JP2015096566A - Luminous transparent resin composition and molded body thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a luminous transparent resin composition emitting with sparkling luminance as stars in the night sky rather than simple luminous luminance in a dark place during light cutoff, and exhibiting beautiful brilliant appearance in the dark place.SOLUTION: There is provided a luminous transparent resin composition containing 100 pts.mass of a transparent resin (A), 0.01 to 5 pts.mass of a luminous material having an average particle diameter Dof 100 to 500 μm (B) and 0.01 to 5 pts.mass of a brilliant pigment having an average particle diameter Dof 50 to 200 μm (C). The transparent resin (A) preferably contains an aromatic polycarbonate resin of 50 to 100 mass% and a (meth)acrylate copolymer of 0 to 50 mass%. Using one having a larger particle diameter than conventional ones as the luminous material (B) provides extremely beautiful luminance which cannot be obtained with luminous materials having a small particle diameter during light cutoff. Appearance deterioration by blending the luminous material (B) having a large particle diameter is improved by blending the brilliant pigment (C).

Description

  The present invention relates to a phosphorescent transparent resin composition and a molded article thereof, and more particularly, it exhibits a bright afterglow like a star in the night sky in a dark place and has a beautiful appearance with a brilliant appearance even in a bright place. The present invention relates to a phosphorescent transparent resin composition exhibiting the above and a molded article formed by molding this phosphorescent transparent 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 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.

  For example, Patent Document 1 proposes a light emitting member made of a phosphorescent substance, a fluorescent substance, and a transparent resin. This Patent Document 1 does not describe the particle size and blending amount of the phosphorescent substance.

  Patent Document 2 proposes a polycarbonate resin composition in which phosphorescent aluminate-based phosphor particles are blended with a polycarbonate resin. In Patent Document 2, phosphorescent phosphor particles are those having an average particle diameter of 10 to 20 μm including particles having a particle diameter of less than 10 μm in a proportion of 40% by mass or less and particles having a particle diameter of more than 50 μm in an amount of 10% by mass or less. In addition, it is described that it is not preferable to contain many particles having a particle diameter exceeding 50 μm.

  Patent Document 3 proposes a polycarbonate resin composition in which a light diffusing agent having an average particle diameter of 1 to 10 μm and a phosphorescent agent having an average particle diameter of 1 to 20 μm are blended with a polycarbonate resin. Patent Document 3 describes that when the average particle size of the phosphorescent agent is larger than 20 μm, the light emitting effect by the combined use with the light diffusing agent cannot be obtained.

  As described above, various resin compositions containing a phosphorescent material have been proposed in the past. However, the particle size of the phosphorescent material to be used is as small as 50 μm or less, and the average particle size is 100 μm or more. A phosphorescent material having a large diameter is not blended.

  In addition, although the polycarbonate resin composition which mix | blended the luster pigment used by this invention is proposed by patent document 4, it has reported conventionally that the luster pigment improves the external appearance deterioration by the fine unevenness | corrugation of the molded object surface. Has not been made.

JP 2005-146125 A JP 2005-82647 A JP 2008-74952 A JP 2012-251083 A

  In recent years, phosphorescent materials that emit light even in the dark for the purpose of improving design and providing functionality and novelty in all fields, including playground equipment for toys, toys, laptop computers, and mobile phones. At that time, road signs are used in fields that require a high degree of design, playfulness, and taste, such as entertainment equipment, toys, laptop computers, and mobile devices such as mobile phones. It is desired to emit light more beautifully so as to stimulate the customer's desire to purchase, not just as a phosphorescent light emitter.

  The present invention is a phosphorescent transparent resin composition containing a phosphorescent material, which emits light with a sparkle like a star in the night sky instead of a simple phosphorescent light emission at the time of light blocking, Then, let it be a subject to provide the luminous storage transparent resin composition which exhibits the beautiful external appearance of glitter, and its molded object.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a phosphorescent material having a particle size larger than that conventionally used, so that the phosphorescent material having a small particle size can be used when light is blocked. It has been found that it is possible to obtain a very beautiful shine that cannot be obtained when using a material.
However, by using a material with a particle size larger than that of a commonly used phosphorescent material, it is possible to obtain a sparkle like a star in the night sky in a dark place. As a result of the slight unevenness formed on the surface of the molded product due to the large phosphorescent material, the reflection of light by this unevenness gives the appearance as if fine dust adhered and was lightly soiled, which is not preferable as a product Was also confirmed.
As a result of intensive studies to eliminate the deterioration of the appearance due to such surface irregularities, the present inventors have formulated a glitter pigment together with the phosphorescent material, resulting in the brightness of the glittering pigment due to the phosphorescent material. It has been found that irregularly reflected light on the surface irregularities to be masked can improve the poor appearance due to the surface irregularities.

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

[1] 100 parts by mass of transparent resin (A), phosphorescent material (B) having an average particle diameter D ₅₀ of 100 to 500 μm, 0.01 to 5 parts by mass, and a bright pigment having an average particle diameter D _{50 of 50} to 200 μm (C) A phosphorescent transparent resin composition comprising 0.01 to 5 parts by mass.

[2] The phosphorescent transparent resin composition according to [1], wherein the transparent resin (A) contains a polycarbonate resin.

[3] The phosphorescent transparent resin according to [1], wherein the transparent resin (A) contains 50 to 100% by mass of an aromatic polycarbonate resin and 0 to 50% by mass of a (meth) acrylate copolymer. Composition.

[4] In any one of [1] to [3], the phosphorescent material (B) is SrAl ₂ O ₄ : Eu, Dy, Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy, and CaAl ₂ O ₄ : Eu, A phosphorescent transparent resin composition, which is one or more selected from the group consisting of Nd.

[5] The phosphorescent transparent resin composition according to any one of [1] to [4], wherein the glitter pigment (C) is flaky glass on which a metal or metal oxide film is formed.

[6] A molded article obtained by molding the luminous luminous resin composition according to any one of [1] to [5].

According to the present invention, as the phosphorescent material (B), a phosphorescent material having a particle size larger than that conventionally used is blended with the transparent resin (A) at a predetermined ratio, so that the phosphorescent material (B) is simply phosphorescent at the time of light blocking. It is possible to provide a phosphorescent transparent resin composition that emits light with a very beautiful shine, such as a star in the night sky, and a molded product thereof.
In addition, the appearance problem due to the surface irregularities of the molded product due to the use of the phosphorescent material (B) having a large particle diameter is improved by blending the glitter pigment (C), so that the glitter pigment (C ) To give a beautiful appearance.

  The phosphorescent transparent resin composition of the present invention and the molded product thereof are very excellent in the brilliancy in a bright place and the design of phosphorescent light emission in a dark place. Not only road signs and signboards, but also mobile devices such as entertainment equipment, toys, laptops, mobile phones, etc., product displays, sign buttons in car interiors and buildings, clock faces, accessories, etc. It can be applied to a wide range of uses as housings, switches, buttons, etc. in the fields of stationery, sports equipment, and various electrical, electronic, and OA equipment. Can be granted.

It is a photograph which shows the external appearance at the time of light irradiation of the test piece of Example 1 (large particle size + metashine) and Comparative Example 2 (large particle size). It is a photograph which shows the external appearance at the time of light irradiation of the test piece of Example 1 (large particle size + metashine) and Comparative Example 2 (large particle size). It is a photograph which shows the light emission state at the time of light interception of the test piece of Example 1 (large particle size + metashine) and Comparative Example 2 (large particle size).

  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.

[1] Luminous Transparent Resin Composition The luminous phosphorous resin composition of the present invention (hereinafter sometimes referred to as “the resin composition of the present invention”) is 100 parts by mass of transparent resin (A) and average particles. It contains 0.01 to 5 parts by mass of a phosphorescent material (B) having a diameter D ₅₀ of 100 to 500 μm and 0.01 to 5 parts by mass of a bright pigment (C) having an average particle diameter D _{50 of 50} to 200 μm. It is characterized by.

[Transparent resin (A)]
As the transparent resin (A) used in the present invention, for example, polystyrene resin, high impact polystyrene resin, 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, polycarbonate resin, amorphous polyalkylene terephthalate resin, polyester resin, amorphous polyamide resin, poly -4-methylpentene-1, cyclic polyolefin resin, amorphous polyarylate resin, polyether sulfone, styrene thermoplastic elastomer, olefin thermoplastic elastomer, polyamide thermoplastic elastomer, Ester thermoplastic elastomers, thermoplastic elastomers such as polyurethane-based thermoplastic elastomers Kyora. These may be used alone or in combination of two or more. Among these, from the viewpoint of transparency, impact resistance, heat resistance, and the like, polycarbonate resins, particularly those having aromatic polycarbonate resin as the main constituent resin are preferable. Here, the main constituent resin means that the ratio of polycarbonate resin such as aromatic polycarbonate resin in the transparent resin (A) is usually 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more. Means that.

  Resin used together with polycarbonate resin such as aromatic polycarbonate resin as the main constituent resin is polystyrene resin, styrene-maleic anhydride copolymer, ABS resin, AS resin, AES resin, ASA resin, polyphenylene ether resin, poly One type or two or more types such as a methacrylic methacrylate resin, a (meth) acrylate copolymer, and a polyester resin can be used, and the form may be an alloy or a copolymer as long as it maintains transparency.

Among these, the (meth) acrylate copolymer is effective for improving the surface hardness of the obtained molded body and can be suitably used.
Hereinafter, an aromatic polycarbonate resin suitable as the transparent resin (A) in the present invention and a (meth) acrylate copolymer suitably used together with the aromatic polycarbonate resin will be described.

<Aromatic polycarbonate resin>
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. From the viewpoint of moldability, strength, etc., the molecular weight of the aromatic polycarbonate resin is measured by gel permeation chromatography. The weight average molecular weight (Mw) in terms of polycarbonate (PC) is 15,000 to 40,000, preferably 15,000 to 30,000. As described above, when the weight average molecular weight is 15,000 or more, the mechanical strength tends to be further improved, and this is more preferable when used for applications requiring high mechanical strength. On the other hand, when the weight average molecular weight is 40,000 or less, for example, when used in combination with the (meth) acrylate copolymer described later, the dispersibility of the (meth) acrylate copolymer is improved and the fluidity is lowered. Tends to be further suppressed and improved, and is more preferable from the viewpoint of improving the moldability.

  The weight average molecular weight of the aromatic polycarbonate resin is preferably 17,000 to 30,000, particularly preferably 19,000 to 27,000. Further, two or more types of aromatic polycarbonate resins having different weight average molecular weights may be mixed. In this case, an aromatic polycarbonate resin having a weight average molecular weight outside the above preferred range may be mixed. In this case, the weight average molecular weight of the mixture is preferably within the above range.

<(Meth) acrylate copolymer>
As the (meth) acrylate copolymer, those containing an aromatic (meth) acrylate unit and a methyl methacrylate unit are preferable.
In the present invention, “(meth) acrylate” refers to one or both of “acrylate” and “methacrylate”. Further, the “unit” refers to a structural portion derived from a raw material monomer used when a (meth) acrylate copolymer is produced by copolymerizing monomers.

  The aromatic (meth) acrylate, which is a monomer constituting the aromatic (meth) acrylate unit, refers to a (meth) acrylate having an aromatic group in the ester moiety. Examples of the aromatic (meth) acrylate include phenyl (meth) acrylate and benzyl (meth) acrylate. These may be used alone or in combination of two or more. Of these, phenyl methacrylate and benzyl methacrylate are preferable, and phenyl methacrylate is more preferable. When the (meth) acrylate copolymer has an aromatic (meth) acrylate unit, the transparency of the resin composition obtained by mixing with the aromatic polycarbonate resin can be improved.

  The monomer constituting the methyl methacrylate unit is methyl methacrylate. The methyl methacrylate unit has an effect of favorably dispersing the aromatic polycarbonate resin and the (meth) acrylate copolymer, and can improve the surface hardness of the obtained molded body.

  The (meth) acrylate copolymer according to the present invention has a mass ratio of aromatic (meth) acrylate units to methyl methacrylate units (aromatic (meth) acrylate units / methyl methacrylate units) of 5 to 80/20 to 95. That is, it contains 5 to 80% by mass of aromatic (meth) acrylate units and 20 to 95% by mass of methyl methacrylate units (provided that the total of aromatic (meth) acrylate units and methyl methacrylate units is 100% by mass). %). If the content of the aromatic (meth) acrylate unit in the (meth) acrylate copolymer is 5% by mass or more and the content of the methyl methacrylate unit is 95% by mass or less, a high addition of the (meth) acrylate copolymer If the transparency is maintained in the region and the content of aromatic (meth) acrylate units is 80% by mass or less and the content of methyl methacrylate units is 20% by mass or more, the compatibility with the aromatic polycarbonate resin is high. However, since the transferability to the surface of the resulting molded body does not decrease, the surface hardness does not decrease.

  Moreover, in the high addition area | region of a (meth) acrylate copolymer, since high surface hardness is expressed, maintaining further transparency, a (meth) acrylate copolymer is aromatic (meth) acrylate unit 8 ~. It is preferable to contain 50 mass% and 50-92 mass% of methyl methacrylate units (however, the sum total of an aromatic (meth) acrylate unit and a methyl methacrylate unit is 100 mass%).

  If the content of aromatic (meth) acrylate units in the (meth) acrylate copolymer is 8% by mass or more and the content of methyl methacrylate units is 92% by mass or less, compatibility with the aromatic polycarbonate resin is achieved. Since it is not too high and the migration to the surface of the molded product does not decrease, the surface hardness does not decrease, the content of aromatic (meth) acrylate units is 50% by mass or less, and the content of methyl methacrylate units is 50% by mass or more. If so, the transparency is maintained in the high addition region of the (meth) acrylate copolymer.

Moreover, the weight average molecular weight of the (meth) acrylate copolymer is preferably 5,000 to 30,000, more preferably 10,000 to 25,000, and particularly preferably 13,000 to 20,000. When the weight average molecular weight of the (meth) acrylate copolymer is 5,000 to 30,000, the dispersibility in the aromatic polycarbonate resin is good, and the surface hardness is effectively improved while maintaining transparency. Can be made.
The weight average molecular weight (Mw) of the (meth) acrylate copolymer is a polystyrene (PS) equivalent value measured by gel permeation chromatography using chloroform or tetrahydrofuran (THF) as a solvent.

  As a polymerization method of the monomer for obtaining the (meth) acrylate copolymer used in the present invention, a known method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method or a bulk polymerization method may be used. it can. A suspension polymerization method and a bulk polymerization method are preferable, and a suspension polymerization method is more preferable. In addition, additives necessary for polymerization can be appropriately added as necessary, and examples of the additive include a polymerization initiator, an emulsifier, a dispersant, a chain transfer agent and the like.

  When the transparent resin (A) contains an aromatic polycarbonate resin and a (meth) acrylate copolymer, the transparent resin (A) contains 50 to 95 mass% of the aromatic polycarbonate resin and the (meth) acrylate copolymer 5 It is preferable that it contains ~ 50 mass% (however, the total of the aromatic polycarbonate resin and the (meth) acrylate copolymer is 100 mass%), more preferably the aromatic polycarbonate resin is 50 to 90 mass%. % Of the (meth) acrylate copolymer is 10 to 50% by mass, particularly preferably 55 to 85% by mass of the aromatic polycarbonate resin, and 15 to 45% by mass of the (meth) acrylate copolymer. is there.

  Transparency of the resin matrix by blending the (meth) acrylate copolymer with the aromatic polycarbonate resin when the mass ratio of the aromatic polycarbonate resin and the (meth) acrylate copolymer is within the above range. It is possible to reliably obtain the effect of maintaining the physical property balance while improving the surface hardness and improving the surface hardness.

[Phosphorescent material (B)]
The phosphorescent material absorbs and stores light when irradiated with light such as ultraviolet light and visible light contained in sunlight or artificial light, and is said to emit light even after light irradiation is stopped, that is, in a dark place. It continues to emit light for a predetermined time. 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, MAl _a O _b : X (M is one or more metal elements selected from calcium, strontium and barium. X is an activator, europium, lanthanum, cerium, praseodymium, One or more elements selected from neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, ruthenium, manganese, tin, bismuth, X content is relative to the metal element represented by M Usually, the aluminate compound represented by 10 mol% or less, for example 0.001 to 10 mol%) Can be mentioned. 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 RMg ₂ Al ₁₆ O ₂₇ : Eu, _{RMg 2 Al 16 O 27: Eu} , Mn, RMg 2 Al 10 O 17: Eu, RMg 2 Al 10 O 17: Eu, Mn ( wherein R 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 present invention has an average particle size _{D 50} as the phosphorescent material (B) is characterized by using those 100 to 500 [mu] m. The average particle size D ₅₀ of less than 100μm of the phosphorescent material (B), can not be obtained specific phosphorescent effect of the present invention, when it exceeds 500 [mu] m, unfavorably that impact resistance of the molded body obtained is poor . The average particle diameter of the phosphorescent material (B) is particularly preferably 150 to 450 μm, particularly preferably 200 to 400 μm.

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.
In the case of using two or more kinds of phosphorescent material (B), all the average particle diameter D ₅₀ of the phosphorescent material (B) was used may be within the above range.

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.

  The compounding amount of the phosphorescent material (B) is 0.01 to 5 parts by mass, preferably 0.02 to 4 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the transparent resin (A). is there. 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. As the blending amount of the phosphorescent material (B) is larger, it is possible to obtain a brilliant sparkle like the stars of the night sky according to the present invention, but if the amount is too much, the impact resistance of the resulting molded article is inferior. Become.

[Bright pigment (C)]
The glitter pigment (C) used in the present invention is not particularly limited and may be an inorganic material or an organic material. For example, the following can be used.
(1) Flake glass with a metal or metal oxide coating
(2) Metal powder

  As the flaky glass on which the metal or metal oxide film of (1) is formed, Al, Cr, Ni, Ti, Mg, Ag, Au, Mo, etc. are added to the flaky glass having an average thickness of about 0.1 to 10 μm. And a metal oxide such as titania, silica, tin oxide, iron oxide or the like, and a film having a thickness of about 0.01 to 1 μm formed by chemical vapor deposition or physical vapor deposition.

  As the metal powder (2), particles made of Al, Ni, Ag, Au, Cu or the like can be used.

In the present invention, the bright pigment (C) having an average particle diameter D50 of ₅₀ to 200 [mu] m is used. When the average particle diameter D ₅₀ of the glitter pigment (C) is less than ₅₀ μm, the effect of improving the appearance by blending the glitter pigment (C) cannot be obtained, and when it exceeds 200 μm, the impact resistance of the resulting molded article Sex is reduced. The average particle diameter D ₅₀ of the glitter pigment (C) is particularly preferably about ₅₀ to 180 μm, and particularly preferably about ₅₀ to 150 μm.

Here, the particle diameter of the glitter pigment (C) refers to the length of the portion where the distance between the glitter pigments (C) is the largest when sandwiched between two parallel plates. . The average particle diameter D ₅₀ of the bright pigment (C) is the same meaning as the average particle diameter D ₅₀ of the phosphorescent material of the above (B), it is possible to employ a catalog value for commercially available products.

  As a specific example of the glitter pigment (C), as the metal-coated glass flake pigment, for example, trade name “Metashine MC5150PS” (average particle diameter: manufactured by Nippon Sheet Glass Co., Ltd.) which is a glass flake pigment coated with silver. 150 μm, average thickness: 5 μm), “Metashine MC5090PS” (average particle size: 90 μm, average thickness: 5 μm), “Metashine MC2080PS” (average particle size: 80 μm, average thickness: 1 μm), glass coated with gold A trade name “Metashine MT2080GP” (average particle diameter: 80 μm, average thickness: 1 μm) manufactured by Nippon Sheet Glass Co., Ltd., which is a flake pigment.

  Further, as the metal oxide-coated glass flake pigment, trade name “Miraval 5320 Scientific Gold” (particle size: 10 to 100 μm) manufactured by Merck, which is a glass flake pigment coated with silica, titanium oxide, and tin oxide, “ “Miraval 5321 Scientific Copper” (particle size: 10 to 100 μm), “Miraval 5411 Magic White” (particle size: 20 to 200 μm), “Miraval 5420 Magic Gold” (particle size: 20 to 200 μm), “Miraval 5421 Cop” (Particle size: 20-200 μm), “Miraval 5422 Magic Red” (particle size: 20-200 μm), “Miraval 5423 Magic Lilac” (particle size: 20-200 μm) ), “Miraval 5424 Magic Blue” (particle size: 20 to 200 μm), “Miraval 5426 Magic Green” (particle size: 20 to 200 μm), “Miraval 5411 Starlit White” (particle size: 30 to 300 μm), and titanium oxide “Metashine MC1080RS / RY / RR / RB / RG” (average particle size: 80 μm, average thickness: 1 μm) manufactured by Nippon Sheet Glass Co., Ltd., which is a glass flake pigment coated with tin oxide and iron oxide. Shine MC1120RS / RY / RR / RB / RG ”(average particle size: 120 μm, average thickness: 1 μm),“ Metashine MC1080TY / TZ / TP / TA ”(average particle size: 80 μm, average thickness: 1 μm),“ Metal ” Shine GT5090RS ”(average particle size 90 μm, Hitoshiatsumi 5 [mu] m), and the like.

  As the metal oxide-coated mica pigment, trade name “Iriodin 103 Rutile Sterling Silver” (particle size: 10 to 60 μm) manufactured by Merck Co., Ltd., which is a mica pigment coated with silica, titanium oxide, and tin oxide, “Colorstream T10-”. 06 Royal Damask ”(particle size: 10 to 60 μm) and the like.

  As metal oxide-coated silica pigments, trade names “Firemist Coloration Blue Topaz 9G680D” (particle size: 13 to 180 μm) manufactured by BASF, which are silica pigments coated with titanium oxide and tin oxide, “Firemist Coloration Ruby 9G480D”. (Particle size: 13 to 180 μm).

  Moreover, as an example of a specific metal powder, as aluminum powder, the aluminum flakes or flakes of the vapor deposition aluminum film which vapor-deposited aluminum on the resin film and peeled or integrated the resin film can also be used. As an aluminum flake, the Toyo Aluminum company make brand name "P1415" (average particle diameter: 61 micrometers) can be illustrated.

In the present invention, one of the glitter pigments (C) may be used alone, or two or more of the pigments having different configurations, metal species, or particle sizes may be used in combination.
In the case of using two or more kinds of bright pigment (C), the average particle diameter D ₅₀ of all the bright pigment using (C) may be within the above range.

  The compounding amount of the glitter pigment (C) is 0.01 to 5 parts by mass, preferably 0.05 to 4 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the transparent resin (A). It is. If the blending amount of the glitter pigment (C) is less than the lower limit, the effect of improving the appearance due to blending of the glitter pigment (C) cannot be sufficiently obtained. When the blending amount of the glitter pigment (C) is too large, the impact resistance of the obtained molded article is inferior.

  The total content of the phosphorescent material (B) and the glitter pigment (C) contained in the phosphorescent transparent resin composition of the present invention is 10 parts by mass or less, particularly 100 parts by mass of the transparent resin (A). 5 parts by mass or less is preferable for preventing a reduction in impact resistance of the obtained molded article.

[Other additives]
The phosphorescent transparent 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 flame retardants, heat stabilizers, antioxidants, ultraviolet absorbers, and mold release agents.

<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 transparent 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 fluoroalkane-sulfonic acid metal salts include perfluorobutane-sodium sulfonate, perfluorobutane-potassium 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 is preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the transparent 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 of 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 transparent 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.

<Heat stabilizer>
The resin composition of the present invention may contain a heat stabilizer in order to improve the heat stability. Preferable heat stabilizers include phosphorus heat stabilizers such as phosphites and phosphates.

  Examples of phosphites include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, trinonyl phosphite, tridecyl phosphite, and trioctyl phosphite. , Trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, monobutyl diphenyl phosphite, monooctyl diphenyl phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butyl Phenyl) pentaerythritol phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-tert) Butylphenyl) triesters of phosphorous acid such as octyl phosphite, diesters, monoesters, and the like.

  Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate, tetrakis (2,4-di-). tert-butylphenyl) -4,4-diphenylphosphonite and the like.

  Among the above phosphorus-based heat stabilizers, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol phosphite, bis (2,6-di-tert-butyl-4) -Methylphenyl) pentaerythritol phosphite and tris (2,4-di-tert-butylphenyl) phosphite are preferred. Among them, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite and Tris (2,4-di-t-butylphenyl) phosphite is particularly preferred.

  In addition, a heat stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type.

  When the resin composition of this invention contains a heat stabilizer, it is preferable that the content is 0.005-0.2 mass part with respect to 100 mass parts of transparent resin (A), 0.01- More preferably, it is 0.1 parts by mass. It is preferable for the content of the thermal stabilizer to be in the above-mentioned range since the thermal stability can be improved without causing hydrolysis or the like.

<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 transparent resin (A). This range is preferable because the antioxidant property can be improved without inhibiting the effects of the present invention.

<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. Examples of the ultraviolet absorber 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 this invention contains a ultraviolet absorber, it is preferable that the content is 0.001-1 mass part with respect to 100 mass parts of transparent resin (A), 0.005-0 Is more preferably 8 parts by mass, and still more preferably 0.01 to 0.5 parts by mass. It is preferable for the content of the ultraviolet absorber to be in the above-mentioned range, since the phosphorescent luminance is not lowered by absorption of excitation light, and the weather resistance can be improved without causing bleed out on the surface of the molded body.

<Release agent>
The resin composition of the present invention may contain a release agent.
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, and 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 transparent 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.

<Others>
The resin composition of the present invention includes, in addition to the above components, an antistatic agent, an antifogging agent, a lubricant / antiblocking agent, a fluidity improver, a colorant, as long as the purpose of the present invention is not impaired as necessary. Plasticizers, 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 and melt-kneading each component by a conventionally known method. As a specific mixing method, a predetermined amount of transparent resin (A), phosphorescent material (B), glitter pigment (C), and other additive components blended as necessary is measured, and a tumbler, a Henschel mixer, etc. Examples thereof include a method of melting and kneading using a Banbury mixer, a roll, a plastic pendder, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader and the like after mixing using the various mixers.

[2] Molded product The molded product of the present invention is formed by molding the above-described phosphorescent transparent resin composition of the present invention.

[Molding method]
As a molding method in the case of producing the molded article of the present invention formed by molding the phosphorescent transparent resin composition of the present invention, a conventionally known method for molding a molded product from a thermoplastic resin material is not limited. Applicable. 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 luminous luminous transparent resin composition of the present invention is very excellent in design of light emission at the time of light blocking, and also has a good appearance in a light place. In addition to road signs and signboards, which are common uses of phosphorescent transparent resin compositions, as well as mobile devices such as playground equipment and toys, laptop computers, and mobile phones in entertainment facilities, product displays, car interiors and buildings It can be applied to a wide range of uses as casings, switches, buttons, etc. in the fields of marking buttons, clock faces, accessories, stationery, sports equipment, and various electric / electronic / OA devices.

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.

<Transparent resin (A)>
a-1: Aromatic polycarbonate resin “Iupilon S-3000F” (Mitsubishi Engineering Plastics) (weight average molecular weight = 26800)
a-2: Styrene-maleic anhydride copolymer “XIRAN SZ08250” manufactured by POLYSCOPE (weight average molecular weight = 250,000, content of maleic anhydride units = 8 mass%, glass transition point = 116 ° C.)
a-3: Mitsubishi Rayon Co., Ltd. (meth) acrylate copolymer “methabrene H880” (aromatic (meth) acrylate unit = phenyl methacrylate unit, aromatic (meth) acrylate unit content: 80 mass%, methyl methacrylate unit contained (Rate: 20% by mass, weight average molecular weight = 14600)

<Phosphorescent material (B)>
b-1: Phosphorescent material “G-300M” manufactured by Nemoto Special Chemical Co., Ltd. (chemical composition = SrAl ₂ O ₄ : Eu, Dy, D ₅₀ = 30 μm, emission color = green)
b-2: Phosphorescent material “G-300L250N” manufactured by Nemoto Special Chemical Co., Ltd. (chemical composition = SrAl ₂ O ₄ : Eu, Dy, D ₅₀ = 250 μm, emission color = green)
b-3: Phosphorescent material “G-300L160” manufactured by Nemoto Special Chemical Co., Ltd. (chemical composition = SrAl ₂ O ₄ : Eu, Dy, D ₅₀ = 160 μm, emission color = green)
b-4: Phosphorescent material “GB-300L160” manufactured by Nemoto Special Chemical Co., Ltd. (chemical composition = Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy, D ₅₀ = 160 μm, emission color = blue green)

<Brightness pigment (C)>
c-1: Titanium oxide-coated glass flake pigment “Metashine GT5090RS” manufactured by Nippon Sheet Glass Co., Ltd. (D ₅₀ = 90 μm, average thickness = 5 μm)

[Examples 1 to 11 and Comparative Examples 1 to 15]
A transparent resin and various additives are blended in the ratios shown in Tables 1 to 3, mixed for 20 minutes with a tumbler, and then subjected to a cylinder temperature using 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 70 rpm, and the extruded strand was cut to produce pellets.
The obtained pellets were dried at 120 ° C. for 5 hours, and then injection-molded with an injection molding machine (“S-2000i150B” manufactured by FANUC) under conditions of a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 50 seconds. And various test pieces were prepared.
The following evaluation was performed about the obtained pellet or test piece, and the result was shown to Tables 1-3.

(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) Izod Impact Strength Based on ASTM D256, Izod impact strength (unit: J / m) was measured at a temperature of 23 ° C. for a notched Izod impact test piece (thickness: 3.2 mm).
(3) Tensile strength Tensile strength (unit: MPa) was measured using an ASTM multipurpose test piece (thickness: 3.2 mm) according to the ASTM D638 standard.
(4) Tensile Fracture Point Strain Tensile fracture point strain (unit:%) was measured according to ASTM D638 standard using an ASTM multipurpose test piece (thickness: 3.2 mm).
(5) Flexural modulus and flexural strength Using an ASTM multipurpose test piece (thickness: 6.4 mm), the flexural modulus (unit: MPa) and flexural strength (unit: MPa) were measured according to ASTM D790 standard.
(6) Deflection temperature under load (DTUL)
Using an ASTM multipurpose test piece (thickness: 6.4 mm), the deflection temperature under load (unit: ° C.) at a load of 1.8 MPa was measured in accordance with the ASTM D648 standard.
(7) Surface appearance Three-plate test pieces of 90 mm × 60 mm × thickness 3 mm, 2 mm, and 1 mm were visually observed under visible light and evaluated according to the following criteria.
A: Overall, it has a glittering glitter and exhibits a very good appearance.
B: It has a glittering glitter and exhibits a good appearance.
C: Slightly lustrous, but has a slightly soiled appearance with dust attached.
D: Appears as if a fine dust adheres to it and becomes slightly soiled.
(8) Afterglow brightness The test piece used in the evaluation of the above-mentioned surface appearance was Matsushita Electric Works 'fluorescent lamp magnet light and Matsushita Electric Works' black light blue (FL4BL-B: wavelength 352 nm). After irradiating with ultraviolet rays using the attached device, it was placed in a dark place, and the state of luminous light emission at that time was visually observed and evaluated according to the following criteria.
A: It glows very beautifully like a starry sky and emits light.
B: Emits light with a sparkle like a star in the night sky.
C: Light is emitted, but there is no glitter.
D: No light is emitted.
(9) Pencil Hardness According to JIS K5400, a 90 mm × 50 mm × 1.5 mmt test piece was subjected to 5 scratch tests to evaluate pencil hardness.

  In addition, the photograph which shows the external appearance (state when light is irradiated) of the test piece in Example 1 (large particle size + metashine) and Comparative Example 2 (large particle size) is shown in FIGS. Moreover, the photograph of the test piece at the time of the afterglow luminance evaluation (at the time of light interruption) is shown in FIG.

These results indicate that the average particle diameter D ₅₀ using a large phosphorescent material having a particle diameter of 100 to 500 [mu] m (B), obtained in the case of using a small phosphorescent material particle size conventionally used for (B) It is not possible to obtain an afterglow luminance with a very beautiful shine, and in this case, by using a predetermined amount of the brilliant pigment (C) in combination, it is possible to obtain a particle size with a beautiful luminescence. It turns out that the bad surface appearance at the time of using a big luminous material (B) can be eliminated.

Claims (6)

100 parts by weight of transparent resin (A), 0.01 to 5 parts by weight of phosphorescent material (B) having an average particle diameter D ₅₀ of 100 to 500 μm, and a glittering pigment (C) having an average particle diameter D _{50 of 50} to 200 μm 0.01-5 mass parts is contained, The luminous luminous transparent resin composition characterized by the above-mentioned.   The luminous resin composition according to claim 1, wherein the transparent resin (A) contains a polycarbonate resin.   In Claim 1, the said transparent resin (A) contains 50-100 mass% of aromatic polycarbonate resins, and 0-50 mass% of (meth) acrylate copolymers, The luminous translucent transparent resin composition characterized by the above-mentioned. In any one of claims 1 to 3, wherein the phosphorescent material (B) is _{SrAl 2 O 4: Eu, Dy} , Sr 4 Al 14 O 25: Eu, Dy, and CaAl ₂ O _4: Eu, consisting Nd A phosphorescent transparent resin composition, which is one or more selected from the group.   5. The phosphorescent transparent resin composition according to claim 1, wherein the glitter pigment (C) is a flaky glass having a metal or metal oxide film formed thereon.   The molded object formed by shape | molding the luminous translucent resin composition of any one of Claim 1 thru | or 5.

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