JP2006124600A - Highly reflective polycarbonate resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly reflective polycarbonate resin composition having excellent light resistance and light reflection characteristics.
SOLUTION: Polycarbonate resin (component A) 100 parts by weight, cyclic imino ester UV absorber (component B) having a single melting point peak in differential scanning calorimetry (DSC) measurement based on JIS K7121 (more preferably) Is a light highly reflective polycarbonate resin composition comprising 0.01 to 10 parts by weight of YI value) in the range of -15 to 0, and 3 to 30 parts by weight of titanium dioxide pigment (component C), and light thereof. Reflective material.
[Selection figure] None

Description

  The present invention relates to a light highly reflective polycarbonate resin composition and a method for producing the same. More specifically, the present invention relates to a light highly reflective polycarbonate resin composition excellent in light reflectance and weather resistance (ultraviolet light resistance) of a molded product and a method for producing the same.

  Polycarbonate resins have excellent transparency, heat resistance, mechanical strength, and the like, and thus are widely used in electrical, mechanical, automotive, and medical applications. Furthermore, there is a resin composition that is highly filled with a white pigment typified by a titanium dioxide pigment and excellent in light reflectivity. Molded articles made of the resin composition are used in backlight reflectors for liquid crystal display devices, reflectors for illuminated push switches and photoelectric switches, display internal frames for vending machines, and strobe reflectors.

  In such a resin composition, yellowing during long-term use is not preferable. This is because such yellowing reduces light reflection characteristics. In order to suppress such a decrease (that is, to improve light resistance), an ultraviolet absorber may be further blended. However, such UV absorber formulations often reduce light reflectivity. Therefore, an ultraviolet absorber that does not reduce the light reflectivity has been demanded. In recent years, white LEDs have increased as a light source of the light reflecting material. In order to make use of the high brightness and high white hue, a good hue is also required for the light reflecting material.

  A resin composition in which a cyclic imino ester-based ultraviolet absorber is blended with a polycarbonate resin is known (see Patent Document 1). The resin composition which mix | blended the cyclic imino ester type ultraviolet absorber and the heat stabilizer with polycarbonate resin is well-known (refer patent document 2 and patent document 3). Furthermore, a cyclic imino ester ultraviolet absorber having a yellow index of less than 0 and a sodium content of less than 50 ppm is known (see Patent Document 4). According to this document, the cyclic imino ester is produced from recrystallized isatoic anhydride as a raw material. Further, according to this document, it is described that the cyclic imino ester is difficult to decompose the polycarbonate resin.

Japanese Patent Publication No.62-31027 Special table 2003-534430 gazette WO03 / 095557 pamphlet WO03 / 035735 pamphlet

  However, useful knowledge about the polycarbonate resin composition containing an ultraviolet absorber and having improved light reflection characteristics has not been found in the conventional technology.

  An object of the present invention is to provide a highly light-reflective polycarbonate resin composition having excellent light resistance and light reflection characteristics. The resin composition provides a light reflective molded article having excellent light reflection characteristics. A further object of the present invention is to provide a light-reflective molded article suitable for a light-emitting device using a white LED as a light source.

  The present inventors have intensively studied to solve the above problems. As a result, it has been found that such problems can be solved by blending a titanium dioxide pigment and a specific cyclic imino ester with a polycarbonate resin, and the present invention has been completed.

  According to the present invention, the object of the present invention is (1) 100 parts by weight of a polycarbonate resin (component A) and a cyclic imino ester having a single melting point peak in a differential scanning calorimeter (DSC) measurement based on JIS K7121. This is solved by a highly reflective polycarbonate resin composition comprising 0.01 to 10 parts by weight of an ultraviolet absorber (B component) and 3 to 30 parts by weight of a titanium dioxide pigment (C component).

  The melting point peak in DSC measurement is considered to be an indicator of the purity of the measurement compound. Therefore, according to the present invention, it has been found that the cyclic imino ester-based ultraviolet absorber is important in improving light reflectivity. The cyclic imino ester compound has a fluorescence emission property as well as an ultraviolet absorption property. It is considered that the higher the purity of the cyclic imino ester-based ultraviolet absorber, the more effective the fluorescence emission is and the light reflectivity is improved.

One of the preferred embodiments of the present invention is that (2) the light-reflective polycarbonate resin of the constitution (1), wherein the ultraviolet absorber of the component B consists essentially of a compound of the following formula (I) It is a composition.

  The ultraviolet absorber is widely known as a cyclic imino ester-based ultraviolet absorber, has effective characteristics, and is easily available. Therefore, the ultraviolet absorber is a particularly preferred embodiment in the present invention.

  One of the preferred embodiments of the present invention is: (3) The light of the constitution (1) to (2), wherein the B component ultraviolet absorber has a yellow index (YI value) in the range of -15 to 0. It is a highly reflective polycarbonate resin composition. It is considered that the cyclic imino ester ultraviolet absorber satisfying such YI value emits fluorescence more effectively and achieves good light reflectivity. A cyclic imino ester-based ultraviolet absorber that satisfies such conditions is known from Patent Document 4.

  One of the preferred embodiments of the present invention is that (4) the titanium dioxide pigment (component C) is surface-treated with alkylalkoxysilane and / or hydrogenpolysiloxane. It is a highly reflective polycarbonate resin composition. According to the present invention, it has been found that the use of titanium dioxide pigments surface-treated with these compounds is effective in achieving good light reflectivity. In order to improve the thermal stability of titanium dioxide pigments, it is known to treat the surface with alkylalkoxysilanes and / or hydrogenpolysiloxanes. However, it has not been known that the titanium dioxide pigment subjected to such treatment effectively exhibits its effect even in combination with a specific cyclic imino ester ultraviolet absorber. Due to this effect, according to the configuration (4), a resin composition having further excellent light reflectivity is provided.

  According to another preferred embodiment of the present invention, the object of the present invention is as follows: (5) produced by reacting an isatoic anhydride raw material purified by recrystallization treatment with a terephthalic acid dichloride raw material; A step of preparing a cyclic imino ester-based ultraviolet absorber represented by the general formula (I) (step-i), 100 parts by weight of a polycarbonate resin (component A), 0.01 to 10 parts by weight of the ultraviolet absorber, and This is achieved by a method for producing a highly light-reflective polycarbonate resin composition comprising a step of melt-kneading 3 to 30 parts by weight of a titanium dioxide pigment (component C) (step-ii).

  The cyclic imino ester-based ultraviolet absorber obtained by the above step-i is known in Patent Document 4 (EXAMPLE 1). According to the invention, it has been found that such UV absorbers have particularly good light reflectivity.

One of the preferred embodiments of the present invention is (6) a light highly reflective polycarbonate resin composition produced by the method of constitution (5). Furthermore, one of the preferred embodiments of the present invention is (7) a light reflecting material formed from the light highly reflective polycarbonate resin composition of the above constitutions (1) to (4) and (6). A white LED is particularly suitable as the light source of the light reflecting material of the present invention.
Details of the present invention will be described below.

<About component A>
The component A in the highly reflective polycarbonate resin composition of the present invention is a polycarbonate resin that is a main component of the resin composition. A typical polycarbonate resin (hereinafter sometimes simply referred to as “polycarbonate”) is obtained by reacting a dihydric phenol and a carbonate precursor. The reaction may be performed by an interfacial polycondensation method, a molten ester, or the like. Examples thereof include an exchange method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  Specific examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as “bisphenol”). A ″), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4, 4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropylidene) Phenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4- Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5-dibromo- 4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Is mentioned. Among these, bis (4-hydroxyphenyl) alkane, especially bisphenol A (hereinafter sometimes abbreviated as “BPA”) is widely used.

  In the present invention, in addition to the general-purpose polycarbonate bisphenol A-based polycarbonate, a special polycarbonate produced using other dihydric phenols can be used as the A component.

  For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that the component A constituting the resin composition is a copolymerized polycarbonate of the following (1) to (3). is there.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Of 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Is 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis -Copolymer polycarbonate in which TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).

  These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.

  The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

Of the various polycarbonates described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition, etc. have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where form stability is required.
(I) polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and Tg of 120 to 180 ° C, or (ii) Tg of 160 to 250 ° C, Polycarbonate which is preferably 170 to 230 ° C. and has a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

  Here, the water absorption of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.

  On the other hand, carbonyl halide, carbonate ester, haloformate, or the like is used as the carbonate precursor, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing a polycarbonate from such a dihydric phenol and a carbonate precursor by an interfacial polymerization method, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The polycarbonate may be a branched polycarbonate copolymerized with a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound used here include 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxy). Phenyl) ethane and the like.

When a polyfunctional compound that produces a branched polycarbonate is included, the amount thereof is 0.001 to 1 mol%, preferably 0.005 to 0.9 mol%, particularly preferably 0.01 to 0.8 mol, based on the total amount of the polycarbonate. Mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The amount of the branched structure is also 0.001 to 1 mol%, preferably 0.005 to 0.9% in the total amount of the polycarbonate. Those having a mol%, particularly preferably 0.01 to 0.8 mol% are preferred. The ratio of the branched structure can be calculated by ¹ H-NMR measurement.

  Further, the polycarbonate of the present invention is a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, and a copolymer obtained by copolymerizing a bifunctional alcohol (including alicyclic). Polycarbonate and polyester carbonate obtained by copolymerizing such a bifunctional carboxylic acid and a bifunctional alcohol may also be used. Moreover, the mixture which blended 2 or more types of the obtained polycarbonate may be used.

  The aliphatic bifunctional carboxylic acid used here is preferably an α, ω-dicarboxylic acid. Examples of the aliphatic bifunctional carboxylic acid include, for example, sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and the like, and saturated aliphatic dicarboxylic acid and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.

  Furthermore, in the present invention, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can be used as the component A.

  The component A polycarbonate may be a mixture of two or more of the above-mentioned polycarbonates having different dihydric phenols, polycarbonates containing branched components, polyester carbonates, polycarbonate-polyorganosiloxane copolymers and the like. . Furthermore, what mixed 2 or more types of polycarbonates from which a manufacturing method differs, a polycarbonate from which a terminal terminator differs, etc. can also be used.

  In the polycarbonate polymerization reaction, the reaction by the interfacial polycondensation method is usually a reaction between a dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound can be used. . At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

  In such a polymerization reaction, a terminal terminator is usually used. Monofunctional phenols can be used as such end terminators. As monofunctional phenols, for example, monofunctional phenols such as phenol, p-tert-butylphenol, and p-cumylphenol are preferably used. Furthermore, as monofunctional phenols, long chain alkyl groups having 10 or more carbon atoms such as decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and triacontylphenol. A monofunctional phenol substituted with a nucleus can be exemplified, and the phenol is effective in improving fluidity and hydrolysis resistance. Such end terminators may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and the alcohol or alcohol produced by mixing the dihydric phenol and the carbonate ester with heating in the presence of an inert gas. It is carried out by a method of distilling phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but in most cases is in the range of 120 to 350 ° C. In the latter stage of the reaction, the reaction system is decompressed to about 1.33 × 10 ^{3 to} 13.3 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

  Examples of the carbonate ester include esters such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms which may have a substituent. Among them, diphenyl carbonate is preferable.

A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salt and potassium salt of dihydric phenol; alkaline earth metal compounds such as calcium hydroxide, barium hydroxide and magnesium hydroxide; Nitrogen-containing basic compounds such as methylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, and triethylamine can be used. Furthermore, alkoxides of alkali (earth) metals, organic acid salts of alkali (earth) metals, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds, etc., esterification reaction, transesterification The catalyst used for the reaction can be used. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is preferably selected in the range of 1 × 10 ⁻⁹ to 1 × 10 ⁻⁵ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ equivalents, relative to 1 mol of dihydric phenol as a raw material. It is.

  In the reaction by the melt transesterification method, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate, 2-ethoxycarbonyl is used at the later stage or after completion of the polycondensation reaction for the purpose of reducing the phenolic end groups of the produced polycarbonate. Compounds such as phenylphenyl carbonate can be added.

  Furthermore, in the melt transesterification method, it is preferable to use a deactivator that neutralizes the activity of the catalyst. The amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst. Moreover, it is suitable to use in the ratio of 0.01-500 ppm with respect to the polycarbonate after superposition | polymerization, More preferably, it is 0.01-300 ppm, Most preferably, it is a ratio of 0.01-100 ppm. Examples of preferable quenching agents include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecyl benzyl sulfate.

  The viscosity average molecular weight of the polycarbonate resin of component A is not limited. However, when the viscosity average molecular weight is less than 10,000, the strength and the like are lowered, and when it exceeds 50,000, the molding process characteristics are lowered. Therefore, the range of 10,000 to 50,000 is preferable. The range of 15,000 to 30,000 is more preferable, and the range of 15,000 to 28,000 is more preferable. In this case, it is also possible to mix a polycarbonate having a viscosity average molecular weight outside the above range within a range in which moldability and the like are maintained. For example, a high molecular weight polycarbonate component having a viscosity average molecular weight exceeding 50,000 can be blended.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of aromatic polycarbonate in 100 ml of methylene chloride at 20 ° C. with a specific viscosity (η _SP ) calculated by the following formula. ,
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is the drop time of methylene chloride, t is the drop time of the sample solution]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  In addition, calculation of the viscosity average molecular weight in the light highly reflective polycarbonate resin composition of this invention is performed in the following way. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. From a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride, the specific viscosity at 20 ° C. is obtained in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.

<About B component>
The B component of the present invention is a cyclic imino ester ultraviolet absorber having a single melting point peak in differential scanning calorimetry (DSC) measurement based on JIS K7121. The cyclic imino ester compound as the cyclic imino ester ultraviolet absorber of the present invention refers to a compound represented by the following general formula (II).

（ここでｎは１〜３であり、Ｒ^１は単結合またはｎの価数を有し、更にヘテロ原子を含有してもよい炭化水素残基であり、Ｒ^２は水素原子、ハロゲン原子、ニトロ基、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、もしくは炭素数１〜８のアルケニロキシ基である。）

(Wherein n is 1 to 3, R ¹ is a single bond or a hydrocarbon residue having a valence of n and may further contain a hetero atom, R ² is a hydrogen atom, a halogen atom, A nitro group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 1 to 8 carbon atoms.)

  Therefore, the cyclic imino ester-based ultraviolet absorber of the present invention consists essentially of the compound represented by the general formula (II), but may contain a slight amount of other impurities other than the compound. It can be called an agent.

  Specific examples of such cyclic imino ester compounds include 2,2′-bis (3,1-benzoxazin-4-one), 2,2′-p-phenylenebis (3,1-benzoxazin-4-one). ), 2,2′-m-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one) 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one), 2,2 ′-(1,5-naphthalene) bis (3,1-benzoxazine-4-one) ON), 2,2 ′-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2-nitro-p-phenylene) bis (3,1 -Benzoxazin-4-one), and 2,2 '-(2-chloro Etc. p- phenylene) bis (3,1-benzoxazin-4-one) is illustrated.

  Among these, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) represented by the following formula (I) is preferable. The cyclic imino esters can be used alone or in combination of two or more.

  The ultraviolet absorber of the B component of the present invention has a single melting point peak as described above. Furthermore, according to the present invention, it has been found that the narrower the melting point peak, the better the light reflection characteristics. More specifically, the temperature difference between the peak rising temperature and the peak temperature is preferably within 10 ° C. From the above points, it is expected that the higher the purity of the cyclic iminoester ultraviolet absorber, the better the light reflection characteristics.

As described above, the preferred cyclic iminoester ultraviolet absorber of the present invention has a YI value in the range of -15 to 0. The YI value is more preferably in the range of −10 to 0. The YI value of the cyclic imino ester is a value measured in the following manner. A quartz glass cylindrical container having a plate thickness of 2 mm, an inner surface height of 12 mm, and an inner diameter of 30.5 mm is prepared. In order to avoid the formation of voids in such a container, the powder of the cyclic imino ester ultraviolet absorber to be measured is put while tapping lightly. The powder has an average particle size of about 100 μm (100 mesh pass and 200 mesh on using Tyler standard sieve). Such a sample is placed in a color machine, and its YI value is measured by a reflection method. The light source uses CIELab. Based on ASTM-E1925 from the measured X, Y and Z values, the following formula is used.
YI = [100 (1.28X-1.06Z)] / Y

  Furthermore, the cyclic imino ester ultraviolet absorber of the present invention preferably has a Na content of 100 ppm or less, and a chlorine content of 10 ppm or less. Na-containing compounds (especially sodium hydroxide) are often used during the synthesis of cyclic imino ester compounds and during washing of the products. Therefore, some residue is inevitable. When there is too much Na content, it will have a bad influence with respect to light reflectivity. When a Na-containing compound is used in the production of the cyclic imino ester-based ultraviolet absorber, the Na content is preferably made not more than the predetermined amount by a method of repeating water washing. For the Na content and the chlorine content, the sample is immersed in warm water for 1 hour to extract these components into water, and the aqueous solution is subjected to atomic absorption spectrometry measurement (Na content) and potentiometric titration (chlorine content). Is measured. The sample used for the measurement has an average particle size of about 100 μm (100 mesh pass 200 mesh on using Tyler standard sieve).

  Chlorine remains when there is an unreacted component because a carboxylic acid chloride compound is used as a raw material. Since such components are also liable to adversely affect light reflectivity, it is preferable to reduce them as much as possible. Such components can be reduced by washing the product compound with the Na-containing compound (especially sodium hydroxide).

  “CEi-P” sold by Takemoto Yushi Co., Ltd. is a commercially available product of a suitable cyclic iminoester ultraviolet absorber of the present invention. However, such “CEi-P” does not satisfy the preferred YI value range. A more preferred cyclic imino ester ultraviolet absorber of the present invention is the ultraviolet absorber described in Patent Document 4 (more specifically, EXAMPLE1). The ultraviolet absorber is a cyclic imino ester-based ultraviolet absorber represented by the above formula (I) produced by reacting an isatoic anhydride raw material purified by recrystallization treatment with a terephthalic acid dichloride raw material. It is. Such an ultraviolet absorber is available as “CEi-PA” from Takemoto Yushi Co., Ltd.

<About component C>
The C component of the present invention is a titanium dioxide pigment. As the titanium dioxide pigment, those usually used for various coloring applications can be used, and they are well known per se. There is also a titanium dioxide pigment composed of 100% by weight of TiO ₂ (in the present invention, the titanium dioxide component of the titanium dioxide pigment is expressed as “TiO ₂ ”, and the entire pigment including the surface treatment agent is referred to as “titanium dioxide pigment”. write). However, surface treatment is usually performed with oxides of various metals such as aluminum, silicon, titanium, zirconium, antimony, tin, and zinc. Also in the present invention, preferred titanium dioxide pigments are those obtained by surface treatment of other metal oxides. Therefore, in the preferred embodiment of the titanium dioxide pigment of the present invention, the content of TiO _{2 in} 100% by weight of the titanium dioxide pigment is 89 to 97% by weight, and the surface treatment is performed with the metal oxide represented above. It is a titanium dioxide pigment. A more preferred embodiment is such a titanium dioxide pigment, which is a titanium dioxide pigment that has been surface-treated with at least Al ₂ O ₃ , and among them, the content ratio of the Al ₂ O ₃ is preferably 100% by weight of the titanium dioxide pigment. The titanium dioxide pigment is 0.5 to 4% by weight, more preferably 1.5 to 3.5% by weight, and still more preferably 2 to 3.5% by weight.

Such a preferable titanium dioxide pigment is more preferably a TiO ₂ content ratio of 91 to 95% by weight in 100% by weight of the titanium dioxide pigment.
The preferred titanium dioxide pigment is more preferably surface-treated with SiO ₂ and / or ZrO ₂ in addition to Al ₂ O ₃ , and particularly preferably surface-treated with SiO ₂ . Therefore, a more preferable embodiment of the titanium dioxide pigment of the present invention is the above-mentioned preferable titanium dioxide pigment, and further 0.5 to 5% by weight, more preferably 1 to 3% by weight, in 100% by weight of the titanium dioxide pigment. more preferably a titanium dioxide pigment surface treatment with SiO ₂ of 1 to 2.5% by weight have been made.
The metal oxide component for these surface treatment need not necessarily be present only on the surface of the TiO _2, part may be a mode which is present inside the TiO ₂ particles.

TiO ₂ in the C component may be either anatase type or rutile type in crystal form, and they can be mixed and used as necessary. A rutile type is more preferable in terms of initial mechanical properties and long-term weather resistance. A rutile type crystal may contain an anatase type crystal. Furthermore TiO ₂ production process is sulfuric acid method, chlorine method, but those which have been prepared by various other methods can be used, the chlorine method is more preferred. Further, the titanium dioxide pigment of the present invention is not particularly limited in its shape, but is preferably in the form of particles. The average particle diameter of the titanium dioxide pigment is preferably 0.01 to 0.4 μm, more preferably 0.1 to 0.3 μm, and still more preferably 0.15 to 0.25 μm. Such an average particle diameter is calculated by measuring the number of individual single particles and observing the number average thereof through observation with an electron microscope.

The coating with various metal oxides on the surface of TiO ₂ can be performed by various commonly used methods. For example, it is manufactured from the following steps 1) to 8). That is, 1) untreated TiO ₂ after dry pulverization is made into an aqueous slurry, 2) the slurry is wet pulverized and atomized, 3) a fine particle slurry is collected, and 4) a metal salt is soluble in the fine particle slurry. Add compound 5) Neutralize and coat TiO ₂ surface with metal hydrated oxide 6) Remove by-products, adjust slurry pH, filter, and clean with pure water 7) Washed Examples thereof include a method of drying the cake, and 8) crushing the dried product with a jet mill or the like. In addition to this method, for example, a method of reacting TiO ₂ particles with an active metal compound in a gas phase can be mentioned. Further, in the coating of the metal oxide surface treatment agent on the TiO ₂ surface, firing after the surface treatment, surface treatment again after the surface treatment, and firing after the surface treatment and surface treatment again are performed. Is possible. As the surface treatment with the metal oxide, either a high-density treatment or a low-density (porous) treatment can be selected.

  The component C titanium dioxide pigment is more preferably surface-treated with an organic compound. As such a surface treatment agent, various treatment agents such as polyol, amine, and silicone can be used. Examples of the polyol-based surface treatment agent include pentaerythritol, trimethylolethane, and trimethylolpropane. Examples of the amine-based surface treatment agent include triethanolamine acetate and trimethylolamine acetate. Examples of the silicone-based surface treatment agent include alkylchlorosilanes (such as trimethylchlorosilane), alkylalkoxysilanes (such as methyltrimethoxysilane), and hydrogen polysiloxane. Examples of the hydrogen polysiloxane include alkyl hydrogen polysiloxane and alkylphenyl hydrogen polysiloxane. Such an alkyl group is preferably a methyl group or an ethyl group. The titanium dioxide pigment surface-treated with such an alkylalkoxysilane and / or hydrogen polysiloxane gives good light reflectivity to the resin composition of the present invention.

  The amount of the organic compound to be surface-treated is preferably 1% by weight or less, more preferably 0.6% by weight or less, and further preferably 0.4% by weight or less per 100% by weight of the C component. On the other hand, the lower limit is 0.05% by weight or more. The surface treatment agent for the organic compound is preferably made in advance on titanium dioxide particles (more preferably titanium dioxide particles coated with other metal oxides). However, a method may be used in which the surface treatment agent is separately added when the raw material of the resin composition is melt-kneaded and the surface treatment of the titanium dioxide pigment is performed in the melt-kneading step.

<About the content of each component>
The highly reflective polycarbonate resin composition of the present invention comprises 100 parts by weight of A component, 0.01 to 10 parts by weight of B component, and 3 to 30 parts by weight of C component. The light highly reflective polycarbonate resin composition of the present invention can be produced by blending the A component, the B component, and the C component. The content of component B is preferably 0.05 to 3.5 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of component A. When the component B is less than the lower limit, the ultraviolet absorption performance is insufficient and sufficient ultraviolet resistance is difficult to obtain. On the other hand, even if the B component exceeds the above upper limit, no remarkable improvement is observed in terms of ultraviolet resistance. On the other hand, since the B component is hardly dissolved in the polycarbonate resin, the mechanical properties are easily adversely affected. The content of component C is preferably 7 to 28 parts by weight, more preferably 10 to 25 parts by weight, based on 100 parts by weight of component A. If the C component is less than the lower limit, the light reflectivity tends to be insufficient, and even if the C component exceeds the upper limit, no significant improvement in light reflectivity is observed, but the thermal stability of the resin composition decreases. It is not preferable.

<About other ingredients>
The highly reflective polycarbonate resin composition of the present invention comprises the A component, B component, and C component as essential components, but may contain other components as needed in addition to these components. it can. Components other than the A component to the C component will be described below.

(I) Phosphorus stabilizer It is preferable that various phosphorous stabilizers are further blended in the highly reflective polycarbonate resin composition of the present invention. The main purpose of blending such a phosphorus stabilizer is to improve the thermal stability during molding of the resin composition and to obtain good light reflectivity. Examples of such phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.

  Specific examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl. Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylpheny) ) Phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, etc. And the like.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Examples include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) octyl phosphite, and the like.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, And diisopropyl phosphate are exemplified, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, Bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, and bis (2,4-di-tert-butylphenyl) ) -Phenyl-phenylphosphonite is more preferred. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

  Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

  Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphite compounds or phosphonite compounds are preferable. The most preferred phosphite compound is tris (2,4-di-tert-butylphenyl) phosphite. Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite and these And a mixture of these is most preferable. The weight ratio between the two (the former / the latter) is preferably in the range of 90/10 to 70/30, more preferably in the range of 85/15 to 75/25. A combination of these and a phosphate compound is also a preferred embodiment.

(Ii) Hindered phenol stabilizer The resin composition is mainly used for the purpose of improving the heat stability, heat aging resistance, and ultraviolet resistance during molding of the highly reflective polycarbonate resin composition of the present invention. A hindered phenol-based stabilizer may be blended. Examples of such hindered phenol-based stabilizers include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2 -Tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N- Dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4 -Ethyl-6-tert-butylphenol), 4,4'-methylenebis (2, -Di-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2 ' -Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert) -Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) Ru-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3- Methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4 ′ -Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodie Renbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert- Butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Cyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate and tetrakis [methylene-3- (3,5-di-tert-butyl -4-hydroxyphenyl) propionate] methane and the like. Among these, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (CIBA SPECILITY CHEMICALS: Irganox 1076 (trade name)) is preferable as a typical commercial product. All of the above-mentioned hindered phenol antioxidants are easily available, and these can be used alone or in combination of two or more.

  The blending amount of the above (i) phosphorus stabilizer and (ii) hindered phenol antioxidant is 0.0001 to 1 part by weight, preferably 0.001 to 0.1 based on 100 parts by weight of component A. Parts by weight, more preferably 0.005 to 0.1 parts by weight. When the amount of the stabilizer is too much less than the above range, it is difficult to obtain a good stabilizing effect. When the amount exceeds the above range, the physical properties of the composition may be lowered.

  In the highly reflective polycarbonate resin composition of the present invention, an antioxidant other than the hindered phenol-based antioxidant can be used in order to further stabilize the hue at the time of heat treatment of the molded product. Examples of such other antioxidants include lactone stabilizers represented by reaction products of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers). Are described in JP-A-7-233160), and pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthio And sulfur-containing stabilizers such as propionate. The blending amount of these other antioxidants is preferably 0.001 to 0.05 parts by weight based on 100 parts by weight of component A. Further, the light highly reflective polycarbonate resin composition of the present invention can also contain a hindered amine light stabilizer.

(Iii) Flame Retardant Various compounds known as flame retardants for polycarbonate resins may be blended in the highly reflective polycarbonate resin composition of the present invention. The compounding of such a compound brings about an improvement in flame retardancy, but besides that, based on the properties of each compound, for example, an improvement in antistatic property, fluidity, rigidity and thermal stability is brought about. Examples of such flame retardants include (i) organometallic salt flame retardants (for example, alkali (earth) organic sulfonate metal salts, borate metal salt flame retardants, stannate metal salt flame retardants, etc.), and (ii) Organophosphorous flame retardants (for example, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), (iii) silicone flame retardants comprising silicone compounds, and (iv) halogens And flame retardant (for example, brominated epoxy resin, brominated polystyrene, brominated polycarbonate (including oligomers), brominated polyacrylate, chlorinated polyethylene, etc.).

(Iii-i) Organometallic salt-based flame retardant An organometallic salt-based flame retardant is advantageous in that heat resistance is substantially maintained and antistatic properties can be imparted. The organometallic salt flame retardant most advantageously used in the present invention is a fluorine-containing organometallic salt compound. The fluorine-containing organometallic salt compound of the present invention refers to a metal salt compound comprising an anion component composed of an organic acid having a fluorine-substituted hydrocarbon group and a cation component composed of a metal ion. More preferred specific examples include metal salts of fluorine-substituted organic sulfonic acids, metal salts of fluorine-substituted organic sulfates, and metal salts of fluorine-substituted organic phosphates. Fluorine-containing organometallic salt compounds can be used alone or in combination of two or more. Among them, a metal salt of a fluorine-substituted organic sulfonic acid is preferable, and a metal salt of a sulfonic acid having a perfluoroalkyl group is particularly preferable. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1-18, more preferably in the range of 1-10, and still more preferably in the range of 1-8.

  The metal constituting the metal ion of the organometallic salt flame retardant is an alkali metal or an alkaline earth metal. Examples of the alkali metal include lithium, sodium, potassium, rubidium and cesium. Examples of the alkaline earth metal include beryllium. , Magnesium, calcium, strontium and barium. More preferred is an alkali metal. Accordingly, a preferred organometallic salt flame retardant is an alkali metal perfluoroalkyl sulfonate. Among such alkali metals, rubidium and cesium are suitable when transparency requirements are higher, but these are not general-purpose and difficult to purify, resulting in disadvantages in terms of cost. is there. On the other hand, although lithium and sodium are advantageous in terms of cost and flame retardancy, they may be disadvantageous in terms of transparency. In consideration of these, the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used, but perfluoroalkylsulfonic acid potassium salt having an excellent balance of properties is most suitable in any respect. Such potassium salts and alkali metal salts of perfluoroalkylsulfonic acid composed of other alkali metals can be used in combination.

  Such alkali metal perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, perfluorobutanesulfone. Acid sodium, sodium perfluorooctane sulfonate, lithium trifluoromethane sulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethane sulfonate, cesium perfluorobutane sulfonate, cesium perfluorooctane sulfonate, Cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perful B hexane sulfonate rubidium, and these may be used in combination of at least one or two. Of these, potassium perfluorobutanesulfonate is particularly preferred.

  The fluorine-containing organic metal salt preferably has a fluoride ion content measured by ion chromatography of 50 ppm or less, more preferably 20 ppm or less, and even more preferably 10 ppm or less. The lower the fluoride ion content, the better the light resistance and the better the light reflectivity. The lower limit of the fluoride ion content can be substantially zero, but is practically preferably about 0.2 ppm in view of the balance between the refining man-hour and the effect. Such alkali metal salt of perfluoroalkylsulfonic acid having a fluoride ion content is purified, for example, as follows. The perfluoroalkylsulfonic acid alkali metal salt is dissolved in 2 to 10 times by weight of the metal salt in ion-exchanged water in the range of 40 to 90 ° C. (more preferably 60 to 85 ° C.). The alkali metal salt of perfluoroalkylsulfonic acid is a method of neutralizing perfluoroalkylsulfonic acid with an alkali metal carbonate or hydroxide, or perfluoroalkylsulfonyl fluoride with an alkali metal carbonate or hydroxide. It is produced by a neutralizing method (more preferably by the latter method). The ion-exchanged water is particularly preferably water having an electric resistance value of 18 MΩ · cm or more. The solution in which the metal salt is dissolved is stirred at the above temperature for 0.1 to 3 hours, more preferably 0.5 to 2.5 hours. Thereafter, the liquid is cooled to 0 to 40 ° C, more preferably in the range of 10 to 35 ° C. Crystals precipitate upon cooling. The precipitated crystals are removed by filtration. This produces a suitable purified perfluoroalkylsulfonic acid alkali metal salt.

  The compounding amount of the fluorine-containing organometallic salt compound is preferably 0.005 to 0.6 parts by weight, more preferably 0.005 to 0.2 parts by weight, still more preferably 0.00 based on 100 parts by weight of the component A. 008 to 0.13 parts by weight. The more preferable range is, the effects (for example, flame retardancy and antistatic property) expected from the blending of the fluorine-containing organic metal salt are exhibited, and the adverse effect on the light resistance of the resin composition is reduced.

  In addition, as an organic metal salt flame retardant other than the fluorine-containing organic metal salt compound, a metal salt of an organic sulfonic acid not containing a fluorine atom is suitable. Examples of the metal salt include an alkali metal salt of an aliphatic sulfonic acid, an alkaline earth metal salt of an aliphatic sulfonic acid, an alkali metal salt of an aromatic sulfonic acid, and an alkaline earth metal salt of an aromatic sulfonic acid (any Also does not contain a fluorine atom).

  Preferable examples of the aliphatic sulfonic acid metal salt include an alkali (earth) metal salt of an alkyl sulfonate, and these can be used alone or in combination of two or more (here, alkali The (earth) metal salt is used to include both alkali metal salts and alkaline earth metal salts). Preferred examples of the alkane sulfonic acid used for the alkali (earth) metal salt of the alkyl sulfonate include methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, methyl butane sulfonic acid, hexane sulfonic acid, and heptane. Examples thereof include sulfonic acid and octanesulfonic acid, and these can be used alone or in combination of two or more.

  The aromatic sulfonic acid used in the aromatic (earth) metal salt of aromatic sulfonate includes monomeric or polymeric aromatic sulfide sulfonic acid, aromatic carboxylic acid and ester sulfonic acid, monomeric or polymeric sulfonic acid. Aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfonic acid, aromatic ketone sulfonic acid, heterocyclic sulfonic acid, Examples include at least one acid selected from the group consisting of sulfonic acids of aromatic sulfoxides and condensates of methylene type bonds of aromatic sulfonic acids, and these are used alone or in combination of two or more. be able to.

  Specific examples of the aromatic (earth) metal salt of an aromatic sulfonate include, for example, disodium diphenyl sulfide-4,4′-disulfonate, dipotassium diphenyl sulfide-4,4′-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate 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) polysulfonate, potassium sulfonate of benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, naphthalene-2 , 6-disulfonic acid dipotassium, biphenyl-3,3'-disulfonic acid calcium, diphenylsulfone-3-sulfonic acid sodium, diphenylsulfone-3-sulfonic acid potassium, diphenylsulfone-3,3'-disulfonic acid dipotassium, diphenylsulfone Α, α, α-trifluoroacetophenone sodium 4-sulfonate, dipotassium benzophenone-3,3′-disulfonate, Nene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, naphthalene Examples thereof include a formalin condensate of sodium sulfonate and a formalin condensate of sodium anthracene sulfonate.

  On the other hand, the alkali (earth) metal salt of sulfate ester may include, in particular, the alkali (earth) metal salt of sulfate ester of monovalent and / or polyhydric alcohols. Alcohol sulfates include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono, di, tri, tetrasulfate, and lauric acid monoglyceride. And sulfuric acid esters of palmitic acid monoglyceride and stearic acid monoglyceride sulfate. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate.

  Examples of other alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides such as saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, N Examples include-(N'-benzylaminocarbonyl) sulfanilimide and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanilimide.

  Of these, preferred metal salts of organic sulfonic acids that do not contain fluorine atoms are alkali (earth) metal salts of aromatic sulfonates, and potassium salts are particularly preferred. When blending such an alkali (earth) sulfonate metal salt, the content is 0.001 to 1 part by weight based on 100 parts by weight of component A, more preferably 0.005 to 0.5. Part by weight, more preferably 0.01 to 0.1 part by weight.

(Iii-ii) Organophosphorus Flame Retardant As the organophosphorus flame retardant of the present invention, an aryl phosphate compound is suitable. This is because such a phosphate compound is generally excellent in hue and hardly adversely affects high light reflectivity. Moreover, since the phosphate compound has a plasticizing effect, it is advantageous in that the moldability of the resin composition of the present invention can be improved. As the phosphate compound, various known phosphate compounds as conventional flame retardants can be used, and more preferably, one or more phosphate compounds represented by the following general formula (III) can be mentioned.

（但し前記式中のＸは、二価フェノールから誘導される二価の有機基を表し、Ｒ^１１、Ｒ^１２、Ｒ^１３、およびＲ^１４はそれぞれ一価フェノールから誘導される一価の有機基を表し、ｎは０〜５の整数を表す。）

(However, X in the above formula represents a divalent organic group derived from a dihydric phenol, and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each a monovalent organic group derived from a monohydric phenol. And n represents an integer of 0 to 5.)

  The phosphate compound of the above formula may be a mixture of compounds having different n numbers, in which case the average n number is preferably 0.5 to 1.5, more preferably 0.8 to 1. 2, More preferably, it is 0.95-1.15, Most preferably, it is the range of 1-1.14.

  Preferable specific examples of the dihydric phenol for deriving X include hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4 -Hydroxyphenyl) ketone and bis (4-hydroxyphenyl) sulfide are exemplified, among which resorcinol, bisphenol A, and dihydroxydiphenyl are preferable.

Preferable specific examples of the monohydric phenol for deriving R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ include phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. Are phenol and 2,6-dimethylphenol.

  Such a monohydric phenol may substitute a halogen atom. Specific examples of the phosphate compound having a group derived from the monohydric phenol include tris (2,4,6-tribromophenyl) phosphate and tris. Examples include (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, and the like.

  On the other hand, specific examples of phosphate compounds not substituted with halogen atoms include monophosphate compounds such as triphenyl phosphate and tri (2,6-xylyl) phosphate, and resorcinol bisdi (2,6-xylyl) phosphate). Preferred are phosphate oligomers mainly composed of phosphate oligomers, phosphate oligomers mainly composed of 4,4-dihydroxydiphenyl bis (diphenyl phosphate), and phosphate oligomers mainly composed of bisphenol A bis (diphenyl phosphate). Indicates that a small amount of other components having different degrees of polymerization may be included, and more preferably, the component of n = 1 in the formula (VI) is 80% by weight or more, more preferably 85% by weight or more, and still more preferably Containing 90% by weight or more Show.).

(Iii-iii) Silicone Flame Retardant The silicone compound used as the silicone flame retardant of the present invention improves flame retardancy by a chemical reaction during combustion. As the compound, various compounds conventionally proposed as a flame retardant for aromatic polycarbonate resin can be used. The silicone compound binds itself during combustion or binds to a component derived from the resin to form a structure, or gives a flame retardant effect to the polycarbonate resin by a reduction reaction during the structure formation. It is considered. Therefore, it is preferable that a group having high activity in such a reaction is contained, and more specifically, a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (ie, Si—H group) is contained. preferable. As a content rate of this group (alkoxy group, Si-H group), the range of 0.1-1.2 mol / 100g is preferable, the range of 0.12-1 mol / 100g is more preferable, 0.15-0. The range of 6 mol / 100 g is more preferable. Such a ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkali decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

Generally, the structure of a silicone compound is constituted by arbitrarily combining the following four types of siloxane units. That is,
M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 Monofunctional siloxane units such as (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _1/2 ,
D unit: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO Bifunctional siloxane units such as
T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) SiO _3/2 , (C ₆ H ₅ ) SiO _3/2 etc. A trifunctional siloxane unit of
Q unit: a tetrafunctional siloxane unit represented by SiO ₂ .

Specifically, the structure of the silicone compound used in the silicone-based flame retardant is represented by the following formulas: D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _m D _n T _{p , M m D n Q q,} M m T p Q q, M m D n T p Q q, D n T p, D n Q q, include _{D n} T p _{Q q.} Among these, preferable structures of the silicone compound are M _m D _n , M _m T _p , M _m D _n T _p , and M _m D _n Q _q , and more preferable structures are M _m D _n or M _m D _n. T _p .

  Here, the coefficients m, n, p, and q in the above formula are integers of 1 or more that indicate the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound. . This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, still more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The better the range, the better the flame retardancy. Further, as described later, a silicone compound containing a predetermined amount of an aromatic group is excellent in transparency and hue. As a result, good reflected light can be obtained.

  When any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with the coefficient can be two or more types of siloxane units having different hydrogen atoms or organic residues to be bonded. .

  The silicone compound may be linear or have a branched structure. The organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such organic residues include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, And aralkyl groups such as tolyl groups. More preferably, they are a C1-C8 alkyl group, an alkenyl group, or an aryl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable.

  Further, the silicone compound used as the silicone flame retardant preferably contains an aryl group. More preferably, the ratio (aromatic group amount) of the aromatic group represented by the following general formula (IV) is 10 to 70% by weight (more preferably 15 to 60% by weight).

（式（IV）中、Ｘはそれぞれ独立にＯＨ基、炭素数１〜２０の一価の有機残基を示す。ｎは０〜５の整数を表わす。さらに式（IV）中においてｎが２以上の場合はそれぞれ互いに異なる種類のＸを取ることができる。）

(In formula (IV), each X independently represents an OH group or a monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. Further, in formula (IV), n is 2) In these cases, different types of X can be taken.)

  The silicone compound used as the silicone-based flame retardant may contain a reactive group in addition to the Si-H group and the alkoxy group. Examples of the reactive group include an amino group, a carboxyl group, an epoxy group, and a vinyl group. Examples thereof include a group, a mercapto group, and a methacryloxy group.

  As the silicone compound having a Si—H group, a silicone compound containing at least one of structural units represented by the following general formulas (V) and (VI) is preferably exemplified.

（式（V）および式（VI）中、Ｚ^１〜Ｚ^３はそれぞれ独立に水素原子、炭素数１〜２０の一価の有機残基、または下記一般式（V II）で示される化合物を示す。α１〜α３はそれぞれ独立に０または１を表わす。ｍ１は０もしくは１以上の整数を表わす。さらに式（V）中においてｍ１が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (V) and formula (VI), Z ^{1 to} Z ³ are each independently a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a compound represented by the following general formula (V II). Α1 to α3 each independently represents 0 or 1. m1 represents 0 or an integer of 1 or more, and in formula (V), when m1 is 2 or more, the repeating units are each a plurality of different repeating units. Can take

（式（VII）中、Ｚ^４〜Ｚ^８はそれぞれ独立に水素原子、炭素数１〜２０の一価の有機残基を示す。α４〜α８はそれぞれ独立に０または１を表わす。ｍ２は０もしくは１以上の整数を表わす。さらに式（VII）中においてｍ２が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (VII), Z ^{4 to} Z ⁸ each independently represents a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α 4 to α 8 each independently represents 0 or 1. m 2 represents 0. Alternatively, it represents an integer of 1 or more, and the repeating unit in the case where m2 is 2 or more in formula (VII) can take a plurality of different repeating units.

  Examples of the silicone compound having an alkoxy group in the silicone compound used for the silicone-based flame retardant include at least one compound selected from compounds represented by the general formula (VIII) and the general formula (IX).

（式（VIII）中、β^１はビニル基、炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示す。γ^１、γ^２、γ^３、γ^４、γ^５、およびγ^６は炭素数１〜６のアルキル基およびシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示し、少なくとも１つの基がアリール基またはアラルキル基である。δ^１、δ^２、およびδ^３は炭素数１〜４のアルコキシ基を示す。）

(In formula (VIII), β ¹ represents a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms. Γ ¹ , γ ² , γ ³ , γ ⁴ , γ ⁵ , and γ ⁶ represent an alkyl group and a cycloalkyl group having 1 to ⁶ carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms, and at least one group is aryl. And δ ¹ , δ ² , and δ ³ are each an alkoxy group having 1 to 4 carbon atoms.)

（式（IX）中、β^２およびβ^３はビニル基、炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示す。γ^７、γ^８、γ^９、γ^１０、γ^１１、γ^１２、γ^１３およびγ^１４は炭素数１〜６のアルキル基、、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示し、少なくとも１つの基がアリール基またはアラルキルである。δ^４、δ^５、δ^６、およびδ^７は炭素数１〜４のアルコキシ基を示す。）

(In Formula (IX), β ² and β ³ represent a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms. γ ⁷ , γ ⁸ , γ ⁹ , γ ¹⁰ , γ ¹¹ , γ ¹² , γ ^13, and γ ¹⁴ are each an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and 6 to 12 carbon atoms. And at least one group is an aryl group or an aralkyl group, and δ ⁴ , δ ⁵ , δ ⁶ , and δ ⁷ represent an alkoxy group having 1 to 4 carbon atoms.)

(Iii-iv) Halogen flame retardant As the halogen flame retardant of the present invention, brominated polycarbonate (including oligomers) is particularly suitable. The light reflecting material is often exposed to a high temperature by a light source. Therefore, brominated polycarbonate having excellent heat resistance may be required. In the brominated polycarbonate used in the present invention, the structural unit represented by the following general formula (X) is at least 60 mol%, preferably at least 80 mol%, particularly preferably substantially the following general formula. It is a brominated polycarbonate compound composed of the structural unit represented by (X).

（式（X）中、Ｘは臭素原子、Ｒは炭素数１〜４のアルキレン基、炭素数１〜４のアルキリデン基または−ＳＯ_２−である。）

(In the formula (X), X is a bromine atom, R represents an alkylene group having 1 to 4 carbon atoms, an alkylidene group or -SO ₂ 1 to 4 carbon atoms - a.)

In the formula (X), R preferably represents a methylene group, an ethylene group, an isopropylidene group, —SO ₂ —, and particularly preferably an isopropylidene group.

  The brominated polycarbonate has a small number of remaining chloroformate groups and preferably has a terminal chlorine content of 0.3 ppm or less, more preferably 0.2 ppm or less. The amount of terminal chlorine is determined by dissolving a sample in methylene chloride, adding 4- (p-nitrobenzyl) pyridine and allowing it to react with terminal chlorine (terminal chloroformate). -3200). When the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the aromatic polycarbonate resin composition becomes better, and a resin composition excellent in light reflectivity and molding processability is provided.

The brominated polycarbonate preferably has a small number of remaining hydroxyl terminals. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, more preferably 0.0003 mol or less with respect to 1 mol of the structural unit of brominated polycarbonate. The amount of terminal hydroxyl groups can be determined by dissolving a sample in deuterated chloroform and measuring it by ¹ H-NMR method. Such a terminal hydroxyl group amount is preferable because the thermal stability of the resin composition is further improved.

  The specific viscosity of the brominated polycarbonate is preferably in the range of 0.015 to 0.1, more preferably in the range of 0.015 to 0.08. The specific viscosity of the brominated polycarbonate is calculated according to the formula for calculating the specific viscosity used in calculating the viscosity average molecular weight of the aromatic polycarbonate resin which is the component A of the present invention.

(Iv) Anti-dripping agent The highly reflective polycarbonate resin composition of the present invention can contain an anti-dripping agent. By using such an anti-dripping agent in combination with the flame retardant, better flame retardancy can be obtained. Examples of the anti-dripping agent include a fluorinated polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene, tetrafluoroethylene copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymers). , Etc.), partially fluorinated polymers as shown in U.S. Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, etc., preferably polytetrafluoroethylene (hereinafter referred to as PTFE). Is).

Polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability has a very high molecular weight, and exhibits a tendency to bind PTFE to each other by an external action such as shearing force to form a fiber. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise.

  Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there. Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell are also preferably used.

  Examples of such commercially available fibrillated PTFE include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L from Daikin Chemical Industries, Ltd., and the like. Commercially available aqueous dispersions of fibrillated PTFE include: Fluon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers, Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui A representative example is Teflon (registered trademark) 30J manufactured by DuPont Fluorochemical Co., Ltd.

  As a mixed form of fibrillated PTFE, (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-agglomerated mixture (JP-A-60-258263). (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). Described method), (3) A method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos. 06-220210, (Method described in Japanese Patent Application Laid-Open No. 08-188653), (4) A method of polymerizing monomers forming an organic polymer in an aqueous dispersion of fibrillated PTFE (Method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion. Thereafter, those obtained by a method for obtaining a mixture (a method described in JP-A No. 11-29679) can be used. Examples of commercially available fibrillated PTFE in a mixed form include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

  The light highly reflective polycarbonate resin composition of the present invention may require high surface smoothness. Therefore, the fibrillated PTFE is preferably finely dispersed. As a means of achieving such fine dispersion, the mixed form of fibrillated PTFE is advantageous. A method of directly supplying an aqueous dispersion in a melt kneader is also advantageous for fine dispersion. However, in the case of the aqueous dispersion form, consideration is required in that the hue is slightly deteriorated. The proportion of fibrillated PTFE in the mixed form is preferably 10 to 80% by weight, more preferably 15 to 75% by weight, in 100% by weight of the mixture. When the ratio of fibrillated PTFE is in such a range, good dispersibility of fibrillated PTFE can be achieved.

  The content of the fibrillated PTFE in the highly reflective polycarbonate resin composition is preferably 0.001 to 1 part by weight, more preferably 0.1 to 0.7 part by weight based on 100 parts by weight of the component A. is there.

(V) Optical brightener The optically highly reflective polycarbonate resin composition of the present invention can contain an optical brightener as necessary. Inclusion of a fluorescent brightening agent increases the amount of reflected light. As the optical brightener, known bisbenzoxazole, coumarin, bis (styryl) biphenyl, and the like can be used. Among them, a coumarin-based fluorescent brightener is preferable in that the B component and the fluorescent brightener do not cancel each other's effects. Examples of the coumarin fluorescent whitening agent include triazine-phenylcoumarin, benzotriazole-phenylcoumarin, and naphthotriazole-phenylcoumarin. For example, a fluorescent brightener represented by the following formula (XI) is preferable.

（但し、上記式中Ｒ_１はアミノ基、アルキル基置換アミノ基、水酸基、および下記式（XI-i）、（XI-ii）または（XI-iii）のいずれかを示し、Ｒ_２は水素原子またはフルオロアルキル基を示し、Ｒ_３は水素原子、アルキル基、またはアリール基のいずれかを示す。）

(In the above formula, R ₁ represents an amino group, an alkyl group-substituted amino group, a hydroxyl group, and any one of the following formulas (XI-i), (XI-ii) or (XI-iii), and R ₂ represents hydrogen) An atom or a fluoroalkyl group, and R ₃ represents a hydrogen atom, an alkyl group, or an aryl group.)

  The content of the optical brightener is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, and still more preferably 0.001 to 0. 1 part by weight. In such a range, better light reflectivity is achieved.

(Vi) Release agent The highly reflective polycarbonate resin composition of the present invention may contain a release agent. As the release agent, for example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), Examples include silicone compounds, fluorine compounds (fluorine oil typified by polyfluoroalkyl ether, etc.), paraffin wax, beeswax and the like. The amount of the release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 0.8 parts by weight, based on 100 parts by weight of component A.

  Among such release agents, saturated fatty acid esters, particularly partial esters and / or full esters of higher fatty acids and polyhydric alcohols are preferred. Full esters are particularly preferred. Here, the higher fatty acid refers to an aliphatic carboxylic acid having 10 to 32 carbon atoms, and specific examples thereof include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid). ), Heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid, docosanoic acid, hexacosanoic acid and other saturated aliphatic carboxylic acids, as well as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaene Mention may be made of unsaturated aliphatic carboxylic acids such as acids and cetoleic acid. Among these, the aliphatic carboxylic acid preferably has 10 to 22 carbon atoms, and more preferably has 14 to 20 carbon atoms. In particular, saturated aliphatic carboxylic acids having 14 to 20 carbon atoms, particularly stearic acid and palmitic acid are preferred. The aliphatic carboxylic acid such as stearic acid is usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Also in the saturated fatty acid ester, ester compounds obtained from stearic acid or palmitic acid which are produced from such natural fats and oils and are in the form of a mixture containing other carboxylic acid components are preferably used.

  On the other hand, as a polyhydric alcohol which is a structural unit of saturated fatty acid ester, a C3-C32 thing is more preferable. Specific examples of such polyhydric alcohols include glycerin, diglycerin, polyglycerin (for example, decaglycerin), pentaerythritol, dipentaerythritol, diethylene glycol, propylene glycol, and the like.

  The acid value in the saturated fatty acid ester of the present invention is preferably 20 or less (can take substantially 0), and the hydroxyl value is more preferably in the range of 20 to 500 (more preferably 50 to 400). Further, the iodine value is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K 0070.

  The content of the release agent is 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight, preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the component A. In such a range, the resin composition achieves both good releasability and light reflectivity.

(Vii) Reinforcing filler Various fillers known as reinforcing fillers can be blended in the highly reflective polycarbonate resin composition of the present invention. However, since the resin composition of the present invention is required to have a high whiteness, a silicate mineral filler or a glass filler having a high whiteness is preferable as the reinforcing filler. Examples of such silicate mineral fillers include talc, mascobite mica, synthetic fluorine mica, smectite, and wollastonite. Examples of the glass filler include glass fiber, glass flake, and glass milled fiber. As the silicate mineral filler and the glass filler, fillers whose surfaces are coated with metal oxides such as titanium oxide, zinc oxide, cerium oxide, and silicon oxide can also be used.

  The reinforcing filler may be surface-treated with various surface treatment agents in advance. Such surface treatment agents include silane coupling agents (including alkylalkoxysilanes and polyorganohydrogensiloxanes), higher fatty acid esters, acid compounds (for example, phosphorous acid, phosphoric acid, carboxylic acid, and carboxylic acid anhydrides). Etc.) and various surface treatment agents such as wax. Furthermore, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes.

  The reinforcing filler can be blended up to 100 parts by weight based on 100 parts by weight of component A. The upper limit is preferably 25 parts by weight, more preferably 20 parts by weight. When there are too many compounding quantities of a reinforcing filler, a hue will deteriorate and light reflectivity will fall easily. Further, the loss of surface smoothness is not preferable as a light reflecting material.

(Viii) Antistatic agent The highly reflective polycarbonate resin composition of the present invention may require antistatic performance, and in such a case, it is preferable to include an antistatic agent. Examples of such antistatic agents include (1) organic sulfonic acid phosphonium salts such as (1) aryl sulfonic acid phosphonium salts represented by dodecylbenzene sulfonic acid phosphonium salts, and alkyl sulfonic acid phosphonium salts, and tetrafluoroboric acid phosphonium salts. Examples thereof include phosphonium borate salts. The content of the phosphonium salt is suitably 5 parts by weight or less based on 100 parts by weight of the component A, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, still more preferably. The range is 1.5 to 3 parts by weight.

  Antistatic agents include, for example: (2) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate And organic sulfonate alkali (earth) metal salts. Such metal salts are also used as flame retardants as described above. More specific examples of such metal salts include metal salts of dodecylbenzene sulfonic acid and metal salts of perfluoroalkane sulfonic acid. The content of the organic sulfonate alkali (earth) metal salt is suitably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, more preferably based on 100 parts by weight of the component A. 0.005 to 0.2 part by weight. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

  Examples of the antistatic agent include (3) organic sulfonic acid ammonium salts such as alkylsulfonic acid ammonium salt and arylsulfonic acid ammonium salt. The ammonium salt is suitably 0.05 parts by weight or less based on 100 parts by weight of component A. Examples of the antistatic agent include (4) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The polymer is suitably 5 parts by weight or less based on 100 parts by weight of component A.

(Ix) Other additives The light-reflective polycarbonate resin composition of the present invention includes a thermoplastic resin other than the component A, a rubbery polymer, a light diffusing agent, a dye / pigment other than the fluorescent brightening agent, A quality agent, an antibacterial agent, a dispersant such as liquid paraffin, a photocatalytic antifouling agent, a heat ray absorbent, and a photochromic agent can be blended.

  Examples of the thermoplastic resin other than the component A include styrene resins (for example, acrylonitrile-styrene copolymer resin (AS resin), acrylonitrile-butadiene-styrene copolymer resin (ABS resin), and polystyrene resin), aromatics, and the like. Polyester resins (polyethylene terephthalate resin (PET resin), polybutylene terephthalate resin (PBT resin), cyclohexanedimethanol copolymerized polyethylene terephthalate resin (so-called PET-G resin), polyethylene naphthalate resin, polybutylene naphthalate resin, etc.) Polymethyl methacrylate resin (PMMA resin), cyclic polyolefin resin, polylactic acid resin, polycaprolactone resin, thermoplastic fluororesin (eg, represented by polyvinylidene fluoride resin), Olefin resins (polyethylene resins, ethylene - (alpha-olefin) copolymer resins, polypropylene resins, and propylene - (alpha-olefin) copolymer resins, etc.) are exemplified. Examples of the rubbery polymer include various core-shell type graft copolymers and thermoplastic elastomers. The thermoplastic resin and the rubbery polymer are preferably 20 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight of the component A. On the other hand, when the thermoplastic resin and the rubbery polymer are blended, 0.05 parts by weight or more is preferable based on 100 parts by weight of the component A.

  Examples of the light diffusing agent include polymer fine particles (preferably acrylic crosslinked particles and silicone crosslinked particles having a particle diameter of several μm), low refractive index inorganic fine particles other than the reinforcing filler, and composites thereof. The content is 20 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight of component A. Moreover, when mix | blending a light-diffusion agent, 0.005 weight part or more is preferable on the basis of 100 weight part A component.

  As dyes and pigments other than the fluorescent brightening agent, so-called bluing agents are more preferably blended. In addition, various dyes can be used in accordance with the hue when the hue of the reflected light needs to be adjusted. When using such a dye / pigment, the content thereof is preferably 0.00001 to 0.1 parts by weight, more preferably 0.00005 to 0.05 parts by weight, based on 100 parts by weight of the component A.

<About the manufacturing method of a resin composition>
In manufacturing the highly reflective polycarbonate resin composition of the present invention, the manufacturing method is not particularly limited. However, in order to achieve good dispersion of the titanium dioxide pigment, a preferred method for producing the resin composition of the present invention is a method in which each component is melt-kneaded using a multi-screw extruder such as a twin-screw extruder.

  A typical example of the twin screw extruder is ZSK (trade name, manufactured by Werner & Pfleiderer). Specific examples of similar types include TEX (trade name, manufactured by Nippon Steel Works, Ltd.), TEM (trade name, manufactured by Toshiba Machine Co., Ltd.), KTX (product name, manufactured by Kobe Steel, Ltd.), and the like. Can be mentioned. In addition, melt kneaders such as FCM (manufactured by Farrel, trade name), Ko-Kneader (manufactured by Buss, trade name), and DSM (manufactured by Krauss-Maffei, trade name) can also be given as specific examples. Among the above, the type represented by ZSK is more preferable. In such a ZSK type twin screw extruder, the screw is a fully meshed type, and the screw includes various screw segments having different lengths and pitches, and various kneading disks having different widths (and corresponding kneading segments). It consists of

  A more preferable embodiment in the twin screw extruder is as follows. As the screw shape, one, two, and three screw screws can be used, and in particular, a two-thread screw having a wide range of application in both the ability to convey the molten resin and the shear kneading ability can be preferably used. The ratio (L / D) of the screw length (L) to the diameter (D) in the twin-screw extruder is preferably 20 to 45, more preferably 28 to 42. When L / D is large, uniform dispersion is likely to be achieved, whereas when it is too large, decomposition of the resin is likely to occur due to thermal degradation. The screw needs to have one or more kneading zones composed of kneading disk segments (or kneading segments corresponding thereto) for improving kneadability, and preferably 1 to 3 kneading zones.

  Furthermore, as an extruder, what has a vent which can deaerate the water | moisture content in a raw material and the volatile gas generate | occur | produced from melt-kneading resin can be used preferably. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such screens include wire meshes, screen changers, sintered metal plates (disk filters, etc.) and the like.

  Furthermore, the method for supplying the component B, component C and other additives (simply referred to as “additive” in the following examples) to the extruder is not particularly limited, but the following methods are typically exemplified. (I) A method of supplying the additive into the extruder independently of the polycarbonate resin. (Ii) A method in which the additive and the polycarbonate resin powder are premixed using a mixer such as a super mixer and then supplied to the extruder. (Iii) A method of melt-kneading an additive and a polycarbonate resin in advance to form a master pellet.

  One of the methods (ii) is a method in which all necessary raw materials are premixed and supplied to the extruder. In another method, a master agent containing a high concentration of additives is prepared, and the master agent is independently or further premixed with the remaining polycarbonate resin and then supplied to the extruder. The master agent can be selected from either a powder form or a form obtained by compressing and granulating the powder. Other premixing means include, for example, a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. A high-speed stirring type mixer such as a super mixer is preferable. Yet another premixing method is, for example, a method in which a polycarbonate resin and an additive are uniformly dispersed in a solvent and then the solvent is removed.

  The resin extruded from the extruder is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer and pelletized. Furthermore, when it is necessary to reduce the influence of external dust or the like, it is preferable to clean the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, various methods already proposed for polycarbonate resin for optical disks are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. In addition, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder more suitably. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

<About a molded product comprising the resin composition of the present invention>
The optically highly reflective polycarbonate resin composition of the present invention obtained as described above can be usually produced by injection molding the pellets produced as described above to produce various products. Furthermore, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion molded product, a direct blow molded product, and an injection molded product without going through pellets.

  In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.

  Moreover, the resin composition of this invention can also be utilized in the form of various profile extrusion-molded articles, sheets, films, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can be formed into a molded product by rotational molding, blow molding or the like.

  Thereby, a molded article of a light highly reflective polycarbonate resin composition having excellent light reflectance and weather resistance is provided. That is, according to the present invention, a highly reflective polycarbonate resin composition comprising 100 parts by weight of the A component, 0.01 to 10 parts by weight of the B component, and 3 to 30 parts by weight of the C component is melt-molded. A molded product is provided.

  A specific example of such a molded article is a backlight reflector for a liquid crystal display device. Examples of the light source of the backlight include cold cathode fluorescent lamps and light emitting diodes (LEDs, particularly white LEDs), and are particularly suitable for white LED arrays.

  Furthermore, various surface treatments can be performed on the molded article made of the highly reflective polycarbonate resin composition of the present invention. Surface treatment here refers to a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. A method used for ordinary polycarbonate resin is applicable. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation).

  Since the highly reflective polycarbonate resin composition of the present invention has excellent light reflectance and weather resistance, it is suitably used for various light reflecting materials. More specifically, various lamp reflectors can be mentioned, for example, reflectors for illumination lamps such as fluorescent lamps, backlight reflectors for various display devices such as liquid crystal display devices, reflectors for switches, and reflectors for LED arrays. In addition, a reflecting plate in which these functions are combined is exemplified. That is, the highly reflective polycarbonate resin composition of the present invention is useful for various applications such as various electronic / electric equipment, OA equipment, vehicle parts, machine parts, other agricultural materials, transport containers, playground equipment, and miscellaneous goods. The industrial effects are exceptional.

  The form of the present invention considered to be the best by the present inventors is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

The following examples further illustrate the present invention. The evaluation was based on the following method.
(1) Light reflectance: An arithmetic mean roughness (Ra) obtained by injection molding is 0.03 μm and a 2 mm-thick molded plate (length 90 mm × width 50 mm) is replaced with a color computer (TC manufactured by Tokyo Denshoku TC). -1800MK-II). Evaluation was made with the lowest reflectance value at wavelengths of 450 nm to 850 nm.

(2) Ultraviolet resistance: Using a xenon weather meter (Suga Test Instruments Co., Ltd .: WEL-SUN: HC-B), a black plate temperature of 63 ° C. and a humidity of 50% using the same molded plate as in the above evaluation (1). The difference between the hue (YI) after 1000 hours and the hue (YI) before processing is indicated as ΔYI.
ΔYI = (YI after treatment) − (YI before treatment)

(3) Melting | fusing point measurement of cyclic imino ester type ultraviolet absorber The powder of cyclic imino ester type ultraviolet absorber was put into the sample pan, and it compressed with the compressor, and obtained the sample for DSC measurement for a measurement. The sample was installed in a DSC measuring apparatus (manufactured by TA Instruments) and heated to 380 ° C. at a temperature rising rate of 10 ° C./min under a nitrogen flow of 50 ml / min by a method according to JIS K7122 to obtain the melting point. .

(4) Measurement of YI value of cyclic imino ester UV absorber The YI value of the cyclic imino ester UV absorber was measured using a color machine by the method described above. The object to be measured was only those whose melting point satisfied the conditions of the present invention.

(5) Measurement of Cl content of cyclic imino ester UV absorber About 5 g of cyclic imino ester UV absorber powder (100 mesh pass 200 mesh on using Tyler standard sieve) was weighed into a flask (m (G)). An electronic balance was used for such weighing. The flask was gently stirred with a magnetic stirrer while heating in a 95 ° C. water bath for 60 minutes in a sealed state with 50 g of ion-exchanged water added. The ion-exchanged water was ion-exchanged water having an electric resistance value of 18 MΩ · cm or more obtained through Yamato Scientific Co., Ltd. Auto Pure WQ500 type. After heating for 60 minutes and taking out from a hot water bath and cooling for 15 minutes, the resulting mixture was filtered using filter paper to collect the extract. The weight of the extract was recorded (referred to as α (g)). About 10 g was collected from the extract and the amount collected was recorded (referred to as β (g)). About 60 g of the same ion exchange water as described above was added to the collected extract. 1 ml of nitric acid was further added to the aqueous solution, and titration was performed with a potentiometric titrator using a 0.1 mol / l silver nitrate standard solution. From the conversion coefficient calculated from (β / α) × m to the chlorine concentration calculated from the aqueous solution, the chlorine concentration (ppm) was calculated per 1 g of the sample.

(6) Measurement of amount of Na in cyclic imino ester-based UV absorber Using atomic absorption spectrometer (Z-8100, manufactured by Hitachi, Ltd.) in which a calibration curve was previously obtained using the extract of (5) above. The amount of Na was calculated by the frame method.

[Examples 1 to 9 and Comparative Examples 1 to 4]
Various additives listed in Table 1 were blended in 100 parts by weight of polycarbonate resin powder produced from bisphenol A and phosgene by the interfacial condensation polymerization method, mixed in a blender, and then vented twin screw extruder ( Nippon Steel Works Co., Ltd .: TEX30α (completely meshed, rotating in the same direction, two-thread screw) was melt kneaded to obtain pellets. Additives other than the titanium dioxide content were preliminarily prepared in advance using a Henschel mixer with a polycarbonate resin powder at a concentration 10 times the blending amount, and the whole was mixed by a blender. The extrusion conditions were a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 280 ° C. from the first supply port to the die part.

  After drying the obtained pellets at 120 ° C. for 5 hours in a hot air circulating dryer, using an injection molding machine, under conditions of a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C., and a firing speed of 50 mm / sec, A smooth flat test piece having a length of 90 mm, a width of 50 mm, a thickness of 2 mm, and a surface arithmetic average roughness (Ra) of 0.03 μm was molded. The injection molding machine used was Mitsubishi Heavy Industries, Ltd .: 80MSP-SC. The evaluation results of the obtained molded plate are shown in Table 1.

In addition, the content of each component indicated by symbols in Table 1 is as follows.
(A component)
PC-1: Linear aromatic polycarbonate resin powder synthesized by interfacial polycondensation from bisphenol A, p-tert-butylphenol as a terminal terminator, and phosgene (manufactured by Teijin Chemicals Ltd .: Panlite L-1225WX (product) Name), viscosity average molecular weight 19,700)
PC-2: Linear aromatic polycarbonate resin powder synthesized by interfacial polycondensation from bisphenol A, p-tert-butylphenol as a terminal terminator, and phosgene (manufactured by Teijin Chemicals Ltd .: CM-1000 (trade name)) , Viscosity average molecular weight 16,000)

(B component)
B-1: Cyclic imino ester-based ultraviolet absorber mainly composed of 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) whose melting point peak by DSC measurement is one point at 314 ° C. (Takemoto Yushi Co., Ltd .: CEi-P (trade name), YI value of this ultraviolet absorber was 15.5, Cl content was 100 ppm, and Na content was 80 ppm.)
B-2: 2,2′-p-phenylenebis (3,1-benzoxazine-, which has a melting point peak by DSC measurement of 314 ° C. and was produced according to the method of EXAMPLE1 in WO03 / 035735 pamphlet 4-Ion) cyclic imino ester-based ultraviolet absorber (manufactured by Takemoto Yushi Co., Ltd .: CEi-PA (trade name), the YI value of this ultraviolet absorber is -1.2, and the amount of Cl is It was not detected and the amount of Na was 3.5 ppm.)
(For comparison of B component)
B-3: Cyclic imino ester system mainly composed of 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) having two melting point peaks at 306 ° C. and 314 ° C. by DSC measurement UV absorber (manufactured by CYTEC: CYASORB UV-3638 (trade name), YI value of this UV absorber was 3.8)

(C component)
C-1: Titanium dioxide (Ishihara Sangyo Co., Ltd. Type PC-3 (trade name), the titanium dioxide pigment has an average particle size of 0.21 μm, and the amount of TiO ₂ in the titanium dioxide pigment is about 93% by weight. A titanium dioxide pigment containing about 2.5% by weight Al ₂ O ₃ and about 1.5% by weight SiO ₂ as an inorganic surface coating and further surface-treated with about 2% by weight polymethylhydrogensiloxane )
(Other)
PTFE: Polytetrafluoroethylene having a fibril forming ability (manufactured by Daikin Industries, Ltd .: Polyflon MPA FA500)
EW: Fatty acid ester containing pentaerythritol tetrastearate as a main component (Rikastar EW-400 manufactured by Riken Vitamin Co., Ltd.)
BayC4: potassium perfluorobutanesulfonate (Bayowet C4 manufactured by Bayer)
HP: hindered phenol antioxidant (Ciba Specialty Chemicals: Irganox 1076)
PSR: Coumarin-based optical brightener (manufactured by Hakkol Chemical Co., Ltd .: Hakkor PSR-B (trade name))

  As is apparent from Table 1 above, it can be seen that the highly reflective polycarbonate resin composition of the present invention has excellent light reflectivity and UV resistance. That is, it can be seen that the resin composition has characteristics suitable for a light reflecting material.

(Examples 10 and 11)
Using the pellets obtained in Examples 8 and 9, a light reflector for an LED array type backlight having a bottomed lattice shape with a length of 6 cm and a width of 4 cm shown in FIG. A liquid crystal display was created by attaching a to each block to create a backlight and replacing it with the backlight unit of the liquid crystal display used in mobile phones. The visually recognized image was highly sharp.

  The present invention provides a polycarbonate resin composition suitable for a light reflecting material. However, other than that, it is also possible to utilize the semiconductor property of the titanium dioxide pigment as a dielectric material and a livestock heat material.

It is a perspective schematic diagram which shows the light reflection board for LED array type backlights produced in the Example.

Explanation of symbols

1 Light reflector main body (length 60mm, width 40mm, height 4mm)
2 Each LED block (depth 2.5mm, the inner periphery of the recess is mirror-finished)
3 LED fixing recess

Claims (7)

  100 parts by weight of a polycarbonate resin (component A), 0.01 to 10 parts by weight of a cyclic imino ester-based ultraviolet absorber (component B) having a single melting point peak in a differential scanning calorimeter (DSC) measurement based on JIS K7121 And a light-reflective polycarbonate resin composition comprising 3 to 30 parts by weight of a titanium dioxide pigment (component C). The light-reflective polycarbonate resin composition according to claim 1, wherein the ultraviolet absorber of the component B is substantially composed of a compound of the following formula (I).

  The light-reflective polycarbonate resin composition according to any one of claims 1 and 2, wherein the B component ultraviolet absorber has a yellow index (YI value) in the range of -15 to 0.   The light-reflective polycarbonate resin composition according to any one of claims 1 to 3, wherein the titanium dioxide pigment (component C) is surface-treated with an alkylalkoxysilane and / or hydrogen polysiloxane. A step of preparing a cyclic imino ester-based ultraviolet absorber represented by the following general formula (I) produced by reacting an isatoic acid raw material highly purified by recrystallization treatment with a terephthalic acid dichloride raw material ( Step-i) and step of melt-kneading 100 parts by weight of polycarbonate resin (component A), 0.01 to 10 parts by weight of the ultraviolet absorber, and 3 to 30 parts by weight of titanium dioxide pigment (component C) (step-ii) The manufacturing method of the light highly reflective polycarbonate resin composition which consists of these.

  A highly reflective polycarbonate resin composition produced by the method according to claim 5.   The light reflection material formed from the highly reflective polycarbonate resin composition of any one of the said Claims 1-4 and Claim 6.

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