JP2009138173A - Flame-retardant polycarbonate resin composition excellent in optical reflection and molded product formed of it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition which is produced by using a flame retardant instead of an organobromine compound or a phosphorus compound from the consideration given to an environment and has excellent optical reflection, flame retardancy, mechanical properties, fluidity, moldability, thermal stability, and appearance. <P>SOLUTION: The flame-retardant polycarbonate resin composition having excellent optical reflection includes 100 pts.wt. of a polycarbonate resin (A), 5-25 pts.wt. of a titanium oxide (B), 0.01-3 pts.wt. of a silicone compound having a branched-structure principal chain with an aromatic group as an organic functional group or with an aromatic group and a hydrocarbon group (except the aromatic group), 0.1-5 pts.wt. of a polyorganosiloxane-containing graft copolymer (D), 0.01-2 pts.wt. of an organometallic salt (E), 0.01-2 pts.wt. of a fiber-forming type fluorine-containing polymer (F), and optionally, 0.001-0.1 pts.wt. of a specific fluorescent brightener. The molded product formed of the flame-retardant polycarbonate resin composition is also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a flame retardant polycarbonate resin composition excellent in light reflectivity, and a light reflecting plate formed from the composition. The resin composition according to the present invention is excellent in light reflectivity, and further in fluidity at the time of molding, flame retardancy, impact resistance, and appearance, so that it is particularly light reflective for liquid crystal frames or lamp holders. It can be suitably used for a plate.

  Polycarbonate resin is a thermoplastic resin excellent in impact resistance, heat resistance, and the like, and is widely used in fields such as electricity, electronics, machinery, and automobiles. On the other hand, in addition to these excellent performances possessed by the polycarbonate resin, in order to satisfy safety requirements in the electrical, electronic and OA fields, a material having high flame retardancy is required. Therefore, various methods for blending various flame retardants such as organic bromine compounds and phosphorus compounds have been proposed and adopted in order to improve the flame retardancy of polycarbonate resins. The same situation applies to the use of light reflectors such as liquid crystal backlights, and specific examples thereof are disclosed. (See Patent Documents 1 to 3.)

  However, when a halogen-based compound such as an organic bromine compound is blended, there is a concern that a gas containing the halogen is generated at the time of combustion, and it is desired to use a flame retardant that does not contain chlorine, bromine or the like from an environmental viewpoint. . Moreover, the present condition is that the new flame retardant which replaces such a flame retardant is calculated | required from the concern which influences an environmental influence even if it is a phosphorus compound.

In addition, when titanium oxide is used to obtain a light-reflective polycarbonate resin material, and when an organic bromine compound or phosphorus compound is used as a flame retardant, mechanical properties such as impact strength are deteriorated. Improvements were sought. Patent Document 4 proposes a method for improving impact strength by using an organic bromine compound and / or a phosphorus compound as a flame retardant and further blending polyorganohydrogensiloxane and an epoxy-modified elastomer.
JP 7-258554 A JP 9-111109 A Japanese Patent Laid-Open No. 10-1600 JP 2000-302959 A

  However, by blending an epoxy-modified elastomer, a decrease in impact strength can be suppressed, but the fluidity of the resin composition tends to decrease, and an improvement in the decrease in moldability resulting from this has been desired. In addition, from the above-mentioned environmental considerations, using flame retardants instead of organic bromine compounds and phosphorus compounds, it has excellent light reflectivity, flame retardancy, mechanical properties, fluidity, moldability, and heat Development of a polycarbonate resin composition excellent in stability and appearance has been desired.

  As a result of intensive studies to solve the above problems, the present inventors have used a polyorganosiloxane-containing graft copolymer having a specific structure as an impact modifier, and this, a specific silicone compound, an organic metal salt, and a fiber. It has been surprisingly found that not only flame retardancy and impact strength but also fluidity can be dramatically improved by using a forming type fluorine-containing polymer and, if desired, a specific fluorescent whitening agent in combination. The present invention has been completed.

That is, the first aspect of the present invention is that the polycarbonate resin (A) is 100 parts by weight, the titanium oxide (B) is 5 to 25 parts by weight, the main chain is a branched structure, and the organic functional group contained is an aromatic group. Or 0.01-3 parts by weight of a silicone compound (C) comprising an aromatic group and a hydrocarbon group (excluding an aromatic group), 0.1-5 parts by weight of a polyorganosiloxane-containing graft copolymer (D) A flame-retardant polycarbonate excellent in light reflectivity, comprising 0.01 to 2 parts by weight of an organic metal salt (E) and 0.01 to 2 parts by weight of a fiber-forming fluoropolymer (F) A resin composition and a molded product formed by molding the resin composition are provided.
The second aspect of the present invention is that the polycarbonate resin (A) is 100 parts by weight, the titanium oxide (B) is 5 to 25 parts by weight, and the main chain has a branched structure and the organic functional group contained is an aromatic group. Or 0.01-3 parts by weight of a silicone compound (C) comprising an aromatic group and a hydrocarbon group (excluding an aromatic group), 0.1-5 parts by weight of a polyorganosiloxane-containing graft copolymer (D) , 0.01 to 2 parts by weight of an organic metal salt (E), 0.01 to 2 parts by weight of a fiber-forming fluorine-containing polymer (F), and 4,4′bis (5-methylbenzoxazol-2-yl) stilbene ( G) or 4,4bis [5-tert-butyl-2-benzoxazolyl-4 ′-(5-tert-octyl-2-benzoxazolyl)] stilbene and 4-4′-bis- (5 -T-Butyl-2-benzoxazolyl) stilbene 4-4′-bis- (5-t-octyl-2-benzoxazolyl) stilbene mixture (H) or 1,4-bis- (5-t-butyl-2-benzoxazolyl) naphthalene ( A flame-retardant polycarbonate resin composition excellent in light reflectivity, characterized by comprising I) in an amount of 0.001 to 0.1 parts by weight, and a molded product formed by molding the flame-retardant polycarbonate resin composition.

  Since the flame retardant polycarbonate resin composition excellent in light reflectivity of the present invention does not use a conventional flame retardant containing bromine or chlorine, generation of a gas containing bromine or chlorine due to the flame retardant during combustion No environmental concerns and no use of phosphorus-based flame retardants. In addition, while maintaining excellent flame retardancy and high light reflectivity, it has excellent fluidity and good impact strength. It is suitable for applications such as the above, and its practical utility value is extremely high.

  The polycarbonate resin (A) used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted. A typical example of the polymer is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

  Examples of the dihydroxydiaryl compound include bisphenol 4-, 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 ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like.

  These are used singly or as a mixture of two or more. However, it is preferable not to be substituted with a halogen from the viewpoint of preventing discharge of a gas containing halogen, which is a concern during combustion, into the environment. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be mixed and used.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include 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.

The viscosity average molecular weight of the polycarbonate resin (A) is usually 10,000 to 100,000, preferably 12,000 to 25,000, and more preferably 14,000 to 18,000. In producing such an aromatic polycarbonate resin, a molecular weight regulator, a catalyst, and the like can be used as necessary. The viscosity average molecular weight is measured by using a methylene chloride as a solvent in a 0.5% by weight solution, measuring the specific viscosity (η _sp ) at a temperature of 20 ° C. using a Canon Fenske type viscosity tube, and converting the concentration into an intrinsic viscosity. [Η] was obtained and calculated from the following SCHNELL equation.
[Η] = 1.23 × 10 ⁻⁴ M ^0.83

  The titanium oxide (B) used in the present invention may be one produced by the chlorine method or the sulfuric acid method, and the crystal form may be either rutile type or anatase type. Further, the particle size of titanium oxide is preferably about 0.1 to 0.5 μm. In particular, titanium oxide surface-treated with polyene phosphorous oxide is preferably used.

Examples of commercially available titanium oxide include DuPont R902, Resino Color Industries DCF 17007, Kronos 2230, Ishihara Sangyo Typek PF740, and the like.

  The compounding quantity of a titanium oxide (B) is 5-25 weight part per 100 weight part of polycarbonate resin (A). If the blending amount is less than 5 parts by weight, the light reflectivity is inferior, and if it exceeds 25 parts by weight, the appearance and mechanical strength (impact strength) are deteriorated. A more preferable blending amount is in the range of 9 to 16 parts by weight.

The silicone compound (C) used in the present invention comprises a branched main chain and an organic functional group comprising an aromatic group, or an aromatic group and a hydrocarbon group (excluding an aromatic group). Is represented by the following general formula (1).
General formula (1)

Here, R1, R2, and R3 represent main chain organic functional groups, and X represents a terminal functional group.
That is, it has a T unit (RSiO _1.5 ) and / or a Q unit (SiO _2.0 ) as a branch unit. These preferably contains more than 20 mol% of the total siloxane units _{(R 3~0 SiO 2~0.5).} (R represents an organic functional group.) The silicone compound (C) preferably contains 20 mol% or more of aromatic groups among the organic functional groups contained.

  The aromatic group contained is phenyl, biphenyl, naphthalene or a derivative thereof, but a phenyl group can be preferably used.

  Of the organic functional groups in the silicone compound (C) attached to the main chain or branched side chain, the organic group other than the aromatic group is preferably a hydrocarbon group having 4 or less carbon atoms, and preferably a methyl group. Can be used. Furthermore, the terminal group is preferably one kind selected from methyl group, phenyl group and hydroxyl group, or a mixture of these two kinds to three kinds.

  The average molecular weight (weight average) of the silicone compound (C) is preferably 3000 to 500000, and more preferably 5000 to 270000.

  The compounding quantity of a silicone compound (C) is 0.01-3 weight part per 100 weight part of polycarbonate resin (A). If the blending amount is out of this range, it is not preferable since a sufficient flame retardant effect cannot be obtained. More preferably, it is in the range of 0.02 to 2 parts by weight.

  The polyorganosiloxane-containing graft copolymer (D) used in the present invention means two or more polymerizable unsaturated bonds in the molecule in the presence of 40 to 90 parts of polyorganosiloxane particles (D-1). 0.5 to 10 parts of a vinyl monomer comprising 100 to 50% by weight of the polyfunctional monomer (D-2) and 0 to 50% by weight of another copolymerizable monomer (D-3) Is a graft copolymer obtained by polymerizing 5 to 50 parts of the vinyl monomer (D-4) (100 parts by weight of D-1 to D-4 together).

  The polyorganosiloxane particles (D-1) have a number average particle size determined by light scattering method or electron microscope observation, preferably 0.008 to 0.6 μm, more preferably 0.01 to 0.2 μm, particularly preferably. Is 0.01 to 0.15 μm.

  The polyorganosiloxane particles (D-1) are not only particles composed of polyorganosiloxane but also other (co) polymers such as polybutyl acrylate, butyl acrylate-styrene copolymer, etc. It may be modified polyorganosiloxane containing no more than%.

  As the polyfunctional monomer (D-2) having two or more polymerizable unsaturated bonds in the molecule, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, ethylene glycol dimethacrylate, di Examples include 1,3-butylene glycol methacrylate and divinylbenzene. These may be used alone or in combination of two or more. Of these, allyl methacrylate can be suitably used.

  Examples of the other monomer (D-3) and vinyl monomer (D-4) copolymerizable with D-2 include styrene, α-methylstyrene, paramethylstyrene, and parabutylstyrene. Aromatic vinyl monomers, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate , (Meth) acrylic acid ester monomers such as hydroxyethyl acrylate, hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate, itaconic acid , (Meth) acrylic acid, fumaric acid, male Carboxyl group-containing vinyl monomers such as acids and the like. These may be used alone or in combination of two or more.

  In the polymerization with the addition of the monomer (D-2) or the monomer D-3 and the monomer D-4 in the presence of the polyorganosiloxane particles (D-1), A portion corresponding to the copolymer branch is not grafted to the trunk component (D-1 in this case), and a so-called free polymer obtained by polymerizing only the branch component alone is also produced as a by-product. Although it can be obtained as a mixture, in the present invention, both are referred to as a polyorganosiloxane-containing graft copolymer (D). The polyorganosiloxane-containing graft copolymer (D) is available as a commercial product, and examples thereof include Kaneace MR01 and Kaneace MR02 manufactured by Kaneka Corporation.

  The compounding quantity of a polyorganosiloxane containing graft copolymer (D) is 0.1-5 weight part per 100 weight part of polycarbonate resin (A). If the blending amount is less than 0.1 parts by weight, the impact strength is inferior, and if it exceeds 5 parts by weight, the fluidity is lowered, which is not preferable. More preferably, it is the range of 0.5-2.0 weight part.

  Examples of the organic metal salt (E) used in the present invention include a metal salt of an aromatic sulfonic acid and a metal salt of a perfluoroalkane sulfonic acid, preferably 4-methyl-N- (4-methyl Phenyl) sulfonyl-benzenesulfonamide potassium salt, potassium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-3′-disulfonate, sodium paratoluenesulfonate, potassium perfluorobutanesulfonate, and the like can be used.

  The compounding amount of the organic metal salt (E) is 0.01 to 2 parts by weight per 100 parts by weight of the polycarbonate resin (A). If the blending amount is less than 0.01 parts by weight, the flame retardancy is lowered, which is not preferable. On the other hand, when the amount exceeds 2 parts by weight, problems such as failure to obtain mechanical properties and flame retardancy and deterioration of the surface appearance occur. A more preferable blending amount is in the range of 0.2 to 1 part by weight.

  The anti-dripping agent (F) used in the present invention is preferably one that forms a fibril structure in the polycarbonate resin (A). For example, polytetrafluoroethylene, a tetrafluoroethylene copolymer (for example, tetra Fluoroethylene / hexafluoropropylene copolymer, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonates produced from fluorinated diphenols, and the like. In particular, polytetrafluoroethylene having a molecular weight of 1,000,000 or more and a fibril-forming ability having a secondary particle diameter of 100 μm or more is preferably used.

  The amount of the anti-dripping agent (F) is 0.01 to 2 parts by weight per 100 parts by weight of the polycarbonate resin. If the blending amount is less than 0.01 parts by weight, the anti-dripping property is inferior, and if it exceeds 2 parts by weight, the surface appearance and mechanical properties (impact strength) deteriorate, which is not preferable. More preferably, it is in the range of 0.2 to 1 part by weight.

  4,4′bis (5-methylbenzoxazol-2-yl) stilbene (G) or 4,4bis [5-t-butyl-2-benzoxazolyl-4 ′-(5 -T-octyl-2-benzoxazolyl)] stilbene and 4-4'-bis- (5-t-butyl-2-benzoxazolyl) stilbene and 4-4'-bis- (5-t- Octyl-2-benzoxazolyl) stilbene mixture (H) or 1,4-bis- (5-tert-butyl-2-benzoxazolyl) naphthalene (I) is blended in polycarbonate resin (A) It is 0.001-0.1 weight part with respect to 100 weight part. If the blending amount is less than 0.001 part by weight, the effect of improving the whiteness is small, and if it exceeds 0.1 part by weight, the light resistance decreases, which is not preferable. More preferably, it is the range of 0.01-0.05 weight part. Further, (G), (H), and (I) can be used in combination.

  Various blending components (A), (B), (C), (D), (E), (F) of the present invention, and the blending method of (G) is not particularly limited depending on necessity, any mixer, For example, these can be mixed by a tumbler, ribbon blender, high-speed mixer, etc., and can be easily melt-kneaded with a normal single-screw or twin-screw extruder. Moreover, there is no restriction | limiting in particular also about these compounding orders.

  Furthermore, various heat stabilizers, antioxidants, fillers, release agents, softeners and other additives, and other polymers are added to the flame-retardant polycarbonate resin composition of the present invention within the range not impairing the effects of the present invention. May be blended.

  Examples of the filler include glass fiber, glass bead, glass flake, carbon fiber, talc powder, clay powder, mica, potassium titanate whisker, wollastonite powder, silica powder, and alumina powder.

  Examples of the other polymer include polyesters such as polyethylene terephthalate and polybutylene terephthalate; styrene polymers such as polystyrene, high impact polystyrene, ABS resin, and AES resin; polypropylene, and polymers usually used after alloying with polycarbonate. .

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. Unless otherwise specified, “%” and “parts” in the examples are based on weight standards.

The raw materials used are as follows.
Polycarbonate resin:
Caliber 301-40 manufactured by Sumitomo Dow
(Viscosity average molecular weight: 16600, hereinafter abbreviated as PC-1)
Caliber 301-22 manufactured by Sumitomo Dow
(Viscosity average molecular weight: 18800, hereinafter abbreviated as PC-2)
Titanium oxide:
DCF 17007 manufactured by Resino Color Industry Co., Ltd. (hereinafter abbreviated as B-1)
Kronos 2230 (hereinafter abbreviated as B-2)

Silicone compound: (hereinafter abbreviated as “silicone compound”)
The silicone compound was produced according to a general production method. That is, a silicone compound partially condensed by dissolving an appropriate amount of diorganodichlorosilane, monoorganotrichlorosilane and tetrachlorosilane, or a partially hydrolyzed condensate thereof in an organic solvent, adding water and hydrolyzing it. Then, triorganochlorosilane was added and reacted to terminate the polymerization, and then the solvent was separated by distillation or the like. The structural characteristics of the silicone compound synthesized by the above method are as follows:
・ D / T / Q unit ratio of main chain structure: 40/60/0 (molar ratio)
-Ratio of phenyl group in all organic functional groups (*): 60 mol%
-Terminal group: methyl group only-Weight average molecular weight (**): 15000
*: The phenyl group is first contained in the T unit in the silicone containing the T unit, and the remaining D group is contained in the D unit. When the phenyl group is attached to the D unit, the one attached is preferential, and when the phenyl group remains, two are attached. Except for the terminal group, the organic functional group is a methyl group except for the phenyl group.
**: Weight average molecular weight is two significant digits.

Polyorganosiloxane-containing graft copolymer:
Kaneka Corporation MR01 (hereinafter abbreviated as D-1)
Kane Ace MR02 manufactured by Kaneka (hereinafter abbreviated as D-2)
Metal salt of perfluoroalkanesulfonic acid:
Sodium paratoluenesulfonate (hereinafter abbreviated as metal salt)
Polytetrafluoroethylene:
Daikin polyflon FA500
(Polytetrafluoroethylene, hereinafter abbreviated as PTFE)
4,4′bis (5-methylbenzoxazol-2-yl) stilbene:
White flow PSN manufactured by Sumika Color Co., Ltd. (hereinafter abbreviated as G)

A method for measuring various evaluation items in the present invention will be described.
(Preparation of resin composition pellets)
In the blending components and blending ratios shown in Tables 2 to 3 below, various blending components are mixed with a tumbler, and the cylinder temperature is set to 280 degrees using a 37-mm diameter twin screw extruder (KTX37 manufactured by Kobe Steel). And kneaded to obtain various pellets.

(Flame retardance)
The obtained pellets were dried at 125 ° C. for 4 hours, and then tested using an injection molding machine (Japan Steel Works J100E-5) at 240 ° C. under an injection pressure of 1600 kg / cm 2 (1.5 mm). ). The above-mentioned test piece is left in a constant temperature room at 23 ° C. and 50% humidity for 168 hours, and is flame retardant according to UL94 test (flammability test of plastic materials for equipment parts) established by Underlatters Laboratory. Evaluation was performed. The classes according to UL94 are shown in Table 1. V-0 was determined to be acceptable (◯), and the others were unacceptable (x).

The after-flame time is the time during which the test piece after the ignition source is moved away from the flame continues burning, and the cotton ignition by drip is the marking cotton that is 300 mm below the lower end of the test piece. It is determined by whether or not it is ignited by a drip.

(Light reflectivity)
The obtained pellets were dried at 125 ° C. for 4 hours, and then an optical measurement test piece (width: 50 mm, length: 300 ° C., injection pressure: 1600 kg / cm 2) using an injection molding machine (J100E-5 manufactured by Nippon Steel). 40 mm in thickness and 2 mm in thickness). The aforementioned test piece was left in a thermostatic chamber at 23 ° C. and 50% humidity for 48 hours, and the Y value at a wavelength of 400 to 800 nm was measured with a spectrophotometer (CMS-35SP manufactured by Murakami Color Research Laboratory).
A Y value of 90% or more was determined to be acceptable (◯), and a value less than 90% was determined to be unacceptable (X).

(Liquidity)
The obtained pellets were dried at 125 ° C. for 4 hours, and then an Archimedes spiral flow mold (width 10 mm, thickness) using an injection molding machine (Japan Steel Works J100E-5) under the conditions of 280 ° C. and injection pressure 1600 kg / cm 2. The flow length was measured using (10 mm).
A spiral flow length of 120 mm or more was regarded as acceptable (◯), and a spiral flow length of less than 120 mm as unacceptable (x).

(Impact resistance)
The obtained pellets were dried at 125 ° C. for 4 hours, and then tested using an injection molding machine (Japan Steel Works J100E-5) under the conditions of 280 ° C. and injection pressure 1600 kg / cm 2 (ISO standard 179- No. 2 test piece, thickness 4 mm) was molded and processed into a notched test piece with a tip angle of 0.25R. The test piece was conditioned for 48 hours in a constant temperature room at 23 ° C. and 50% humidity in accordance with ISO 179-2, and the impact strength was measured with a Charpy impact tester.
A Charpy impact strength of 15 KJ / m ² or more was determined to be acceptable (◯), and less than 15 KJ / m ² was determined to be unacceptable (x).

(Whiteness)
The obtained pellets were dried at 125 ° C. for 4 hours, and then an optical measurement test piece (width: 50 mm, length: 300 ° C., injection pressure: 1600 kg / cm 2) using an injection molding machine (J100E-5 manufactured by Nippon Steel). 40 mm in thickness and 2 mm in thickness). The test piece was left in a constant temperature room at 23 ° C. and 50% humidity for 48 hours, and YI (yellowness) at a wavelength of 400 to 800 nm was measured with a spectrophotometer (CMS-35SP manufactured by Murakami Color Research Laboratory).
A sample having a YI (yellowness) of 2.0% or less was accepted (◯), and a sample having a YI exceeding 2.0% was rejected (x).

(Light resistance)
The obtained pellets were dried at 125 ° C. for 4 hours, and then an optical measurement test piece (width: 50 mm, length: 300 ° C., injection pressure: 1600 kg / cm 2) using an injection molding machine (J100E-5 manufactured by Nippon Steel). 40 mm in thickness and 2 mm in thickness). A Xenon weather meter SX75 manufactured by Suga Test Instruments Co., Ltd. was used for the test piece described above, and after irradiation for 200 hours under the conditions of a black panel temperature of 63 ° C., a humidity of 50%, and an irradiation dose of 150 W / m ² , Degree). The values in the table are the change values (ΔYI) from the initial YI (yellowness).
A change value (ΔYI) from YI (yellowness) of 25 or less was accepted (◯), and a value exceeding 25 was regarded as unacceptable (x).

  As shown in Table 2, when the configuration of the present invention was satisfied (Examples 1 to 8), all the evaluation items had sufficient performance.

On the other hand, as shown in Table 3, when the configuration of the present invention was not satisfied, each case had some drawbacks.
Comparative Example 1 was a case where the blending amount of the polyorganosiloxane-containing graft copolymer was less than the specified amount, and although the combustibility, fluidity, and reflection performance passed, the impact performance was inferior.
Comparative Example 2 was a case where the blending amount of the polyorganosiloxane-containing graft copolymer was larger than the specified amount, and although the impact performance and the reflection performance passed, flame retardance and fluidity were inferior.
Comparative Example 3 was a case where the blending amount of titanium oxide was small, and although the flame retardancy and fluidity passed, the reflection performance was inferior.
Comparative Example 4 was a case where the amount of titanium oxide was large, and the fluidity and reflection performance passed, but the flame retardancy and impact performance were inferior.
The comparative example 5 was a case where there are few compounding quantities of a silicone compound, and the flame retardance was inferior.
The comparative example 6 was a case where there were many compounding quantities of a silicone compound, and the flame retardance was inferior.

  4,4′bis (5-methylbenzoxazol-2-yl) stilbene was further blended at the blending ratio shown in Table 4 to the resin composition having the blending ratio shown in Example 1 in Table 2. Except for this, the same operations as in Example 1 were performed to evaluate various performances. The results are shown in Table 4.

As shown in Table 4, when the configuration of the present invention was satisfied (Examples 9 and 10), all the evaluation items had sufficient performance.
On the other hand, as shown in Comparative Example 7, when the blending amount of 4,4′bis (5-methylbenzoxazol-2-yl) stilbene is larger than the specified amount, the light reflectivity and the initial whiteness pass. However, light resistance was inferior.

  Except for using D-2 instead of D-1 as the polyorganosiloxane-containing graft copolymer, all the same compositions and operations as in Examples 1 to 3 in Table 2 and Comparative Examples 1 and 2 in Table 3 were performed. Performance evaluation was performed. The results are shown in Table 5.

  As shown in Table 5, when the configuration of the present invention was satisfied (Examples 11 to 13), all the evaluation items had sufficient performance.

On the other hand, as shown in Table 5, when the configuration of the present invention was not satisfied, each case had some drawbacks.
Comparative Example 8 was a case where the blending amount of the polyorganosiloxane-containing graft copolymer was less than the specified amount, and although the combustibility, fluidity and reflection performance passed, the impact performance was inferior.
Comparative Example 9 was a case where the blending amount of the polyorganosiloxane-containing graft copolymer was larger than the specified amount, and although the impact performance and the reflection performance passed, the flame retardance and fluidity were inferior.

Claims (11)

  100 parts by weight of polycarbonate resin (A), 5 to 25 parts by weight of titanium oxide (B), the main chain has a branched structure and the organic functional group contained is composed of an aromatic group, or an aromatic group and a hydrocarbon group (aromatic 0.01-3 parts by weight of a silicone compound (excluding a group of groups), 0.1-5 parts by weight of a polyorganosiloxane-containing graft copolymer (D), 0.01- A flame-retardant polycarbonate resin composition excellent in light reflectivity, comprising 2 parts by weight and 0.01 to 2 parts by weight of a fiber-forming fluoropolymer (F).   100 parts by weight of polycarbonate resin (A), 5 to 25 parts by weight of titanium oxide (B), the main chain has a branched structure and the organic functional group contained is composed of an aromatic group, or an aromatic group and a hydrocarbon group (aromatic 0.01-3 parts by weight of a silicone compound (excluding a group of groups), 0.1-5 parts by weight of a polyorganosiloxane-containing graft copolymer (D), 0.01- 2 parts by weight, 0.01 to 2 parts by weight of a fiber-forming fluoropolymer (F) and 4,4′bis (5-methylbenzoxazol-2-yl) stilbene (G) 0.001 to 0.1 parts by weight A flame retardant polycarbonate resin composition having excellent light reflectivity, comprising: Instead of 4,4′bis (5-methylbenzoxazol-2-yl) stilbene (G) according to claim 2, 4,4bis [5-tert-butyl-2-benzoxazolyl-4 ′-(5 -T-octyl-2-benzoxazolyl)] stilbene and 4-4'-bis- (5-t-butyl-2-benzoxazolyl) stilbene and 4-4'-bis- (5-t- 0.001 to 0.1 parts by weight of a mixture (H) of octyl-2-benzoxazolyl) stilbene or 1,4-bis- (5-tert-butyl-2-benzoxazolyl) naphthalene (I) A flame retardant polycarbonate resin composition having excellent light reflectivity, comprising:   The flame-retardant polycarbonate resin composition excellent in light reflectivity according to claim 1 or 2, wherein the polycarbonate resin (A) has a viscosity average molecular weight of 14,000 to 18,000.   In the presence of 40 to 90 parts by weight of polyorganosiloxane particles (D-1), the polyorganosiloxane-containing graft copolymer (D) is 100 to 50% by weight of the polyfunctional monomer (D-2) and other The copolymerizable monomer (D-3) is polymerized from 0.5 to 10 parts by weight of a vinyl monomer composed of 0 to 50% by weight, and further 5 to 50 parts by weight of a vinyl monomer (D-4). 3) A graft copolymer obtained by polymerizing (D-1 to 4 together to make 100 parts by weight), and having excellent light reflectivity according to claim 1 or 2. Flammable polycarbonate resin composition.   The group in which the polyfunctional monomer (D-2) is composed of allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, divinylbenzene The flame retardant polycarbonate resin composition having excellent light reflectivity according to claim 4, wherein the flame retardant polycarbonate resin composition is one or more monomers selected from the group consisting of:   The vinyl monomer (D-4) is selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, (meth) acrylate monomers, and carboxyl group-containing vinyl monomers. The flame retardant polycarbonate resin composition having excellent light reflectivity according to claim 4, wherein the flame retardant polycarbonate resin composition is at least one selected monomer.   The flame retardancy excellent in light reflectivity according to claim 1 or 2, wherein the organic metal salt (E) is a metal salt of an aromatic sulfonic acid or a metal salt of a perfluoroalkanesulfonic acid. Polycarbonate resin composition.   The flame-retardant polycarbonate resin composition excellent in light reflectivity according to claim 1 or 2, wherein the fiber-forming fluorine-containing polymer (F) is polytetrafluoroethylene.   The molded product formed using the flame retardant polycarbonate resin composition excellent in the light reflectivity as described in any one of Claims 1-8.   A light reflecting plate for a liquid crystal frame or a lamp holder formed by using the flame retardant polycarbonate resin composition having excellent light reflectivity according to any one of claims 1 to 8.