JP6958465B2 - Polycarbonate resin composition and its molded product - Google Patents

Description

The present invention relates to a polycarbonate resin composition and a molded product thereof. Specifically, the present invention is a polycarbonate resin composition obtained by blending a phosphorescent material with a polycarbonate resin to impart phosphorescent properties, and is used when irradiated with light, which is peculiar to the phosphorescent resin composition. The present invention relates to a highly-designed polycarbonate resin composition that suppresses yellowing and darkening of the material and has improved whiteness (brightness), and a molded product obtained by molding the polycarbonate resin composition.

When light such as ultraviolet rays 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 a dark place, a predetermined light is emitted. Various polycarbonate resin compositions containing a phosphorescent material that continuously emits light for a long time have been proposed as a molding material for a phosphorescent light emitting member such as a road sign or a signboard, and improvements thereof have been studied.

However, when the phosphorescent material is blended with the polycarbonate resin, the initial hue at the time of light irradiation becomes yellowish or darkened. If the initial hue during light irradiation is yellowish or darkened, the appearance will be significantly inferior, and it cannot be applied to applications that require design.

As a solution to this problem, the addition of aluminum foil has been studied, but there is a problem that the brightness is greatly reduced even if the initial color of yellowing and darkening peculiar to phosphorescence can be changed.
Further, in order to prevent 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 still a problem that the brightness is lowered even if yellowing and darkening are suppressed.

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

2016-28111

INDUSTRIAL APPLICABILITY The present invention is a polycarbonate resin composition obtained by blending a phosphorescent material with a polycarbonate resin to impart phosphorescent properties, and is used during light irradiation peculiar to the phosphorescent resin composition without lowering the brightness when the light is blocked by the phosphorescent material. An object of the present invention is to provide a highly-designed polycarbonate resin composition that suppresses yellowing and darkening and has improved whiteness (brightness), and a molded product obtained by molding this polycarbonate resin composition.

As a result of diligent studies to solve the above problems, the present inventor has determined a specific metal oxide-coated plate-like filler in a polycarbonate resin composition obtained by blending a phosphorescent material with a polycarbonate resin to impart phosphorescent properties. By blending in proportions and by blending the optimum stabilizer with this metal oxide-coated plate-like filler, yellowing and darkening during light irradiation are effectively suppressed without reducing the brightness due to the phosphorescent material. Moreover, it was found that the whiteness (brightness) can be improved.

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

_{[1] 1 to 30 parts by mass of a phosphorescent material (B) having an average particle diameter D 50} of 1 μm or more and less than 100 μm and 0.1 parts of a metal oxide-coated plate-like filler (C) with respect to 100 parts by mass of the polycarbonate resin (A). Polycarbonate resin composition containing ~ 5 parts by mass and 0.01 to 1 part by mass of one or more phosphate stabilizers (D) selected from alkyl acid phosphate, alkenyl acid phosphate and metal salts thereof. The metal oxide-coated plate-like filler (C) is obtained by forming a coating layer containing titanium oxide and tin oxide on a base material made of mica and not containing silicon oxide, and the phosphorescent material. A polycarbonate resin composition having a mass ratio ((C) / (B) mass ratio) of the metal oxide-coated plate-like filler to (B) of 0.01 to 0.5.

[2] In [1], the metal oxide-coated plate-like filler (C) contains 65 to 83.5% by mass of a base material, 15 to 33.5% by mass of titanium oxide, and 0.5 to 2 tons of tin oxide. A polycarbonate resin composition comprising, by mass,%.

[3] The polycarbonate resin composition according to [1], wherein the coating layer of the metal oxide-coated plate-like filler (C) further contains aluminum hydroxide and zirconium oxide.

[4] In [3], the metal oxide-coated plate-like filler (C) contains 65.5 to 83.9% by mass of a base material, 15 to 28.5% by mass of titanium oxide, and 0.1 by mass of tin oxide. A polycarbonate resin composition containing up to 2% by mass, 0.5 to 2% by mass of aluminum hydroxide, and 0.5 to 2% by mass of zirconium oxide.

[5] The polycarbonate resin composition according to any one of [1] to [4], 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 is an alkyl group or an alkenyl group having 9 to 30 carbon atoms, and n represents an integer of 1 or 2. When n is 1, the two Rs may be the same or different. It may be one.)

[6] The polycarbonate resin composition according to [5], wherein R in the formula (I) is an alkyl group or an alkenyl group having any of 13, 18, and 24 carbon atoms.

[7] In [6], the phosphate stabilizer (D) is represented by the following formula (II), and the distearyl acid phosphate of n = 1 and the monostearyl acid phosphate of n = 2 in the formula (II) are used. A polycarbonate resin composition, which is a mixture of.
O = P (OH) _n (OC ₁₈ H ₃₇ ) _3-n ... (II)

[8] In any of [1] to [7], the hydrogen siloxane (E) is further contained in an amount of 0.003 to 0.15 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). Polycarbonate resin composition.

[9] A molded product obtained by molding the polycarbonate resin composition according to any one of [1] to [8].

According to the present invention, in a polycarbonate resin composition in which a phosphorescent material is blended with a polycarbonate resin to impart phosphorescent properties, yellowing and darkening during light irradiation are effective without reducing the brightness when light is blocked by the phosphorescent material. It is possible to provide a highly designed polycarbonate resin composition and a molded product thereof, which are effectively suppressed and have improved whiteness (brightness).

The molded product of the present invention formed by molding the polycarbonate resin composition of the present invention has excellent phosphorescent performance and good hue when irradiated with light, and has an illuminated signboard, a product display, a liquid crystal backlight, a lighting display, and lighting. Lighting equipment covers, traffic signs, safety signs, night visibility improving members, signboards, screens, automobile parts such as reflectors and meter parts, play equipment and toys in entertainment facilities, mobile devices such as laptop computers and mobile phones, automobiles It can be used for a wide range of purposes such as housings, switches, and buttons in fields such as sign buttons in indoors and buildings, clock dials, accessories, stationery, sporting goods, and various electrical, electronic, and OA equipment. ..

Hereinafter, the present invention will be described in detail by showing embodiments and examples, but the present invention is not limited to the embodiments and examples shown below, and is arbitrary as long as it does not deviate from the gist of the present invention. Can be changed to.

[Polycarbonate resin composition]
The polycarbonate resin composition of the present invention (hereinafter, may be referred to as “resin composition of the present invention”) has _{a phosphorescent phosphorescence having an average particle size D 50} of 1 μm or more and less than 100 μm with respect to 100 parts by mass of the polycarbonate resin (A). One or two selected from 1 to 30 parts by mass of the material (B), 0.1 to 5 parts by mass of the metal oxide-coated plate-like filler (C), alkyl acid phosphate, alkenyl acid phosphate, and metal salts thereof. A polycarbonate resin composition containing 0.01 to 1 part by mass of the above-mentioned phosphate-based stabilizer (D), wherein the metal oxide-coated plate-like filler (C) is used as a base material made of mica, and titanium oxide is used as a base material. A coating layer containing tin oxide and not silicon oxide was 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.

[Mechanism of action]
In the polycarbonate resin composition of the present invention, the mechanism of action capable of suppressing yellowing and darkening without lowering the phosphorescent property and afterglow brightness of the phosphorescent material (B) is presumed as follows.

That is, in the resin composition of the present invention, the metal oxide-coated plate-like filler (C) blended in a predetermined ratio with respect to the phosphorescent material (B) is a pearl-like plate-like filler having a high degree of whiteness. By including such a metal oxide-coated plate-shaped filler (C), the metal oxide-coated plate-shaped filler (C) imparts brilliance and polarization, and yellowing during light irradiation due to the phosphorescent material (B). Only is offset and whiteness (brightness) is improved. Further, since the metal oxide-coated plate-like filler (C) used in the present invention is translucent and does not completely absorb light including ultraviolet rays, the phosphorescent material (B) does not reduce the phosphorescent property and afterglow brightness. ..
When the phosphorescent material (B) and the metal oxide-coated plate-shaped filler (C) are mixed with the polycarbonate resin (A) in this way, it is caused by the phosphorescent material (B) and the metal oxide-coated plate-shaped filler (C). Metal pieces during melt-kneading (metal pieces generated by the phosphorescent material (B) and metal oxide-coated plate-like filler (C) that wear the barrel and screw surface during melt-kneading with an extruder) Darkening may occur due to contamination or the rare earth element that is a constituent of the phosphorescent material (B) decomposes the polycarbonate resin (A) under high temperature conditions. However, in the present invention, the phosphate stabilizer (D) ) Or by further blending a hydrogen siloxane (E), this problem can be solved.
According to the present invention, these effects act synergistically to effectively suppress yellowing and darkening during light irradiation without reducing the brightness when light is blocked by the phosphorescent material, and to achieve whiteness (whiteness (). Brightness) can be improved.

[Polycarbonate resin (A)]
As the polycarbonate resin (A) used in the present invention, an aromatic polycarbonate resin is preferable from the viewpoints of transparency, impact resistance, heat resistance and the like.
The aromatic polycarbonate resin is a thermoplastic polymer or copolymer which may be branched, which is obtained by reacting an aromatic dihydroxy compound or a small amount of a polyhydroxy compound with phosgene or a carbonic acid diester. The method for producing 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. When the melting method is used, an aromatic polycarbonate resin having an adjusted amount of OH groups at the terminal groups can be used.

As raw material aromatic dihydroxy compounds, 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. Further, 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 added to the following branching agent, that is, fluoroglucolcin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl). Hepten-2,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenylhepten-3,1,1) Polyhydroxy compounds such as 3,5-tri (4-hydroxyphenyl) benzene and 1,1,1-tri (4-hydroxyphenyl) ethane, and 3,3-bis (4-hydroxyaryl) oxyindole (= isa). It may be replaced with a compound such as tymbisphenol), 5-chloruisatin, 5,7-dichlorousatin, 5-bromuisatin, etc. The amount of these substituted compounds used is usually 0.01 to 10 mol with respect to the aromatic dihydroxy compound. %, Preferably 0.1 to 2 mol%.

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

The above-mentioned aromatic polycarbonate resin may be used alone or in combination of two or more.

In order to adjust the molecular weight of the aromatic polycarbonate resin, a monovalent aromatic hydroxy compound may be used, and examples of the monovalent aromatic hydroxy compound include m- and p-methylphenol, m- and p-. Examples thereof include 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 intended use and may be appropriately selected and determined, but the viscosity average molecular weight (Mv) is preferably 20,000 to 50,000. If the viscosity average molecular weight is less than 20,000, the mechanical strength such as impact resistance of the obtained molded product is lowered, and if it is more than 50,000, the fluidity is deteriorated and a problem arises in moldability. The more preferable viscosity average molecular weight of the aromatic polycarbonate resin is 20,000 to 40,000, and more 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-mentioned suitable range may be mixed. good.

The viscosity average molecular weight (Mv) is defined as the ultimate viscosity (η) (unit: dl / g) at a temperature of 20 ° C. using a Ubbelohde viscometer using methylene chloride as a solvent, and the viscosity formula of Schnell, that is, , Η = 1.23 × 10 ^-4 Mv ^0.83 , which means a value calculated from. The ultimate viscosity (η) is a value calculated by the following formula by measuring _{the specific viscosity (η sp} ) at each solution concentration (C) (g / dl).

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

The phosphorescent material (B) used in the present invention may have the above-mentioned characteristics and is not particularly limited, but is a sulfide-based phosphorescent material such as CaS: Bi, CaSrS: Bi, ZnCdS: Cu, ZnS. : zinc sulfide phosphorescent material such as _{Cu, Sr 2 MgSi 2 O 7} : Eu, silicate-based phosphorescent material such as _{Dy, MAl a O b: X} (1 or more metal M is selected calcium, strontium and barium Element .X is an activator and is one or more selected from europium, lantern, cerium, placeodium, neodium, samarium, gadrinium, terbium, dysprosium, formium, erbium, strontium, itterbium, ruthenium, manganese, tin, bismuth. The content of the element X is usually 10 mol% or less, for example, 0.001 to 10 mol% with respect to the metal element represented by M), and examples thereof include an aluminic acid-based compound. Preferably, hydrolysis resistance, in terms of afterglow _{characteristics,} MAl _{a O} b: a aluminate compound represented by X, as the aluminate compounds include, for _{example, 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, and these may be combined), 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 and the like. Of 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 size D 50} of the phosphorescent material (B) is 1 μm or more and less than 100 μm, preferably 15 to 70 μm, and more preferably 20 to 50 μm. If the particle size of the phosphorescent material is too large, there is a problem that the tensile elongation at break, impact strength, appearance, etc. of the obtained molded product are deteriorated _{. Therefore, the average particle size D 50} is set to less than 100 μm. On the other hand, since the luminous characteristics of the phosphorescent material generally tend to deteriorate when the particle size is too small, the average particle size D ₅₀ is set to 1 μm or more.

The average particle size D _{50 in the present invention refers to the median diameter D 50} measured by a laser diffraction type particle size distribution measuring device, for example, using a “laser diffraction type particle size distribution measuring device SALD-2100” manufactured by Shimadzu Corporation. Although it is measured, the catalog value can be adopted for commercially available 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 blending amount of the phosphorescent material (B) is 1 to 30 parts by mass, preferably 2 to 25 parts by mass, and more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). If the blending amount of the phosphorescent material (B) is less than the above 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) is, the more preferable it is in terms of the phosphorescent effect, but if it is too large, the moldability, thermal stability, mechanical strength of the molded product and the like are impaired.

[Metal oxide coated plate-like filler (C)]
The metal oxide-coated plate-like filler (C) used in the present invention is obtained by forming a coating layer containing titanium oxide and tin oxide on a base material made of mica (mica) and not containing silicon oxide. This coating layer may further contain aluminum hydroxide and zirconium oxide.

When the coating layer of the metal oxide-coated plate-shaped filler (C) used in the present invention contains titanium oxide and tin oxide, the metal oxide-coated plate-shaped filler (C) contains 65 to 83.5% by mass of the base material. It preferably contains 15 to 33.5% by mass of titanium oxide and 0.5 to 2% by mass of tin oxide (however, the total of the base material, titanium oxide and tin oxide is 100% by mass). .. When the contents of the base material, titanium oxide and tin oxide are within the above ranges, the whiteness becomes pearly, and the effect of suppressing yellowing during light irradiation and improving the whiteness (brightness) is excellent. can do.

When the coating layer of the phosphorescent material (B) used in the present invention contains titanium oxide, tin oxide, aluminum hydroxide and zirconium oxide, the metal oxide-coated plate-like filler (C) is a base material 65.5 to 5. 83.9% by mass, titanium oxide 15 to 28.5% by mass, tin oxide 0.1 to 2% by mass, aluminum hydroxide 0.5 to 2% by mass, and zirconium oxide 0.5 to 2% by mass. (However, the total amount of the base material, titanium oxide, tin oxide, aluminum hydroxide, and zirconium oxide is 100% by mass). When the content of the base material, titanium oxide, tin oxide, aluminum hydroxide and zirconium oxide is within the above range, a translucent pearl with whiteness is formed, yellowing during light irradiation is suppressed, and whiteness (whiteness ( It can be said that the effect of improving the brightness) is excellent.

The content of the base material and the metal oxide of the metal oxide-coated plate-shaped filler (C) is determined by a method of converting the metal content by the fluorescent X-ray analysis method or the energy dispersion type X-ray spectroscopy into the amount of oxide. However, the catalog value can be adopted for commercially available products.

As the metal oxide-coated plate-shaped filler (C), in particular, a metal oxide containing titanium oxide and tin oxide, or aluminum hydroxide and zirconium oxide is chemically vapor-deposited on mica having an average thickness of about 0.1 to 10 μm. It is preferable that a coating layer having a thickness of about 0.01 to 1 μm is formed by physical vapor deposition.

A commercially available product can also be used as the metal oxide-coated plate-shaped filler (C). For example, as the metal oxide-coated flake-shaped mica, "Iriodin 6103 Icy White" (particle size) coated with titanium oxide or tin oxide. 5-40 μm), “Iriodin 103 Rurile Starling Silver” (particle size: 10-60 μm), “Colorstream T10-06 Royal Damage” (particle size: 10-60 μm), “Colorstream T10-05 Pacific” 10-60 μm), “TWINKLEPEAL SXC-SO” (particle size 10-40 μm), “TWINKLEPEAL SXB” (particle size 5-30 μm), “ULTIMICA SB-100” (particle size 5-30 μm) manufactured by Nippon Koken Co., Ltd. And so on.

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), but the coating layer. By containing tin oxide together with titanium oxide, a certain degree of decomposition suppressing effect can be obtained. Further, in the present invention, the decomposition of the polycarbonate resin (A) can be suppressed by containing the phosphate-based stabilizer (D) described later and further, the hydrogen siloxane (E).
Here, the pH of the metal oxide-coated plate-shaped filler (C) is a value measured by a pH test paper or a pH meter for a filtrate or a supernatant after boiling the filler in distilled water, and is commercially available. For products, the catalog value is applicable.

_{In the present invention, the average particle size D 50} of the metal oxide-coated plate-like filler (C) is preferably 1 to 500 μm. When the average particle size D ₅₀ of the metal oxide-coated plate-shaped filler (C) is less than 1 μm, the effect of sufficiently suppressing yellowing and darkening during light irradiation by blending the metal oxide-coated plate-shaped filler (C) can be sufficiently obtained. It may not be possible. _{When the average particle size D 50 of the} metal oxide-coated plate-like filler (C) exceeds 500 μm, the impact resistance of the obtained molded product tends to decrease. The average particle size D 50 of the metal oxide-coated plate-like filler (C) is particularly preferably about 3 to 300 μm, particularly preferably about _{5 to 100 μm.}

Here, the particle size of the metal oxide-coated plate-shaped filler (C) is the distance between the plates when the metal oxide-coated plate-shaped filler (C) is sandwiched between two parallel plates. Refers to the length of the part that grows.
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 device, and is measured using, for example, a “laser diffraction type particle size distribution measuring device SALD-2100” manufactured by Shimadzu Corporation. However, the catalog value can be adopted for commercial products.

The above-mentioned metal oxide-coated plate-shaped filler (C) may be used alone or in combination of two or more of the constituent materials of the coating layer or those having different particle sizes.
When two or more kinds of metal oxide-coated plate-shaped fillers (C) are used in combination _{, it is preferable that the average particle size D 50 of} all the metal oxide-coated plate-shaped fillers (C) used is within the above range.

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

In the resin composition of the present invention, the content of the metal oxide-coated plate-like filler (C) is 0.1 to 5 parts by mass, preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). It is by mass, more preferably 0.3 to 2 parts by mass. When the blending amount of the metal oxide-coated plate-shaped filler (C) is smaller than the above lower limit, the effect of sufficiently suppressing yellowing and darkening during light irradiation due to the blending of the metal oxide-coated plate-shaped filler (C) can be sufficiently obtained. If the amount is too large, the impact resistance of the obtained molded product will be inferior.

The content of the metal oxide-coated plate-like filler (C) in the resin composition of the present invention is 0.01 to 0. As a mass ratio ((C) / (B) mass ratio) to the phosphorescent material (B). It is 5, and the mass ratio of (C) / (B) is preferably 0.02 to 0.4, more preferably 0.03 to 0.3. If the mass ratio (C) / (B) is less than the above lower limit, the effect of suppressing yellowing and darkening during light irradiation by the metal oxide-coated plate-like filler (C) cannot be sufficiently obtained. If the mass ratio of (C) / (B) exceeds the above upper limit, the phosphorescent property of the phosphorescent material (B) may be impaired by the metal oxide-coated plate-like 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 represented by the following formula (I). It is preferably a metal salt such as a salt or an aluminum salt.
O = P (OH) _n (OR) _3-n ... (I)
(In the formula (I), R is an alkyl group or an alkenyl group having 9 to 30 carbon atoms, and n represents an integer of 1 or 2. When n is 1, the two Rs may be the same or different. It may be one.)

The alkyl group represented by R in the above formula (I) may be a linear alkyl group or may have a branch. Specific examples of the alkyl group of R include nonyl, isononyl, decyl, isodecyl, dodecyl, tridecylic, isotridecyl, tetradecyl, hexadecyl, octadecyl (stearyl), eikosyl, tetracosyl group and the like. Further, the alkenyl group represented by R may also be a linear alkenyl group and may have a branch. Specific examples of the alkenyl group of R include an oleyl group and the like. n is 1 or 2, and may be a mixture thereof.

The number of carbon atoms of the alkyl group or alkenyl group represented by R in the above formula (I) is more preferably any of 13, 18, and 24, and the alkyl acid phosphate is particularly represented by the following formula (II). It is represented and preferably a mixture of n = 1 distearyl acid phosphate and n = 2 monostearyl acid phosphate in the 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 zinc salt of distearyl acid phosphate represented by the following formula (IIIa) and a zinc salt of monostearyl acid phosphate represented by the following formula (IIIb).

As these phosphate-based stabilizers (D), only one type may be used, or two or more types may be mixed and used.

The blending amount of the phosphate stabilizer (D) is 0.01 to 1 part by mass, preferably 0.02 to 0.5 part by mass, and more preferably 0.03 to 0.1 part by mass with respect to 100 parts by mass of the polycarbonate resin. It is a mass part. If the blending amount of the phosphate stabilizer (D) is less than the above lower limit, the effect of suppressing the decomposition of the polycarbonate resin (A) due to the blending of the phosphate stabilizer (D) cannot be sufficiently obtained, and the phosphate stabilizer cannot be sufficiently obtained. If the amount of the stabilizer (D) blended is larger than the above upper limit, the impact resistance may be lowered and the appearance of the molded product may be impaired.

[Hydrogensiloxane (E)]
The resin composition of the present invention preferably further contains hydrogensiloxane (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 Japanese Patent Publication No. 63-26140 are preferable. As the hydrogen siloxane (E), for example, it is preferable to use 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).

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

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

(In the above formula, A and B are synonymous with each of the above formula (e-2), and t is an integer of 1 to 50.)

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

One of these hydrogen siloxanes (E) may be used alone, or two or more thereof may be used in combination.

When hydrogensiloxane (E) is blended in the resin composition of the present invention, the blending amount thereof is 0.003 to 0.15 parts by mass, more preferably 0.005 to 0 parts by mass with respect to 100 parts by mass of the polycarbonate resin. It is 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 (E) If the blending amount of E) is larger than the above upper limit, gas is generated during melt-kneading, which tends to cause a mold deposit.

[UV 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 period of time, but by adding an ultraviolet absorber, such yellowing can be prevented. Or it can be delayed. As the ultraviolet absorber, a malonic acid ester-based ultraviolet absorber and anilides oxalate ultraviolet absorber are preferably used.

<Malonic acid ester UV absorber>
As the malonic acid ester-based ultraviolet absorber, any conventionally known malonic acid ester-based compound can be used, among which 2- (alkylidene) malonic acid esters, particularly 2- (1-arylalkylidene) malonic acid esters. 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 preferable.

(In the formula (A), Q represents 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 hydrogen atom and a substituent, and R ¹¹ And R ¹² each independently represent an alkyl group having 1 to 6 carbon atoms.)

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

The alkenyl group preferably has an ester group as a substituent, and its carbon number is 3 to 10, preferably 4 to 8, including the number of carbon atoms in the substituent. Of these, those in which Q itself is 2- (alkylidene) malonic acid esters, which is the malonic acid ester moiety of the above formula (A), are preferable, and among them, the same malonic acid centered on the benzene ring of the formula (A). Those having ester residues, particularly those having these at the para position are preferable.

In the formula (A), R ¹¹ and R ¹² are preferably alkyl groups having 1 to 4 carbon atoms, respectively. The ^{alkyl groups represented by R 11} and R ¹² may be linear or branched, respectively, and specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and the like. Examples thereof include n-butyl group, i-butyl group, s-butyl group and t-butyl group. It is preferable that R ¹¹ and R ¹² are methyl groups, respectively.

As a commercially available product of such a malonic acid ester-based ultraviolet absorber, "Hostavin B-CAP" manufactured by Clariant Co., Ltd. (tetraethyl-2,2- (1,4-phenylenedimethylen))-represented by the following structural formula. Bismalonate, molecular weight: 418, melting point: 137 to 139 ° C.) and "Hostavin PR-25" (p-methoxybenzylidene malonic acid dimethyl ester, molecular weight: 250, melting point: 55 to 59 ° C.) can be mentioned.

One of these malonic acid ester-based ultraviolet absorbers may be used alone, or two or more thereof may be used in combination.

<Oxalic acid anilides UV absorber>
As the oxalic acid anilide-based ultraviolet absorber, any conventionally known oxalic acid anilide-based compound can be used, and specific examples thereof include 2-ethoxy-2'-ethyloxalate bisanilide and 2-ethoxy-5-t-. Examples thereof include butyl-2'-ethyloxalate bisanilide and 2-ethoxy-3'-dodecyloxalate bisanilide, preferably 2-ethoxy-2'-ethyloxalate bisanilide.
As a commercially available product of such an oxalic acid anilide-based ultraviolet absorber, "Hostavin VSU"(2-ethoxy-2'-ethyloxalate bisanilide, molecular weight: 312, melting point: 123) manufactured by Clariant AG represented by the following structural formula is used. ~ 127 ° C.).

These oxalic acid anilides-based ultraviolet absorbers may be used alone or in combination of two or more.
Further, one or more of the malonic acid ester-based ultraviolet absorbers and one or more of the oxalic acid anilides-based ultraviolet absorbers may be used in combination.

When the resin composition of the present invention contains the above-mentioned ultraviolet absorber, the content thereof is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the polycarbonate resin (A), preferably 0.005. It is more preferably ~ 0.8 parts by mass, and further preferably 0.01 to 0.5 parts by mass. When the content of the ultraviolet absorber is within the above range, the phosphorescent material (B) does not reduce the luminous property and the metal oxide-coated plate-like filler (C) does not reduce the brilliance or polarization property, and the surface of the molded product bleeds. It is preferable because the weather resistance can be improved without causing out or the like.

[Other ingredients]
The resin composition of the present invention may contain one or more selected from various additives as long as the effects of the present invention are not impaired. Examples of such additives include colorants, mold release agents, flame retardants, antioxidants, UV absorbers other than the above-mentioned malonic acid ester-based UV absorbers and oxalic acid anilides-based UV absorbers (hereinafter, "others". It is called "ultraviolet absorber".) Further, the resin composition of the present invention may contain a resin other than the polycarbonate resin (A).

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

Examples of dyeing pigments 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 flower, petals, chromium oxide, iron black, titanium yellow, and zinc-. Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black, copper-iron black; chrome pigments such as chrome yellow and molybdate orange; fer such as navy blue Russian pigments and the like can be mentioned.

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, and iso. Condensed polycyclic dyes such as indolinone type and quinophthalocyan type; anthraquinone type, heterocyclic dye type, methyl type dye pigments and the like can be mentioned.

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

The above colorants may contain one kind or two or more kinds in any combination and ratio.
Further, as the colorant, one that has been master-batched with the polycarbonate resin (A) or another resin may be used for the purpose of improving the handleability at the time of extrusion and improving the dispersibility in the resin composition.

When the resin composition of the present invention contains a colorant, the content thereof may be appropriately selected according to the required design property, but is usually 0.001 mass by mass with respect to 100 parts by mass of the polycarbonate resin (A). Parts or more, preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and usually 3 parts by mass or less, preferably 2 parts by mass or less, more preferably 1 part by mass or less, still more preferably. It is 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, and if the content of the colorant exceeds the upper limit of the above range, mold devogit or the like occurs. , May cause mold contamination.

<Release agent>
The resin composition of the present invention may contain a mold release agent in order to enhance the mold release property and the surface smoothness of the molded product.
Preferred release agents are compounds selected from aliphatic carboxylic acids, aliphatic carboxylic acid esters, and aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000. Among them, a compound selected from an aliphatic carboxylic acid and an aliphatic carboxylic acid ester is preferably used.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monocarboxylic acids, dicarboxylic acids and tricarboxylic acids. As used herein, the term aliphatic carboxylic acid is used in the sense that it also includes an alicyclic carboxylic acid. 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, araquinic acid, bechenic acid, lignoceric acid, cellotic acid, melisic acid, and tetrariacontanoic acid. , Montanoic acid, glutaric acid, adipic acid, azelaic acid and the like.

As the aliphatic carboxylic acid component constituting the aliphatic carboxylic acid ester, the same one as the above-mentioned aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol component constituting the aliphatic carboxylic acid ester include saturated or unsaturated monohydric alcohols, saturated or unsaturated polyhydric alcohols, and the like. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monohydric or polyhydric 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 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, and dipentaerythritol. And so on. These aliphatic carboxylic acid esters may contain an aliphatic carboxylic acid and / or an alcohol as impurities, or may be a mixture of a plurality of compounds. Specific examples of the aliphatic carboxylic acid ester include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenylate, octyldodecyl behate, glycerin monopalmitate, glycerin monostearate, and glycerin. Examples thereof include distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.

One of these release agents may be used alone, or two or more thereof may be used in combination.

When the resin composition of the present invention contains a mold release agent, the content thereof is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polycarbonate resin (A). When the content of the release agent is in the above range, the hydrolysis resistance is not lowered and the release effect can be obtained, which is preferable.

<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 an organic sulfonic acid metal salt and a silicone compound are suitable.

Examples of the organic sulfonic acid metal salt for the flame retardant include an aliphatic sulfonic acid metal salt and an aromatic sulfonic acid metal salt, and these may be used alone or in combination of two or more. You may. Preferred examples of the metal constituting the organic sulfonic acid metal salt include alkali metal and alkaline earth metal, and examples of the alkali metal and alkaline earth metal include sodium, lithium, potassium, rubidium, cesium, beryllium and magnesium. , Calcium, strontium, barium and the like.

The aliphatic sulfonate is preferably a fluoroalkane-metal sulfonic acid salt, and more preferably a perfluoroalkane-metal sulfonic acid salt. Examples of the fluoroalcan-sulfonic acid metal salt preferably include an alkali metal salt and an alkaline earth metal salt, and more preferably an alkali metal salt and an alkaline earth metal of fluoroalcan sulfonic acid having 4 to 8 carbon atoms. Examples include salt. Specific examples of the fluoroalkane-metal sulfonate include perfluorobutane-sodium sulfonate, perfluorobutane-potassium sulfonate, perfluoromethylbutane-sodium sulfonate, perfluoromethylbutane-potassium sulfonate, perfluorooctane. -Sodium sulfonate, perfluorooctane-potassium sulfonate and the like.

Further, as the aromatic sulfonic acid metal salt, preferably, an alkali metal salt, an alkaline earth metal salt and the like can be mentioned. Specific examples of the aromatic sulfonic acid alkali metal salt and the 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 diphenylsulfon-3-sulfonic acid, potassium salt of diphenylsulfon-3-sulfonic acid, sodium salt of 4,4'-dibromodiphenyl-3-sulfonic acid, 4,4'-dibromophenyl-sulfon Potassium salt of -3-sulfonic acid, 4-chloro-4'-nitrodiphenylsulfone-Calcium salt of-3-sulfonic acid, disodium salt of diphenylsulfon-3,3'-disulfonic acid, diphenylsulfon-3,3' − Examples include the dipotassium salt of disulfonic acid.

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), and 0. It is more preferably 02 to 2 parts by mass, and further preferably 0.03 to 1 part by mass. When the content of the organic sulfonic acid metal salt as the flame retardant is in the above range, the resin composition has flame retardancy and good thermal stability, which is preferable. 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 too small, sufficient flame retardancy cannot be obtained.

As the silicone compound for the flame retardant, the polyorganosiloxane having a linear or branched structure described in JP-A-2006-169451 is preferable. The organic group contained in the polyorganosiloxane includes hydrocarbons such as alkyl groups and substituted alkyl groups having 1 to 20 carbon atoms or vinyl and alkenyl groups, cycloalkyl groups, and aromatic hydrocarbon groups such as phenyl and benzyl. It is selected from among.
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 the present invention contains these silicone compounds for flame retardants, the content thereof is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). When the content of the silicone compound as the flame retardant is in the above range, the flame retardancy is improved without impairing the transparency, appearance, elastic modulus and the like, which is preferable.

The organic sulfonic acid metal salt and the silicone compound may be used in combination.

<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 and 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-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10 -Tetraoxaspiro [5,6] undecane and the like. Of 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 the present invention contains an antioxidant, the content thereof is preferably 0.02 to 0.5 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). Within this range, the antioxidant property can be improved without impairing the effect of the present invention, which is preferable.

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

Specific examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, and 2-hydroxy-4-dodecyloxy-benzophenone. , 2-Hydroxy-4-octadesiloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2', 4,4 '-Tetrahydroxy-benzophenone and the like can be mentioned.

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

Specific examples of the phenyl salicylate-based ultraviolet absorber include phenylsultylate, 2,4-ditershari-butylphenyl-3,5-ditershari-butyl-4-hydroxybenzoate and the like.
Specific examples of the hindered amine-based ultraviolet absorber include bis (2,2,6,6-tetramethylpiperidine-4-yl) sebacate and the like.

One of these may be used alone, or two or more thereof may be used in combination.

When the resin composition of the present invention contains these other ultraviolet absorbers, the content thereof is the same as that in the above-mentioned ultraviolet absorbers, and the content thereof is the above-mentioned malonic acid ester-based ultraviolet absorber and oxalate ester-based. The total amount of the total with the ultraviolet absorber is preferably 0.001 to 1 part by mass, more preferably 0.005 to 0.8 part by mass, based on 100 parts by mass of the polycarbonate resin (A), and is 0. It is more preferably 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 the other resin components include polystyrene resin, high-impact polystyrene resin, and hydrogenated polystyrene resin. , Polyacrylic styrene resin, styrene-maleic anhydride copolymer, ABS resin, AS resin, AES resin, ASA resin, SMA resin, polyalkyl methacrylate resin, (meth) acrylate copolymer, polymethacrylic methacrylate resin, polyphenyl Ether resin, amorphous polyalkylene terephthalate resin, polyester resin, amorphous polyamide resin, poly-4-methylpentene-1, cyclic polyolefin resin, amorphous polyarylate resin, polyether sulfone, styrene-based thermoplastic elastomer , Olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, and other thermoplastic elastomers. One of these may be used alone, or two or more thereof may be mixed and used.

However, while exhibiting the original excellent properties of the polycarbonate resin (A), the phosphorescent material (B), the metal oxide-coated plate-like filler (C), the phosphate stabilizer (D), and the hydrogensiloxane (E) When 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) in that the effect of the present invention can be remarkably obtained by blending. Is preferable.

<Others>
In addition to the above components, the resin composition of the present invention may contain an antistatic agent, an anti-fog agent, a lubricant, an anti-blocking agent, a fluidity improver, and a plasticizer, as long as the object of the present invention is not impaired. , Dispersant, antibacterial agent, etc. 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 a conventionally known method and melt-kneading. Specific mixing methods include a polycarbonate resin (A), a phosphorescent material (B), a metal oxide-coated plate-like filler (C), a phosphate-based stabilizer (D), and a 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 and a Henschel mixer, and then a Banbury mixer, a roll, a plastic pender, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader, etc. There is a method of melt-kneading using.

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

As a molding method for producing a molded product of the present invention obtained 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 method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold Molding method used, foam molding (including supercritical fluid), insert molding, in-mold coating (IMC) molding method, extrusion molding method, sheet molding method, thermal molding method, rotary molding method, laminated molding method, press molding method And so on.

[Use]
The molded product of the present invention formed by molding the polycarbonate resin composition of the present invention has excellent design and can be commercialized without painting, and is used for electrical / electronic equipment, OA equipment, and information terminals. It can be applied to various uses such as equipment, mechanical parts, home appliances, vehicle parts, building materials, various containers, play equipment, toys, leisure goods / sports goods, cosmetics, accessories, stationery and other miscellaneous goods.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded.
The constituent components of the resin composition used in the following Examples and Comparative Examples are as follows.

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

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

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: "DOWN CORNING TORAY SH1107 FLUID" manufactured by Toray Dow Corning (methylhydrodienesiloxane)

<Release agent>
VPG861: "Roxyol VPG861" manufactured by Emery Oreo Chemicals Japan (pentaerythritol tetrastearilate)

[Examples 1 to 11 and Comparative Examples 1 to 3]
Polycarbonate resin and various additives are mixed in the ratio shown in Table 3, mixed with a tumbler for 20 minutes, and then cylinder temperature is 280 ° C. by a single-screw extruder with a vent (“VS-40” manufactured by Tanabe Plastic Co., Ltd.) with a screw diameter of 40 mm. , Kneaded at a screw rotation speed of 80 rpm, and the extruded strands were cut to prepare pellets.
The obtained pellets are dried at 120 ° C. for 5 hours, and then injected by an injection molding machine (“Si80-6” manufactured by Toyo Kinzoku Co., Ltd.) under the 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 obtained pellets or test pieces were evaluated as follows, and the results are shown in Table 3.

(1) Flow value (Q value)
The flow value (Q value) of the pellet was evaluated by the method described in JIS K7210 Annex C. The measurement was performed using a "Flow Tester CFD500D" manufactured by Shimadzu Corporation, using a die with a hole diameter of 1.0 mmφ and a length of 10 mm, and ^{was discharged under the conditions of a test temperature of 278 ° C., a test force of 160 kg / cm 2} , and a residual heat time of 420 sec. The amount of molten resin (unit: cc / sec) was measured.

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

(3) Initial hue A color difference meter (Nippon Electric Co., Ltd.) is used for the 3 mm thick part of the test piece (50 mm (width) x 90 mm (length), 1 mm, 2 mm, and 3 mm thick three-stage plate) obtained by injection molding. L * and b * were measured under the following conditions using "SE6000" manufactured by Color Industry Co., Ltd.). The smaller the b * value, the less yellowish the color, and the larger the L * value, the brighter the reflected light and the better the brightness. The b * value is preferably 7.7 or less, and the L * value is preferably 80 or more.
Reflection _{measurement: D 65} light source 10 degrees perimetry port: 30Fai
Sample holder: White
In addition, the appearance was visually observed, and the initial hue was evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: No yellow B: Slightly yellow C: No yellow D: Black

(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 (sense of brightness) immediately after the light is irradiated and the light is blocked and 60 minutes after the light is blocked is examined by visual observation of the appearance and evaluated according to the following criteria. bottom.
<Evaluation criteria>
⊚: Very bright and the outline of the test piece can be clearly confirmed ○: Normal brightness and the outline of the test piece can be confirmed △: Blurred, but the outline of the test piece can be slightly confirmed Yes x: The outline of the test piece can hardly be confirmed

From Table 3, the present invention of Examples 1 to 11 in which the phosphorescent material (B), the metal oxide-coated plate-like filler (C), and the phosphate-based stabilizer (D) are blended in a predetermined ratio with the polycarbonate resin (A). The resin composition has high afterglow brightness, high L * value (brightness (whiteness)), low b * value, suppressed yellowing, and improved initial hue while maintaining phosphorescence. You can see that it has been done.

On the other hand, the initial hues are inferior in Comparative Examples 1 to 3 in which the metal oxide-coated plate-like filler (C) is not blended.
From the comparison between Comparative Example 1 and Examples 1 to 6, the comparison between Comparative Example 2 and Examples 7 to 9, and the comparison between Comparative Example 3 and Examples 10 to 11, there is a difference in afterglow brightness. However, in the present invention, it can be seen that the phosphorescent property of the phosphorescent material (B) is not impaired even if the metal oxide-coated plate-like filler (C) is blended.

Claims (9)

_{1 to 30 parts by mass of the phosphorescent material (B) having an average particle diameter D 50} of 1 μm or more and less than 100 μm and 0.1 to 5 parts by mass of the metal oxide-coated plate-like filler (C) with respect to 100 parts by mass of the polycarbonate resin (A). A polycarbonate resin composition containing 0.01 to 1 part by mass of one or more phosphate-based stabilizers (D) selected from alkyl acid phosphate, alkenyl acid phosphate and metal salts thereof. ,
The metal oxide-coated plate-like filler (C) is obtained by forming a coating layer containing titanium oxide and tin oxide on a base material made of mica and not containing silicon oxide.
A polycarbonate resin composition having a mass ratio ((C) / (B) mass ratio) of the metal oxide-coated plate-like filler to the phosphorescent material (B) of 0.01 to 0.5. In claim 1, the metal oxide-coated plate-like filler (C) contains 65 to 83.5% by mass of a base material, 15 to 33.5% by mass of titanium oxide, and 0.5 to 2% by mass of tin oxide. A polycarbonate resin composition comprising. The polycarbonate resin composition according to claim 1, wherein the coating layer of the metal oxide-coated plate-like filler (C) further contains aluminum hydroxide and zirconium oxide. In claim 3, the metal oxide-coated plate-like filler (C) contains 65.5 to 83.9% by mass of a base material, 15 to 28.5% by mass of titanium oxide, and 0.1 to 2% by mass of tin oxide. %, 0.5 to 2% by mass of aluminum hydroxide, and 0.5 to 2% by mass of zirconium oxide. The polycarbonate resin composition according to any one of claims 1 to 4, 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 is an alkyl group or an alkenyl group having 9 to 30 carbon atoms, and n represents an integer of 1 or 2. When n is 1, the two Rs may be the same or different. It may be one.) The polycarbonate resin composition according to claim 5, wherein R in the formula (I) is an alkyl group or an alkenyl group having any of 13, 18, and 24 carbon atoms. In claim 6, the phosphate-based 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 present.
O = P (OH) _n (OC ₁₈ H ₃₇ ) _3-n ... (II) The polycarbonate according to any one of claims 1 to 7, further containing 0.003 to 0.15 parts by mass of hydrogensiloxane (E) with respect to 100 parts by mass of the polycarbonate resin (A). Resin composition. A molded product obtained by molding the polycarbonate resin composition according to any one of claims 1 to 8.