and moldability, and thus flame retardancy-impact resistance-molding. There is a problem that the workability balance is poor.

[0011]

DISCLOSURE OF THE INVENTION An object of the present invention is to use a non-halogen / non-phosphorus flame retardant, and to improve the flame retardancy-impact resistance-
It is intended to provide a flame-retardant polycarbonate resin composition excellent in molding processability.

[0012]

As a result of intensive studies on the above problems, the present inventors have found that a specific amount of a polycarbonate resin, a specific polyorganosiloxane compound, a fluorine resin and an antioxidant are each specified. It was found that a flame-retardant polycarbonate resin composition excellent in flame retardancy-impact resistance-molding processability can be obtained when used, and the present invention has been completed.

That is, the present invention relates to (A) a polycarbonate resin 10 having a viscosity average molecular weight of 13,000 to 20,000.
Polyorganosiloxane obtained by polymerizing a vinyl monomer (b-2) in the presence of 0 part (part by weight, the same hereinafter) and (B) (B-1) polyorganosiloxane particles (b-1). Flame Retardant Containing 1 to 20 Parts of (B-2) Polyorganosiloxane Containing Aromatic Group Containing Graft Copolymer or (B-2), 0.05 to 1 Part of (C) Fluorine-Based Resin and 0 to 2 Parts of (D) Antioxidant Of the organic polycarbonate resin composition (claim 1) and the polyorganosiloxane-containing graft copolymer are 40 to 90% by weight of polyorganosiloxane particles (b-1) having an average particle diameter of 0.008 to 0.6 μm (% by weight; The same as the above), which is obtained by polymerizing 60 to 10% of a vinyl monomer (b-2) in the presence of the vinyl monomer, and the vinyl monomer has a solubility of a polymer of the vinyl monomer. The parameter is 9.15
10. The flame-retardant polycarbonate resin composition according to claim 1 (claim 2) and the polyorganosiloxane particles (b-1) in the form of latex, wherein the content is from 10.15 (cal / cm ³ ) ^1/2. The flame-retardant polycarbonate resin composition according to claim 2 (claim 3), wherein the vinyl monomer (b-2) is an aromatic vinyl monomer, a vinyl cyanide monomer, (meth).
The flame-retardant polycarbonate resin composition according to claim 1, which is at least one kind of monomer selected from the group consisting of acrylic acid ester-based monomers and carboxyl group-containing vinyl-based monomers. Item 4).

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant polycarbonate resin composition of the present invention comprises (A) a viscosity average molecular weight of 13,000 to 20.
000 polycarbonate resin (hereinafter, also referred to as polycarbonate resin (A)) 100 parts, (B) (B-1) in the presence of polyorganosiloxane particles (b-1) vinyl monomer (b-2) Polyorganosiloxane-containing graft copolymer obtained by polymerization (hereinafter also referred to as polyorganosiloxane-containing graft copolymer (B-1)) or (B-2) aromatic group-containing polyorganosiloxane (hereinafter aromatic) 1 to 20 parts of group-containing polyorganosiloxane (B-2), 0.05 to 1 part of (C) fluororesin (hereinafter also referred to as fluororesin (C)) and (D)
Antioxidant (hereinafter also referred to as antioxidant (D)) 0 to 2
It consists of parts.

The polycarbonate resin (A) 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, the dihydric phenol and the carbonate precursor solution method or melting method, that is,
A product produced by reacting a dihydric phenol with phosgene or by reacting a dihydric phenol with diphenyl carbonate by a transesterification method can be used.

As the dihydric phenol, various ones may be mentioned, but particularly 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) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis ( 4-hydroxyphenyl) ketone etc. are mentioned.

A particularly preferred dihydric phenol is a bis (hydroxyphenyl) alkane type, especially bisphenol A as a main raw material. Further, the carbonate precursor is carbonyl halide, carbonyl ester, haloformate or the like, and specifically, phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate or the like. In addition to these, examples of the dihydric phenol include hydroquinone, resorcin, and catechol. These dihydric phenols may be used alone or in combination of two or more.

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

As the polycarbonate resin used in the present invention, a bifunctional carboxylic acid such as terephthalic acid,
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 (A) is 13,000 to 20,000, preferably 15,000 to 20,000. If the viscosity average molecular weight is too low, impact resistance tends to be poor, and if the viscosity average molecular weight is too high, moldability tends to be poor. The viscosity average molecular weight (Mv) is determined by measuring the viscosity of a methylene chloride solution at 20 ° C. using an Ubbelohde viscometer and determining the intrinsic viscosity [η] from this, [η] =
It is a value calculated by the formula of 1.23 × 10 −5 Mv 0.83.

The component (B) is a component used as a flame retardant, and at least one of the polyorganosiloxane-containing graft copolymer (B-1) and the aromatic group-containing polyorganosiloxane (B-2) is used. . From the viewpoint of economical efficiency-impact resistance-flame retardance balance, (B-1) is preferable.
The ratio of the component and the component (B-2) used is 5 for the component (B-1).
0% or more, 70% or more, particularly 100% is used.

The polyorganosiloxane-containing graft copolymer (B-1) is obtained by graft-polymerizing the vinyl monomer (b-2) in the presence of the polyorganosiloxane particles (b-1).

The polyorganosiloxane particles (b-1) used in the polyorganosiloxane-containing graft copolymer (B-1) are obtained by light scattering method or electron microscope observation from the viewpoint of flame retardancy. The required average particle size is 0.008 to 0.6 μm, and further 0.008 to 0.2.
μm, further 0.01 to 0.15 μm, especially
It is preferably 0.01 to 0.1 μm. It tends to be difficult to obtain particles having an average particle size of less than 0.008 μm, and if it exceeds 0.6 μm, the flame retardancy tends to deteriorate. Coefficient of variation of particle size distribution of the polyorganosiloxane particles (100 x standard deviation / average particle size)
(%) Is preferably 10 to 70 from the viewpoint that the molded product surface appearance of the resin composition containing the flame retardant of the present invention is good.
%, More preferably 20 to 60%, and particularly preferably 20 to 50%.

The polyorganosiloxane particles (b-1) used in the present invention are not only particles consisting of polyorganosiloxane but also modified polyorganosiloxane containing 5% or less of another (co) polymer. It is a concept that includes. That is, the polyorganosiloxane particles may contain, for example, 5% or less of polybutyl acrylate, butyl acrylate-styrene copolymer and the like in the particles.

The polyorganosiloxane particles (b-
Specific examples of 1) include polydimethylsiloxane particles,
Examples thereof include polymethylphenylsiloxane particles and dimethylsiloxane-diphenylsiloxane copolymer particles. These may be used alone or in combination of two or more.

The polyorganosiloxane particles (b-
1) is, for example, (1) organosiloxane, (2)
Bifunctional silane compound, (3) Organosiloxane and bifunctional silane compound, (4) Organosiloxane and vinyl-based polymerizable group-containing silane compound, (5) Bifunctional silane compound and vinyl-based polymerizable group-containing silane compound, or (6) ) It can be obtained by polymerizing an organosiloxane, a bifunctional silane compound, a vinyl-based polymerizable group-containing silane compound, or the like, or by further adding a trifunctional or higher functional silane compound to them.

The above-mentioned organosiloxane and the bifunctional silane compound are components constituting the main skeleton of the polyorganosiloxane chain. Specific examples of the organosiloxane include hexamethylcyclotrisiloxane (D3) and octamethylcyclotetrasiloxane ( Specific examples of difunctional silane compounds such as D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), and hexadecamethylcyclooctasiloxane (D8). Is diethoxydimethylsilane, dimethoxydimethylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, hepta Perfluoro decyl methyl dimethoxysilane, trifluoropropyl methyl dimethoxy silane, octadecyl methyl dimethoxysilane and the like. Among these, D4 or a mixture of D3 to D7 or D3 from the viewpoints of good economy and flame retardancy.
70 to 100% of the mixture of D8 to 80 to 80%
0%, and the remaining components are 0 to 30 such as diphenyldimethoxysilane and diphenyldiethoxysilane.
%, More preferably 0 to 20% is preferably used.

The vinyl-based polymerizable group-containing silane compound is the organosiloxane, the bifunctional silane compound, or the trifunctional compound.
It is a component for copolymerizing with a functional silane compound or the like to introduce a vinyl-based polymerizable group into the side chain or terminal of the copolymer. The vinyl-based polymerizable group is a vinyl-based monomer (b) described below. -2) acts as a graft active site when chemically bonding to the vinyl-based (co) polymer formed from. Furthermore, it is a component that can be used as a cross-linking agent by radically reacting between graft active points with a radical polymerization initiator to form a cross-linking bond. At this time, the same radical polymerization initiator as that which can be used in the below-mentioned graft polymerization can be used. Even when crosslinking is carried out by a radical reaction, some of them remain as grafting active points, and therefore grafting is possible.

Specific examples of the vinyl-based polymerizable group-containing silane compound include, for example, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane and γ-methacryloyl. Oxypropyldiethoxymethylsilane, γ-acryloyloxypropyldimethoxymethylsilane, γ-
(Meth) acryloyloxy group-containing silane compound such as acryloyloxypropyltrimethoxysilane, p-
Vinylphenyl group-containing silane compounds such as vinylphenyldimethoxymethylsilane and p-vinylphenyltrimethoxysilane, vinyl group-containing silane compounds such as vinylmethyldimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane, mercaptopropyltrimethoxysilane, Examples thereof include mercapto group-containing silane compounds such as mercaptopropyldimethoxymethylsilane. Among these, a (meth) acryloyloxy group-containing silane compound, a vinyl group-containing silane compound, and a mercapto group-containing silane compound are preferably used from the economical point of view.

When the vinyl-based polymerizable group-containing silane compound is of the trialkoxysilane type, it also functions as a trifunctional or higher-functional silane compound shown below.

The trifunctional or higher functional silane compound is copolymerized with the organosiloxane, the bifunctional silane compound, the vinyl-based polymerizable group-containing silane compound or the like to introduce a crosslinked structure into the polyorganosiloxane to impart rubber elasticity. It is used as a cross-linking agent for polyorganosiloxane. Specific examples include tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, trifluoropropyltrimethoxysilane, octadecyl. Examples thereof include trifunctional and trifunctional alkoxysilane compounds such as trimethoxysilane. Among these, tetraethoxysilane and methyltriethoxysilane are preferably used from the viewpoint of high crosslinking efficiency.

The proportion of the organosiloxane, the bifunctional silane compound, the vinyl-based polymerizable group-containing silane compound, and the trifunctional or higher functional silane compound used during the polymerization is usually an organosiloxane and / or a bifunctional silane compound (organosiloxane). The ratio of the difunctional silane compound to the bifunctional silane compound is usually 100/0 to 0/100, further 1
00/0 to 70/30) 50 to 99.9%, and further 6
0 to 99%, vinyl polymerizable group-containing silane compound 0 to 4
It is preferably 0%, more preferably 0.5 to 30%, and a trifunctional or higher functional silane compound 0 to 50%, further preferably 0.5 to 39%. Incidentally, vinyl-based polymerizable group-containing silane compounds, 3
Functional silane compounds do not become 0% at the same time, and it is preferable to use 0.1% or more of any of them.

If the use ratio of the organosiloxane and the bifunctional silane compound is too small, the resin composition obtained by blending tends to be brittle. On the other hand, when the amount is too large, the amounts of the vinyl-based polymerizable group-containing silane compound and the trifunctional or higher functional silane compound are too small, and the effect of using them tends to be difficult to be exhibited. Further, when the ratio of the vinyl-based polymerizable group-containing silane compound or the trifunctional or higher functional silane compound is too small, the flame retardancy-producing effect is low, and when the ratio is too large, The resin composition obtained by blending tends to be brittle.

The polyorganosiloxane particles (b-
1) is, for example, emulsion polymerization of a polyorganosiloxane-forming component obtained by adding a trifunctional or higher functional silane compound used as necessary, such as the aforementioned organosiloxane, a bifunctional silane compound, and a vinyl-based polymerizable group-containing silane compound. It is preferable to manufacture by doing.

The emulsion polymerization can be carried out, for example, by emulsifying and dispersing the above polyorganosiloxane-forming component and water in the presence of an emulsifier by mechanical shearing in water to bring it into an acidic state. In this case, when emulsified droplets of several μm or more are prepared by mechanical shearing, the average particle size of the polyorganosiloxane particles obtained after polymerization is in the range of 0.02 to 0.6 μm depending on the amount of the emulsifier used. Can be controlled. The coefficient of variation of the obtained particle size distribution (100 x standard deviation / average particle size) (%) is 20 to 7
0% can be obtained.

When polyorganosiloxane particles having a particle size distribution of 0.1 μm or less and a narrow particle size distribution are produced, it is preferable to carry out polymerization in multiple stages. For example, 1 to 20% of an emulsion consisting of emulsified droplets of several μm or more obtained by emulsifying the polyorganosiloxane-forming component, water and an emulsifier by mechanical shearing is first emulsion-polymerized in an acidic state,
Using the obtained polyorganosiloxane particles as seeds, the remaining emulsion is additionally polymerized in the presence thereof. The polyorganosiloxane particles thus obtained are
Average particle size is 0.02-0.1 μm depending on the amount of emulsifier
And the coefficient of variation of the particle size distribution can be controlled to 10 to 60%. A more preferable method is, in place of the seed of polyorganosiloxane particles in the multi-stage polymerization,
A vinyl-based (co) polymer obtained by (co) polymerizing a vinyl-based monomer (for example, styrene, butyl acrylate, methyl methacrylate, etc.) used in the graft polymerization described below by a usual emulsion polymerization method is used. When performing multi-stage polymerization,
The average particle size of the obtained polyorganosiloxane (modified polyorganosiloxane) particles is 0.00 depending on the amount of emulsifier.
8 to 0.1 μm and the coefficient of variation of particle size distribution is 10 to 5
It can be controlled to 0%.

The emulsified droplets of several μm or more can be prepared by using a high speed stirrer such as a homomixer.

In the emulsion polymerization, an emulsifier that does not lose its emulsifying ability under acidic conditions is used. Specific examples include alkylbenzene sulfonic acid, sodium alkylbenzene sulfonate, alkyl sulfonic acid, sodium alkyl sulfonate, sodium (di) alkyl sulfosuccinate,
Examples thereof include sodium polyoxyethylene nonylphenyl ether sulfonate, sodium alkylsulfate and the like. These may be used alone or in combination of two or more. Among these, alkylbenzene sulfonic acid, sodium alkylbenzene sulfonate, alkyl sulfonic acid, sodium alkyl sulfonate,
Sodium (di) alkylsulfosuccinate is preferable because the emulsion stability of the emulsion is relatively high. Furthermore, alkylbenzenesulfonic acid and alkylsulfonic acid are particularly preferable because they also act as a polymerization catalyst for the polyorganosiloxane-forming component.

In the acidic state, the system may be an inorganic acid such as sulfuric acid or hydrochloric acid, an alkylbenzenesulfonic acid, an alkylsulfonic acid,
It can be obtained by adding an organic acid such as trifluoroacetic acid, and the pH is preferably adjusted to 1 to 3 in terms of not corroding the production facility and obtaining an appropriate polymerization rate, and further 1.0 to 2 It is more preferable to adjust to 0.5.

The heating for the polymerization is preferably 60 to 120 ° C., and 70 to 10 from the viewpoint that an appropriate polymerization rate can be obtained.
0 ° C is more preferable.

Under acidic conditions, the Si--O--Si bond forming the skeleton of the polyorganosiloxane is in an equilibrium state of cleavage and formation, and this equilibrium changes with temperature, so the stability of the polyorganosiloxane chain is stable. For
It is preferable to neutralize by adding an aqueous alkaline solution such as sodium hydroxide, potassium hydroxide or sodium carbonate. Furthermore, in the equilibrium, a higher molecular weight or a higher degree of cross-linking is more likely to be generated on the production side as the temperature becomes lower. Therefore, in order to obtain a high molecular weight or a high degree of cross-linking,
It is preferable that the polyorganosiloxane-forming component is polymerized at 60 ° C. or higher, then cooled to room temperature or lower and held for 5 to 100 hours, and then neutralized.

Thus, when the obtained polyorganosiloxane particles are formed by polymerizing, for example, an organosiloxane or a bifunctional silane compound, and further by adding a vinyl type polymerizable group-containing silane compound to them, they are usually randomly generated. Copolymerizes into a polymer having a vinyl-based polymerizable group. When a trifunctional or higher functional silane compound is copolymerized, it has a crosslinked network structure.
Furthermore, when a vinyl-based polymerizable group is cross-linked by a radical reaction with a radical polymerization initiator used in the below-mentioned graft polymerization, it has a cross-linked structure in which vinyl-based polymerizable groups are chemically bonded, and Part of the unreacted vinyl-based polymerizable group remains. Toluene insoluble amount of the polyorganosiloxane particles, that is, 0.5 g of the particles
When 80 ml of toluene is immersed in 80 ml of toluene at room temperature for 24 hours, the amount of toluene-insoluble matter is preferably 95% or less, more preferably 90% or less from the viewpoint of the balance of flame retardancy-impact resistance-molding processability.

By subjecting the polyorganosiloxane particles obtained in the above process to graft polymerization of the vinyl monomer (b-2), a flame retardant for a thermoplastic resin comprising a polyorganosiloxane-containing graft copolymer can be obtained.

The flame retardant has a structure in which the vinyl-based monomer (b-2) is grafted onto the polyorganosiloxane particles, and the graft ratio is 5 to 150%, further 15 to 120%. However, it is preferable from the viewpoint of good balance between flame retardancy and impact resistance.

The vinyl-based monomer (b-2) is a component used to obtain a flame retardant composed of a polyorganosiloxane-containing graft copolymer. Furthermore, the flame retardant is used as a thermoplastic resin. When blended to impart flame retardancy, it is also a component used to ensure compatibility between the flame retardant and the thermoplastic resin and to uniformly disperse the flame retardant in the thermoplastic resin. Therefore, the vinyl-based monomer (b-2) has a solubility parameter of a polymer of the vinyl-based monomer of 9.15 to 10.15 [(cal / cm ³ ) ^1/2 ], Furthermore, 9.17 to 10.10 [(cal / c
m ³ ) ^1/2 ], especially 9.20 to 10.05 [(cal
/ Cm ³ ) ^1/2 ].
If the solubility parameter deviates from the above range, the flame retardancy tends to decrease.

The solubility parameter is John
"Polymer Handbook" published by Wiley & Son, Inc. 1
999, 4th Edition, Section VII Nos. 682-685.
The values are calculated by using the group parameter of Small by the group contribution method described in page). For example, polymethylmethacrylate (repeating unit molecular weight 100 g / mo
l, density 1.19 g / cm ³ ) 9.25 [(ca
1 / cm ³ ) ^1/2 ], polybutyl acrylate (repeating unit molecular weight 128 g / mol, density 1.06 g / cm ³ ) 8.97 [(cal / cm ³ ) ^1/2 ], polymethacryl Butylate (repeating unit molecular weight: 142 g / mol, density: 1.06 g / cm ³ ) 9.47 [(cal / c
m ³ ) ^1/2 ], polystyrene (repeating unit molecular weight 104, density 1.05 g / cm ³ ) 9.03 [(cal / c
m ³ ) ^1/2 ], polyacrylonitrile (repeating unit molecular weight 5
3, with a density of 1.18 g / cm ³ ) 12.71 [(c
al / cm ³ ) ^1/2 ]. The density of each polymer is
"Ullmans Encyclopedia" published by VCH
Of Industrial Chemistry (ULLMAN
N'S ENCYCLOPEDIA OF INDUS
TRIAL CHEMISTRY) ", 1992, Vol. A21, page 169. As for the solubility parameter δc of the copolymer, the value of the main component is used when the weight fraction is less than 5%, and the additivity is established by the weight fraction when the weight fraction is 5% or more. That is, it can be calculated by the formula (1) from the solubility parameter δn of the homopolymer of each vinyl monomer constituting the copolymer composed of m kinds of vinyl monomers and the weight fraction Wn thereof.

[0047]

[Equation 1] For example, the solubility parameter of a copolymer of 75% styrene and 25% acrylonitrile is 9.03 [(cal / c
m ³ ) ^1/2 ], and the solubility parameter of polyacrylonitrile 12.71 [(cal / cm ³ ) ^1/2 ], which is substituted into the formula (1) to obtain 9.95 [(cal / cm ³ ) ^{1 / 2} ] value can be obtained.

Also, the solubility parameter δs of the vinyl polymer obtained by polymerizing the vinyl monomer in two or more steps and changing the kind of the vinyl monomer in each step.
Is the value obtained by dividing the total weight of the finally obtained vinyl-based polymer by the weight of the vinyl-based polymer obtained in each stage, that is, the weight fraction, and the additivity is established. That is, it can be calculated by the equation (2) from the solubility parameter δi of the polymer obtained in each stage and the weight fraction Wi thereof obtained in each stage.

[0049]

[Equation 2] For example, polymerize in 2 stages, 75% styrene in the 1st stage
Assuming that 50 parts of a copolymer of 25% acrylonitrile and 50 parts of a polymer of methyl methacrylate are obtained in the second step, the solubility parameter of the polymer obtained in the second step is styrene. Solubility parameter of 95% and acrylonitrile 25% copolymer 9.95
[(Cal / cm ³ ) ^1/2 ] and solubility parameter of polymethylmethacrylate 9.25 [(cal / cm ³ ) ^1/2 ]
By substituting into equation (2) using 9.60 [(cal / cm
³ ) ^1/2 ] can be obtained.

The amount of the vinyl-based monomer (b-2) used is 40 to 90 of the polyorganosiloxane particles (b-1).
%, Further 50 to 80%, especially 50 to 75%, so that the total amount is 100%, it is 60 to 10%, further 50 to 20%, and especially 50 to 25%. preferable.

When the amount of the vinyl-based monomer (b-2) used is too large or too small, the flame retardancy tends not to be sufficiently exhibited.

As the vinyl-based monomer (b-2),
For example, aromatic vinyl monomers such as styrene, α-methylstyrene, paramethylstyrene, parabutylstyrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, acrylic acid. Propyl, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, hydroxy methacrylate Examples thereof include (meth) acrylic acid ester-based monomers such as ethyl, carboxyl group-containing vinyl-based monomers such as itaconic acid, (meth) acrylic acid, fumaric acid and maleic acid. As described above, these may be used alone or in combination of two or more as long as the solubility parameter of the polymer falls within the range described above.

As the graft polymerization, a general seed emulsion polymerization can be applied, and the polyorganosiloxane particles (b-1)
Radical polymerization of the vinyl-based monomer (b-2) may be performed in the latex. In addition, vinyl-based monomers (b-
2) may be polymerized in one step or in two or more steps.

The radical polymerization may be carried out by a method in which the reaction is proceeded by thermally decomposing a radical polymerization initiator, or in a redox system using a reducing agent without any particular limitation.

Specific examples of the radical polymerization initiator include cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, di-t-butylperoxide and t-butylperoxy. Organic peroxides such as laurate, lauroyl peroxide, succinic acid peroxide, cyclohexane nonoxide, acetylacetone peroxide, inorganic peroxides such as potassium persulfate and ammonium persulfate, 2,2′-azobisisobutyro Nitrile, 2,2'-azobis-2,4-
Examples thereof include azo compounds such as dimethylvaleronitrile. Among these, organic peroxides or inorganic peroxides are particularly preferable because of their high reactivity.

As the reducing agent used in the redox system, ferrous sulfate / glucose / sodium pyrophosphate, ferrous sulfate / dextrose / sodium pyrophosphate, or ferrous sulfate / sodium formaldehyde sulfoxylate / Examples include a mixture of ethylenediamine acetate and the like.

The amount of the radical polymerization initiator used is usually 0.005 to 20 parts, more preferably 0.0 to 100 parts of the polyorganosiloxane particles (b-1) used.
It is preferably 1 to 10 parts, and particularly preferably 0.03 to 5 parts. When the amount of the radical polymerization initiator is less than 0.005 part, the reaction rate is low and the production efficiency tends to be poor, and when it exceeds 20 parts, heat generation during the reaction tends to be large and production tends to be difficult. is there.

Further, a chain transfer agent can be used if necessary in radical polymerization. The chain transfer agent is not particularly limited as long as it is used in ordinary emulsion polymerization.

Specific examples of the chain transfer agent include t-dodecyl mercaptan, n-octyl mercaptan and n-
Examples thereof include tetradecyl mercaptan and n-hexyl mercaptan.

The chain transfer agent is an optional component, but when used, it is preferably used in an amount of 0.01 to 5 parts with respect to 100 parts of the vinyl-based monomer (b-2). If the amount of the chain transfer agent is less than 0.01 part, the effect used cannot be obtained, and if it exceeds 5 parts, the polymerization rate tends to be slow and the production efficiency tends to be low.

The reaction temperature during the polymerization is usually 30 to 1
It is preferably 20 ° C.

In the above-mentioned polymerization, when the polyorganosiloxane particles (b-1) contain a vinyl-based polymerizable group, when the vinyl-based monomer (b-2) is polymerized by the radical polymerization initiator, Polyorganosiloxane particles (b-
A graft is formed by reacting with the vinyl polymerizable group of 1). Polyorganosiloxane particles (b-
When a vinyl polymerizable group does not exist in 1), if a specific radical initiator such as t-butylperoxylaurate is used, hydrogen is extracted from an organic group such as a methyl group bonded to a silicon atom to generate hydrogen. The radicals cause the vinyl-based monomer (b-2) to polymerize to form a graft.

Further, 0.1 to 10%, preferably 0.5 to 5% of the vinyl-based monomer (b-2) is polymerized using a vinyl-based polymerizable group-containing silane compound, and the pH is 5 or less. Grafts are formed even when the redistribution reaction is carried out under the acidic condition of.
This is because the Si-O-Si bond of the main skeleton of the polyorganosiloxane is in an equilibrium state of cleavage and formation in an acidic state, and therefore, in this equilibrium state, the vinyl monomer and the vinyl polymerizable group-containing silane compound are When copolymerized, the side chain silane of the vinyl-based copolymer being produced or produced by the polymerization reacts with the polyorganosiloxane chain to produce a graft. The vinyl-based polymerizable group-containing silane compound,
If necessary, the same as the one used in the production of the polyorganosiloxane particles (b-1) may be used. When the amount of the vinyl-based polymerizable group-containing silane compound is less than 0.1%, the vinyl-based polymerizable group-containing silane compound may be used. When the grafting ratio of the monomer (b-2) is reduced and exceeds 10%, the stability of the latex tends to be low.

In the polymerization of the vinyl-based monomer (b-2) in the presence of the polyorganosiloxane particles, the portion corresponding to the branch of the graft copolymer, here, the vinyl-based monomer (b-2) is used. A so-called free polymer obtained by polymerizing the polymer alone by the branch component alone without being grafted to the trunk component, here the polyorganosiloxane particles (b-1), is also a by-product, and is a mixture of the graft copolymer and the free polymer. In the present invention, both of them are collectively referred to as a graft copolymer.

The flame retardant composed of a graft copolymer obtained by emulsion polymerization may be used as a latex, but since it has a wide range of application, it is preferable to separate the polymer from the latex and use it as a powder. preferable. Examples of the method for separating the polymer include a usual method, for example, a method in which a metal salt such as calcium chloride, magnesium chloride or magnesium sulfate is added to the latex to coagulate, separate, wash, dehydrate and dry the latex. Also, a spray drying method can be used.

Thus, the polyorganosiloxane-containing graft copolymer (B-1) used as a flame retardant is obtained.

The aromatic group-containing polyorganosiloxane (B-2) is one in which a part of the organo groups in the polyorganosiloxane is an aromatic group. Particularly, it is preferable that the aromatic group is a phenyl group from the economical viewpoint.

The content of the aromatic group is 30 to 30 with respect to 100 mol% of the total amount of the organo groups in the polyorganosiloxane.
It is 90 mol%, preferably 30 to 85 mol%. If the content of the aromatic group is too small or too large, the dispersibility in the resin tends to be poor and the flame retardancy tends to be low.

Specific examples of such aromatic group-containing polyorganosiloxanes include polyphenylmethylsilsesquioxane, polyphenylmethylsiloxane, polydiphenylsiloxane, and modified products thereof. These are commercially available from silicone manufacturers and are easily available. For example, GE Toshiba Silicone Co., Ltd. XC99B-B5664, Shin-Etsu Chemical Co., Ltd. X-40-9805, X-40-9843, X -40-9844 etc. are mentioned.

As the component (B) of the present invention, the above polyorganosiloxane-containing graft copolymer (B-1) or the above aromatic group-containing polyorganosiloxane (B-2) is used. Good.

The fluorine-based resin (C) is a polymer resin having a fluorine atom and is a component used as a drip preventing agent during combustion. Specific examples that are preferable in that they have a large anti-dripping effect include fluorinated polyolefin resins such as polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene / hexafluoroethylene copolymer, and polyfluorine. Examples thereof include vinylidene chloride resin. Further, a fluorinated polyolefin resin is preferable, and a fluorinated polyolefin resin having an average particle diameter of 700 μm or less is particularly preferable. The average particle diameter here and the average particle diameter of the secondary particles formed by aggregating the primary particles of the fluorinated polyolefin resin. Further, the fluorinated polyolefin resin is preferably a fluorinated polyolefin resin having a density / bulk density ratio (density / bulk density) of 6.0 or less. The density and bulk density referred to here are JIS-K68.
It is measured by the method described in 91. The fluororesin (C) may be used alone or in combination of two or more kinds.

In the present invention, the antioxidant (D) is a component not only for suppressing oxidative decomposition of the resin during molding, but also for improving flame retardancy. . The antioxidant is not particularly limited as long as it is used in ordinary molding. Specific examples include tris [N- (3,5-di-t-butyl-4-hydroxybenzyl)] isocyanurate (Adeka Stab AO-20 manufactured by Asahi Denka Co., Ltd.), tetrakis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (manufactured by Ciba Specialty Chemicals, Irganox 1010), butylidene-1,1-bis- (2-methyl-4-hydroxy-).
5-t-butyl-phenyl) (Asahi Denka Co., Ltd., ADEKA STAB AO-40, etc.), 1,1,3-tris (2-
Methyl-4-hydroxy-5-t-butylphenyl) butane (Yoshinox 930 manufactured by Yoshitomi Fine Chemical Co., Ltd.) and other phenolic antioxidants, bis (2,6, di-t-butyl-4-methylphenyl) Pentaerythritol phosphite (Asahi Denka Co., Ltd., ADEKA STAB PEP-36, etc.), Tris (2,4-di-
t-Butylphenyl) phosphite (manufactured by Asahi Denka Co., Ltd., Adekastab 2112), 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite (manufactured by Asahi Denka Co., Ltd., Adekastab HP-10) And the like), dilauryl 3,3′-thio-dipropionate (Yoshinox DLTP manufactured by Yoshitomi Fine Chemical Co., Ltd.), dimyristyl 3,3′-
Examples thereof include sulfur-based antioxidants such as thio-dipropionate (Yoshinox DMTP manufactured by Yoshitomi Fine Chemical Co., Ltd.).

The flame-retardant polycarbonate resin composition of the present invention contains the component (B) (polyorganosiloxane-containing graft copolymer (B-1) or aromatic group-containing component) based on 100 parts of the polycarbonate resin (A). 1 to 20 parts of polyorganosiloxane (B-2), preferably 1 to 10
Parts, fluorine-based resin (C) 0.05 to 1 part, preferably 0.1 to 0.5 part, and antioxidant (D) 0 to 2 parts, preferably 0.05 to 1 part can get.
If the amount of the component (B) used is too small, the flame retardancy tends to decrease, and if it is too large, the cost of the composition tends to increase, and its value in the market tends to decrease. Further, if the amount of the fluororesin (C) used is too small, the flame retardancy tends to decrease, and if it is too large, the surface of the molded body tends to become rough. Further, if the amount of the antioxidant (D) used as needed is too small, the effect of use is not seen, and if it is too large, moldability tends to be deteriorated.

The method for producing the flame-retardant polycarbonate resin composition of the present invention is not particularly limited, and a usual method can be used. For example, a method of mixing with a Henschel mixer, a ribbon blender, a roll, an extruder, a kneader and the like can be mentioned.

At this time, commonly used compounding agents, that is, plasticizers, stabilizers, lubricants, ultraviolet absorbers, pigments, glass fibers, fillers, polymer processing aids, polymer lubricants, impact modifiers, etc. Can be blended. The filler is used to further improve the rigidity and flame retardancy of the molded product. Specific examples of preferable fillers include talc, mica, kaolin, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, glass fiber, carbon fiber, potassium titanate fiber and the like. Among them, plate-shaped talc, mica and the like, and fibrous fillers are preferable. As talc, a hydrous magnesium silicate, which is generally commercially available, can be used. The average particle size of the filler such as talc is 0.1 to 5
It is 0 μm, preferably 0.2 to 20 μm. A preferred specific example of the polymer processing aid is a methacrylate (co) polymer such as methyl methacrylate-butyl acrylate copolymer.
Polymers are preferred, and preferred specific examples of the impact resistance improver include butadiene rubber-based impact resistance improver (MBS resin),
Examples thereof include a butyl acrylate rubber-based impact resistance improver and a butyl acrylate rubber / silicone rubber composite rubber-based impact resistance improver. In addition, other flame retardants may be used in combination in order to exhibit higher flame retardancy. For example, preferred specific examples of the flame retardant to be used in combination include triphenyl phosphate, condensed phosphoric acid ester, phosphorus compounds such as stabilized red phosphorus, cyanuric acid, triazine compounds such as melamine cyanurate, boron oxide, zinc borate and the like. Examples of the boron compounds include: From the viewpoint of effect-cost balance, the preferable amount of these compounding agents used is 0.1 to 20 parts, and more preferably 0.2 to 100 parts of the thermoplastic resin.
-10 parts, especially 0.3-5 parts.

The molding method of the obtained flame-retardant polycarbonate resin composition is a molding method used for molding a usual thermoplastic resin composition, that is, an injection molding method, an extrusion molding method, a blow molding method, or a calender molding. Laws etc. can be applied.

The use of the molded article obtained from the flame-retardant polycarbonate resin composition of the present invention is not particularly limited, but examples thereof include desktop type computers, notebook type computers, tower type computers, server type computers, printers and copying machines. , FAX
Machine, mobile phone, PHS, TV, VCR, etc.
A / Information / Household and chassis parts of home electric appliances, various building material members, various automobile members, and other applications requiring flame retardancy.

[0078]

EXAMPLES The present invention will be specifically described based on examples, but the present invention is not limited to these.

The measurements and tests in the following examples and comparative examples were carried out as follows. [Polymerization conversion rate] Latex was dried in a hot air dryer at 120 ° C to 1
After drying for an hour, the solid component amount was obtained and calculated by 100 × solid component amount / charged monomer amount (%). [Toluene-insoluble amount] 0.5 g of solid polyorganosiloxane particles obtained by drying from latex was immersed in 80 ml of toluene at room temperature for 24 hours, and 12,000 rp
The mixture was centrifuged at m for 60 minutes, and the weight fraction (%) of the toluene-insoluble portion of the polyorganosiloxane particles was measured. [Grafting rate] 1 g of the graft copolymer was immersed in 80 ml of acetone at room temperature for 48 hours, and the rate was 6 at 12000 rpm.
The insoluble content (w) of the graft copolymer obtained by centrifugation for 0 minutes was obtained, and the graft ratio was calculated by the following formula.

Graft ratio (%) = 100 × {(w-1 ×
(Polyorganosiloxane component fraction in graft copolymer) / (1 × polyorganosiloxane component fraction in graft copolymer)} [Average particle diameter] The average particle diameter of the polyorganosiloxane particles and the graft copolymer is It was measured in the state of latex. As a measuring device, LEED & NORTHRUP INSTRUUM
The number average particle diameter (μm) and the coefficient of variation of the particle diameter distribution (standard deviation / number average particle diameter) (%) were measured by a light scattering method using MICROTRAC UPA manufactured by ENTS). [Impact Resistance] According to ASTM D-256, an Izod test was performed at 23 ° C. using a notched 1/8 inch bar. The state of the test piece after the test was visually observed, and the case where the test piece broke without splitting was defined as ductile fracture, and the case where the test piece was split into 2 was defined as brittle fracture. Evaluation,
Six test pieces were tested, and the ductile fracture rate (100 x number of ductile fractures / 6 (%)) was evaluated as ◯, Δ, and x as follows. ◯: Ductile fracture rate higher than 60%, Δ: Ductile fracture rate 60%
Below 50%, x: Ductile fracture rate 50% or less [Flame retardancy] The vertical combustion test method based on the UL94 V test was used to measure and evaluate the total combustion time of 5 samples. [Moldability] The melt flow index (MI) of pellets dried at 120 ° C for 5 hours is determined by JIS K721.
Based on 0, the measurement was performed at 260 ° C. under a load of 5 kg.

Reference Example 1 Production of Polyorganosiloxane Particles (S-1) An aqueous solution containing the following components was mixed with a homomixer to obtain 1000
An emulsion was prepared by stirring at 0 rpm for 5 minutes.

Component Amount (parts) Pure water 251 Sodium dodecylbenzenesulfonate (SDBS) 0.5 Octamethylcyclotetrasiloxane (D4) 100 γ-methacryloyloxypropyl dimethoxymethylsilane (DSMA) 5 This emulsion is stirred and refluxed. Cooler, nitrogen inlet,
A 5-neck flask equipped with a monomer addition port and a thermometer was charged in a batch. While stirring the system, 1 part (solid content) of a 10% aqueous solution of dodecylbenzenesulfonic acid (DBSA) was added, and the temperature was raised to 80 ° C over about 40 minutes, and then the reaction was carried out at 80 ° C for 6 hours. Then, it was cooled to 25 ° C. and left for 20 hours, then the pH of the system was returned to 6.8 with sodium hydroxide to terminate the polymerization, and a latex containing polyorganosiloxane particles (S-1) was obtained. The polymerization conversion rate, the average particle size of the latex of polyorganosiloxane particles, and the toluene insoluble content were measured, and the results are shown in Table 1.

(Reference Example 2) Production of polyorganosiloxane particles (S-2) An aqueous solution containing the following components was mixed with a homomixer to obtain 1000
An emulsion was prepared by stirring at 0 rpm for 5 minutes.

Ingredients Amount (parts) Pure water 251 SDBS 0.5 D4 70 DSMA 5 This emulsion was stirred using a stirrer, reflux condenser, nitrogen inlet,
A 5-neck flask equipped with a monomer addition port and a thermometer was charged in a batch. While stirring the system, 10% DBSA aqueous solution 1
Parts (solid content) were added, and the temperature was raised to 80 ° C. over about 40 minutes. After reacting at 80 ° C. for 1 hour, 30 parts of diphenyldimethoxysilane (DPhS) was added dropwise over 3 hours. After the dropping, the mixture was stirred for 2 hours, then cooled to 25 ° C. and left for 20 hours. The pH of the system was returned to 6.5 with sodium hydroxide to terminate the polymerization, and a latex containing polyorganosiloxane particles (S-2) was obtained. Polymerization conversion rate,
The average particle size of the latex of polyorganosiloxane particles and the amount of toluene-insoluble matter were measured, and the results are shown in Table 1.

Reference Example 3 Production of Polyorganosiloxane Particles (S-3) In a five-necked flask equipped with a stirrer, a reflux condenser, a nitrogen blowing port, a monomer addition port, and a thermometer, the component amounts ( Part) Pure water 189 SDBS 1.2 was charged. Next, the system was heated to 70 ° C. while substituting with nitrogen, and 1 part of pure water and potassium persulfate (KPS) 0.02 were added.
After adding an aqueous solution of 1 part, a mixed solution of component amount (part) styrene (St) 0.7 butyl methacrylate (BMA) 1.3 was added all at once, and the mixture was stirred for 1 hour to carry out polymerization. Upon completion, a St-BMA copolymer latex was obtained. The polymerization conversion rate was 99%. The obtained latex had a solid content of 1.0% and an average particle size of 0.01 μm. The coefficient of variation at this time was 38%.
The amount of solvent-insoluble matter in the St-BMA copolymer was 0%.

Separately, a mixture of the following components was stirred with a homomixer at 10,000 rpm for 5 minutes to prepare an emulsion of polyorganosiloxane-forming components.

Ingredients Amount (parts) Pure water 70 SDBS 0.5 D4 94 Mercaptopropyldimethoxymethylsilane 4 Subsequently, 8 parts of latex containing St-BMA copolymer was added.
After keeping at 0 ° C., 1.5 parts (solid content) of 10% aqueous solution of DBSA was added to the system, and then the emulsion of the above polyorganosiloxane-forming component was added all at once, followed by stirring for 6 hours and then cooling to 25 ° C. And left for 20 hours. Then, the pH was adjusted to 6.6 with sodium hydroxide and the polymerization was terminated to obtain a latex containing polyorganosiloxane particles (S-3). The polymerization conversion rate, the average particle size of the latex of polyorganosiloxane particles, and the toluene insoluble content were measured, and the results are shown in Table 1. The polyorganosiloxane particles in the latex containing the polyorganosiloxane particles consist of 98% of the polyorganosiloxane component and 2% of the St-BMA copolymer component, depending on the charged amount and the conversion rate.

[0088]

[Table 1] (Reference Examples 4 to 6) 300 parts of pure water, sodium formaldehyde sulfoxylate (SFS) 0.2 were placed in a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen blowing port, a monomer addition port and a thermometer. Parts, 0.01 parts of ethylenediaminetetraacetic acid disodium salt (EDTA), 0.002 of ferrous sulfate
5 parts and polyorganosiloxane particles shown in Table 2 were charged, and the system was heated to 60 ° C. under a nitrogen stream while stirring. After reaching 60 ° C., a mixture of the monomer and the radical polymerization initiator shown in Table 2 was added dropwise in one step or two steps over 3 hours as shown in Table 2 and then stirred at 60 ° C. for 1 hour. By continuing, a latex of the graft copolymer was obtained.

Subsequently, the latex was diluted with pure water to make the solid content concentration 15%, and then 2 parts (solid content) of a 10% calcium chloride aqueous solution was added to obtain a coagulated slurry.
Coagulation The coagulated slurry was heated to 80 ° C., cooled to 50 ° C., dehydrated, and then dried to obtain powders of the polyorganosiloxane-containing graft copolymer (SG-1 to SG-3). Table 2 shows the polymerization conversion rate, average particle size, and graft rate.

In Table 2, MMA is methyl methacrylate, AN is acrylonitrile (above, monomer), CH
P is cumene hydroperoxide (radical polymerization initiator), and SP is the solubility parameter obtained by the method described in the specification.

[0091]

[Table 2] (Examples 1 to 7 and Comparative Examples 1 to 6) Polycarbonate resin (PC-1: Teflon FN manufactured by Idemitsu Petrochemical Co., Ltd.)
1700A, viscosity average molecular weight 21500, PC-2: Idemitsu Petrochemical Co., Ltd. Tufflon FN1900A, viscosity average molecular weight 19000, PC-3: Idemitsu Petrochemical Co., Ltd. Tufflon FN1700A, viscosity average molecular weight 1750
0), the polyorganosiloxane-containing graft copolymers (SG-1 to SG-3) obtained in Reference Examples 4 to 6, and the aromatic-containing polyorganosiloxane (XC99: GE Toshiba Silicone Co., Ltd. XC99B-5664, phenyl). Group content 38 mol%), PTFE (polytetrafluoroethylene: polyfluorocarbon FA-50 manufactured by Daikin Industries, Ltd.)
0) and an antioxidant (AO-30: ADEKA STAB AO-30 manufactured by Asahi Denka Co., Ltd., PEP-36: ADEKA STAB PEP-36 manufactured by Asahi Denka Co., Ltd.) and blended in the composition shown in Table 3.

The obtained blend was melt-kneaded at 260 ° C. with a single screw extruder (HW-40-28 manufactured by Tabata Kikai Co., Ltd.) to produce pellets. Obtained pellets at 120 ℃
After drying for 5 hours at room temperature, FAS1 manufactured by FANUC Co., Ltd. with the cylinder temperature set at 280 ° C.
A 1/8 inch Izod test piece and a 1/16 inch flame retardancy evaluation test piece were prepared with a 00B injection molding machine. The obtained test pieces were used for evaluation according to the evaluation method described above.

The results are shown in Table 3.

[0094]

[Table 3] From Table 3, it can be seen that the composition of the present invention has an excellent balance of flame retardancy-impact resistance-molding processability.

[0095]

According to the present invention, a flame-retardant polycarbonate resin composition having an excellent balance of flame retardancy-impact resistance-molding processability can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 27:12) F term (reference) 4J002 BD123 BN172 CG001 CP032 EJ026 EJ036 EJ046 EU186 EV066 EW066 FD076 FD132 FD203 GQ00 4J026 AB44 AC32 AC36 BA04 BA25 BA27 BA31 BB10 DA04 DB04 DB12 DB13 DB16

Claims (4)

[Claims] 1. (A) viscosity average molecular weight 13,000 to 20
100 parts by weight of 000 polycarbonate resin, (B)
(B-1) A polyorganosiloxane-containing graft copolymer obtained by polymerizing a vinyl monomer (b-2) in the presence of the polyorganosiloxane particles (b-1), or (B-
2) A flame-retardant polycarbonate resin composition comprising 1 to 20 parts by weight of an aromatic group-containing polyorganosiloxane, (C) 0.05 to 1 part by weight of a fluororesin, and (D) 0 to 2 parts by weight of an antioxidant. 2. The polyorganosiloxane-containing graft copolymer comprises a vinyl monomer (b) in the presence of 40 to 90% by weight of polyorganosiloxane particles (b-1) having an average particle diameter of 0.008 to 0.6 μm. b-2) Obtained by polymerizing 60 to 10% by weight, wherein the vinyl monomer has a solubility parameter of a polymer of the vinyl monomer of 9.1.
The flame-retardant polycarbonate resin composition according to claim 1, which is ^{5 to} 10.15 (cal / cm ³ ) ^1/2 . 3. Polyorganosiloxane particles (b-1)
The flame-retardant polycarbonate resin composition according to claim 1 or 2, which is in the form of latex. 4. The vinyl monomer (b-2) is an aromatic vinyl monomer, a cyanide vinyl monomer, a (meth) acrylic acid ester monomer and a carboxyl group-containing vinyl monomer. The flame-retardant polycarbonate resin composition according to claim 1, which is at least one monomer selected from the group consisting of: