JP5369052B2 - Polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition which can give a molding free of appearance defects such as burn marks and silver streaks, good in impact characteristics, and excellent in moldability such as fluidity and mold release and to provide a molding made therefrom. <P>SOLUTION: There are provided a polycarbonate resin composition comprising 100 pts.mass (A) aromatic polycarbonate resin, 1-22 pts.mass (B) titanium oxide particles surface-treated with a polyol, and 0.01-0.75 pt.mass (C) methoxy-containing organopolysiloxane and a molding made therefrom. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a polycarbonate resin composition and a molded article comprising the resin composition, and particularly gives a molded article having good appearance and no impact defects such as burns and silver, and has moldability such as fluidity and releasability. The present invention relates to an excellent polycarbonate resin composition and a molded product comprising the same.

A light-shielding property is required for the housing due to the high output of the liquid crystal projector.
In addition, the appearance is required to have a design, and from the viewpoint of environmental considerations, there is also a need for no painting.
In addition, not only liquid crystal projectors but also various products such as personal computers and communication device terminal devices are required to have design characteristics, particularly whiteness.
In order to color the above-mentioned electronic / electric equipment casing in white, titanium oxide is often used.
However, since titanium oxide easily decomposes polycarbonate (PC) resin, it is necessary to take measures for preventing decomposition such as surface coating treatment in order to simply use it as a coloring material.
In addition, there is a need for technological development to obtain a good appearance in terms of materials in order to achieve white and no coating.
In order to obtain a good appearance, it is required to improve the stability of staying heat and further to improve the impact strength as the product is downsized.

In the PC resin / titanium oxide system, as described above, the PC resin is decomposed due to the influence of titanium oxide, so that the molecular weight of the PC resin is lowered and the occurrence of silver during molding is a problem.
In addition, it is considered that the occurrence of burns and black spots is induced during molding due to the influence of the decomposition product of the PC resin.
In order to prevent decomposition of the PC resin and the like, modification of titanium oxide has been studied.
In Patent Document 1, a polysiloxane-coated titanium oxide generally considered suitable for a PC resin is studied.
Also in Patent Document 2, a polysiloxane-coated titanium oxide is studied.
Patent Documents 3 and 4 relate to a PC resin composition containing titanium oxide, but only titanium oxide having a siloxane coating has been studied.
However, according to the study by the present inventors, when titanium oxide coated with polysiloxane is used, the occurrence of silver which is a problem in appearance during molding is observed, and silver cannot be suppressed.
Moreover, the examination regarding the titanium oxide surface-treated with the polyol of the present application has not been made to date.
Most of the metal salt compounds of organic sulfonic acid used for flame retardancy in many prior arts such as Patent Documents 5 and 6 are metal salts of perfluorobutane sulfonic acid. In the present invention, high impact strength is obtained. As for titanium oxide, only siloxane-coated titanium oxide has been evaluated.

JP 2006-37090 A JP 2006-77114 A JP 2007-191499 A JP-A-2005-15657 JP 2006-8132 A JP 2003-183428 A

  The present invention reduces appearance defects such as silver generated on the surface of molded products due to the influence of titanium oxide during molding, gives molded products with good impact characteristics, and excels in moldability such as fluidity and releasability. Another object of the present invention is to provide a polycarbonate resin composition and a molded product comprising the same.

  As a result of intensive studies to achieve the above object, the present inventors have formulated a surface of a molded article by blending an aromatic polycarbonate resin with a titanium oxide surface-treated with a polyol and an organopolysiloxane having a methoxy group. Appearance defects such as silver generated in the resin are reduced, and a molded product with good impact characteristics is obtained, and a polycarbonate resin composition excellent in moldability such as fluidity and releasability and a molded product comprising the same are obtained. As a result, the present invention has been completed.

That is, the present invention
(1) (A) 1 to 22 parts by mass of titanium oxide particles surface-treated with polyol, and (C) 0.01 to 0.01 part of organopolysiloxane having a methoxy group, with respect to 100 parts by mass of (A) aromatic polycarbonate resin A polycarbonate resin composition containing 0.75 parts by mass;
(2) The polycarbonate resin composition according to 1 above, wherein the amount of component (C) is 2 to 10% by mass of component (B),
(3) Furthermore, (D) The polycarbonate resin composition according to the above 1 or 2, comprising 1 to 8 parts by mass of talc and / or mica as an inorganic filler,
(4) Furthermore, (E) alkali metal salt or alkaline earth metal salt of para-toluenesulfonic acid, alkali metal salt or alkaline earth metal salt of perfluoroalkanesulfonic acid, and polyorganosiloxane-containing graft as flame retardant The polycarbonate resin composition according to any one of 1 to 3 above, containing 0.01 to 1 part by mass of at least one selected from copolymer-type flame retardants,
(5) Furthermore, the polycarbonate resin composition in any one of said 1-4 containing 0.1-0.7 mass part of (F) fluorine-containing dripping inhibitors,
(6) Furthermore, the polycarbonate resin composition in any one of said 1-5 containing 0.01-1 mass part of (G) phosphorus antioxidant and / or phenolic antioxidant,
(7) The polycarbonate resin composition according to any one of 1 to 6, further comprising (H) 0.00001 to 0.1 parts by mass of carbon black,
(8) A molded article comprising the polycarbonate resin composition according to any one of 1 to 7,
(9) The molded product according to 8 above, which is a part for electrical / electronic equipment,
(10) The molded article as described in 9 above, which is a casing for an electric / electronic device.

According to the present invention, by blending a polycarbonate resin with a titanium oxide surface-treated with a polyol and an organosiloxane compound having a methoxy group, appearance defects such as burns and silver generated during molding can be significantly reduced. .
Moreover, even if a polyorganosiloxane-containing graft copolymer type flame retardant is blended as a metal salt flame retardant or a silicone flame retardant for flame retardancy, an effect of reducing silver can be obtained.
Furthermore, by using a specific para-toluenesulfonic acid alkali metal salt or alkaline earth metal salt, preferably a specific para-toluenesulfonic acid alkali metal salt as the flame retardant, the residence heat stability in high-temperature molding can be improved. improves. Furthermore, by using a specific phosphorus-based antioxidant, preferably a specific phosphite-based antioxidant as the antioxidant, the residence heat stability in high temperature molding is dramatically improved.

Hereinafter, the present invention will be described in detail.
The polycarbonate resin composition of the present invention is a polycarbonate resin composition comprising (A) an aromatic polycarbonate resin, (B) titanium oxide surface-treated with a polyol, and (C) an organopolysiloxane having a methoxy group as essential components. .

The aromatic polycarbonate resin which is the component (A) of the present invention is not particularly limited and includes various types. Usually, an aromatic polycarbonate produced by a reaction between a dihydric phenol and a carbonate precursor is used. it can.
For example, a dihydric phenol and a carbonate precursor are used by a solution method or a melting method, specifically, a reaction of a dihydric phenol and phosgene, or a transesterification reaction of a dihydric phenol and diphenyl carbonate or the like. be able to.

Examples of the dihydric phenol include various compounds. For example, 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) sulfide Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone and the like.
Among these, particularly preferred dihydric phenols are bis (hydroxyphenyl) alkanes, particularly those using bisphenol A as a main raw material.
In addition, examples of the dihydric phenol include hydroquinone, resorcin, and catechol. These dihydric phenols may be used alone or in combination of two or more.
A suitable branching agent may be used together with the dihydric phenol. As this branching agent, a trihydric or higher polyhydric phenol, specifically 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′ , Α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, phloroglucin, isatin bis (o-cresol) and the like.
Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate. Specific examples include phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, and diethyl carbonate.

The molecular weight regulator used as the molecular terminal group of the PC resin as the component (A) may be any one that is usually used for polymerization of polycarbonate, and various monohydric phenols can be used.
Specific examples include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, bromophenol, tribromophenol, and nonylphenol.

  In the PC resin composition of the present invention, in addition to the above-mentioned aromatic PC resin, a bifunctional such as a polycarbonate-polyorganosiloxane copolymer having a polyorganosiloxane portion and terephthalic acid is within the range in which the object of the present invention is not impaired. A copolymer resin such as a polyester-polycarbonate resin obtained by polymerizing a polycarbonate in the presence of an ester precursor such as a functional carboxylic acid or an ester-forming derivative thereof, or other polycarbonate resin can be appropriately contained. .

The component (A) of the present invention preferably has a raw material molecular weight (viscosity average molecular weight) [Mv] of 17,000 to 23,000 from the viewpoint of obtaining high impact strength.
This viscosity average molecular weight (Mv) is obtained by measuring the viscosity of a methylene chloride solution at 20 ° C. using an Ubbelohde viscometer, obtaining the intrinsic viscosity [η] from this, and calculating the viscosity by the following formula.
[Η] = 1.23 × 10 ⁻⁵ Mv ^0.83

In the PC resin composition of the present invention, titanium oxide particles surface-treated with a polyol are blended as the component (B).
The coating amount of the polyol as the component (B) is preferably 0.5 to 5% by mass with respect to the titanium oxide particles, and if the coating amount is within this range, the titanium oxide particles are sufficiently hydrophobized. The affinity with the PC resin is improved, and a desired effect is obtained.
A preferable coating amount is 0.5 to 4% by mass.
Polyol also has the effect of reducing the amount of moisture adsorbed to some extent.

  Specific examples of the polyol that can be used in the present invention include trimethylolpropane, trimethylolethane, ditrimethylolpropane, trimethylolpropane ethoxylate, pentaerythritol, and the like, and trimethylolpropane and trimethylolethane are preferable. .

(B) The average particle diameter of a component becomes like this. Preferably it is 0.05-0.5 micrometer.
When the average particle diameter is in the above range, the light shielding property and light reflectance are good, and silver or the like is hardly generated on the surface of the molded product, or the impact strength is hardly lowered.
(B) The average particle diameter of a component becomes like this. More preferably, it is 0.1-0.5 micrometer, More preferably, it is 0.15-0.35 micrometer.

The titanium oxide particles are preferably titanium oxide particles produced by a chlorine method.
Titanium oxide particles produced by the chlorine method are superior in terms of whiteness and the like as compared with titanium oxide particles produced by the sulfuric acid method.
As the crystal form of the titanium oxide particles, rutile type titanium oxide particles are preferable, and are superior in terms of whiteness, light reflectance and weather resistance as compared with anatase type titanium oxide particles.

In general, commercially available titanium oxide particles are usually surface-treated with an inorganic oxide such as silica, alumina, zirconia and the like from the viewpoint of handling.
However, according to the study by the present inventors, although the dispersibility of the titanium oxide particles is improved by such an inorganic treatment, silver is generated in the molded product, resulting in poor appearance.
Similarly, titanium oxide particles surface-treated with polysiloxane also generate silver in the molded product, resulting in poor appearance.

(B) The compounding quantity of a component is 1-22 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-18 mass parts, More preferably, it is 3-15 mass parts.
When the blending amount is less than 1 part by mass, it is difficult to obtain a sufficient light-shielding property (concealment), and when it exceeds 22 parts by mass, there is a problem that impact strength and flame retardancy are likely to be lowered.

In the PC resin composition of the present invention, (C) an organopolysiloxane having a methoxy group is blended.
(C) The organopolysiloxane having a methoxy group is not particularly limited as long as it has a methoxy group, and examples thereof include BY16-161 manufactured by Toray Dow Corning and KR-511 manufactured by Shin-Etsu Chemical Co., Ltd.
When the organopolysiloxane has a methoxy group, there are effects such as suppressing the decrease in the molecular weight of the polycarbonate resin.

(C) The compounding quantity of component is 0.01-0.75 mass part with respect to 100 mass parts of (A) component, Preferably it is 0.01-0.7, More preferably, it is 0.1-0. .5 parts by mass.
When the blending amount is less than 0.01 parts by mass, the impact strength is reduced, and the discoloration easily occurs during high temperature molding retention, and when it exceeds 0.75 parts by mass, the adhesion to the mold and the flame retardancy are likely to occur. There is.
The amount of the component (C) is preferably 2 to 10% by mass of the component (B) so as not to generate silver on the surface of the molded product.

If desired, talc and / or mica is further blended in the PC resin composition of the present invention as an inorganic filler (D).
Talc is one of layered clay minerals, the main component of which is represented by 4SiO ₂ .3MgO.H ₂ O, and is called “hydrous magnesium silicate”.
Talc has different compositions of impurities depending on the place of production, but if there are many impurities such as Fe ₂ O ₃ or Al ₂ O ₃ , the thermal stability of the resulting resin composition will be adversely affected, so these impurities are small. Talc is preferred.

Mica is one of layered clay minerals such as muscovite, biotite, phlogopite, and artificial phlogopite. The main component is SiO ₂ , and Si—O is very strong with a covalent bond.
In the mica crystal, SiO regular tetrahedrons are connected in a hexagonal mesh, and the two plates form a set.
In addition, an ion (for example, Al ³⁺ , Mg ²⁺ ) bond having an octahedral position is formed between the plates.
This is called a tablet, which is stacked in layers, and ions of alkali metal or alkaline earth metal (for example, K ⁺ ) are connected by ionic bonds between the tablets.
These ions are called interlayer ions and are surrounded by 12 oxygens.
And since this bond is very weak, mica tends to peel off into a plate shape.
As for the particle diameters of talc and mica, it is preferable to use those having an average particle diameter of 3 to 12 μm because a resin composition having a good appearance can be obtained without sacrificing the physical properties of the composition.
The particle diameter of mica was measured by a centrifugal sedimentation type particle size distribution measuring method.

(D) The compounding quantity of a component is 1-8 mass parts with respect to 100 mass parts of (A) component, Preferably it is 2-7 mass parts.
When the blending amount of the component (D) is in the above range, the obtained molded product is improved in mechanical strength, step stability, flame retardancy and the like without causing poor appearance.
As the component (D), talc is preferable.

In the polycarbonate resin composition of the present invention, it is preferable to blend a compound selected from (E) an organic sulfonate of an alkali metal or an alkaline earth metal and a polyorganosiloxane-containing graft copolymer as a flame retardant.
Examples of organic sulfonates of the above alkali metals or alkaline earth metals (hereinafter sometimes referred to as “alkali (earth) metals”) include perfluoroalkylsulfonic acids and alkali metals or alkaline earths. Examples thereof include metal salts of fluorine-substituted alkyl sulfonic acids such as metal salts with metals, and metal salts of aromatic sulfonic acids with alkali metals or alkaline earth metal salts.

Examples of the alkali metal include lithium, sodium, potassium, rubidium and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium and barium.
More preferred is an alkali metal.
Among these alkali metals, potassium and sodium are preferable from the viewpoints of flame retardancy and thermal stability, and potassium is particularly preferable.
A potassium salt and a sulfonic acid alkali metal salt composed of another alkali metal can also be used in combination.

Specific examples of the alkali metal perfluoroalkylsulfonate include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, Sodium perfluorobutanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctane Cesium sulfonate, cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate and Perfluorohexane sulfonate rubidium, and these may be used in combination of at least one or two.
Here, 1-18 are preferable, as for carbon number of a perfluoroalkyl group, 1-10 are more preferable, More preferably, it is 1-8.
Of these, potassium perfluorobutane sulfonate is particularly preferred.

Specific examples of the alkali (earth) metal salt of aromatic sulfonate include, for example, diphenyl sulfide-4,4′-disulfonic acid disodium, diphenyl sulfide-4,4′-disulfonic acid dipotassium, and 5-sulfoisophthalic acid potassium. , Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, poly (2,6-dimethylphenylene oxide) polysulfonate Sodium, poly (1,3-phenylene oxide) polysulfonic acid polysodium, poly (1,4-phenylene oxide) polysulfonic acid polysodium, poly (2,6-diphenylphenylene oxide) polysulfonic acid poly Lithium, poly (2-fluoro-6-butylphenylene oxide) lithium polysulfonate, potassium benzenesulfonate, sodium benzenesulfonate, sodium p-toluenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, p-benzenedisulfonic acid Dipotassium, naphthalene-2,6-disulfonate dipotassium, calcium biphenyl-3,3′-disulfonate, sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, diphenylsulfone-3,3′-disulfone Dipotassium acid, diphenylsulfone-3,4′-disulfonic acid dipotassium, α, α, α-trifluoroacetophenone-4-sulfonic acid sodium salt, benzophenone-3,3′-disulfonic acid diacid Lithium, thiophene-2,5-disulfonate disodium, thiophene-2,5-disulfonate dipotassium, thiophene-2,5-disulfonate calcium, benzothiophene sodium sulfonate, diphenyl sulfoxide-4-potassium sulfonate, Examples include a formalin condensate of sodium naphthalene sulfonate and a formalin condensate of sodium anthracene sulfonate.
Among these aromatic sulfonic acid alkali (earth) metal salts, sodium salts and potassium salts are particularly preferable.

The polyorganosiloxane-containing graft copolymer is not particularly limited, and preferred specific examples include (a) polyorganosiloxane particles (b) in the presence of 40 to 90 parts by mass of polyorganosiloxane particles. (F-1) Polymerize 0.5 to 10 parts by mass of a vinyl monomer composed of 100 to 50% by mass and other copolymerizable monomer (f-2) 0 to 50% by mass, c) A polyorganosiloxane-containing graft copolymer obtained by polymerizing 5 to 50 parts by mass of the vinyl monomer [(a), (b) and (c) in total 100 parts by mass)].
Further, a preferred polyorganosiloxane-containing graft copolymer is (a) in the presence of 60 to 80 parts by mass of polyorganosiloxane particles, (b) 1 to 5 parts by mass of a vinyl monomer, and (c) vinyl. It is obtained by polymerizing 15 to 39 parts by mass of the system monomer so that the total amount becomes 100 parts by mass.

The polyfunctional monomer (f-1) is a compound containing two or more polymerizable unsaturated bonds in the molecule. Specific examples include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate. , Ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, divinylbenzene and the like. These may be used alone or in combination of two or more.
In these, use of allyl methacrylate is preferable from the point of economical efficiency and an effect.

Specific examples of the copolymerizable monomer (f-2) include aromatic vinyl monomers such as styrene, α-methylstyrene, paramethylstyrene, and parabutylstyrene, acrylonitrile, and methacrylonitrile. Vinyl cyanide monomers such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, methyl methacrylate , (Meth) acrylic acid ester monomers such as ethyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate, itaconic acid, (meth) acrylic acid, fumaric acid, maleic acid, etc. Carboxyl group-containing vinyl monomers It is below.
These may be used alone or in combination of two or more.

The above (c) vinyl monomer is a component used to obtain a polyorganosiloxane-containing graft copolymer, and the graft copolymer is further blended with an aromatic polycarbonate resin to provide flame retardancy and resistance. When improving impact properties, it is also a component used to ensure the compatibility of the graft copolymer and the aromatic polycarbonate resin and to uniformly disperse the graft copolymer in the aromatic polycarbonate resin.
For this reason, as the vinyl monomer (c), the solubility parameter of the polymer of the vinyl monomer is 9.15 to 10.15 [(cal / cm ³ ) ^1/2 ], It is preferably selected to be 9.17 to 10.10 [(cal / cm ³ ) ^1/2 ], particularly 9.20 to 10.05 [(cal / m ³ ) ^1/2 ].
When the solubility parameter is within the above range, flame retardancy is improved.
Details of the solubility parameter are described in JP-A No. 2003-238639.

The average particle diameter of the polyorganosiloxane-containing graft copolymer is 0.1 to 1.0 μm as a value determined from observation with an electron microscope, and it is sufficient that the average particle diameter is 0.1 to 1.0 μm. Flame retardancy, rigidity and impact strength are obtained.
The said polyorganosiloxane containing graft copolymer can be used individually or in combination of 2 or more types.

One type of the above component (E) may be used, or two or more types may be used in combination.
In particular, when using a metal salt of a fluorine-substituted alkyl sulfonic acid, such as a metal salt of perfluoroalkyl sulfonic acid and alkali metal or alkaline earth metal, to increase impact strength, polyorganosiloxane-containing graft copolymer Use in combination with coalescence is preferred.
(E) The compounding quantity of a component is 0.01-1 mass part with respect to 100 mass parts of (A) aromatic polycarbonate resin, Preferably it is 0.05-0.8 mass part, More preferably, it is 0.00. It is 1-0.5, More preferably, it is 0.1-0.3 mass part.
When the blending amount of the component (E) is within the above range, the flame retardancy and impact resistance are improved without lowering the dispersibility of the component (E).
Further, by blending the component (E), appearance defects such as silver generated during molding can be further reduced.
In addition, in order to improve the thermal stability in high temperature molding, the component (E) includes a specific paratoluenesulfonic acid alkali metal salt or alkaline earth metal salt, preferably a specific paratoluenesulfonic acid alkali metal. Salts, particularly sodium paratoluenesulfonate, are preferred.

In order to improve the flame retardancy, it is preferable to blend (F) a fluorine-containing anti-dripping agent into the PC resin composition of the present invention.
The component (F) gives the resin composition of the present invention a melt dripping preventing effect and exhibits excellent thin flame retardancy.
The component (F) preferably has a fibril forming ability.
Here, “fibril forming ability” means that resins tend to be bonded and become fibrous due to an external action such as shearing force.
Examples of the component (F) include polytetrafluoroethylene, tetrafluoroethylene copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymers) and the like.
Of these, polytetrafluoroethylene (PTFE) is preferred.
PTFE having fibril-forming ability has a very high molecular weight and is a number average molecular weight determined from the standard specific gravity, and is usually 500,000 or more, preferably 500,000 to 15 million, more preferably 1,000,000 to 10 million.
Specifically, tetrafluoroethylene is polymerized in an aqueous solvent in the presence of sodium, potassium or ammonium peroxydisulfide at a pressure of about 7 to 700 kPa and a temperature of about 0 to 200 ° C., preferably 20 to 100 ° C. Can be obtained.

In addition to solid forms, those in the form of an aqueous dispersion can also be used, and those classified as type 3 according to the ASTM standard can be used.
Examples of commercially available products classified into Type 3 include “Teflon 6-J” (trade name, manufactured by Mitsui DuPont Fluoro Chemical Co., Ltd.), “Polyflon D-1” and “Polyflon F-103” [trade name. , Manufactured by Daikin Industries, Ltd.].
Other than Type 3, “Algoflon F5” (trade name, manufactured by Solvay Solexis), “Polyflon MPAFA-100” [trade name, manufactured by Daikin Industries, Ltd.], and the like can be given.
The PTFE may be used alone or in combination of two or more.

(F) The compounding quantity of a component is about 0.1-0.7 mass part with respect to 100 mass parts of (A) component, Preferably it is 0.2-0.6 mass part.
When the blending amount of the component (F) is in the above range, it does not drip at the time of combustion, and it is possible to ensure thin-walled flame retardancy, and the flow characteristics of the molten resin composition are not deteriorated and the moldability is improved.

The PC resin composition of the present invention preferably contains (G) an antioxidant.
As the antioxidant, phosphorus-based antioxidants and / or phenol-based antioxidants are preferably used.
Examples of phosphorus antioxidants include triphenyl phosphite, diphenyl nonyl phosphite, diphenyl (2-ethylhexyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, trisnonyl phenyl phosphite. , Diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, diphenylisodecyl phosphite, diphenylmono (tridecyl) phosphite, phenyldiisodecyl phosphite, phenyldi ( Tridecyl) phosphite, Tris (2-ethylhexyl) phosphite, Tris (isodecyl) phosphite, Tris (tridecyl) phosphite, Dibutyl hydrogen phosphite, Trilauryl trithiophosphite, Te Trakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite, 4,4′-isopropylidene diphenol dodecyl phosphite, 4,4′-isopropylidene diphenol tridecyl phosphite 4,4′-isopropylidene diphenol tetradecyl phosphite, 4,4′-isopropylidene diphenol pentadecyl phosphite, 4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) ditridecyl phosphite Phyto, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) penta Erythritol diphosphite, distearyl-pentaerythritol di Sulphite, phenylbisphenol A pentaerythritol diphosphite, tetraphenyldipropylene glycol diphosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, 3,4,5,6-dibenzo-1,2-oxaphosphane, triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, tris- (p-tolyl) phosphine, tris- (p-nonylphenyl) phosphine, tris -(Naphthyl) phosphine, diphenyl- (hydroxymethyl) -phosphine, diphenyl- (acetoxymethyl) -phosphine, diphenyl- (β-ethylcarboxyethyl) -phosphine, tris- (p-chlorophenyl) phosphine, tris- ( p-fluorophenyl) phosphine, diphenylbenzylphosphine, diphenyl-β-cyanoethylphosphine, diphenyl- (p-hydroxyphenyl) -phosphine, diphenyl-1,4-dihydroxyphenyl-2-phosphine, phenylnaphthylbenzylphosphine and the like. .

  Examples of phosphorus antioxidants include Irgafos 168 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irgafos 12 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irgafos 38 (manufactured by Ciba Specialty Chemicals Co., Ltd.) Trademark), ADK Stab C (trade name), ADK Stab 329K (trade name) manufactured by ADEKA Corporation, ADK Stab PEP36 (trade name, manufactured by ADEKA Corporation), ADK Stab PEP-8 (trade name, manufactured by ADEKA Corporation) Trademark), JC263 (trade name, manufactured by Johoku Chemical Co., Ltd.), Sardstab P-EPQ (trade name, manufactured by Clariant), Weston 618 (trade name, manufactured by GE), Weston 619G (trade name, manufactured by GE) and West Examples include commercial products such as ton 624 (trade name, manufactured by GE).

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

  Examples of phenolic antioxidants include Irganox 1010 (trade name, manufactured by Ciba Japan Co., Ltd.), Irganox 1076 (trade name, manufactured by Ciba Japan Co., Ltd.), Irganox 1330 (trade name, manufactured by Ciba Japan Co., Ltd.), Irganox 3114 (Ciba Japan). Japan Co., Ltd., Trademark), Irganox 3125 (Ciba Japan Co., Ltd., Trademark), BHT (Takeda Pharmaceutical Co., Ltd., Trademark), Cyanox 1790 (Cyanamide Co., Trademark), and Sumizer GA-80 (Sumitomo Chemical Co., Ltd.) , Trademarks) and the like.

(G) The compounding quantity of a component is about 0.01-1 mass part with respect to 100 mass parts of (A) component, Preferably it is 0.1-0.3 mass part, More preferably, it is 0.05-. 0.3 parts by mass.
When the blending amount of the component (G) is in the above range, the thermal stability in the granulation step / molding step can be maintained, and it is difficult to cause a decrease in molecular weight.
In order to improve the thermal stability in high temperature molding, the (G) component is particularly preferably a phosphite antioxidant.

The polycarbonate resin composition of the present invention preferably contains (H) carbon black for the purpose of improving impact strength.
Examples of carbon black include commercial products such as MA100 (trademark, manufactured by Mitsubishi Chemical Corporation).

(H) The compounding quantity of a component is about 0.00001-0.1 mass part with respect to 100 mass parts of (A) component, Preferably it is 0.001-0.01 mass part.
When the blending amount of the component (H) is in the above range, the impact strength is improved.

The PC resin composition of the present invention preferably contains (I) a release agent in order to improve the releasability.
The release agent is not particularly limited as long as it can be mixed with a polycarbonate resin to improve the release property at the time of molding.
In particular, organic compounds such as beeswax, glycerin monostearate, glycerin tristearate, pentaerythritol monostearate, pentaerythritol tristearate, pentaerythritol tetrastearate, montanic acid ester wax, carboxylic acid ester have excellent release properties. Shown and used preferably.
These include, for example, beeswax golden brand from Miki Chemical Industry Co., Ltd., Rikenmar S-100A, SL-900, Riquester EW-440A from Riken Vitamin Co., Roxyol VPG861 from Cognis Japan, Licowax E from Clariant Japan, Cognis Japan Roxyol EP-32 from the company is listed.

(I) As for the compounding quantity of a component, about 0.5-1.5 mass parts is preferable with respect to 100 mass parts of (A) component.
If the blending amount of the component (I) is in the above range, the mold release property is good and the moldability is good without lowering the flow characteristics of the molten resin composition.

Furthermore, additive components commonly used in other synthetic resins, elastomers, and thermoplastic resins may be included as necessary.
These additives include antistatic agents, polyamide polyether block copolymers (permanent antistatic performance), benzotriazole and benzophenone UV absorbers, hindered amine light stabilizers (weathering agents), plasticizers, Antibacterial agents, compatibilizers, colorants (dyes, pigments) and the like can be mentioned.
The amount of the optional component is not particularly limited as long as the characteristics of the polycarbonate resin composition of the present invention are maintained.

Next, the manufacturing method of the polycarbonate resin composition of this invention is demonstrated.
In the polycarbonate resin composition of the present invention, the above components (A) to (H), and if necessary, the component (I) are blended in the above proportions, and various optional components used as necessary are blended in suitable proportions. And kneading.
Compounding and kneading are premixed with commonly used equipment such as a ribbon blender, drum tumbler, etc., Henschel mixer, Banbury mixer, single screw extruder, twin screw extruder, multi screw extruder and It can be performed by a method using a conida or the like.
The heating temperature at the time of kneading is usually appropriately selected within the range of 240 to 320 ° C.
As the melt-kneading molding, it is preferable to use an extrusion molding machine, in particular, a vent type extrusion molding machine.
In addition, the components other than the polycarbonate resin can be added in advance as a master batch with melt-kneading with the polycarbonate resin or other thermoplastic resin.

The PC resin composition of the present invention is an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum molding method, using the above melt-kneading molding machine or the obtained pellets as a raw material. Various molded products can be manufactured by a foam molding method or the like.
In particular, the obtained pellets can be used suitably for the production of injection molded products by injection molding and injection compression molding.
The molded product comprising the PC resin composition of the present invention is, for example,
(1) Parts for electrical and electronic equipment such as TVs, radio cassettes, video cameras, video tape recorders, audio players, DVD players, air conditioners, mobile phones, displays, computers, registers, calculators, copiers, printers, facsimiles, etc. ,
(2) It can be suitably used as the above-mentioned case 1 for electrical / electronic equipment.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not restrict | limited at all by these.
The performance evaluation method and the molding material used are shown below.
[Performance evaluation method]
(1) Silver evaluation After a resin composition was retained in a cylinder for 20 minutes at a cylinder temperature of 340 ° C. using an injection molding machine (Toshiba Machine EC40N), a test piece having a length of 40 mm, a width of 80 mm, and a thickness of 4 mm was obtained. Molded.
The appearance of the test piece was visually observed to evaluate the presence or absence of silver generation. The case where silver was generated on the surface of the test piece was evaluated as x, and the case where silver was not generated was evaluated as ◯.
(2) Bending strength (MPa)
Using an injection molding machine (Toshiba Machine IS-100EN), a test piece was prepared at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., and measured according to ASTM D790.
(3) Tensile yield strength (MPa)
Using an injection molding machine (Toshiba Machine IS-100EN), a test piece was prepared at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., and measured according to ASTM D638.
(4) Thermal stability evaluation (color difference ΔE)
Using a resin composition that has been dried at 120 ° C for 5 hours with an injection molding machine (EC40N manufactured by Toshiba Machine Co., Ltd.), the resin composition stays in the cylinder for 20 minutes at a cylinder temperature of 340 ° C and 360 ° C. Then, a test piece having a length of 40 mm, a width of 80 mm, and a thickness of 4 mm was formed. The color difference of the molded product before and after staying for 20 minutes was measured using SZ-Σ90 (manufactured by Nippon Denshoku Industries Co., Ltd.).
(5) IZOD (Izod impact strength)
Using raw material pellets dried at 120 ° C. for 5 hours, a test piece is prepared using an injection molding machine (IS-100EN manufactured by Toshiba Machine Co., Ltd., molding temperature 280 ° C., mold temperature 80 ° C.), and ASTM D256 is used. The measurement was performed at 23 ° C.
Five tests with a thickness of 1/8 inch were conducted and the average value was shown. Unit: kJ / m ²
(6) Flammability Measured according to UL94 combustion test.
The test piece thickness was 1.5 mm and 1.2 mm, and a vertical combustion test was performed according to Underwriters Laboratory Subject 94.

[Molding material]
(A) Component A-1: Aromatic polycarbonate resin [made by Idemitsu Kosan Co., Ltd., “FN1500”, Mv = 14,500]
A-2: Aromatic polycarbonate resin [manufactured by Idemitsu Kosan Co., Ltd., “FN1700A”, Mv = 17,000]
A-3: Aromatic polycarbonate resin [manufactured by Idemitsu Kosan Co., Ltd., “FN1900A”, Mv = 19,500]

(B) Component B-1: CR-60-2; Titanium oxide particles coated with polyol (Ishihara Sangyo Co., Ltd., average particle size 0.21 μm)
B-2: CR-50-2; Titanium oxide particles coated with polyol (Ishihara Sangyo Co., Ltd., average particle size 0.25 μm)
B-3: CR-90-2: Titanium oxide particles coated with polyol (Ishihara Sangyo Co., Ltd., average particle 0.25 μm)
B-4: PF726; titanium oxide particles whose surface is coated with silica-alumina (total 5-6 mass%) (Ishihara Sangyo Co., Ltd., average particle size 0.21 μm)
B-5: PC-3; PF-726 coated with polysiloxane (Ishihara Sangyo Co., Ltd., average particle size 0.21 μm)

Component (C) (organopolysiloxane having a methoxy group)
C-1: Methoxy-modified silicone BY16-161 (manufactured by Dow Corning Toray)
(D) component (talc)
D-1: TP-A25 (manufactured by Fuji Talc Kogyo; average particle size; 4.9 μm)
(E) component (flame retardant)
E-1: Potassium perfluorobutanesulfonate (trade name: F-top KFBS, manufactured by Gemco Co., Ltd.)
E-2: Sodium paratoluenesulfonate (DAH DIING CHEMICAL INDUSTRY, purity 93% or more, sodium sulfate 3% by mass or less, impurities 5% by mass or less)
E-3: Polyorganosiloxane-containing graft copolymer type flame retardant (trade name: MR-01, manufactured by Kaneka Corporation)

(F) component (fluorine-containing anti-dripping agent)
F-1: CD076 (Asahi Glass Co., Ltd.)
(G) component (antioxidant)
G-1: JC263 (manufactured by Johoku Chemical Industry Co., Ltd .; triphenylphosphine)
G-2: Irgafos 168 (manufactured by Ciba Specialty Chemicals; Tris (2,4-di-t-butylphenyl) phosphite)
G-3: Irganox 1076 (manufactured by Ciba Specialty Chemicals; octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate)
G-4: ADK Stab C (manufactured by ADEKA Corporation, diphenyl (2-ethylhexyl) phosphite)
(H) component (carbon black)
H-1: MA100 (Mitsubishi Chemical Corporation)
(I) component (release agent)
I-1: S-100A (Riken Vitamin Co., Ltd .; glycerin monostearate)
I-2: EW-440A (manufactured by Riken Vitamin Co., Ltd .; pentaerythritol tetrastearate)

Examples 1 , 2 , 4, 5, 7 to 20 and Comparative Examples 1 to 15 and Reference Examples Tables 1 to 3 were mixed with each component, and a vent type twin screw extruder (Toshiba Machine Co., Ltd .: TEM35). The sample was melt kneaded at a barrel temperature of 280 ° C., a screw rotation speed of 300 to 600 rotations, and a discharge rate of 30 kg / hr to obtain a pellet sample for evaluation.
Using the pellet sample for evaluation, a test piece for performing each test at a cylinder temperature of 280 to 340 ° C. was produced by an injection molding machine, and each test was performed.
The results are shown in Tables 1-3.

Tables 1 and 2 revealed the following.
In Examples 1 to 15, there is no occurrence of silver, and a polycarbonate resin composition is obtained that gives a molded product having an excellent balance between bending strength and tensile yield strength.
In Comparative Examples 1 to 12, all silver was generated.

Table 3 shows the following.
In order to improve the thermal stability in high temperature molding, the component (E) is preferably an alkali metal salt of paratoluenesulfonic acid, particularly sodium paratoluenesulfonate, and the component (G) is a phosphite-based antioxidant. Agents are preferred.
Further, when the component (I) is added, the impact strength is improved.
Furthermore, a thin flame retardance of 1.5 mmV-0 / 1.5 mm5 VB was achieved.

  The molded product made of the PC resin composition of the present invention has no appearance defect such as silver and is excellent in moldability such as impact characteristics, fluidity and releasability. For example, parts for electric / electronic devices, electric / electronic It can be suitably used as a device casing (liquid crystal projector housing, personal computer housing, communication device terminal device housing, etc.).

Claims (10)

(A) 1 to 11.11 parts by mass of (B) titanium oxide particles surface-treated with polyol, and (C) 0.01 to 0 organopolysiloxane having a methoxy group with respect to 100 parts by mass of the aromatic polycarbonate resin. A polycarbonate resin composition containing 75 parts by mass.   The polycarbonate resin composition according to claim 1, wherein the amount of the component (C) is 2 to 10% by mass of the component (B).   Furthermore, the polycarbonate resin composition of Claim 1 or 2 which contains 1-8 mass parts of talc and / or mica as (D) inorganic filler.   Further, (E) as a flame retardant, an alkali metal salt or alkaline earth metal salt of paratoluenesulfonic acid, an alkali metal salt or alkaline earth metal salt of perfluoroalkanesulfonic acid, and a polyorganosiloxane-containing graft copolymer type The polycarbonate resin composition according to any one of claims 1 to 3, comprising 0.01 to 1 part by mass of at least one selected from flame retardants.   Furthermore, the polycarbonate resin composition in any one of Claims 1-4 which contains 0.1-0.7 mass part of (F) fluorine-containing dripping inhibitors.   Furthermore, the polycarbonate resin composition in any one of Claims 1-5 containing 0.01-1 mass part of (G) phosphorus antioxidant and / or a phenolic antioxidant.   Furthermore, the polycarbonate resin composition in any one of Claims 1-6 containing 0.00001-0.1 mass part of (H) carbon black.   A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 7.   The molded article according to claim 8, which is a part for an electric / electronic device.   The molded article according to claim 9, which is a casing for an electric / electronic device.