JP2002348457A - Aromatic polycarbonate resin composition and its molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin component of which the molded article is excellent in surface appearance, impact strength and flame retardance and a molded article of the same. SOLUTION: The aromatic polycarbonate resin composition contains (A) 100 mass pts. of an aromatic polycarbonate resin, (B) 5-80 mass pts. of titanium dioxide, (C) 0.5-30 mass pts. of a rubbery polymer impregnated with a silicone compound and (D) 2-30 mass pts. of a flame retarder. It is desirable to contain in 100 mass pts. of the aromatic polycarbonate resin 0.1-8 mass pts. of (E) polytetrafluoroethylene or (E') a modified polytetrafluoroethylene with a particle diameter of 10 μm or below which consists of a polytetrafluoroethylene particle and an organic polymer and contains 0.5-80 mass % of the above polytetrafluoroethylene particle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic polycarbonate resin having excellent appearance, high light reflectivity and flame retardancy while maintaining the original mechanical physical properties such as impact resistance and heat resistance. The present invention relates to a composition and a molded article thereof.

[0002]

2. Description of the Related Art For example, a plated product obtained by plating a resin molded product has been used as a light reflecting material. But,
Such a plated product requires a complicated plating process,
Because of the high cost, there has been a demand for a light reflecting plate material which does not need to be plated and has high reflectivity in the resin molded product itself. Therefore, it has been proposed to add titanium oxide to an aromatic polycarbonate resin which is excellent in mechanical properties, dimensional stability, heat resistance and the like and which is suitable for use as a reflector, to impart reflectivity. However, since the aromatic polycarbonate resin is excellent in transparency, if the amount of titanium oxide is small, the amount of transmitted light is large and the required high light reflectivity cannot be obtained. On the other hand, if the amount of titanium oxide is increased, the mechanical properties inherent to the polycarbonate resin such as impact resistance may be impaired. Further, with the reduction in weight and thickness of products, further reduction in thickness, good appearance, and flame retardancy of aromatic polycarbonate resin reflectors have been required.

[0003] Therefore, methods for improving appearance and flame retardancy while maintaining mechanical properties have been studied. For example, Japanese Patent Application Laid-Open No. 4-202476 proposes a method of adding titanium oxide surface-treated with a specific polyorganosiloxane to a polycarbonate resin when titanium oxide is blended with the aromatic polycarbonate resin. Japanese Patent Application Laid-Open No. 9-12853 proposes a method of adding a specific rubbery polymer.

[0004]

However, in the invention described in JP-A-4-202476 or JP-A-9-12853, it is possible to impart a certain level of light reflection performance and mechanical properties, The properties, surface appearance, impact resistance, flame retardancy, etc. of the molded product were not sufficiently satisfied. The present invention has been made in view of these circumstances, and an object of the present invention is to provide an aromatic polycarbonate resin composition having excellent surface appearance, impact resistance, and flame retardancy of a molded article, and to provide the molded article. And

[0005]

The aromatic polycarbonate resin composition according to the present invention comprises titanium oxide (B) 5 to 80 with respect to 100 parts by mass of the aromatic polycarbonate resin (A).
Parts by mass, 0.5 to 30 parts by mass of a rubbery polymer (C) impregnated with a silicone compound, and 2 to 30 parts of a flame retardant (D)
Parts by mass are at least blended. At this time, the rubbery polymer (C) is a rubber graft copolymer in which a vinyl monomer is graft-polymerized to a diene polymer, an acrylic rubber polymer, or a silicone-acryl composite rubber polymer. Is preferred. Moreover, it consists of polytetrafluoroethylene (E) or polytetrafluoroethylene and an organic polymer, and the content of the polytetrafluoroethylene is 0.5 to 80% by mass.
It is preferable that 0.1 to 8 parts by mass of the modified polytetrafluoroethylene (E ′) having a particle diameter of 10 μm or less is mixed with 100 parts by mass of the aromatic polycarbonate resin (A). Further, a molded article of the aromatic polycarbonate resin composition of the present invention is a molded article of the above-described aromatic polycarbonate resin composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The aromatic polycarbonate resin (A) used in the aromatic polycarbonate resin composition of the present invention is a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate. A polymer obtained by a transesterification method of reacting,
A typical example is a polycarbonate produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

Examples of the dihydroxydiaryl compound include, in addition to bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) ) Butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3)
-Methylphenyl) propane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-
Bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-
Bis (hydroxyaryl) alkanes such as 3,5-dichlorophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-
Bis (hydroxyaryl) cycloalkanes such as (hydroxyphenyl) cyclohexane,

Dihydroxydiaryl ethers such as 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; 4,4'-dihydroxydiphenyl sulfide;
Dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; 4,4'-dihydroxydiphenyl sulphoxide;
Dihydroxydiarylsulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone,
And dihydroxydiarylsulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone. These can be used alone or as a mixture of two or more kinds. In addition, piperazine, dipiperidyl hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, and the like may be used in combination.

Further, the above-mentioned dihydroxyaryl compound and a phenol compound having three or more valences as shown below may be mixed and used. Phloroglucin, 4,6-dimethyl-2,4,6-tri-
(4-hydroxyphenyl) -heptene-2,4,6-
Dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -Ethane and 2,2-bis-
[4,4- (4,4′-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

[0010] The viscosity average molecular weight of the aromatic polycarbonate resin (A) is not particularly limited, but is preferably from 10,000 to 100,000 from the viewpoint of moldability and strength. More preferably, it is 15,000 to 35,000.
Also, when producing an aromatic polycarbonate resin,
A molecular weight regulator, a catalyst and the like may be used as needed.

The titanium oxide (B) is not particularly limited. For example, titanium oxide produced by any method such as a chlorine method or a sulfuric acid method may be used. Further, any of a rutile type and an anatase type may be used, but a rutile type is more preferable in terms of thermal stability, weather resistance and the like. Further, the shape of the fine powder particles of titanium oxide (B) is not particularly limited, and can be appropriately selected and used, such as a flaky shape, a spherical shape, and an irregular shape.

The surface of the titanium oxide (B) is formed of a hydrated oxide of aluminum such as hydrated alumina and / or silicon such as hydrated silica, an amine compound such as triethanolamine, and a polyol compound such as trimethylolethane. Treated is preferred. Further, the titanium oxide (B) is more preferably treated with an organic surface treating agent. Examples of the organic surface treating agent include siloxanes such as alkylpolysiloxane, alkylarylpolysiloxane, and alkylhydrogenpolysiloxane, and organosilicon such as alkylalkoxysilane and amino-based silane coupling agent. Among them, particularly preferred organic surface treatment agents include methyl hydrogen polysiloxane, methyl trimethoxy silane, trimethyl methoxy silane, N-β (aminoethyl) -γ-aminopropyl trimethoxy silane, N-β
(Aminoethyl) -γ-aminopropylmethyldimethoxysilane and the like. The organic surface treating agent may contain a stabilizer or a dispersant in an amount that does not impair the effects of the present invention.

The treatment with an organic surface treating agent improves the uniform dispersibility of titanium oxide (B) and the stability of the dispersed state in the aromatic polycarbonate resin composition, and also provides a flame retardant (D ) Is also preferred, since the affinity with) is also improved and a uniform composition can be obtained.

The surface treatment method of the titanium oxide (B) is not particularly limited, and can be appropriately carried out by any method.
Although the amount of the surface treatment agent applied to the surface of the titanium oxide (B) particles by this surface treatment is not particularly limited,
The content is preferably 1 to 15% by mass based on the titanium oxide (B). When the amount of the surface treatment agent is less than 1% by mass relative to titanium oxide (B), the light reflectivity of the finally obtained molded article of the aromatic polycarbonate resin composition may be insufficient, and may be 15% by mass. If it exceeds 300, the moldability of the aromatic polycarbonate resin composition may be reduced. In the composition of the present invention, the particle diameter of the titanium oxide powder used as the titanium oxide (B) is not particularly limited, but the weight average particle diameter is preferably from 0.1 to 0.5 μm. When the content is within the above range, the light reflectivity can be efficiently improved, so that the amount of titanium oxide (B) added can be reduced.

The titanium oxide (B) is added to the aromatic polycarbonate resin composition of the present invention in an amount of 5 to 8 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin composition.
0 parts by mass is contained. When the content of titanium oxide (B) is less than 5 parts by mass, high light reflectivity cannot be obtained. If the amount exceeds 80 parts by mass, the aromatic polycarbonate resin is decomposed by the surface hydroxyl groups of titanium oxide (B), and mechanical properties, particularly impact strength, may be reduced. Further, the flame retardancy may decrease.

The rubbery polymer (C) impregnated with a silicone compound is not particularly limited as long as the rubbery polymer is impregnated with the silicone compound, but it is not limited to a diene polymer such as polybutadiene, or polybutyl acrylate. A rubber graft copolymer obtained by graft-polymerizing a vinyl monomer to an acrylic rubber polymer of the above or a silicone-acryl composite rubber polymer in which polyorganosiloxane and poly n-butyl acrylate are compounded. Is preferred. As such a rubber graft copolymer, a commercially available methyl methacrylate-butadiene-styrene (MBS) -based reinforcing agent, an acrylic rubber-based reinforcing agent, a silicone-acrylic composite rubber-based reinforcing agent, or the like may be used. it can.

The silicone compound impregnated in the rubbery polymer is not particularly limited. For example, as typical silicone compounds, R ₃ SiO _0.5 , R _3
2 SiO, RSiO _1.5 , SiO ₂ , R ¹ R ₂ SiO _0.5 , R
¹ RSiO, (R ¹ ) ₂ SiO units and mixtures thereof, wherein R represents a saturated or unsaturated monovalent hydrocarbon group,
R ¹ represents the same group as R or a functional group selected from the group consisting of a hydrogen atom, hydroxyl, alkoxyl, aryl, vinyl or allyl group. However, when both R ¹ and R are present, they may be the same or different from each other). Silicone compounds having a siloxy unit chemically bonded to those selected from R ¹ and R may be mentioned.

The amount of the silicone compound impregnated into the rubbery polymer is 5 to 2 parts per 100 parts by weight of the rubbery polymer.
It is preferably 0 parts by mass. If the impregnation amount of the silicone compound is less than 5% by mass, the effect of improving the surface appearance and the effect of imparting flame retardancy may not be sufficiently exhibited. Also,
If the content exceeds 20% by mass, bleeding may occur on the surface of a molded article comprising the finally obtained aromatic polycarbonate resin composition.

The compounding ratio of the rubbery polymer (C) impregnated with the silicone compound used in the present invention is 0.5 to 100 parts by mass of the aromatic polycarbonate resin (A).
Preferably it is 30 parts by mass. With this range,
The aromatic polycarbonate has a good effect of suppressing a decrease in the molecular weight, and an excellent surface appearance, mechanical properties, and an effect of imparting flame retardancy can be obtained. By using such a rubbery polymer impregnated with a silicone compound, it is possible to improve the surface appearance of the molded article and to improve the flame retardancy.

The flame retardant (D) is not particularly limited as long as it suppresses flammability, but is preferably a halogen-based flame retardant and / or a phosphoric ester-based flame retardant and / or an organic sulfonic acid. It is selected from salt. Examples of the halogen-based flame retardant include aromatic halogen compounds, halogenated epoxy resins, halogenated polycarbonate resins, halogenated aromatic vinyl polymers, halogenated cyanurate resins, halogenated polyphenyl ethers, halogenated polyphenylthioethers, and the like. Can be Among them, preferably decabromodiphenyl oxide, brominated bisphenol-based epoxy resin, brominated bisphenol-based phenoxy resin, brominated bisphenol-based polycarbonate resin, brominated polystyrene resin, brominated cross-linked polystyrene resin, brominated bisphenol cyanurate resin, brominated Polyphenylene oxide, polydibromophenylene oxide, decabromodiphenyl oxide bisphenol condensate (tetrabromobisphenol A, an oligomer thereof, etc.).

Further, as the phosphate ester flame retardant,
For example, phosphoric acid esters and oligomeric phosphoric acid esters can be used. These phosphate esters
It is obtained by reacting an alcohol or phenol compound with a phosphorus compound such as phosphorus oxychloride or phosphorus pentachloride. In addition, 1 as a phenol compound
When a divalent phenol compound such as resorcinol, hydroquinone, and diphenol compound is used together with the divalent phenol compound, an oligomeric phosphate ester is obtained.

Specific examples of the phosphoric ester flame retardant include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxycotyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl. Non-halogen phosphates such as phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, bis (2,3 dibromopropyl) 2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate, bis Halogen-containing phosphoric acid esters such as (chloropropyl) monooctyl phosphate are exemplified. The organic metal sulfonate is not particularly limited, and examples thereof include potassium perfluorobutanesulfonate, potassium trichlorobenzenesulfonate, and potassium diphenylsulfon-3-sulfonate.

As the polytetrafluoroethylene (E), those capable of forming fibrils in the aromatic polycarbonate resin composition are particularly preferable. For example, Daikin Industries, Ltd.
Polyflon TFEF-201L can be used

The modified polytetrafluoroethylene (E ') is composed of polytetrafluoroethylene and an organic polymer, and has a weight average particle size of 10 μm or less. The content of polytetrafluoroethylene in the modified polytetrafluoroethylene is 0.5 to 80% by mass.
Furthermore, polytetrafluoroethylene in powder
It is necessary that the aggregates not exceed m.

Such a modified polytetrafluoroethylene (E ') is obtained by mixing an aqueous dispersion of polytetrafluoroethylene particles having a weight average particle diameter of 0.05 to 1.0 μm with an aqueous dispersion of organic polymer particles. Are mixed, and the resulting mixed solution is preferably poured into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, solidified, and then dried and powdered. Alternatively, it is preferably obtained by pulverizing the mixed solution by spray drying. Alternatively, after the monomer constituting the organic polymer is polymerized in the presence of an aqueous dispersion of polytetrafluoroethylene particles having a particle diameter of 0.05 to 1.0 μm, it is pulverized by coagulation with a metal salt or spray drying. It is preferably obtained by the following method. Or, a particle size of 0.05 to
After a monomer having an ethylenically unsaturated bond is emulsion-polymerized in a dispersion obtained by mixing an aqueous dispersion of 1.0 μm polytetrafluoroethylene particles and an aqueous dispersion of organic polymer particles, a metal salt It is preferably obtained by coagulation or powdering by spray drying.

Modified polytetrafluoroethylene (E ')
Particle size of 0.05 to 1.0 μm used to obtain
The aqueous dispersion of polytetrafluoroethylene particles is obtained by polymerizing a tetrafluoroethylene monomer by emulsion polymerization using a fluorinated surfactant.
During the emulsion polymerization of polytetrafluoroethylene monomer,
Fluorinated olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, and perfluoroalkylvinyl ether, and perfluoroalkyl (meth) acrylate as copolymerization components as long as the properties of the obtained polytetrafluoroethylene are not impaired. Can be used. The content of such a copolymer component is 10% by mass based on the weight of tetrafluoroethylene.
The following is preferred.

An aqueous dispersion of polytetrafluoroethylene particles is commercially available, and a typical example thereof is Asahi IC
Product name Fluon AD-1, AD manufactured by I Fluoropolymer
-936, trade name Polyflon D manufactured by Daikin Industries, Ltd.
1, D-2 and Teflon 30J (trade name, manufactured by Mitsui Dupont Fluorochemicals Co., Ltd.).

Modified polytetrafluoroethylene (E ')
The organic polymer constituting is not particularly limited, but from the viewpoint of improving dispersibility when blended into the aromatic polycarbonate resin composition, has a high affinity with the aromatic polycarbonate resin used. Preferably, it is Specific examples of the monomer constituting such an organic polymer include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, t-butylstyrene, o-ethylstyrene, and p-chlorostyrene. , O-chlorostyrene, 2,4-dichlorostyrene, p-methoxystyrene, o-methoxystyrene, aromatic vinyl monomers such as 2,4-dimethylstyrene, methyl acrylate, methyl methacrylate, ethyl acrylate , Ethyl methacrylate, butyl acrylate, butyl methacrylate,
2-ethylhexyl acrylate, methacrylic acid-2-
(Meth) acrylate monomers such as ethylhexyl, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate;

Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; α, such as maleic anhydride;
β-unsaturated carboxylic acid, N-phenylmaleimide, N-
Maleimide monomers such as methylmaleimide and N-cyclohexylmaleimide, glycidyl group-containing monomers such as glycidyl methacrylate, vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether, vinyl acetate and vinyl butyrate Examples include vinyl carboxylate monomers, olefin monomers such as ethylene, propylene and isobutylene, and diene monomers such as butadiene, isoprene and dimethylbutadiene. These monomers can be used alone or as a mixture of two or more. Particularly preferred among these monomers are
The aromatic vinyl-based monomer, the (meth) acrylate-based monomer, and the vinyl cyanide have good dispersibility in the aromatic polycarbonate resin composition, and are preferable in terms of flame retardancy and surface appearance of the molded article. It is a system monomer.

Modified polytetrafluoroethylene (E ')
The content of polytetrafluoroethylene in is 0.5 to
80% by mass. When the content of polytetrafluoroethylene is less than 0.5% by mass, the anti-dripping property, which is one index of flame retardancy, may not be imparted. When the content exceeds 80% by mass, the surface appearance of the molded article is deteriorated. May be.

The polytetrafluoroethylene (E) or the modified polytetrafluoroethylene (E ') is used in the aromatic polycarbonate resin composition of the present invention in an amount of 0.1 to 100 parts by mass of the aromatic polycarbonate resin (A). ~ 8
It is preferred to be compounded by mass. If the blending amount of polytetrafluoroethylene (E) or modified polytetrafluoroethylene (E ') is less than 0.1 part by mass, the flame retardancy tends to decrease. Tend to have a reduced surface appearance.

The aromatic polycarbonate resin composition of the present invention comprises the above components (A) to (D) and, if necessary, (E) or (E '). In the production method, for example, components (A) to (E) are charged into a V-type blender, a ribbon mixer, a tumbler, or the like, uniformly mixed, and then melt-kneaded with a normal single-screw or twin-screw extruder. After cooling, cut into pellets. At this time, a filler such as titanium oxide or a part of other components may be added in the middle of the extruder. Alternatively, after some of the components are previously mixed and kneaded, the remaining components may be added and extruded.

The aromatic polycarbonate resin composition of the present invention may contain, if necessary, polyester, polyamide, AB
Other resins such as S and polyphenylene ether may be contained. Further, for example, a reinforcing agent such as whiskers such as talc, mica, glass fiber, carbon fiber, fibrous titanium oxide, potassium titanate whisker, and aluminum borate whisker may be blended. Further, the aromatic polycarbonate resin composition may contain various additives, if necessary, in an amount exhibiting the effect thereof, for example, phosphite-based stabilizers, phosphate-based stabilizers, and antioxidants such as hindered phenol-based compounds. Agents, fluidity modifiers such as polycaprolactone, and other release agents, ultraviolet absorbers, antistatic agents, dyes and pigments, and the like.

In the above-mentioned aromatic polycarbonate resin composition of the present invention, titanium oxide (B) 5 to 80 parts by mass is used per 100 parts by mass of the aromatic polycarbonate resin (A).
Parts by mass, 0.5 to 30 parts by mass of a rubbery polymer (C) impregnated with a silicone compound, and 2 to 30 parts of a flame retardant (D)
Parts by mass, the titanium oxide (B) improves reflectivity, the rubbery polymer (C) impregnated with a silicone compound (C) improves the surface appearance and mechanical properties, and the flame retardant ( D) results in improved flame retardancy. Moreover, since the compounding ratio of each component is specifically set in the above-described specific range, the obtained aromatic polycarbonate resin composition has properties such as mechanical properties, surface appearance of a molded product, light reflectivity, and flame retardancy. It will have both.

The rubbery polymer (C) is a rubber graft copolymer obtained by graft-polymerizing a vinyl monomer to a diene polymer, an acrylic rubber polymer, or a silicone-acryl composite rubber polymer. Since these rubber graft copolymers can be dispersed well in an aromatic polycarbonate resin, not only can the surface appearance and flame retardancy of a molded article be improved, but the rubber graft copolymer also has an excellent resin reinforcing agent. Thus, the mechanical properties of the aromatic polycarbonate resin can be further improved.

The aromatic polycarbonate resin composition comprises polytetrafluoroethylene (E) or polytetrafluoroethylene and an organic polymer, and the content of polytetrafluoroethylene is 0.5 to 80.
When the modified polytetrafluoroethylene (E ′) having a particle diameter of 10 μm or less is 0.1 to 8 parts by mass based on 100 parts by mass of the aromatic polycarbonate resin (A), the polytetrafluoroethylene contains Since a domain having a particle diameter of more than 10 μm is not formed by itself and the compounding amount thereof is an appropriate amount, it can be well dispersed in an aromatic polycarbonate resin. As a result, polytetrafluoroethylene is efficiently fibrillated in the polycarbonate resin composition, and the anti-dripping property, which is one index of flame retardancy, and the surface appearance of a molded article can be further improved.

Such an aromatic polycarbonate resin composition can be easily molded by a method such as extrusion molding, injection molding, or compression molding, and can also be molded by blow molding, vacuum molding, or the like. The molded product obtained by molding is excellent in mechanical properties and surface appearance, and has high light reflectivity and flame retardancy, so that it can be suitably used for electronic / OA products. Among them, it is particularly suitable as a material for a liquid crystal backlight reflector.

[0038]

The present invention will be described in more detail with reference to the following examples. In the Reference Examples, Examples and Comparative Examples, “parts” and “%” mean “parts by mass” and “% by mass”, respectively. The measurement of each characteristic value was obtained by the following method. (1) Solid content concentration: It was determined by drying the particle dispersion at 170 ° C. for 30 minutes and measuring the weight before and after drying. (2) Particle size distribution, weight average particle size: ELS manufactured by Otsuka Electronics Co., Ltd. was prepared by diluting a particle dispersion with water as a sample liquid.
The measurement was performed by dynamic light scattering at a temperature of 25 ° C. and a scattering angle of 90 °. (3) Zeta potential: 0.01 mol / l of the particle dispersion
The sample was diluted with an aqueous solution of NaCl, and ELS800 manufactured by Otsuka Electronics Co., Ltd. was used as a sample solution. The measurement was performed by electrophoresis at a temperature of 25 ° C. and a scattering angle of 10 °.

(4) Izod impact strength (unit: J /
m): Using a 75t injection molding machine, test 1/8 inch thick
Specimens were molded and evaluated according to ASTM D256. (5) Deflection temperature under load (unit: ° C): 75t injection molding machine
A test piece is formed by using the method described above, and based on ASTM D-648.
Was evaluated. The load was 18.5 kgf / cm ^Twoage
Was. (6) Light reflectance: Spectrophotometer U- manufactured by Hitachi, Ltd.
3500, and Y at a wavelength of 400 to 800 nm.
The value was measured. When the Y value is 92% or more, a reflection plate product
Available as (7) Combustion test: Thickness 1/1 using 75t injection molding machine
A 6-inch test piece is molded and UL Standard 94-V Plasti
The evaluation was made based on the test method for combustion in the fire. (8) Surface appearance: using a 75t injection molding machine, thickness 1/1
A 6-inch test piece was molded, and the surface appearance of the molded product was
It was visually evaluated by reference. ：: Very good surface appearance ：: Smooth and good appearance ×: Very rough surface and poor appearance

[Examples 1 to 8 and Comparative Examples 1 to 7] A rubber obtained by drying an aromatic polycarbonate resin (A) at 120 ° C. for 5 hours and then impregnating the same with titanium oxide (B) and a silicone compound. Polymer (C), various flame retardants (D) and polytetrafluoroethylene (E) or modified polytetrafluoroethylene (E '), rubbery polymer (F), phosphorus-based stabilizer (trimethyl phosphate: Daihachi) (TMP manufactured by Chemical Industry Co., Ltd.) were mixed in a blending ratio shown in Table 1 using a blender. The obtained mixture was extruded with a vented twin-screw extruder at a cylinder temperature of 280 ° C. while being degassed, and pelletized. The obtained pellets were dried by a hot air circulating drier at 120 ° C. for 6 hours, and then a sample plate was heated at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. by a 75t injection molding machine.
A test piece for measuring impact strength and deflection temperature under load and a test piece for combustion test were formed. The test piece for measuring impact strength and deflection temperature under load and the test piece for combustion test are 23 ° C, 50%
After conditioning for 48 hours under the condition of RH, it was used for measurement. Using the test pieces thus obtained, the tests (1) to (8) described above were performed. Table 1 shows the results of Examples 1 to 8, and Table 2 shows the results of Comparative Examples 1 to 7.

[0041]

[Table 1]

[0042]

[Table 2]

In Examples 1 to 8, titanium oxide (B) 5 to 100 parts by mass of aromatic polycarbonate resin (A) were used.
Since 80 parts by mass, 0.5 to 30 parts by mass of the silicone compound-impregnated rubbery polymer (C) and 2 to 30 parts by mass of the flame retardant (D) are blended, Izod impact strength, deflection temperature under load, And the light reflectance was high. In the combustion test, the condition of V-0 was satisfied. Also, the surface appearance was excellent.

On the other hand, Comparative Examples 1 to 3 in which a rubbery polymer not impregnated with a silicone compound was used,
d Impact strength, deflection temperature under load, and light reflectance were low. In the combustion test, only the condition of V-2 was satisfied. In addition, the surface appearance was particularly poor. Comparative Example 4, in which the amount of titanium oxide was out of the range of the present invention, was particularly low in impact strength and flame retardancy, and was inferior in surface appearance. Comparative Example 5, which did not contain the silicone compound-impregnated rubbery polymer,
In particular, the impact strength was low and the surface appearance was poor. Comparative Example 6 containing no flame retardant had particularly low flame retardancy. Comparative Example 7, which did not contain the silicone compound-impregnated rubbery polymer and polytetrafluoroethylene, was particularly low in impact strength and flame retardancy.

The components used are as follows. Aromatic polycarbonate resin (A) (A-1) Bisphenol A type polycarbonate: NOVAREX 7022A manufactured by Mitsubishi Engineering-Plastics Corporation

Titanium oxide (B) (B-1) Titanium oxide: CR-93 manufactured by Ishihara Sangyo Co., Ltd.
Crystal system; rutile, manufacturing method; chlorine method, main processing agent; alumina / silica (B-2) titanium oxide: PC-2 manufactured by Ishihara Sangyo Co., Ltd .; crystal system; rutile, manufacturing method; chlorine method, main processing agent ; Alumina, silica, methyl hydrogen polysiloxane

Silicone compound-impregnated rubbery polymer (C) (C-1) Silicone compound-impregnated silicone-acrylic composite rubber-based graft copolymer: 2 parts of tetraethoxysilane, γ-methacryloyloxypropyldimethoxymethylsilane 5 parts and 97.5 parts of octamethylcyclotetrasiloxane are mixed, and a siloxane mixture 180 is mixed.
Got a part. 100 parts of the above siloxane mixture was added to 200 parts of distilled water in which 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonic acid were respectively dissolved, and the mixture was preliminarily stirred at 10,000 rpm with a homomixer. Next, the mixture was emulsified and dispersed with a homogenizer at a pressure of 30 MPa to obtain an organosiloxane latex.
This organosiloxane latex was transferred to a separable flask equipped with a condenser and a stirring blade, and heated at 80 ° C. for 5 hours while stirring and mixing. Thereafter, the mixture was allowed to stand at 20 ° C., and after 48 hours, the pH of this latex was neutralized to 7.0 with an aqueous sodium hydroxide solution to complete the polymerization, thereby obtaining a polyorganosiloxane rubber latex (I). The polymerization rate of the obtained polyorganosiloxane rubber is 89.6%.
And the weight average particle diameter of the polyorganosiloxane rubber was 0.17 μm.

100 parts of the above-mentioned polyorganosiloxane rubber latex (I) was collected and placed in a separable flask equipped with a stirrer, and 120 parts of distilled water was added thereto. Next, a mixed liquid of 37.5 parts of n-butyl acrylate, 2.5 parts of allyl methacrylate and 0.3 part of tert-butyl hydroperoxide was charged into a separable flask and stirred for 30 minutes, and the mixed liquid was mixed with polyorganosiloxane rubber particles. Infiltrated. Then, a mixture of 0.0003 parts of ferrous sulfate, 0.001 part of disodium ethylenediaminetetraacetate, 0.17 part of Rongalite and 3 parts of distilled water is charged to generate radicals and initiate radical polymerization. Was. Thereafter, the temperature in the separable flask was maintained at 70 ° C. for 2 hours, and the polymerization was completed to obtain a silicone-acryl composite rubber latex. A portion of this silicone-acrylic composite rubber latex was collected and the weight average particle diameter was measured to be 0.20 μm. The silicone-acrylic composite rubber latex was dried to obtain a solid, and the solid was extracted with toluene at 90 ° C. for 12 hours, and the gel content was measured to be 91.2%. This silicone
A mixture of 0.3 part of tert-butyl hydroperoxide, 9 parts of acrylonitrile and 21 parts of styrene was dropped at 70 ° C. over 45 minutes to the acrylic composite rubber latex, and then kept at 70 ° C. for 4 hours to obtain a silicone-acrylic mixture. A graft copolymer obtained by grafting acrylonitrile and styrene on the composite rubber was obtained.

The polymerization rate of the obtained graft copolymer is 9
8.2%. This graft copolymer latex was dropped into hot water of 5% calcium chloride to coagulate and separate the graft copolymer. After washing, it was dried at 75 ° C. for 16 hours to obtain a silicone-acryl composite rubber-based graft copolymer. 85 parts of the obtained silicone-acrylic composite rubber-based graft copolymer was charged into a Henschel mixer, and stirred at 2000 rpm.
Dimethyl silicone oil (SH-200 manufactured by Dow Corning Toray Silicone Co., Ltd .; 30,000 cSt) 1
5 parts were added. The mixture was stirred for 3 minutes to obtain a silicone-acrylic composite rubber-based graft copolymer (C-1) impregnated with a silicone-based compound.

(C-2) MBS impregnated with silicone compound
Resin: 150 parts of deionized water in a pressure-resistant autoclave,
85 parts of 1,3-butadiene, 15 parts of styrene, 0.5 parts of t-dodecyl mercaptan, 0.4 parts of diisopropylbenzene hydroperoxide, 1.5 parts of sodium pyrophosphate
Part, ferrous sulfate 0.02 part, dextrose 1.0 part,
Then, 1.0 part of potassium oleate was charged and reacted at 50 ° C. for 15 hours with stirring to produce a butadiene-based rubber-polymerized latex. 65 parts (as solid content) of the above butadiene rubber polymerized latex were charged into a flask,
It was replaced with nitrogen. Then, a 10% aqueous sodium hydrogen carbonate solution containing 1.2 parts of sodium hydrogen carbonate was added thereto, and the mixture was stirred for 30 minutes. Next, 1 part of potassium oleate was added as a 7% aqueous solution and the latex was stabilized. Then, 0.6 part of Rongalite was added, and the internal temperature was maintained at 70 ° C. to obtain a monomer mixture having the following composition. 35 parts were graft-polymerized.

With the total graft monomer mixture being 100 parts, the first stage of grafting was 40 parts of methyl methacrylate,
A monomer mixture of 5 parts of ethyl acrylate and 0.1 part of tertiary butyl hydroperoxide (t-BH) was added dropwise over 1 hour, and polymerized for 2 hours with stirring. Next, as a second stage of grafting, a mixture of 40 parts of styrene and 0.1 part of t-BH was added dropwise over 1 hour, and polymerization was performed for 2 hours with stirring. Then, 15 parts of methyl methacrylate and t-BH 0.05
Part of the monomer mixture was added dropwise over 1 hour and polymerized for 2 hours with stirring to obtain an MBS resin latex. 2,6-di-t-butyl-4-
After adding 0.5 parts of methyl-phenol (BHT),
A 0.2% aqueous sulfuric acid solution was added for coagulation, followed by heat treatment and solidification at 90 ° C. Thereafter, the obtained coagulated product was washed with warm water and further dried to obtain an MBS resin powder. M obtained
The MBS resin (C-2) impregnated with the silicone compound was obtained by impregnating the BS resin powder with dimethyl silicone oil in the same manner as the silicone-acryl composite rubber-based graft copolymer (C-1).

(C-3) Acrylic graft copolymer impregnated with a silicone compound: 195 parts of distilled water and 0.1 part of sodium dodecylbenzenesulfonate were added to a separable flask equipped with a stirrer, and the mixture was purged with nitrogen.
The temperature was raised to ° C. Next, a mixed solution of 0.002 part of ferrous sulfate, 0.006 part of disodium ethylenediaminetetraacetate, 0.26 part of Rongalit and 5 parts of distilled water was charged, 70 parts of n-butyl acrylate substituted with nitrogen, and allyl methacrylate. Radical polymerization was initiated by charging a mixture of 0.75 parts and 0.4 parts of tert-butyl hydroperoxide. Thereafter, the polymerization was terminated by maintaining the internal temperature at 70 ° C. for 2 hours to obtain an acrylic rubber latex. A part of this acrylic rubber latex was collected and the weight average particle diameter was measured to be 0.21 μm.

To this acrylic rubber latex, tert
A mixture of 0.06 parts of butyl hydroperoxide and 30 parts of methyl methacrylate was added dropwise at 70 ° C. for 15 minutes, and then maintained at 70 ° C. for 4 hours to obtain an acrylic rubber copolymer obtained by grafting methyl methacrylate onto an acrylic rubber. A polymer latex was obtained. The final polymerization rate of methyl methacrylate was 98.9%, and the weight average particle diameter was 0.23 μm. The obtained acrylic graft copolymer latex was dropped into 200 parts of hot water containing 1.5% of calcium chloride, coagulated and separated. After washing the obtained coagulated product, it was dried at 75 ° C. for 16 hours to obtain an acrylic graft copolymer powder. The obtained acrylic graft copolymer powder is impregnated with dimethyl silicone oil in the same manner as the silicone-acryl composite rubber-based graft copolymer (C-1), so that the acrylic graft copolymer impregnated with the silicone compound is obtained. Polymer (C-
3) was obtained.

Flame retardant (D) (D-1) Triphenyl phosphate (TPP): TPP polytetrafluoroethylene (E) and modified polytetrafluoroethylene (E ') manufactured by Daihachi Chemical Industry Co., Ltd. (E-1) Modified polytetrafluoroethylene: stirring blade,
A separable flask equipped with a condenser, a thermocouple, and a nitrogen inlet was charged with 190 parts of distilled water, 1.5 parts of sodium dodecylbenzenesulfonate, 100 parts of styrene, and 0.5 part of cumene hydroperoxide.
The temperature was raised to ° C. Subsequently, a mixed solution of 0.001 part of iron (II) sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.24 part of Rongalit salt and 10 parts of distilled water was added to start radical polymerization. After the end of the heat generation due to the heat of polymerization, the polymerization temperature was maintained at 40 ° C. for 1 hour to terminate the polymerization, thereby obtaining a styrene polymer particle dispersion (P-1). The solid content concentration of the styrene polymer particle dispersion (P-1) is 3
At 3.2%, the particle size distribution showed a single peak, the weight average particle size was 89 nm, and the surface potential was -31 mV.

As the polytetrafluoroethylene-based particle dispersion, Fluon AD manufactured by Asahi ICI Fluoropolymers Co., Ltd.
936 was used. The solid concentration of Fluon AD936 is 6
3.0%, containing 5 parts of polyoxyethylene alkylphenyl ether per 100 parts of polytetrafluoroethylene. Further, when the particle size distribution of Fluon AD936 was measured, it showed a single peak, the weight average particle size was 292 nm, and the surface potential was -22 mV. Add 833 parts of Fluon AD936 to distilled water 1167
The resulting mixture was added to obtain a polytetrafluoroethylene particle dispersion (TF-1) having a solid content concentration of 26.1%. The polytetrafluoroethylene particle dispersion (TF-1) contains 25% of polytetrafluoroethylene particles and 1.2% of polyoxyethylene nonylphenyl ether. Next, a polytetrafluoroethylene particle dispersion (TF-
1) 160 parts (that is, 40 parts of polytetrafluoroethylene) and a styrene polymer particle dispersion (P-1) 18
1.8 parts (that is, 60 parts of polystyrene) were charged into a separable flask equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet, and stirred at room temperature for 1 hour while flowing nitrogen. Thereafter, the temperature was raised to 80 ° C. and maintained for 1 hour. No solids were separated through these series of operations, and a uniform particle dispersion was obtained. The solid concentration of the particle dispersion is 29.
3%, the particle size distribution was relatively broad, and the weight average particle size was 169 nm.

341.8 parts of the particle dispersion is poured into 700 parts of hot water at 85 ° C. containing 5 parts of calcium chloride to separate a solid, and the obtained solid is filtered and dried to obtain polytetrafluorocarbon. 98 parts of an ethylene-containing mixed powder (E-1) was obtained. This polytetrafluoroethylene-containing mixed powder (E-1) was shaped into strips at 250 ° C. by a press molding machine, and ultrathin sections were observed with a microtome without staining using a transmission electron microscope. . As a result of observation, 10
No aggregates larger than μm were observed.

(E-2) Modified polytetrafluoroethylene: A polytetrafluoroethylene particle dispersion (TF-1) was placed in a separable flask equipped with a stirring blade, a condenser, a thermocouple, a nitrogen inlet, and a dropping funnel. Parts (that is, 40 parts of polytetrafluoroethylene), 1.0 part of dodecylbenzenesulfonic acid, and 70 parts of distilled water, and the temperature was raised to 80 ° C. while flowing nitrogen. Then, iron sulfate (I
I) 0.001 part, disodium ethylenediaminetetraacetate 0.003 part, Rongalit salt 0.24 part, distilled water 1
After adding 0 parts of the mixture, n-butyl acrylate 20
, 40 parts of styrene, and 0.3 part of tertiary butyl peroxide were dropped from a dropping funnel to allow radical polymerization to proceed. This was continued for 90 minutes, and after dropping was completed, the internal temperature was kept at 80 ° C. and maintained for 1 hour. No solids were separated through these series of operations, and a uniform particle dispersion was obtained. The solid concentration of the particle dispersion is 33.2.
%, The particle size distribution is relatively broad and the weight average particle size is 2
It was 48 nm.

301.5 parts of this particle dispersion is put into 700 parts of hot water at 85 ° C. containing 5 parts of calcium chloride,
The solid was separated, and the obtained solid was filtered and dried to obtain a polytetrafluoroethylene-containing mixed powder (E-2) 98.
Got a part. This polytetrafluoroethylene-containing mixed powder (E-2) was shaped into strips at 250 ° C. by a press molding machine, and ultrathin sections were observed with a microtome without staining using a transmission electron microscope. . As a result of observation, 1
Aggregates larger than 0 μm were not observed.

(E-3) Modified polytetrafluoroethylene: 0.1 part of azobisdimethylvaleronitrile was dissolved in a mixture of 75 parts of dodecyl methacrylate and 25 parts of methyl methacrylate. A mixed solution of 2.0 parts of sodium dodecylbenzenesulfonate and 300 parts of distilled water was added thereto, and the mixture was stirred at 10,000 rpm for 4 minutes using a homomixer. Thereafter, the stirred mixture was passed twice through a homogenizer at a pressure of 30 MPa to obtain a stable dodecyl methacrylate-methyl methacrylate preliminary dispersion. This was charged into a separable flask equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet, and the inside temperature was increased to 80 ° C. while flowing nitrogen, followed by stirring for 3 hours to perform radical polymerization.
Then, a dodecyl methacrylate-methyl methacrylate copolymer particle dispersion (P-2) was obtained. The solid content of this dodecyl methacrylate-methyl methacrylate copolymer particle dispersion (P-2) was 25.1%, and the particle size distribution was measured. As a result, it showed a single peak, and the weight average particle size was 198 nm. The potential was -39 mV.

The polytetrafluoroethylene particle dispersion (TF-1) used in the production of the polytetrafluoroethylene-containing mixed powder (E-1) was mixed with 160 parts (that is, 40 parts of polytetrafluoroethylene) and dodecyl methacrylate. -Methyl methacrylate copolymer particle dispersion (P-
2) 159.4 parts (that is, 40 parts of dodecyl methacrylate-methyl methacrylate copolymer) and a stirring blade,
The mixture was charged into a separable flask equipped with a condenser, a thermocouple, a nitrogen inlet, and a dropping funnel, and stirred at room temperature for 1 hour while flowing nitrogen. Thereafter, the temperature was raised to 80 ° C., and iron sulfate (I
I) 0.001 part, disodium ethylenediaminetetraacetate 0.003 part, Rongalit salt 0.24 part, distilled water 1
After adding 0 parts of the mixture, a mixture of 20 parts of methyl methacrylate and 0.1 part of tertiary butyl peroxide was added dropwise over 30 minutes. After the completion of the dropwise addition, the internal temperature was maintained at 80 ° C. for 1 hour to terminate the radical polymerization. No solids were separated through these series of operations, and a uniform particle dispersion was obtained. The solid content concentration of the particle dispersion is 28.5%, the particle size distribution is relatively broad, and the weight average particle size is 248 n.
m.

349.7 parts of this particle dispersion liquid was poured into 600 parts of hot water at 75 ° C. containing 5 parts of calcium chloride to separate solids, and the obtained solid was filtered and dried to obtain polytetrafluorocarbon. 97 parts of an ethylene-containing mixed powder (E-3) was obtained. This polytetrafluoroethylene-containing mixed powder (E-3) was shaped into strips at 220 ° C. by a press molding machine, and ultrathin sections were observed with a microtome without staining using a transmission electron microscope. . As a result of observation, 10
No aggregates larger than μm were observed. (E-4) Polytetrafluoroethylene: Polykin TFE F-201L manufactured by Daikin Industries, Ltd.

Rubbery polymer (F): (F-1) Silicone-acrylic composite rubber-based graft copolymer: In the production of silicone compound-impregnated silicone-acrylic composite rubber-based graft copolymer (C-1),
Silicone before impregnation with silicone compound
An acrylic composite rubber-based graft copolymer was used. (F-2) MBS resin: In the production of MBS resin impregnated with silicone compound (C-2), the MBS resin in the stage before impregnation with the silicone compound was used. (F-3) Acrylic graft copolymer: Silicone compound impregnation In the production of the acrylic graft copolymer component (C-3), the acrylic graft copolymer before the impregnation of the silicone compound was used.

[0063]

According to the present invention, the aromatic polycarbonate resin, titanium oxide, a rubbery polymer impregnated with a silicone compound, and the flame retardant are in a specific range, so that the obtained aromatic polycarbonate resin The resin composition has properties such as mechanical properties, surface appearance of a molded article, light reflectivity, and flame retardancy.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 51:00) (C08L 69/00 27:18) (72) Inventor Koichi Ito Miyuki Otake, Hiroshima Prefecture No. 20-1 in the Mitsubishi Rayon Co., Ltd. Otake Works (72) Inventor Hideyuki Shigemitsu No. 20-1, Miyukicho, Otake City, Hiroshima Pref. In the Mitsubishi Rayon Co., Ltd. Otake Works F-term (reference) BC114

Claims (4)

[Claims] 1. Aromatic polycarbonate resin (A) 10
5 parts to 80 parts by mass of titanium oxide (B) with respect to 0 parts by mass,
Rubbery polymer impregnated with silicone compound (C)
An aromatic polycarbonate resin composition comprising at least 0.5 to 30 parts by mass and 2 to 30 parts by mass of a flame retardant (D). 2. The rubbery polymer (C) is a rubber graft copolymer in which a vinyl monomer is graft-polymerized to a diene polymer, an acrylic rubber polymer, or a silicone-acryl composite rubber polymer. The aromatic polycarbonate resin composition according to claim 1, wherein 3. A particle diameter of 10 μm or less comprising polytetrafluoroethylene (E) or polytetrafluoroethylene and an organic polymer, wherein the content of polytetrafluoroethylene is 0.5 to 80% by mass. Of modified polytetrafluoroethylene (E ′) is 0.1 to 100 parts by mass of the aromatic polycarbonate resin (A).
The aromatic polycarbonate resin composition according to claim 1 or 2, which is blended in an amount of 8 parts by mass. 4. A molded article of the aromatic polycarbonate resin composition, wherein the aromatic polycarbonate resin composition according to claim 1 is molded.