JP2019183017A - Polycarbonate resin composition and molded article thereof - Google Patents

Abstract

To provide a polycarbonate resin composition with high designability, to which a luminous material is blended, in which yellowish or blacking during light irradiation specific for a luminous resin composition is suppressed, and whiteness (brightness) is enhanced.SOLUTION: There is provided a polycarbonate resin composition containing 100 pts.mass of a polycarbonate resin (A), 1 to 30 pts.mass of a luminous material (B) having average particle diameter Dof over 10 μm and less than 100 μm, 0.1 to 5 pts.mass of a metal oxide coating tabular filler (C), and 0.01 to 1 pts.mass of one or more kind of phosphate stabilizer selected from alkyl acid phosphate, alkenyl acid phosphate and metal salts thereof. The metal oxide coating tabular filler (C) has a coating layer containing titanium oxide and tin oxide or the like formed on a substrate consisting of mica, glass or silica. A mass ratio of the metal oxide coating tabular filler (C) to the luminous material (B), ((C)/(B) mass ratio) is 0.01 to 0.5.SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition and a molded product thereof, and more specifically, a polycarbonate resin composition in which a phosphorescent material is blended with a polycarbonate resin to impart a phosphorescent property, at the time of light irradiation peculiar to the phosphorescent resin composition The present invention relates to a highly-designed polycarbonate resin composition that suppresses yellowing and darkening and improves whiteness (brightness), and a molded product formed by molding this polycarbonate resin composition.

  When light such as ultraviolet light or visible light contained in sunlight or artificial light is irradiated, the light is absorbed and stored, and even after the light irradiation is stopped, that is, even in the dark, in the form of light emission. Various polycarbonate resin compositions containing phosphorescent materials that continue to emit light for a long time have been proposed as molding materials for phosphorescent light emitting members such as road signs and signboards, and their improvement has been studied.

  However, when the phosphorescent material is blended with the polycarbonate resin, the initial hue upon light irradiation becomes yellowish or blackish. When the initial hue at the time of light irradiation is yellowish or darkened, the appearance is remarkably inferior and cannot be applied to applications that require design properties.

In order to solve this problem, the addition of aluminum foil and the like has been studied, but there is a problem that the luminance is greatly lowered even if the initial color of yellowing or darkening peculiar to phosphorescence can be changed.
In order to prevent the darkening caused by the phosphorescent material during melt kneading or molding of the composition by lowering the processing temperature of the resin, alloying with ABS is also being studied. Since the material resin becomes opaque, there is a problem that the luminance is lowered even if yellowishness or darkening is suppressed.

  In Patent Document 1, an alkyl acid phosphate and / or an alkyl acid phosphate metal salt as a stabilizer is used to improve the problem of darkening that occurs during melt-kneading or molding of a polycarbonate resin composition in which a phosphorescent material is blended with a polycarbonate resin. It is proposed that the fatty acid ester compound, which is a mold release agent, is used in combination at a predetermined ratio, but the problem of yellowing and darkening can be solved only by blending these stabilizers and the mold release agent. I couldn't.

Japanese Patent Publication No. 2006-28111

  The present invention is a polycarbonate resin composition obtained by blending a phosphorescent material with a polycarbonate resin and imparting phosphorescent properties, and without reducing the luminance at the time of light blocking by the phosphorescent material, at the time of light irradiation peculiar to the phosphorescent resin composition It is an object of the present invention to provide a highly-designed polycarbonate resin composition that suppresses yellowing and darkening and has improved whiteness (brightness) and a molded product formed by molding the polycarbonate resin composition.

  As a result of intensive studies to solve the above problems, the present inventor has added a specific metal oxide-coated plate-like filler to a polycarbonate resin composition in which a phosphorescent material is blended with a polycarbonate resin to impart a phosphorescent property. In addition to blending in proportions, this metal oxide-coated platy filler is combined with an optimal stabilizer to effectively suppress yellowing and darkening during light irradiation without reducing the brightness of the phosphorescent material. And it discovered that whiteness (brightness) could be improved.

  The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] to the polycarbonate resin (A) 100 parts by mass of, except the average particle diameter _{D 50} of phosphorescent material of less than 100μm exceed 10 [mu] m (B) 1 to 30 parts by weight, the aluminum-coated glass flakes, the average particle diameter D ₅₀ to ₅ to 200 μm of metal oxide-coated plate filler (C) 0.1 to 5 parts by mass, and one or more phosphate-based stabilizers selected from alkyl acid phosphates, alkenyl acid phosphates, and metal salts thereof A polycarbonate resin composition containing 0.01 to 1 part by mass of an agent (D), wherein the metal oxide-coated platy filler (C) is formed of mica on a substrate made of titanium oxide, tin oxide, and oxidation. Titanium oxide and tin oxide are applied to a metal oxide-coated plate filler (CA) on which a coating layer containing silicon is formed, and a base material made of glass or silica. The metal oxide-coated plate-like filler (CB) on which a coating layer is formed, and the mass ratio of the metal oxide-coated plate-like filler to the phosphorescent material (B) ((C) / (B ) Mass ratio) is 0.01 to 0.5.

[2] In [1], the base material of the metal oxide-coated platy filler (CB) is made of glass, the coating layer further contains silicon oxide, the base material is 40 to 85% by mass, and the titanium oxide is 5 to 20 A polycarbonate resin composition comprising: mass%, tin oxide: 0-2 mass%, and silicon oxide: 10-40 mass%.

[3] The polycarbonate resin composition according to [1] or [2], wherein the alkyl acid phosphate or alkenyl acid phosphate is represented by the following formula (I):
O = P (OH) _n (OR) _3-n (I)
(In the formula (I), R represents an alkyl group or alkenyl group having 9 to 30 carbon atoms, and n represents an integer of 1 or 2. When n is 1, two Rs may be the same or different. It may be a thing.)

[4] The polycarbonate resin composition according to [3], wherein R in the formula (I) is an alkyl group or an alkenyl group having any of 13, 18, and 24 carbon atoms.

[5] In [4], the phosphate stabilizer (D) is represented by the following formula (II), and n = 1 distearyl acid phosphate and n = 2 monostearyl acid phosphate in the formula (II): A polycarbonate resin composition characterized by being a mixture of
O = P (OH) _n (OC ₁₈ H ₃₇ ) _3-n (II)

[6] In any one of [1] to [5], 0.003 to 0.15 parts by mass of hydrogen siloxane (E) is further contained with respect to 100 parts by mass of the polycarbonate resin (A). A polycarbonate resin composition.

[7] A molded product formed by molding the polycarbonate resin composition according to any one of [1] to [6].

  According to the present invention, in a polycarbonate resin composition obtained by adding a phosphorescent material to a polycarbonate resin and imparting luminous properties, yellowing and darkening at the time of light irradiation are effective without reducing the luminance at the time of light blocking by the phosphorescent material. In addition, it is possible to provide a highly-designed polycarbonate resin composition and a molded product thereof that are suppressed and have improved whiteness (brightness).

  The molded product of the present invention formed by molding the polycarbonate resin composition of the present invention is excellent in luminous performance and has a good hue at the time of light irradiation, and is an electric decoration signboard, product display, liquid crystal backlight, illumination display, illumination Automobile parts such as equipment covers, traffic signs, safety signs, night visibility improving members, sign boards, screens, reflectors and meter parts, mobile equipment such as entertainment equipment, toys, laptops, mobile phones, etc. It can be used in a wide range of applications such as indoor and building sign buttons, clock dials, accessories, stationery, sports equipment, various electrical, electronic, and office equipment, switches, buttons, etc. .

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples described below, and may be arbitrarily selected without departing from the scope of the present invention. It can be implemented by changing.

[Polycarbonate resin composition]
The polycarbonate resin composition of the present invention (hereinafter sometimes referred to as "resin composition of the present invention".), Compared polycarbonate resin (A) 100 parts by mass of the average particle size D ₅₀ of less than 100μm exceed 10μm 1 to 30 parts by mass of phosphorescent material (B), 0.1 to 5 parts by mass of metal oxide-coated platy filler (C) having an average particle diameter D50 of ₅ to 200 μm, excluding aluminum-coated flaky glass, and alkyl A polycarbonate resin composition containing 0.01 to 1 part by mass of one or more phosphate stabilizers (D) selected from acid phosphates, alkenyl acid phosphates and metal salts thereof, wherein the metal oxidation The metal oxide coating is obtained by forming a coating layer containing titanium oxide, tin oxide, and silicon oxide on a base material made of mica, with a material-coated plate-like filler (C). It is selected from a plate-like filler (CA) and a metal oxide-coated plate-like filler (CB) in which a coating layer containing titanium oxide and tin oxide is formed on a substrate made of glass or silica. The mass ratio ((C) / (B) mass ratio) of the metal oxide-coated platy filler to the material (B) is 0.01 to 0.5.

[Action mechanism]
In the polycarbonate resin composition of the present invention, the action mechanism capable of suppressing yellowing and darkening without lowering the luminous properties and afterglow luminance due to the luminous material (B) is estimated as follows.

That is, in the resin composition of the present invention, the metal oxide-coated plate-like filler (C) blended at a predetermined ratio with respect to the phosphorescent material (B) is a pearl-like or metallic-like plate-like filler with high whiteness. By including such a metal oxide-coated platy filler (C), it is caused by the phosphorescent material (B) due to the glitter, polarization or pearl tone imparted by the metal oxide-coated platy filler (C). Yellowing at the time of light irradiation is offset and whiteness (brightness) is improved. Further, the metal oxide-coated plate-like filler (C) used in the present invention is translucent and does not completely absorb light including ultraviolet rays, so that the phosphorescent property and afterglow luminance due to the phosphorescent material (B) are not reduced. .
When the phosphorescent material (B) and the metal oxide-coated platy filler (C) are blended with the polycarbonate resin (A), the phosphorescent material (B) and the metal oxide-coated platy filler (C) are used. Of the metal piece during melt kneading (the metal piece generated by this abrasion by the phosphorescent material (B) and the metal oxide-coated plate filler (C) when melt kneading with an extruder) Although there is a risk that darkening may occur due to contamination or the rare earth element which is a constituent of the phosphorescent material (B) decomposes the polycarbonate resin (A) under a high temperature condition, in the present invention, a phosphate stabilizer (D ) Or further hydrogen siloxane (E), this problem can be solved.
According to the present invention, these effects act synergistically to effectively suppress yellowing and darkening at the time of light irradiation without reducing the luminance at the time of light blocking by the phosphorescent material, and the whiteness ( Brightness) can be improved.

[Polycarbonate resin (A)]
As polycarbonate resin (A) used by this invention, aromatic polycarbonate resin is preferable from surfaces, such as transparency, impact resistance, and heat resistance.
The aromatic polycarbonate resin is an optionally branched thermoplastic polymer or copolymer obtained by reacting an aromatic dihydroxy compound or a small amount of a polyhydroxy compound with phosgene or a carbonic acid diester. The production method of the aromatic polycarbonate resin is not particularly limited, and those produced by a conventionally known phosgene method (interfacial polymerization method) or melting method (transesterification method) can be used. Moreover, when the melting method is used, an aromatic polycarbonate resin in which the amount of OH groups in the terminal groups is adjusted can be used.

  As the raw material aromatic dihydroxy compound, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4 , 4-dihydroxydiphenyl and the like, preferably bisphenol A. In addition, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound can also be used.

  In order to obtain a branched aromatic polycarbonate resin, a part of the above-mentioned aromatic dihydroxy compound is mixed with the following branching agents, that is, phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl). Heptene-2,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenylheptene-3,1, Polyhydroxy compounds such as 3,5-tri (4-hydroxyphenyl) benzene and 1,1,1-tri (4-hydroxyphenyl) ethane, and 3,3-bis (4-hydroxyaryl) oxindole (= isa) Tin bisphenol), 5-chloruisatin, 5,7-dichloroisatin, 5-bromoisatin, etc. Dose, the aromatic dihydroxy compound is usually 0.01 to 10 mol%, preferably 0.1 to 2 mol%.

  As the aromatic polycarbonate resin, among the above-mentioned, polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy Polycarbonate copolymers derived from the compounds are preferred. Further, it may be a copolymer mainly composed of a polycarbonate resin, such as a copolymer with a polymer or oligomer having a siloxane structure.

  The aromatic polycarbonate resin mentioned above may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  In order to adjust the molecular weight of the aromatic polycarbonate resin, a monovalent aromatic hydroxy compound may be used. Examples of the monovalent aromatic hydroxy compound include m- and p-methylphenol, m- and p-. And propylphenol, p-tert-butylphenol, p-long chain alkyl-substituted phenol and the like.

  The molecular weight of the aromatic polycarbonate resin used in the present invention is arbitrary depending on the application, and may be appropriately selected and determined. The viscosity average molecular weight (Mv) is preferably 20,000 to 50,000. When the viscosity average molecular weight is less than 20,000, mechanical strength such as impact resistance of the obtained molded product is lowered. When the viscosity average molecular weight is more than 50,000, the fluidity is deteriorated and the moldability is problematic. The viscosity average molecular weight of the aromatic polycarbonate resin is more preferably 20,000 to 40,000, and further preferably 21,000 to 30,000. Two or more kinds of aromatic polycarbonate resins having different viscosity average molecular weights may be mixed and used. In this case, an aromatic polycarbonate resin having a viscosity average molecular weight outside the above preferred range may be mixed. Good.

The viscosity average molecular weight (Mv) is obtained by using methylene chloride as a solvent and obtaining the intrinsic viscosity (η) (unit dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer, , Η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity (η) is a value calculated from the following equation by measuring the specific viscosity (η _sp ) at each solution concentration (C) (g / dl).

[Phosphorescent material (B)]
The phosphorescent material (B) absorbs and stores light when irradiated with light such as ultraviolet light or visible light contained in sunlight or artificial light, even after light irradiation is stopped, that is, in a dark place. It emits light for a predetermined time in the form of light emission. The phosphorescent material has an afterglow persistence of several minutes to several tens of hours after the end of photoexcitation, and is distinguished from a general fluorescent whitening agent in which light emission is rapidly attenuated after the light irradiation is stopped.

The phosphorescent material (B) used in the present invention is not particularly limited as long as the phosphorescent material (B) has the above-mentioned characteristics. However, sulfide-based phosphorescent materials such as CaS: Bi, CaSrS: Bi, and ZnCdS: Cu, ZnS : Zinc sulfide-based phosphorescent material such as Cu, Sr ₂ MgSi ₂ O ₇ : Silicate-based phosphorescent material such as Eu, Dy, MAl _a O _b : X (M is one or more metals selected from calcium, strontium and barium) Element X is an activator and is one or more selected from europium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, ruthenium, manganese, tin, and bismuth. Element X. The content of X is usually 10 mol% or less with respect to the metal element represented by M, for example 0 .001 to 10 mol%). Preferably, from the viewpoint of hydrolysis resistance and afterglow characteristics, it is an aluminate compound represented by MAl _a O _b : X, and examples of the aluminate compound include GMg ₂ Al ₁₆ O ₂₇ : Eu, _{GMg 2 Al 16 O 27: Eu} , Mn, GMg 2 Al 10 O 17: Eu, GMg 2 Al 10 O 17: Eu, Mn ( where G is Sr or Ba, or a combination of these), SrAl ₂ O ₄ : Eu, SrAl ₂ O ₄ : Eu, Dy, Sr ₄ Al ₁₄ O ₂₅ : Eu, Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy, CaAl ₂ O ₄ : Eu, Nd, etc. Among these, SrAl ₂ O ₄ : Eu, Dy, Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy, and CaAl ₂ O ₄ : Eu, Nd are particularly preferable.

The average particle diameter D50 of the phosphorescent material (B) is more than 10 μm and less than 100 μm, preferably 15 to 70 μm, more preferably 20 to ₅₀ μm. If the particle size of the phosphorescent material is too large, the molded article tensile elongation at break obtained, since the impact strength, appearance or the like is a problem to decrease the average particle diameter D ₅₀ is less than 100 [mu] m. Meanwhile, phosphorescent material generally to the emission characteristic particle size is too small tends to decrease, the average particle diameter D ₅₀ is to exceed 10 [mu] m.

The average particle size D ₅₀ in the present invention refers to a median diameter D ₅₀ measured by a laser diffraction type particle size distribution measuring apparatus, for example, by using a Shimadzu Corporation "laser diffraction particle size distribution measuring apparatus SALD-2100" Although measured, catalog values can be used for commercial products.

  In the present invention, one type of phosphorescent material (B) may be used alone, or two or more types having different chemical compositions and particle sizes may be used in combination.

  The compounding quantity of a luminous material (B) is 1-30 mass parts with respect to 100 mass parts of polycarbonate resin (A), Preferably it is 2-25 mass parts, More preferably, it is 3-20 mass parts. If the blending amount of the phosphorescent material (B) is less than the lower limit, the phosphorescent effect due to the blending of the phosphorescent material (B) cannot be sufficiently obtained. The larger the amount of the phosphorescent material (B), the better from the viewpoint of the phosphorescent effect, but if it is too much, the moldability, thermal stability, mechanical strength of the molded product, etc. are impaired.

[Metal oxide coated plate filler (C)]
The metal oxide-coated platy filler (C) used in the present invention is one having an average particle diameter D50 of ₅ to 200 μm, excluding aluminum-coated flaky glass,
Metal oxide coated platy filler (CA) in which a coating layer containing titanium oxide, tin oxide and silicon oxide is formed on a base material made of mica
And a metal oxide-coated plate-like filler (CB) in which a coating layer containing titanium oxide and tin oxide is formed on a substrate made of glass or silica
It is 1 type, or 2 or more types chosen from the group which consists of.

  Among the metal oxide-coated plate-like fillers (CA), the metal oxide-coated plate-like filler whose substrate is made of mica (mica) is oxidized by 20 to 30% by mass of the substrate, 30 to 45% by mass of titanium oxide, and oxidation. It is preferable that it contains 0 to 2% by mass of tin and 30 to 40% by mass of silicon oxide (however, the total of the base material, titanium oxide, tin oxide and silicon oxide is 100% by mass). When the content of the base material and the titanium oxide, tin oxide and silicon oxide constituting the coating layer is within the above range, the yellowing effect during light irradiation was suppressed and the whiteness (brightness) was improved. Can be.

  Of the metal oxide-coated plate-like fillers (CA), the metal oxide-coated plate-like filler whose substrate is made of glass preferably further contains silicon oxide in the coating layer, and particularly 40 to 85% by mass of the substrate. , 5 to 20% by mass of titanium oxide, 0 to 2% by mass of tin oxide, and 10 to 40% by mass of silicon oxide (however, the total of the base material, titanium oxide, tin oxide and silicon oxide is 100% by mass) It is preferable that When the content of the base material and the titanium oxide, tin oxide and silicon oxide constituting the coating layer is within the above range, the yellowing effect during light irradiation was suppressed and the whiteness (brightness) was improved. Can be.

  The metal oxide-coated plate-like filler (CB) contains 50 to 90% by mass of silica, which is a base material, 15 to 45% by mass of titanium oxide, and 2 to 4% by mass of tin oxide (however, the base material and oxidation). The total of titanium and tin oxide is preferably 100% by mass). When the content of the base material and the titanium oxide and tin oxide constituting the coating layer are within the above ranges, the yellowing effect during light irradiation is suppressed and the whiteness (brightness) is improved. be able to.

  In addition, the base material and metal oxide content of the metal oxide-coated platy filler (C) are determined by a method of converting the metal content by the fluorescent X-ray analysis method or energy dispersive X-ray spectroscopy as the oxide amount. However, catalog values can be adopted for commercial products.

  As the metal oxide-coated plate-like filler (C), in particular, a metal oxide such as titanium oxide or tin oxide is formed on a substrate having an average thickness of about 0.1 to 10 μm by chemical vapor deposition or physical vapor deposition. What formed the coating layer about 1 micrometer thick is preferable.

  Commercially available products may be used as the metal oxide-coated plate-like filler (C). For example, the metal oxide-coated flaky glass is an aluminoborosilicate glass pigment coated with titanium oxide, tin oxide, or silicon oxide. MERCK products “Myraval 5400” (particle size 20-200 μm), “Colorstream T10-07 Luxwin Twin” (particle size 20-200 μm), “Colorstream T10-08 Royal Twink” (particle size 20-200 μm) “Colorstream T10-09 Pacific Twinkle” (particle size 20 to 200 μm), trade name “Fire Mist Blue Topaz9G680D” (particle size 13 to 180 μm), “Fire Mist Rub” manufactured by BASF 9G480D "(particle size 13~180μm), made by Nippon Sheet Glass coated with titanium oxide and tin oxide" Metashine GT5090RS "(thickness 5 [mu] m, size 90 [mu] m), and the like.

  As the metal oxide-coated flaky silica, trade name “Firemist Coloration Blue Topaz 9G680D” (particle size: 13 to 180 μm) manufactured by BASF which is a silica pigment coated with titanium oxide and tin oxide, “Firemist Colormotion Ruby 9G480D”. (Particle size: 13 to 180 μm). In addition, trade names “Colorstream F10-00 Autumn Mystery” (particle size 5 to 50 μm), “Colorstream T10-01 Viola Fantasy” (particle size 5 to 50 μm), “Colorstream T10-02 Arctic Fibre” manufactured by MERCK, Inc. Diameter 5-50 μm), “Colorstream T10-03 Tropic Sunrise” (particle diameter 5-50 μm), “Colorstream T10-04 Lapis Sunlight” (particle diameter 5-50 μm), and the like.

  Examples of the metal oxide-coated flaky mica include trade name “Pyrisma T30-01” (particle size: 10 to 60 μm) manufactured by MERCK, which is a mica pigment coated with titanium oxide, tin oxide, and silicon oxide.

Although these metal oxide-coated plate-like fillers (C) vary from product to product, they usually exhibit a relatively high pH of about 8 to 12 and may decompose the polycarbonate resin (A). By containing tin oxide together with titanium oxide, a certain degree of decomposition suppression effect can be obtained. Moreover, in this invention, decomposition | disassembly of polycarbonate resin (A) can be suppressed also by including the below-mentioned phosphate stabilizer (D) and also hydrogensiloxane (E).
Here, the pH of the metal oxide-coated platy filler (C) is a value measured with a pH test paper or a pH measuring instrument for the filtrate or supernatant after boiling the filler in distilled water. Catalog values apply to products.

In the present invention, the average particle diameter _{D 50} of the metal oxide coated plate-like filler (C) is 5 to 200 [mu] m. When the average particle diameter D ₅₀ of the metal oxide-coated platy filler (C) is less than 5 μm, the effect of suppressing yellowing or darkening at the time of light irradiation by blending the metal oxide-coated platy filler (C) is sufficiently obtained. It may not be possible. When the average particle diameter D ₅₀ of the metal oxide coated plate-like filler (C) is more than 200 [mu] m, impact resistance of the molded article obtained tends to decrease. The average particle diameter D50 of the metal oxide-coated platy filler (C) is preferably 7 to 100 μm, more preferably about 10 to ₆₀ μm.

Here, the particle size of the metal oxide-coated plate filler (C) is the distance between the plates when the metal oxide-coated plate filler (C) is sandwiched between two parallel plates. Indicates the length of the part to be enlarged.
The average particle diameter D ₅₀ in the present invention refers to the median diameter D ₅₀ measured by a laser diffraction particle size distribution measuring device, and is measured using, for example, “Laser diffraction particle size distribution measuring device SALD-2100” manufactured by Shimadzu Corporation. However, catalog values can be used for commercial products.

The metal oxide-coated platy filler (C) may be used alone or in combination of two or more of the constituent materials or particle sizes of the coating layer.
When two or more metal oxide coated plate-like filler (C), it is preferable that all the average particle diameter D ₅₀ of the metal oxide coated plate-like filler (C) was used in the range described above.

  The metal oxide-coated plate-like filler (C) was surface-treated with a surface treatment agent such as a silane coupling agent in order to improve the adhesion with the polycarbonate resin (A). Also good.

  In the resin composition of the present invention, the content of the metal oxide-coated platy filler (C) is 0.1 to 5 parts by mass, preferably 0.2 to 3 parts per 100 parts by mass of the polycarbonate resin (A). It is a mass part, More preferably, it is 0.3-2 mass part. When the blending amount of the metal oxide-coated platy filler (C) is less than the above lower limit, the effect of suppressing yellowing or darkening at the time of light irradiation due to blending the metal oxide-coated platy filler (C) is sufficiently obtained. If the amount is too large, the resulting molded article has poor impact resistance.

  In addition, the content of the metal oxide-coated platy filler (C) in the resin composition of the present invention is 0.01 to 0.00 as a mass ratio ((C) / (B) mass ratio) to the phosphorescent material (B). The mass ratio (C) / (B) is preferably 0.02 to 0.3, more preferably 0.03 to 0.2. When the mass ratio (C) / (B) is less than the above lower limit, the effect of suppressing yellowing or darkening at the time of light irradiation by the metal oxide-coated platy filler (C) cannot be sufficiently obtained. If the mass ratio (C) / (B) exceeds the above upper limit, the phosphorescent property of the phosphorescent material (B) may be impaired by the metal oxide-coated plate filler (C).

[Phosphate stabilizer (D)]
The alkyl acid phosphate or alkenyl acid phosphate of the phosphate stabilizer (D) used in the present invention is preferably represented by the following formula (I). That is, the alkyl acid phosphate or the alkenyl acid phosphate is represented by the following formula (I), and the alkyl acid phosphate metal salt or the alkenyl acid phosphate metal salt is zinc of the alkyl acid phosphate or alkenyl acid phosphate represented by the following formula (I). A metal salt such as a salt or an aluminum salt is preferred.
O = P (OH) _n (OR) _3-n (I)
(In the formula (I), R represents an alkyl group or alkenyl group having 9 to 30 carbon atoms, and n represents an integer of 1 or 2. When n is 1, two Rs may be the same or different. It may be a thing.)

  The alkyl group represented by R in the above formula (I) may be a straight chain alkyl group or may have a branch. Specific examples of the alkyl group for R include nonyl, isononyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl (stearyl), eicosyl, and tetracosyl groups. Also, the alkenyl group represented by R may be a straight chain alkenyl group or may have a branch. Specific examples of the alkenyl group for R include an oleyl group. n is 1 or 2, and may be a mixture thereof.

The carbon number of the alkyl group or alkenyl group represented by R in the above formula (I) is more preferably any one of 13, 18, and 24. As the alkyl acid phosphate, in particular, in the following formula (II) Preferred is a mixture of n = 1 distearyl acid phosphate and n = 2 monostearyl acid phosphate in formula (II).
O = P (OH) _n (OC ₁₈ H ₃₇ ) _3-n (II)

  The metal salt of alkyl acid phosphate is preferably a mixture of a distearyl acid phosphate zinc salt represented by the following formula (IIIa) and a monostearyl acid phosphate zinc salt represented by the following formula (IIIb).

  These phosphate stabilizers (D) may be used alone or in combination of two or more.

  The blending amount of the phosphate stabilizer (D) is 0.01 to 1 part by weight, preferably 0.02 to 0.5 part by weight, more preferably 0.03 to 0.1 part per 100 parts by weight of the polycarbonate resin. Part by mass. If the amount of the phosphate stabilizer (D) is less than the above lower limit, the effect of inhibiting the decomposition of the polycarbonate resin (A) due to the incorporation of the phosphate stabilizer (D) cannot be sufficiently obtained, and the phosphate type When there are more compounding quantities of a stabilizer (D) than the said upper limit, impact resistance may fall and there exists a possibility that the external appearance of a molded article may be impaired.

[Hydrogensiloxane (E)]
The resin composition of the present invention preferably further contains hydrogen siloxane (E) in order to more reliably prevent the decomposition of the polycarbonate resin (A).

  The molecular weight of the hydrogen siloxane (E) used in the present invention is not particularly limited, and may belong to any group of oligomers and polymers. More specifically, polyorganohydrogensiloxanes represented by the formulas (A) to (C) described in JP-B 63-26140 are preferable. As the hydrogen siloxane (E), for example, a polysiloxane having the following formula (e-1) as a repeating unit and a compound represented by the following formula (e-2) or (e-3) are preferably used.

(R ^a ) _α (H) _β SiO (e-1)
(In the above formula, R ^a is ^a linear or branched alkyl group having 1 to 10 carbon atoms, and the sum of α and β is 2.)

(In the above formula, A and B are each a group selected from the following group, and r is an integer of 1 to 500.)

(In said formula, A and B are synonymous with each in said Formula (e-2), and t is an integer of 1-50.)

  As the hydrogen siloxane (E), a commercially available silicone oil, for example, SH1107 (product of Toray Dow Corning Co., Ltd.) can be used.

  These hydrogen siloxanes (E) may be used individually by 1 type, and may use 2 or more types together.

  When hydrogen siloxane (E) is mix | blended with the resin composition of this invention, the compounding quantity is 0.003-0.15 mass part with respect to 100 mass parts of polycarbonate resin, More preferably, 0.005-0. 12 parts by mass, more preferably 0.01 to 0.1 parts by mass. If the blending amount of the hydrogen siloxane (E) is less than the above lower limit, the effect of suppressing the decomposition of the polycarbonate resin (A) due to the blending of the hydrogen siloxane (E) cannot be sufficiently obtained, and the hydrogen siloxane ( When the blending amount of E) is larger than the above upper limit, gas is generated during melt-kneading, which tends to cause mold deposit.

[Ultraviolet absorber]
The resin composition of the present invention may contain an ultraviolet absorber.
Resin-molded products tend to become yellowish due to ultraviolet rays when exposed to light such as sunlight or fluorescent lamps for a long time, but the addition of UV absorbers prevents such yellowing. Or it can be delayed. As the ultraviolet absorber, a malonic ester ultraviolet absorber and an oxalic anilide ultraviolet absorber are preferably used.

<Malonic acid ester UV absorber>
As the malonic ester UV absorber, any conventionally known malonic ester compound can be used. Among them, 2- (alkylidene) malonic esters, particularly 2- (1-arylalkylidene) malonic esters are preferred. Is preferable from the viewpoint of the initial hue of the resin composition. As the 2- (1-arylalkylidene) malonic acid esters used in the present invention, those represented by the following formula (A) are particularly preferable.

(In Formula (A), Q represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, or an alkenyl group having 2 to 10 carbon atoms, which may have a substituent, and R ^11. And R ¹² each independently represents an alkyl group having 1 to 6 carbon atoms.)

  In the formula (A), Q is preferably a hydrogen atom, an alkyl group, an alkoxy group, or an alkenyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. The alkyl group in the alkyl group or alkoxy group represented by Q may be linear or branched, and specifically includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group. , N-butyl group, i-butyl group, s-butyl group, t-butyl group and the like.

  Moreover, as an alkenyl group, what has an ester group as a substituent is preferable, and the carbon number is 3-10 including the carbon number in a substituent, Preferably it is 4-8. Among them, Q itself is preferably a 2- (alkylidene) malonic acid ester which is a malonic acid ester moiety of the above-described formula (A), and among them, the same malonic acid with the benzene ring of the formula (A) as the center. Those having an ester residue, particularly those having a para-position thereof are preferred.

In formula (A), R ¹¹ and R ¹² are each preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group represented by R ¹¹ and R ¹² may be linear or branched, and specifically includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, Examples include n-butyl group, i-butyl group, s-butyl group, t-butyl group. R ¹¹ and R ¹² are each preferably a methyl group.

  As a commercial item of such a malonic ester-based ultraviolet absorber, “Hostavin B-CAP” (tetraethyl-2,2- (1,4-phenylenedimethylidene)-) manufactured by Clariant, represented by the following structural formula: Bismalonate, molecular weight: 418, melting point: 137-139 ° C.) and “Hostavin PR-25” (p-methoxybenzylidene malonic acid dimethyl ester, molecular weight: 250, melting point: 55-59 ° C.).

  These malonic ester UV absorbers may be used alone or in combination of two or more.

<Oxalic acid anilide UV absorber>
As the oxalic acid anilide ultraviolet absorber, any conventionally known oxalic acid anilide compound can be used. Specific examples thereof include 2-ethoxy-2′-ethyl oxalic acid bisanilide, 2-ethoxy-5-t- Examples thereof include butyl-2'-ethyl oxalic acid bisanilide and 2-ethoxy-3'-dodecyl oxalic acid bisanilide, and 2-ethoxy-2'-ethyl oxalic acid bisanilide is preferable.
As a commercial item of such an oxalic acid anilide-based ultraviolet absorber, “Hostavin VSU” (2-ethoxy-2′-ethyl oxalic acid bisanilide, molecular weight: 312, melting point: 123, manufactured by Clariant Corporation represented by the following structural formula: ~ 127 ° C).

These oxalic anilide ultraviolet absorbers may be used alone or in combination of two or more.
Moreover, you may use combining the 1 type (s) or 2 or more types of a malonic acid ester type ultraviolet absorber, and the 1 type (s) or 2 or more types of an oxalic acid anilide type ultraviolet absorber.

  When the resin composition of this invention contains said ultraviolet absorber, it is preferable that the content is 0.001-1 mass part with respect to 100 mass parts of polycarbonate resin (A), 0.005. More preferably, it is -0.8 mass part, and it is still more preferable that it is 0.01-0.5 mass part. When the content of the ultraviolet absorber is in the above range, the phosphorescent property due to the phosphorescent material (B) and the glitter and polarization properties due to the metal oxide-coated plate filler (C) do not occur, and the surface of the molded product is bleed. This is preferable because the weather resistance can be improved without causing an out or the like.

[Other ingredients]
The resin composition of the present invention may contain one or more selected from various additives within a range not impairing the effects of the present invention. Examples of such additives include colorants, mold release agents, flame retardants, antioxidants, ultraviolet absorbers other than the above-described malonic ester-based ultraviolet absorbers and oxalic anilide-based ultraviolet absorbers (hereinafter “others”). And so on). Moreover, the resin composition of this invention may contain other resins other than polycarbonate resin (A).

<Colorant>
The resin composition of the present invention may contain various dyes and pigments as a colorant as desired. By containing the dye / pigment, the concealability and weather resistance of the resin composition of the present invention can be improved, and the design of a molded product obtained by molding the resin composition of the present invention can be improved.

  Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes.

  Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments.

  Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, iso Examples thereof include condensed polycyclic dyes such as indolinone and quinophthalone; anthraquinone, heterocyclic and methyl dyes.

  Of these, titanium oxide, carbon black, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.

As for said coloring agent, 1 type may contain and 2 or more types may contain it by arbitrary combinations and a ratio.
Moreover, what was masterbatched with polycarbonate resin (A) and another resin may also be used for the objective of the improvement of the handleability at the time of extrusion, and the dispersibility improvement in a resin composition as a coloring agent.

  When the resin composition of the present invention contains a colorant, the content may be appropriately selected according to the required design properties, but is usually 0.001 mass per 100 mass parts of the polycarbonate resin (A). Part or more, preferably 0.005 part by weight or more, more preferably 0.01 part by weight or more, and usually 3 parts by weight or less, preferably 2 parts by weight or less, more preferably 1 part by weight or less, more preferably 0.5 parts by mass or less. If the content of the colorant is less than the lower limit of the above range, the coloring effect may not be sufficiently obtained. If the content of the colorant exceeds the upper limit of the above range, a mold deposit or the like occurs. , May cause mold contamination.

<Release agent>
The resin composition of the present invention may contain a release agent in order to improve the release property and improve the surface smoothness of the molded product.
A preferable mold release agent is a compound selected from an aliphatic carboxylic acid, an aliphatic carboxylic acid ester, and an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15000. Among these, compounds selected from aliphatic carboxylic acids and aliphatic carboxylic acid esters are preferably used.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid. In the present specification, the term “aliphatic carboxylic acid” is used to include alicyclic carboxylic acids. Among the aliphatic carboxylic acids, mono- or dicarboxylic acids having 6 to 36 carbon atoms are preferable, and aliphatic saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellic acid, tetrariacontanoic acid. , Montanic acid, glutaric acid, adipic acid, azelaic acid and the like.

  As the aliphatic carboxylic acid component constituting the aliphatic carboxylic acid ester, the same aliphatic carboxylic acid as that described above can be used. On the other hand, examples of the alcohol component constituting the aliphatic carboxylic acid ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the aliphatic alcohol also includes an alicyclic alcohol. Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc. These aliphatic carboxylic acid esters may contain an aliphatic carboxylic acid and / or alcohol as impurities, or may be a mixture of a plurality of compounds. Specific examples of the aliphatic carboxylic acid ester include beeswax (mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, octyldodecyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin Examples thereof include distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.

  These release agents may be used alone or in combination of two or more.

  When the resin composition of this invention contains a mold release agent, it is preferable that the content is 0.01-1 mass part with respect to 100 mass parts of polycarbonate resin (A). It is preferable for the content of the release agent to be in the above range since there is no decrease in hydrolysis resistance and a release effect can be obtained.

<Flame Retardant>
The resin composition of the present invention may contain a flame retardant in order to obtain flame retardancy. The flame retardant is not particularly limited as long as it maintains the transparency of the polycarbonate resin (A) and improves the flame retardancy of the composition, but organic sulfonic acid metal salts and silicone compounds are suitable.

  The organic sulfonic acid metal salt for the flame retardant is preferably an aliphatic sulfonic acid metal salt or an aromatic sulfonic acid metal salt. These may be used alone or in combination of two or more. You may do it. The metal constituting the organic sulfonic acid metal salt is preferably an alkali metal, an alkaline earth metal, etc., and the alkali metal and the alkaline earth metal include sodium, lithium, potassium, rubidium, cesium, beryllium, magnesium. , Calcium, strontium and barium.

  As the aliphatic sulfonate, a fluoroalkane-sulfonic acid metal salt is preferable, and a perfluoroalkane-sulfonic acid metal salt is more preferable. Preferred examples of the fluoroalkane-sulfonic acid metal salt include alkali metal salts and alkaline earth metal salts, and more preferred are alkali metal salts and alkaline earth metals of fluoroalkanesulfonic acid having 4 to 8 carbon atoms. Examples include salt. Specific examples of the fluoroalkane-sulfonic acid metal salt include perfluorobutane-sodium sulfonate, potassium perfluorobutane-sulfonate, perfluoromethylbutane-sodium sulfonate, perfluoromethylbutane-potassium sulfonate, perfluorooctane. -Sodium sulfonate, perfluorooctane-potassium sulfonate, etc. are mentioned.

  Moreover, as an aromatic sulfonic acid metal salt, Preferably, an alkali metal salt, an alkaline-earth metal salt, etc. are mentioned. Specific examples of the aromatic sulfonesulfonic acid alkali metal salt and aromatic sulfonic acid metal salt include 3,4-dichlorobenzenesulfonic acid sodium salt, 2,4,5-trichlorobenzenesulfonic acid sodium salt, and benzenesulfonic acid sodium salt. Sodium salt of diphenylsulfone-3-sulfonic acid, potassium salt of diphenylsulfone-3-sulfonic acid, sodium salt of 4,4′-dibromodiphenyl-sulfone-3-sulfonic acid, 4,4′-dibromophenyl-sulfone -3- potassium salt of sulfonic acid, calcium salt of 4-chloro-4'-nitrodiphenylsulfone-3-sulfonic acid, disodium salt of diphenylsulfone-3,3'-disulfonic acid, diphenylsulfone-3,3 ' -Dipotassium salt of disulfonic acid and the like.

  When the resin composition of the present invention contains these organic sulfonic acid metal salts, the content thereof is preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). More preferably, it is 02-2 mass parts, and it is further more preferable that it is 0.03-1 mass parts. It is preferable for the content of the organic sulfonic acid metal salt as the flame retardant to be in the above range because the resin composition has flame retardancy and good thermal stability. If the content of the organic sulfonic acid metal salt is more than the above range, the transparency of the resin composition may be impaired, and if it is less, sufficient flame retardancy cannot be obtained.

As the silicone compound for the flame retardant, polyorganosiloxane having a linear or branched structure described in JP-A No. 2006-169451 is preferable. The organic group possessed by the polyorganosiloxane is a hydrocarbon such as an alkyl group having 1 to 20 carbon atoms and a substituted alkyl group, or a vinyl and alkenyl group, a cycloalkyl group, and an aromatic hydrocarbon group such as phenyl or benzyl. It is chosen from among them.
The polydiorganosiloxane may not contain a functional group or may contain a functional group. In the case of a polydiorganosiloxane containing a functional group, the functional group is preferably a methacryl group, an alkoxy group or an epoxy group.

  When the resin composition of this invention contains these silicone compounds for flame retardants, it is preferable that the content is 0.5-10 mass parts with respect to 100 mass parts of polycarbonate resin (A). It is preferable for the content of the silicone compound as a flame retardant to be in the above range because flame retardancy is improved without impairing transparency, appearance, elastic modulus, and the like.

  In addition, you may use together the said organic sulfonic acid metal salt and a silicone compound.

<Antioxidant>
The resin composition of the present invention may contain an antioxidant.
As the antioxidant, a phenolic antioxidant is preferable, and more specifically, 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-). tert-butyl-4′-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-tert-butyl- 4-hydroxybenzyl) isocyanurate, 4,4′-butylidenebis- (3-methyl-6-tert-butylphenyl), triethylene glycol-bis [3- (3-tert-butyl-hydroxy-5-methylphenyl) Propionate], and 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylpheny And l) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,6] undecane. Among these, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane is preferable.
These antioxidants may be used alone or in combination of two or more.

  When the resin composition of this invention contains antioxidant, it is preferable that the content is 0.02-0.5 mass part with respect to 100 mass parts of polycarbonate resin (A). This range is preferable because the antioxidant property can be improved without inhibiting the effects of the present invention.

<Other UV absorbers>
The resin composition of the present invention may contain other ultraviolet absorbers other than the aforementioned malonic ester ultraviolet absorber and oxalic anilide ultraviolet absorber. Examples of other ultraviolet absorbers include benzophenone, benzotriazole, phenyl salicylate, and hindered amine.

  Specific examples of benzophenone ultraviolet absorbers include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone. 2-hydroxy-4-octadecyloxy-benzophenone, 2,2′-dihydroxy-4-methoxy-benzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-benzophenone, 2,2 ′, 4,4 And '-tetrahydroxy-benzophenone.

  Specific examples of the benzotriazole ultraviolet absorber include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1- Methyl-1-phenylmethyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol, 2,4-di-tert-butyl- 6- (5-chlorobenzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetrabutyl) phenol, 2,2′-methylenebis [ 6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetrabutyl) phenol] and the like.

Specific examples of the phenyl salicylate UV absorber include phenylsaltylate, 2,4-ditertiary-butylphenyl-3,5-ditertiary-butyl-4-hydroxybenzoate, and the like.
Specific examples of the hindered amine ultraviolet absorber include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

  These may be used alone or in combination of two or more.

  When the resin composition of the present invention contains these other UV absorbers, the content thereof is the same as that in the above-described UV absorber, for the same reason as in the above-mentioned malonic ester UV absorber and oxalate ester. The total amount with the ultraviolet absorber is preferably 0.001 to 1 part by mass, more preferably 0.005 to 0.8 part by mass with respect to 100 parts by mass of the polycarbonate resin (A). More preferably, the content is 0.01 to 0.5 parts by mass.

<Other resin components>
The resin composition of the present invention may contain a resin component other than the polycarbonate resin (A). In this case, examples of other resin components include polystyrene resin, high impact polystyrene resin, and hydrogenated polystyrene resin. , Polyacryl styrene resin, styrene-maleic anhydride copolymer, ABS resin, AS resin, AES resin, ASA resin, SMA resin, polyalkyl methacrylate resin, (meth) acrylate copolymer, polymethacryl methacrylate resin, polyphenyl Ether resin, amorphous polyalkylene terephthalate resin, polyester resin, amorphous polyamide resin, poly-4-methylpentene-1, cyclic polyolefin resin, amorphous polyarylate resin, polyethersulfone, styrenic thermoplastic elastomer Olefin-based Thermoplastic elastomers, polyamide thermoplastic elastomers, polyester thermoplastic elastomers, thermoplastic elastomers such as polyurethane-based thermoplastic elastomers Kyora. These may be used alone or in combination of two or more.

  However, the polycarbonate resin (A) exhibits the original excellent characteristics, and the phosphorescent material (B), the metal oxide-coated plate filler (C), the phosphate stabilizer (D), and further the hydrogen siloxane (E) In the case where these other resin components are blended, the content thereof is 50 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A). It is preferable.

<Others>
The resin composition of the present invention includes, in addition to the above components, an antistatic agent, an antifogging agent, a lubricant, an antiblocking agent, a fluidity improver, and a plasticizer, as long as the purpose of the present invention is not impaired as necessary. , Dispersants, antibacterial agents and the like can be blended.
These may be used alone or in combination of two or more.

[Production method]
The resin composition of the present invention can be produced by mixing each component by melt-kneading by a conventionally known method. Specific mixing methods include polycarbonate resin (A), phosphorescent material (B), metal oxide-coated plate filler (C), phosphate stabilizer (D), and hydrogen siloxane blended as necessary ( E) and other additive components are weighed in a predetermined amount and mixed using various mixers such as a tumbler or Henschel mixer, and then Banbury mixer, roll, plastic appender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. And a method of melt-kneading using the above.

〔Molding〕
The molded article of the present invention is formed by molding the polycarbonate resin composition of the present invention as described above.

  As a molding method for producing the molded product of the present invention formed by molding the polycarbonate resin composition of the present invention, a conventionally known method of molding a molded product from a thermoplastic resin material can be applied without limitation. . Specifically, general injection molding methods, ultra-high speed injection molding methods, injection compression molding methods, two-color molding methods, hollow molding methods such as gas assist, molding methods using heat insulating molds, rapid heating molds Molding method used, foam molding (including supercritical fluid), insert molding, in-mold coating (IMC) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method Etc.

[Usage]
The molded product of the present invention formed by molding the polycarbonate resin composition of the present invention is excellent in design and can be commercialized without being coated, and can be produced as an electric / electronic device, OA device, information terminal. The present invention can be applied to various uses such as equipment, machine parts, household electrical appliances, vehicle parts, building members, various containers, play equipment, toys, leisure goods / sports goods, cosmetics, accessories, stationery, etc.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.
In addition, the structural component of the resin composition used in the following Examples and Comparative Examples is as follows.

<Polycarbonate resin (A)>
Aromatic polycarbonate resin "Iupilon S-3000F" manufactured by Mitsubishi Engineering Plastics (viscosity average molecular weight = 21500)

<Phosphate stabilizer (D)>
AX-71: “ADEKA STAB AX-71” manufactured by ADEKA (mixture of monostearyl acid phosphate and distearyl acid phosphate represented by the formula (II))
JP-513: “JP-513” (isotridecyl acid phosphate represented by the following formula (IV)) manufactured by Johoku Chemical Co., Ltd.

JP-518-O: “JP-518-O” manufactured by Johoku Chemical Co., Ltd. (oleyl acid phosphate represented by the following formula (V))

JP-524R: “JP-524R” manufactured by Johoku Chemical Co., Ltd. (tetracosyl acid phosphate represented by the following formula (VI))

<Hydrogensiloxane (E)>
SH1107: “DOW CORNING TORAY SH1107 FLUID” (methylhydrogensiloxane) manufactured by Toray Dow Corning

<Release agent>
VPG861: "Roxyol VPG861" (pentaerythritol tetrastearate) manufactured by Emery Oleochemicals Japan

[Examples 1-12 and Comparative Examples 1-3]
Polycarbonate resin and various additives were blended in the proportions shown in Tables 3 and 4, mixed for 20 minutes with a tumbler, and then cylinder temperature was measured with a single screw extruder with a screw diameter of 40 mm (“VS-40” manufactured by Tanabe Plastics). The mixture was kneaded at 280 ° C. and a screw rotation speed of 80 rpm, and the extruded strand was cut to produce pellets.
The obtained pellets were dried at 120 ° C. for 5 hours, and then injected with an injection molding machine (“Si80-6” manufactured by Toyo Metal Co., Ltd.) under conditions of a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 45 seconds. Molding was performed to prepare various test pieces.
The following evaluation was performed about the obtained pellet or test piece, and the results are shown in Tables 3 and 4.

(1) Flow value (Q value)
The pellet flow value (Q value) was evaluated by the method described in JIS K7210 Appendix C. The measurement was performed using a “flow tester CFD500D” manufactured by Shimadzu Corporation, using a die having a hole diameter of 1.0 mmφ and a length of 10 mm, under conditions of a test temperature of 278 ° C., a test force of 160 kg / cm ² , and a preheating time of 420 sec. The amount of molten resin (unit: cc / sec) was measured.

(2) Charpy impact strength (notched)
ISO standard multipurpose test piece (ISO 3167 typeA, thickness 3 mm) using a notching machine (Toyo Seiki "notching tool A-4 type"), single-tooth V cutter (45 °, R = 0.25 mm), Notch processing was carried out with a notch rotation speed of 300 rpm and a notch cutting frequency of 2, and at the same time, a center part was cut out by 80 mm with a slicer. A Charpy impact test was performed in accordance with ISO 179 using the obtained notched Charpy test piece. The measurement was performed using a Charpy impact tester (“DG-CB” manufactured by Toyo Seiki Co., Ltd.) with a hammer capacity of 4.0 J and a measurement temperature of 23 ° C.

(3) Initial Hue Color difference meter (Nippon Denki Co., Ltd.) for the 3mm thick part of the test piece (50mm (width) x 90mm (length), 3mm plate with 1mm, 2mm and 3mm thickness) obtained by injection molding. L * and b * were measured under the following conditions using “SE6000” manufactured by Color Industrial Co., Ltd. Smaller b * values indicate less yellowness, and larger L * values indicate brighter reflected light and better luminance. The b * value is preferably 10 or less, and the L * value is preferably 70 or more.
Reflection measurement: D ₆₅ light source 10 degree field of view Measurement port: 30φ
Sample holder: white

(4) for 3mm portion of the thickness of the same test piece as in the measurement of the afterglow luminance the initial hue, after blocking for 24 hours light _was irradiated for 20 minutes with illuminant _{D 65} (200LX). The state of afterglow brightness (sensation of brightness) was examined by visual observation of the appearance immediately after the light was cut off and the light was cut off, and 60 minutes after the light was turned off, and evaluated according to the following criteria. did.
<Evaluation criteria>
◎: Very bright and the contour of the specimen can be confirmed clearly ○: Normal brightness, the contour of the specimen can be confirmed △: Although it is slightly blurred, the contour of the specimen can be slightly confirmed Yes ×: Almost no outline of specimen can be confirmed

  From Tables 3 and 4, the book of Examples 1-12 which mix | blended phosphorescent material (B), the metal oxide covering plate-like filler (C), and the phosphate stabilizer (D) with the polycarbonate resin (A) in the predetermined ratio. The resin composition of the invention has a high afterglow luminance, a high L * value (brightness (whiteness)), a low b * value, suppressed yellowing, and maintains initial phosphorescence while maintaining luminous properties. It can be seen that is improved.

On the other hand, in Comparative Examples 1 to 3 in which the metal oxide-coated plate filler (C) is not blended, the initial hue is inferior.
From the comparison between Comparative Example 1 and Examples 1-5, the comparison between Comparative Example 2 and Examples 6-11, and the comparison between Comparative Example 3 and Example 12, there is no difference in afterglow luminance. In this invention, even if it mix | blends a metal oxide covering plate-shaped filler (C), it turns out that the luminous property by the luminous material (B) is not impaired.

Claims (7)

With respect to 100 parts by mass of the polycarbonate resin (A), 1 to 30 parts by mass of the phosphorescent material (B) having an average particle diameter D ₅₀ of more than 10 μm and less than 100 μm and an average particle diameter D ₅₀ of 5 excluding the aluminum-coated flake-like glass are 5 0.1 to 5 parts by mass of a metal oxide-coated platy filler (C) of ˜200 μm, and one or more phosphate stabilizers selected from alkyl acid phosphates, alkenyl acid phosphates and their metal salts (D ) 0.01 to 1 part by weight of a polycarbonate resin composition,
The metal oxide-coated platy filler (C) is a base material made of mica, a metal oxide-coated platy filler (CA) in which a coating layer containing titanium oxide, tin oxide and silicon oxide is formed, glass or A base material made of silica is selected from a metal oxide-coated plate-like filler (CB) in which a coating layer containing titanium oxide and tin oxide is formed,
A polycarbonate resin composition, wherein a mass ratio ((C) / (B) mass ratio) of the metal oxide-coated platy filler to the phosphorescent material (B) is 0.01 to 0.5.   In Claim 1, The base material of the said metal oxide covering plate-like filler (CB) consists of glass, and a coating layer contains a silicon oxide further, 40-85 mass% of base materials, 5-20 mass% of titanium oxides, A polycarbonate resin composition comprising 0 to 2% by mass of tin oxide and 10 to 40% by mass of silicon oxide. 3. The polycarbonate resin composition according to claim 1 or 2, wherein the alkyl acid phosphate or alkenyl acid phosphate is represented by the following formula (I).
O = P (OH) _n (OR) _3-n (I)
(In the formula (I), R represents an alkyl group or alkenyl group having 9 to 30 carbon atoms, and n represents an integer of 1 or 2. When n is 1, two Rs may be the same or different. It may be a thing.)   The polycarbonate resin composition according to claim 3, wherein R in the formula (I) is an alkyl group or an alkenyl group having any of 13, 18, and 24 carbon atoms. 5. The phosphate stabilizer (D) according to claim 4, wherein the phosphate stabilizer (D) is represented by the following formula (II), and is a mixture of n = 1 distearyl acid phosphate and n = 2 monostearyl acid phosphate in the formula (II): A polycarbonate resin composition characterized by being.
O = P (OH) _n (OC ₁₈ H ₃₇ ) _3-n (II)   The polycarbonate according to any one of claims 1 to 5, further comprising hydrogen siloxane (E) in an amount of 0.003 to 0.15 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). Resin composition.   A molded article formed by molding the polycarbonate resin composition according to any one of claims 1 to 6.