JP2017025137A - Luminous polycarbonate resin composition and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a luminous polycarbonate resin composition which improves a problem of darkening of the luminous polycarbonate resin composition obtained by blending a polycarbonate resin with a luminous material, and can provide a molded article that has excellent color tone and is excellent in luminous properties.SOLUTION: There is provided a luminous polycarbonate resin composition which contains 1-30 pts.mass of a luminous material, 0.01-1 pts.mass of alkyl acid phosphate represented by formula (I): O=P(OH)(OR), and 0.1-2 pts.mass of a fatty acid ester compound with respect to 100 pts.mass of a polycarbonate resin. The alkyl acid phosphate as a stabilizer and the fatty acid ester compound as a release agent are used together and blended with each other at a predetermined ratio, and thus, an excellent resin composition free from darkening can be obtained. In the formula (I), R is an alkyl group having 9 to 30 carbon atoms, and n represents an integer of 1 or 2. When n is 1, two R may be the same or different.SELECTED DRAWING: None

Description

  The present invention relates to a phosphorescent polycarbonate resin composition and a molded product thereof, and more specifically, a phosphorescent polycarbonate resin composition in which the darkening problem of a phosphorescent polycarbonate resin composition in which a phosphorescent material is blended with a polycarbonate resin is improved, and this The present invention relates to a molded product obtained by molding a phosphorescent polycarbonate resin composition.

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

However, a polycarbonate resin composition obtained by blending a phosphorescent material in a polycarbonate resin and melt-kneading produces darkness, and further darkening occurs when molding this, and the resulting molded product is gray to dark gray There was a problem that the aesthetics were impaired and the commercial value was significantly reduced.
In addition, if the resin composition is dark and the molded product is dark gray, the light absorption efficiency and light emission efficiency are also reduced, so that the phosphorescent performance (emission luminance and afterglow time) commensurate with the amount of phosphorescent material is obtained. There is also a problem that cannot be done.

  In order to solve this problem, Patent Document 1 uses aluminate-based phosphorescent phosphor particles having a specific particle size distribution and uses phosphorous acid to stabilize the molecular weight and hue of the resin during processing. Although it has been proposed to incorporate an ester, the effect of improving darkening is still not sufficient. Patent Documents 2 and 3 propose that an organic silane compound and / or a silicone compound be blended. However, a siloxane-based heat stabilizer can suppress darkening, but it may be cloudy or silvery. It remains as a problem that the appearance is damaged by generation.

  In order to suppress the decomposition of the polycarbonate resin due to heating by lowering the processing temperature of the polycarbonate resin, it has also been studied to alloy with the ABS resin as a resin component. Since it becomes opaque, even if darkening is suppressed, the light emission luminance by the phosphorescent material is lowered.

JP 2005-82647 A JP 2009-215415 A JP 2010-159319 A

  The present invention relates to a phosphorescent polycarbonate resin composition that improves the darkening problem of a phosphorescent polycarbonate resin composition in which a phosphorescent material is blended with a polycarbonate resin, provides a molded article having a good hue and excellent phosphorescence, and the molded article thereof It is an issue to provide.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have become darkened by combining the alkyl acid phosphate as a stabilizer and the fatty acid ester compound as a mold release agent in combination at a predetermined ratio. It was found that a good resin composition free from the above could be obtained.

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

[1] It is characterized by containing 1 to 30 parts by mass of a phosphorescent material, 0.01 to 1 part by mass of an alkyl acid phosphate, and 0.1 to 2 parts by mass of a fatty acid ester compound with respect to 100 parts by mass of a polycarbonate resin. A phosphorescent polycarbonate resin composition, wherein the alkyl acid phosphate is represented by the following formula (I):
O = P (OH) _n (OR) _3-n (I)
(In the formula (I), R represents an alkyl group having 9 to 30 carbon atoms, and n represents an integer of 1 or 2. When n is 1, two Rs may be the same or different. May be.)

[2] In [1], the phosphorescent material is selected from the group consisting of SrAl ₂ O ₄ : Eu, Dy, Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy, and CaAl ₂ O ₄ : Eu, Nd, or A phosphorescent polycarbonate resin composition characterized by being two or more.

[3] The phosphorescent polycarbonate resin composition according to [1] or [2], wherein R in the formula (I) is an alkyl group having 13, 18, or 24 carbon atoms.

[4] The phosphorescent polycarbonate resin composition according to any one of [1] to [3], wherein the fatty acid ester compound is pentaerythritol tetrastearate and / or stearyl stearate.

[5] The phosphorescent polycarbonate resin composition according to any one of [1] to [4], further containing an organic phosphor in an amount of 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the polycarbonate resin. object.

[6] In [5], the organic phosphor is one or more selected from the group consisting of naphthalene compounds, perylene compounds, quinoline compounds, coumarin compounds, benzoxazole derivatives, and rare earth complex compounds. A phosphorescent polycarbonate resin composition characterized by that.

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

  According to the present invention, the darkness of the resin composition in which a phosphorescent material is blended with a polycarbonate resin is improved, the hue is good and the appearance is excellent, and the original phosphorescence performance due to the blending of the phosphorescent material can be sufficiently exerted. A high molded article can be provided.

  The molded product of the present invention formed by molding the phosphorescent polycarbonate resin composition of the present invention is excellent in hue and phosphorescent performance, and can be excellent in mechanical strength, heat resistance, etc. , Merchandise displays, LCD backlights, lighting displays, luminaire covers, traffic signs, safety signs, night visibility improving parts, signboards, screens, reflectors, meter parts and other automotive parts, entertainment facilities playground equipment and toys, notebooks Cases and switches in the fields of mobile devices such as personal computers and mobile phones, marking buttons in automobiles and buildings, clock dials, accessories, stationery, sports equipment, various electrical, electronic and OA equipment It can be used for a wide range of applications such as buttons.

  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] Phosphorescent polycarbonate resin composition The phosphorescent polycarbonate resin composition of the present invention (hereinafter sometimes referred to as “the resin composition of the present invention”) is a phosphorescent material 1 to 100 parts by mass of the polycarbonate resin. It contains 30 parts by mass, 0.01 to 1 part by mass of an alkyl acid phosphate represented by the following formula (I), and 0.1 to 2 parts by mass of a fatty acid ester compound.
O = P (OH) _n (OR) _3-n (I)
(In the formula (I), R represents an alkyl group having 9 to 30 carbon atoms, and n represents an integer of 1 or 2. When n is 1, two Rs may be the same or different. May be.)

[Action mechanism]
The inventors of the present invention are that the resin composition in which the phosphorescent material is blended with the polycarbonate resin generates darkening at the time of melt kneading and molding, because the hardness of the phosphorescent material particles is high, when melt kneading with an extruder. It is thought that the cause is that the barrel or screw surface is worn and the metal pieces generated by this wear are mixed into the resin, and that the rare earth element that is a constituent of the phosphorescent material decomposes the polycarbonate resin under high temperature conditions. In order to reduce these two factors, various studies were repeated, using alkyl acid phosphate as a heat stabilizer, using a fatty acid ester compound as a mold release agent, and combining them in a predetermined ratio, It has been found that darkening can be prevented.

That is, the alkyl acid phosphate prevents the polycarbonate resin from decomposing due to the phosphorescent material, and the fatty acid ester compound reduces the friction between the resin composition and the barrel and screw surface of the extruder, and the inner surface of the molding machine. Prevent darkening by preventing contamination.
Conventionally, phosphorous acid esters (Patent Literature 1) and siloxane-based materials (Patent Literatures 2 and 3) have been used as heat stabilizers to be blended in phosphorescent polycarbonate resin compositions. Esters cannot sufficiently prevent the polycarbonate resin from being decomposed by the phosphorescent material. Siloxane-based materials have problems such as white turbidity and silver, and cannot suppress decomposition of the polycarbonate resin.
On the other hand, if it is an alkyl acid phosphate, decomposition | disassembly of polycarbonate resin by a phosphorescent material can be suppressed, without causing the problem of cloudiness or silver.
In addition, many release agents have been proposed, but the inventors of the present application use a fatty acid ester compound, among other conventional release agents, and when this is used in combination with an alkyl acid phosphate, It has been found that a good darkening prevention effect can be obtained without causing appearance defects due to white turbidity or silver.

  In the present invention, as described above, the alkyl acid phosphate is used among the stabilizers, and the fatty acid ester compound is used among the mold release agents. The present invention provides a phosphorescent polycarbonate resin composition having excellent phosphorescent performance and a molded product thereof.

[Polycarbonate resin]
The polycarbonate resin used in the present invention is preferably an aromatic polycarbonate resin from the viewpoints of transparency, impact resistance, heat resistance and the like.
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 use and may be appropriately selected and determined, but from the viewpoint of moldability, strength, etc., the molecular weight of the aromatic polycarbonate resin uses methylene chloride as a solvent, The viscosity average molecular weight calculated from the solution viscosity measured at a temperature of 25 ° C. is preferably 14,000 to 30,000, more preferably 15,000 to 28,000. When the viscosity average molecular weight is within this range, a resin composition that generally has good moldability and gives a molded article having high mechanical strength can be obtained.

  The viscosity average molecular weight of the aromatic polycarbonate resin is preferably 16,000 to 26,000. Two or more types of aromatic polycarbonate resins having different viscosity average molecular weights may be mixed. In this case, an aromatic polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed. In this case, the viscosity average molecular weight of the mixture is preferably within the above range.

[Phosphorescent material]
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 used in the present invention is not particularly limited as long as it has the above-mentioned characteristics. However, sulfide-based phosphorescent materials such as CaS: Bi, CaSrS: Bi, and ZnCdS: Cu, ZnS: Cu, and the like. Zinc sulfide based phosphorescent material, Sr ₂ MgSi ₂ O ₇ : Eu, Dy and other silicic acid based phosphorescent materials, MAl _a O _b : X (M is one or more metal elements selected from calcium, strontium and barium. X Is an activator, one or more elements selected from europium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, ruthenium, manganese, tin, and bismuth. Is usually 10 mol% or less, for example 0.00% with respect to the metal element represented by M. 1-10 mol%.) Aluminate compounds represented by Preferably, from the viewpoint of hydrolysis resistance and afterglow characteristics, it is an aluminate compound represented by MAl _a O _b : X. Examples of the aluminate compound include GMg ₂ Al ₁₆ O ₂₇ : Eu, GMg ₂ Al ₁₆ O ₂₇ : Eu, Mn, GMg ₂ Al ₁₀ O ₁₇ : Eu, GMg ₂ Al ₁₀ O ₁₇ : Eu, Mn (where G is Sr or Ba, which 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, 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.

No particular limitation is imposed on the average particle diameter _{D 50} of the phosphorescent material, 10 to 300 [mu] m, in particular 15 to 100 m, it is preferable that especially 20 to 50 m. If the particle size of the phosphorescent material is too large, the molded article tensile elongation at break obtained, because there is a problem that impact strength, appearance or the like is reduced, it is preferable that the average particle diameter D ₅₀ is less than the upper limit. Meanwhile, phosphorescent material generally to the emission characteristic particle size is too small tends to decrease, it is preferable that the average particle size D ₅₀ is lower than the lower limit.

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

  In the present invention, one kind of phosphorescent material may be used alone, or two or more kinds having different chemical compositions and particle sizes may be used in combination.

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

[Alkyl acid phosphate]
The alkyl acid phosphate used in the present invention is represented by the following formula (I).
O = P (OH) _n (OR) _3-n (I)
(In the formula (I), R represents an alkyl group having 9 to 30 carbon atoms, and n represents an integer of 1 or 2. When n is 1, two Rs may be the same or different. May be.)

The alkyl group represented by R in the above formula (I) may be a straight-chain alkyl group or may have a branch, but has 9 to 30 carbon atoms. Iso) nonyl, (iso) decyl, (iso) undecyl, (iso) dodecyl, (iso) tridecyl, (iso) tetradecyl, (iso) pentadecyl, iso (hexadecyl), (iso) heptadecyl, iso (octadecyl) (= (Iso) stearyl), (iso) nonadecyl, (iso) icosyl, (iso) eicosyl, (iso) henecosyl, (iso) docosyl, (iso) tricosyl, (iso) tetracosyl, (iso) pentacosyl, (iso) hexacosyl , (Iso) heptacosyl, (iso) octacosyl, (iso) nonacosyl, and (iso) triacontyl. Here, the description of “(iso) alkyl” means “alkyl” and “isoalkyl”. For example, “(iso) tetracosyl” means “tetracosyl” and “isotetracosyl”.
n is 1 or 2, and may be a mixture thereof.

Among these, as the alkyl acid phosphate, those in which R is an alkyl group having 13 to 24 carbon atoms are preferable. Particularly, the alkyl acid phosphate is represented by the following formula (Ia), and n = 1 (iso) trimethyl in the formula (Ia). A mixture of decyl acid phosphate and n = 2 mono (iso) tridecyl acid phosphate, represented by the following formula (Ib), and n = 1 di (iso) stearyl acid phosphate in formula (Ib) and n = A mixture of mono (iso) stearyl acid phosphate of 2 and represented by the following formula (Ic), where n = 1 di (iso) tetracosyl acid phosphate and n = 2 mono (iso) as a mixture of tetracosyl acid phosphate is preferable _{O = P (OH) n (} OC 13 H 27) 3-n ... (I )
O = P (OH) _n (OC ₁₈ H ₃₇ ) _3-n (Ib)
O = P (OH) _n (OC ₂₄ H ₄₉ ) _3-n (Ic)

  When the carbon number of the alkyl group of R that the alkyl acid phosphate has is 8 or less, it tends to be a gas and becomes a deposit on the mold at the time of molding, thereby reducing productivity. Acid phosphates having an excessively large number of carbon atoms in the alkyl group of R may have a large molecular weight and may not have the effect of preventing darkening commensurate with the blending amount due to the small number of blending moles relative to the blending mass.

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

  The compounding amount of the alkyl acid phosphate is 0.01 to 1 part by mass, preferably 0.02 to 0.5 part by mass, more preferably 0.03 to 0.1 part by mass with respect to 100 parts by mass of the polycarbonate resin. . If the blending amount of the alkyl acid phosphate is less than the above lower limit, the effect of preventing darkening due to the blending of the alkyl acid phosphate cannot be sufficiently obtained, and if the blending amount of the alkyl acid phosphate is larger than the above upper limit, Degradability deteriorates, and physical properties may decrease due to a decrease in molecular weight in a high temperature and high humidity environment.

[Fatty acid ester compound]
Examples of the fatty acid ester compound used in the present invention, that is, the aliphatic carboxylic acid constituting the ester compound of an aliphatic carboxylic acid and an alcohol include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid or tricarboxylic acid. it can. 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.

  On the other hand, examples of the alcohol component constituting the fatty acid ester compound 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.

  The fatty acid ester compound may contain an aliphatic carboxylic acid and / or alcohol as an impurity, or may be a mixture of a plurality of compounds.

  Specific examples of fatty acid ester compounds include beeswax (mixture based on myristyl palmitate), stearyl stearate, behenyl beherate, octyldodecyl beherate, glycerin monopalmitate, glycerin monostearate, glycerin Distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate can be mentioned. It is preferable to use pentaerythritol tetrastearate and / or stearyl stearate.

  These fatty acid ester compounds may be used individually by 1 type, and may use 2 or more types together.

  The compounding quantity of a fatty acid ester compound is 0.1-2 mass parts with respect to 100 mass parts of polycarbonate resin, Preferably it is 0.2-1.5 mass parts, More preferably, it is 0.3-1 mass part. It is preferable for the amount of the fatty acid ester compound to be within the above-mentioned range since there is no decrease in hydrolysis resistance and an effect of preventing darkening is obtained.

[Organic phosphor]
The phosphorescent polycarbonate resin composition of the present invention can further contain an organic phosphor. In the phosphorescent polycarbonate resin composition of the present invention, a bright appearance can be obtained when the organic phosphor is blended with the phosphorescent material by improving the darkening due to the phosphorescent material.

  The organic phosphor used in the present invention is preferably a phosphor that emits fluorescence when irradiated with ultraviolet rays, and can maintain the transparency of the obtained molded body. For example, naphthalene compounds, perylene compounds, quinoline compounds are preferable. Compounds, coumarin compounds, benzoxazole derivatives and rare earth complex compounds are preferred.

As such an organic phosphor, commercially available products can be used. For example, as a yellow light emitting phosphor, “Lumogen Yellow 083”, “Logengen Yellow 170”, and “Lumogen Orange 240” manufactured by BASF are red. BASF's “Lumogen Pink 285” and “Lumogen Red 305” are used as the light emitting phosphors, and “Lumogen Violet 570” and “Lumogen Blue 650” are used as the blue to purple light emitting phosphors. As the luminescent phosphor, “Lumogen Green 850” manufactured by BASF Corporation can be used.
One of these phosphors may be used alone, or two or more of those emitting light of the same color or different color may be used in combination.

  The organic phosphor used in the present invention is preferably a phosphor whose maximum absorption wavelength is close to the emission peak wavelength of the phosphorescent material. By bringing the emission peak wavelength of the phosphorescent material close to the maximum absorption wavelength of the phosphor, for example, the absolute value of the difference between the emission peak wavelength of the phosphorescent material and the maximum absorption wavelength of the organic phosphor is 100 nm or less, preferably 50 nm or less. Thus, it is possible to emit light in a color different from the original emission color when irradiated with ultraviolet rays. For example, when Lumogen Orange 240 (maximum absorption wavelength 524 nm) is used in combination with a phosphorescent material having an emission peak wavelength of 520 nm (yellowish green) or 510 nm (blue green), it emits white light when irradiated with ultraviolet rays. In the case of the above combination, since the emission peak wavelength of the yellow-green phosphorescent material is closer to the maximum absorption wavelength of the phosphor than the emission peak wavelength of the blue-green phosphorescent material, light is emitted more white.

The upper limit of the maximum absorption wavelength of the organic phosphor used in the present invention is preferably 600 nm, more preferably 550 nm, and even more preferably 530 nm. The lower limit of the maximum absorption wavelength is not particularly limited, but 350 nm is preferable.
Furthermore, the upper limit of the maximum excitation wavelength is preferably 630 nm, more preferably 600 nm, further preferably 570 nm, and particularly preferably 550 nm. The lower limit of the maximum excitation wavelength is not particularly limited, but 400 nm is preferable.

  In the phosphorescent polycarbonate resin composition of the present invention, the compounding amount of the organic phosphor is 0.001 to 0.1 parts by mass, preferably 0.002 to 0.05 parts by mass, with respect to 100 parts by mass of the polycarbonate resin. Preferably it is 0.005-0.02 mass part. If the blending amount of the organic phosphor is too small, sufficient fluorescence emission characteristics cannot be obtained, and if it is too large, the transparency may be impaired, and it causes a decrease in the molecular weight and thermal stability of the polycarbonate resin. .

[Other ingredients]
The phosphorescent polycarbonate resin composition of the present invention may contain one or more selected from various additives and a resin component other than the polycarbonate resin as long as the effects of the present invention are not impaired. Examples of such additives include flame retardants, anti-dripping agents, antioxidants, ultraviolet absorbers, and light scattering components.

<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 and improves the flame retardancy of the composition, but a phosphoric acid ester compound and an organic sulfonic acid metal salt are preferable.

  As the phosphate ester compound, for example, a compound represented by the following formula (II) is preferable.

(In the formula (II), R ¹ , R ² , R ³ and R ⁴ each independently represents an aryl group which may be substituted, and Q represents a divalent aromatic which may have a substituent. And m represents a number of 0 to 5.)

Examples of the aryl group represented by R ^{1 to} R ⁴ in the above formula (II) include a phenyl group and a naphthyl group. Examples of the divalent aromatic group represented by Q include a phenylene group, a naphthylene group, and a group derived from bisphenol. Examples of these substituents include an alkyl group, an alkoxy group, and a hydroxy group. When m is 0, it is a phosphate ester, and when m is greater than 0, it is a condensed phosphate ester (including a mixture).

  Specific examples include bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, resorcinol-diphenyl phosphate, and substituted and condensates thereof. Examples of commercially available products that can be suitably used as such components include, from Daihachi Chemical Industry Co., Ltd., “CR733S” (resorcinol bis (diphenyl phosphate)), “CR741” (bisphenol A bis (diphenyl phosphate)), Asahi Denka Kogyo Co., Ltd. sells under the trade name “FP500” (resorcinol bis (dixylenyl phosphate)).

  When the resin composition of the present invention contains a phosphate ester compound as a flame retardant, the content thereof is preferably 1 to 50 parts by mass, and 3 to 40 parts by mass with respect to 100 parts by mass of the polycarbonate resin. Is more preferably 5 to 30 parts by mass. It is preferable for the content of the phosphoric acid ester compound for the flame retardant to be in the above range since the resin composition has flame retardancy and good heat resistance.

  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. 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. The organic sulfonic acid metal salt can also be used by mixing two or more kinds of salts.

  Preferred examples of the aliphatic sulfonate include a metal fluoroalkane sulfonate, and more preferably a metal metal perfluoroalkane sulfonate. Preferred examples of the fluoroalkanesulfonic acid metal salt include alkali metal salts and alkaline earth metal salts, and more preferred are alkali metal salts and alkaline earth metal salts of fluoroalkanesulfonic acids having 4 to 8 carbon atoms. Etc. Specific examples of the fluoroalkanesulfonic acid metal salt include sodium perfluorobutanesulfonate, potassium perfluorobutanesulfonate, sodium perfluoromethylbutanesulfonate, potassium perfluoromethylbutanesulfonate, sodium perfluorooctanesulfonate, Examples include potassium fluorooctane sulfonate.

  The aromatic sulfonic acid metal salt is preferably an aromatic sulfone sulfonic acid, an alkali metal salt of an aromatic sulfonic acid, an alkaline earth metal salt, or the like. Specific examples thereof include 3,4-dichlorobenzenesulfonic acid sodium salt, 2,4,5-trichlorobenzenesulfonic acid sodium salt, benzenesulfonic acid sodium salt, diphenylsulfone-3-sulfonic acid sodium salt, diphenylsulfone- Potassium salt of 3-sulfonic acid, sodium salt of 4,4′-dibromodiphenyl-sulfone-3-sulfonic acid, potassium salt of 4,4′-dibromophenyl-sulfone-3-sulfonic acid, 4-chloro-4 ′ -Calcium salt of nitrodiphenylsulfone-3-sulfonic acid, disodium salt of diphenylsulfone-3,3'-disulfonic acid, dipotassium salt of diphenylsulfone-3,3'-disulfonic acid, and the like.

  When the resin composition of this invention contains these organic sulfonic acid metal salt, it is preferable that the content is 0.01-5 mass parts with respect to 100 mass parts of polycarbonate resin, and 0.02-3 mass Part is more preferable, and 0.03 to 2 parts by mass is even more preferable. It is preferable for the content of the organic sulfonic acid metal salt for flame retardant to be in the above range since the resin composition has flame retardancy and good thermal stability.

<Anti-dripping agent>
An anti-dripping agent may be added to the resin composition of the present invention for the purpose of preventing dripping during combustion. A preferable example of the anti-dripping agent is a fluororesin. More specifically, a fluoroethylene structure such as a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, or a copolymer of tetrafluoroethylene and an ethylene monomer not containing fluorine is used. Including polymers and copolymers. Among these, polytetrafluoroethylene (PTFE) is preferable. The average molecular weight is preferably 500,000 or more, more preferably 500,000 to 10,000,000.

  In addition, when polytetrafluoroethylene having a fibril forming ability is used, it is possible to impart higher melt dripping prevention property. Although there is no restriction | limiting in particular in polytetrafluoroethylene (PTFE) which has a fibril formation ability, For example, what is classified into the type 3 in ASTN specification is mentioned. Specific examples thereof include Teflon (registered trademark) 6-J (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), Polyflon D-1, Polyflon F-103, Polyflon F201 (Daikin Industries, Ltd.), CD076 (Asahi) Ic eye fluoropolymers Co., Ltd.). Other than those classified as type 3, for example, Argoflon F5 (manufactured by Montefluos Co., Ltd.), polyflon MPA, polyflon FA-100 (manufactured by Daikin Industries, Ltd.) and the like can be mentioned. These polytetrafluoroethylene (PTFE) may be used independently and may combine 2 or more types. Polytetrafluoroethylene (PTFE) having the fibril-forming ability as described above is prepared by, for example, using tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium, ammonium peroxydisulfide, at a pressure of 1 to 100 psi, at a temperature of 0. It is obtained by polymerizing at ˜200 ° C., preferably 20˜100 ° C.

  When the resin composition of this invention contains a dripping inhibitor, it is preferable that the content is 0.05-2 mass parts with respect to 100 mass parts of polycarbonate resin, and is 0.1-1 mass part. Is more preferable. It is preferable for the content of the anti-dripping agent to be in the above range since the anti-dripping property is improved without impairing the appearance of the molded product.

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

  When the resin composition of this invention contains antioxidant, it is preferable that the content is 0.02-0.5 mass part with respect to 100 mass parts of polycarbonate resin. 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, hindered amine, and malonic ester.

  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.

  Specific examples of the malonic ester UV absorber include dimethyl 2- (p-methoxybenzylidene) malonate, tetraethyl-2,2- (1,4-phenylenedimethylidene) bismalonate, 2- (p-methoxybenzylidene) -Bis (1,2,2,6,6-pentamethyl 4-piperidinyl) malonate and the like.

  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 polycarbonate resin, and 0.005-0.8 mass. More preferably, it is 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 because weatherability can be improved without causing a decrease in luminous luminous intensity due to absorption of excitation light and without causing bleeding out on the surface of the molded product.

<Light scattering component>
The light scattering component is for increasing the whiteness of a molded product obtained by scattering light. For example, the light scattering component is incompatible with the polycarbonate resin of the matrix and has a refractive index of 0.01 to 0 than that of the polycarbonate resin. A transparent or translucent material that is about 2 smaller.

  Here, the “incompatible” with the polycarbonate resin refers to a material that does not become a mixture showing only a single melting point when melt-kneaded with the polycarbonate resin.

  In addition, “transparent or translucent” means that a flat plate having a thickness of 1 mm is formed using only the material, and the total light transmittance measured by a turbidimeter is 30% or more according to JIS K-7105, Preferably it is 50% or more.

  If the difference in refractive index between the light scattering component and the polycarbonate resin is less than 0.01, a sufficient light scattering effect cannot be obtained by adding this light scattering component, and the difference in refractive index exceeds 0.2. Then, the light transmittance is remarkably lowered, so that the light emission luminance of the phosphorescent material that can be recognized on the surface of the molded product is lowered. The light scattering component preferably has a refractive index of 0.05 to 0.12 smaller than that of the polycarbonate resin.

  The light scattering component may be any material that is incompatible with the polycarbonate resin, has a refractive index difference in the above range, and is transparent or translucent. The materials include organic materials, inorganic materials, and organic-inorganic composites. Any material can be used, and there is no particular limitation. Examples thereof include the following resin materials, resin fine particles, and inorganic material fine particles such as glass.

(Resin material)
Examples of the resin material suitable as the light scattering component include the following. In the following, numerical values in parentheses indicate typical refractive indexes of the resin. The same applies to examples of resin fine particles and inorganic material fine particles.
Olefin resins such as polyethylene resin (1.53) and polypropylene resin (1.49), polystyrene resin (1.59), AS resin (1.57), ABS resin (1.53), MS resin (1.58) ), MBS resin (1.54), AES resin (1.53), etc. Styrenic resin PMMA resin (1.49), etc. Methacrylic resin Polyamide 6 (1.53), Polyamide 66 (1.53), etc. Polyolefin resin of ARTON (trade name: 1.51), ZEONEX (trade name: 1.53), APEL (trade name: 1.54), etc. Cycloolefin resin Polyethylene terephthalate (PET) resin (1.58 ), Polyester-based resins such as polybutylene terephthalate (PBT) resin (1.58) Among these, ABS is a non-crystalline resin. Fat, AES resin, AS resin, MBS resin, MS resin, PMMA resin, and the like.
These resins may be used alone or in combination of two or more.

(Resin fine particles)
Resin fine particles suitable as a light scattering component include acrylic fine particles (1.49), silicone fine particles (1.45), styrene fine particles (1.59), epoxy fine particles (1.60), and urethane fine particles. (1.60), melamine fine particles (1.59), and the like.
Of these, acrylic fine particles and silicone fine particles are preferable, and those having a crosslinked structure are particularly preferable.
These resin fine particles may be used alone or in combination of two or more.

(Inorganic material fine particles)
Examples of inorganic material fine particles suitable as a light scattering component include glass beads (1.51) and silica beads (1.45).
Of these, easily available and inexpensive glass beads can be preferably used.
These inorganic material fine particles may be used alone or in combination of two or more.

  As the light scattering component, two or more of the above resin material, resin fine particles, and inorganic material fine particles may be used in combination.

In addition, when using a particulate thing as a light-scattering component, if the particle size is too small, handleability will be bad, and the transparency will be too good to make it look white. On the other hand, if the particle size is excessively large, the moldability is impaired and the surface appearance of the molded product may be inferior. Therefore, the particle size of the fine particles of the light scattering component has an average particle diameter _{D 50} 0.1 to 30 [mu] m, it is particularly preferably 0.5 to 20 [mu] m.

  When the resin composition of this invention contains a light-scattering component, it is preferable that the content is 0.1-100 mass parts with respect to 100 mass parts of polycarbonate resin, and is 0.5-50 mass parts. Is more preferably 1 to 30 parts by weight. If the content of the light scattering component is less than the above range, the effect of improving the whiteness due to the blending of the light scattering component cannot be sufficiently obtained, and if it is too much, the scattering effect is large and the phosphorescent action is inhibited. Therefore, the light emission luminance is reduced.

<Other resin components>
The resin composition of the present invention may contain a resin component other than the polycarbonate resin. In this case, examples of other resin components include polystyrene resins other than light scattering components, high impact polystyrene resins, and hydrogenated products. Polystyrene resin, polyacryl styrene resin, styrene-maleic anhydride copolymer, ABS resin, AS resin, AES resin, ASA resin, SMA resin, polyalkyl methacrylate resin, (meth) acrylate copolymer, polymethacryl methacrylate resin, Polyphenyl ether resin, amorphous polyalkylene terephthalate resin, polyester resin, amorphous polyamide resin, poly-4-methylpentene-1, cyclic polyolefin resin, amorphous polyarylate resin, polyether sulfone, styrenic heat Plastic elastomer, male Fin-based thermoplastic elastomers, polyamide thermoplastic elastomers, polyester thermoplastic elastomers, thermoplastic elastomers such as polyurethane-based thermoplastic elastomers Kyora. These may be used alone or in combination of two or more.
However, these other resin components are used in that the effects of the present invention, in which the excellent effects inherent in the polycarbonate resin are exhibited and the problem of darkening when a phosphorescent material is blended with the polycarbonate resin, are remarkably obtained. When mix | blending, it is preferable that the content is 50 mass parts or less with respect to 100 mass parts of polycarbonate resin.

<Others>
The resin composition of the present invention includes, in addition to the above components, an antistatic agent, an antifogging agent, a lubricant, an antiblocking agent, a fluidity improver, and a colorant, as long as the purpose of the present invention is not impaired. 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 each component by melt-kneading by a conventionally known method. As a specific mixing method, a predetermined amount of polycarbonate resin, phosphorescent material, alkyl acid phosphate, fatty acid ester compound and other additive components blended as necessary is weighed, and various mixers such as a tumbler and a Henschel mixer are used. And then kneading and mixing using a Banbury mixer, roll, plastic appender, single-screw kneading extruder, twin-screw kneading extruder, kneader, and the like.

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

[Molding method]
As a molding method in the case of producing the molded product of the present invention formed by molding the phosphorescent polycarbonate 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.

[L * value and molecular weight reduction]
The molded article of the present invention formed by molding the phosphorescent polycarbonate resin composition of the present invention exhibits a good hue due to the effect of preventing darkening caused by the combined use of an alkyl acid phosphate and a fatty acid ester compound. The hue varies depending on the blending amount of the phosphorescent material in the resin composition, but the L * value for a molded article having a thickness of 3 mm measured by the method described in the Examples section below is 62 or more, and in particular, 63 It exhibits good brightness as described above, and its color tone has a beautiful and clean appearance almost close to white.

  Moreover, the phosphorescent polycarbonate resin composition of this invention can suppress the fall of the molecular weight of the polycarbonate resin at the time of shaping | molding by the decomposition | disassembly inhibitory effect of polycarbonate resin by using together an alkyl acid phosphate and a fatty acid ester compound. The degree of decrease in the molecular weight varies depending on the blending amount of the phosphorescent material in the resin composition, but the viscosity-average molecular weight and residence time of the polycarbonate resin during normal molding measured by the method described in the Examples section below. The difference from the viscosity average molecular weight of the polycarbonate resin at the time of molding can be suppressed to 600 or less, particularly 300 or less. By suppressing the decrease in molecular weight, the appearance is excellent and excellent mechanical properties can be obtained.

[Usage]
Since the molded product of the present invention formed by molding the phosphorescent polycarbonate resin composition of the present invention is excellent in hue and phosphorescent performance, only road signs and signboards which are general uses of conventional phosphorescent resin compositions Rather than mobile equipment such as playground equipment and toys, laptops, and mobile phones in entertainment facilities, product displays, sign buttons in car interiors and buildings, clock dials, accessories, stationery, sports equipment, and more In various fields such as electric / electronic / OA devices, the present invention can be applied to a wide range of uses as a casing, a switch, and buttons.

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.

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

<Phosphorescent material>
G-300M: Nemoto Special Chemicals phosphorescent material “G-300M” (chemical composition = SrAl ₂ O ₄ : Eu, Dy, D ₅₀ = 30 μm, emission color = yellowish green, emission peak wavelength = 520 nm)
BG-300M: phosphorescent material “BG-300M” manufactured by Nemoto Special Chemical Co., Ltd. (chemical composition = Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy, D ₅₀ = 30 μm, emission color = blue green, emission peak wavelength = 490 nm)
V-300M: Photoluminescent material “V-300M” manufactured by Nemoto Special Chemical Co., Ltd. (chemical composition = CaAl ₂ O ₄ : Eu, Nd, D ₅₀ = 25 μm, emission color = purple, emission peak wavelength = 430 nm)
PB-025: Phosphorescent material “Clite Bright PB-025” manufactured by Ryohin Co., Ltd. (chemical composition = Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy, D ₅₀ = 25 μm, emission color = blue green, emission peak wavelength = 510 nm)
P170: phosphorescent material “P170” manufactured by Kasei Optonics Co., Ltd. (chemical composition = Sr ₂ MgSi ₂ O ₇ : Eu, Dy, D ₅₀ = 31 μm, emission color = blue, emission peak wavelength = 480 nm)

<Stabilizer>
AX-71: “ADEKA STAB AX-71” manufactured by ADEKA (mixture of monostearyl acid phosphate and distearyl acid phosphate represented by the formula (Ib))
JP-513: “JP-513” manufactured by Johoku Chemical Co., Ltd. (mixture of monoisotridecyl acid phosphate and diisotridecyl acid phosphate represented by the formula (Ia))
JP-524R: “JP-524R” manufactured by Johoku Chemical Co., Ltd. (a mixture of monotetracosyl acid phosphate and ditetracosyl acid phosphate represented by the formula (Ic))
ADK2112: “ADEKA STAB 2112” (Tris (2,4-di-tert-butylphenyl) phosphite) manufactured by ADEKA
SH1107: “DOW CORNING TORAY SH1107 FLUID” (methyl hydrogen siloxane) manufactured by Toray Dow Corning

<Release agent>
VPG861: "Roxyol VPG861" (pentaerythritol tetrastearate) manufactured by Emery Oleochemicals Japan
PE520: “Licowax PE520” (polyethylene wax) manufactured by Clariant Japan

<Organic phosphor>
Lumogen Orange 240: Perylene organic phosphor “Lumogen Orange 240” manufactured by BASF (maximum absorption wavelength = 524 nm, maximum excitation wavelength = 539 nm)
Lumogen Yellow 083: Perylene organic phosphor “Lumogen Yellow 083” manufactured by BASF (maximum absorption wavelength = 476 nm, maximum excitation wavelength = 490 nm)
Lumogen Red 305: Perylene organic phosphor “Lumogen Red 305” manufactured by BASF (maximum absorption wavelength = 578 nm, maximum excitation wavelength = 613 nm)

[Examples 1 to 24 and Comparative Examples 1 to 10]
Polycarbonate resin and various additives are blended in the ratios shown in Tables 1 to 3, mixed for 20 minutes with a tumbler, and then cylinder temperature by 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 54 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 on an injection molding machine (“S-2000i150B” manufactured by FANUC) under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 30 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 Fracture Strength Using an ASTM multipurpose test piece (thickness 3.2 mm), tensile fracture strength (unit: MPa) was measured in accordance with 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) Molecular weight measurement In addition to the above injection molding, after performing four-shot molding (normal molding) at a cylinder temperature of 320 ° C. and a normal cycle time (30 seconds) with the same injection molding machine, the resin composition is placed in the cylinder. Then, the first shot after resuming molding (retention molding) was sampled, and the viscosity average molecular weight of the polycarbonate resin during normal molding and the viscosity average molecular weight of the polycarbonate resin during retention molding were measured.
The amount of decrease in molecular weight was calculated by the difference between the viscosity average molecular weight during normal molding and the viscosity average molecular weight during residence molding. The smaller this value, the lower the molecular weight during molding and the better the thermal stability of residence.

(6) In accordance with JIS K7105, a color difference meter (3 mm thick portion of a toning test piece (50 mm (width) x 90 mm (length), 1 mm, 2 mm, and 3 mm three-stage plate)) L *, a *, and b * were measured under the following conditions using “Nippon Denshoku Industries Co., Ltd.“ SE6000 ”). A higher L * value indicates no darkening.
Reflection measurement: C light source 2 degree field of view Sample holder: White

(7) Appearance The presence or absence of silver or turbidity was confirmed visually with respect to the above test specimen for toning.

From the results of Tables 1 to 3, the following can be understood.
In Comparative Examples 1 and 10 in which neither a stabilizer nor a release agent is used, the L * value is low due to darkening, the molecular weight is greatly reduced, and the mechanical properties are slightly inferior.
In Comparative Example 2 where a fatty acid ester compound is used as a mold release agent but a siloxane compound is used as a stabilizer and no alkyl acid phosphate is used, the L * value is high and there is no problem of darkening, but the appearance is silver or cloudy. It becomes defective and the molecular weight is greatly reduced.
In Comparative Example 3, a fatty acid ester compound is used as a mold release agent and a phosphite ester type is used as a stabilizer, but the L * value is low and there is a problem of darkening, and the molecular weight is greatly reduced.
Even in the case of using alkyl acid phosphate as a stabilizer, Comparative Example 4 using polyethylene wax as a release agent has a high L * value, blackening is suppressed, and a decrease in molecular weight is small, but the appearance is poor due to silver or cloudiness. There's a problem.
Further, in Comparative Example 5 in which alkyl acid phosphate is used as a stabilizer and no release agent is used, the L * value is low and there is a problem of darkening.
In Comparative Examples 6 to 9 in which a fatty acid ester compound is used as a mold release agent and no stabilizer is used, all of them have low L * values, blackening problems, and a large decrease in molecular weight. Degradation of physical properties is also great.

On the other hand, in Examples 1 to 15 where alkyl acid phosphate was used as the stabilizer and fatty acid ester compound was used as the mold release agent, all L * values were high, there was no problem of darkening, and molecular weight reduction was also suppressed. ing.
Moreover, also about Examples 16-21 containing a yellow and orange organic fluorescent substance, all have a high L * value, there is no problem of darkening, and the molecular weight fall is also suppressed.
About Examples 22-24 containing a red organic fluorescent substance, although L * value is low, there is no problem of darkening and the molecular weight fall is also suppressed.

Claims (7)

1 to 30 parts by mass of a phosphorescent material, 0.01 to 1 part by mass of an alkyl acid phosphate, and 0.1 to 2 parts by mass of a fatty acid ester compound with respect to 100 parts by mass of a polycarbonate resin A phosphorescent polycarbonate resin composition, wherein the alkyl acid phosphate is represented by the following formula (I).
O = P (OH) _n (OR) _3-n (I)
(In the formula (I), R represents an alkyl group having 9 to 30 carbon atoms, and n represents an integer of 1 or 2. When n is 1, two Rs may be the same or different. May be.) According to claim 1, wherein the phosphorescent material is _{SrAl 2 O 4: Eu, Dy} , Sr 4 Al 14 O 25: Eu, Dy, and CaAl ₂ O _4: Eu, 1 kind or two or more kinds selected from the group comprising Nd A phosphorescent polycarbonate resin composition characterized by the above.   The phosphorescent polycarbonate resin composition according to claim 1 or 2, wherein R in the formula (I) is an alkyl group having 13, 18, or 24 carbon atoms.   4. The phosphorescent polycarbonate resin composition according to claim 1, wherein the fatty acid ester compound is pentaerythritol tetrastearate and / or stearyl stearate.   The phosphorescent polycarbonate resin composition according to any one of claims 1 to 4, further comprising an organic phosphor in an amount of 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the polycarbonate resin.   6. The organic phosphor according to claim 5, wherein the organic phosphor is one or more selected from the group consisting of naphthalene compounds, perylene compounds, quinoline compounds, coumarin compounds, benzoxazole derivatives, and rare earth complex compounds. A phosphorescent polycarbonate resin composition.   The molded article formed by shape | molding the luminous polycarbonate resin composition of any one of Claim 1 thru | or 6.