JP2005082647A - Polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition which has an excellent heat stability during processing and a good color tone, effectively exhibits the luminescent ability of an alminate-based fluorescent material and hence has a high practical value, and to provide a molding composed of the composition. <P>SOLUTION: This polycarbonate resin composition comprises 100 pts.wt. polycarbonate resin (component A) and 0.01-100 pts.wt. fluorescent particles with an alminate as the mother crystal (component B). Component B contains ≤40 wt.% particles having a particle diameter of <10 μm and ≤10 wt.% particles having a particle diameter of >50 μm in 100 wt.% of the component (B). The molding is composed of the composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polycarbonate resin composition containing a phosphor having an aluminate having a specific particle size distribution as a base crystal, and a molded article comprising the same. More specifically, by containing such a specific phosphor, a polycarbonate resin that is excellent in thermal stability and hue during processing and that effectively exhibits the light-emitting performance of the phosphor, and as a result has high utility. The present invention relates to a composition and a molded article comprising the composition.

  Resin materials in which a phosphor is blended with a synthetic resin are widely known. Among such phosphors, resin materials blended with phosphorescent phosphors having phosphorescent properties are widely used in nocturnal signs and decorative articles. For example, ZnS: Cu, (Ca, Sr) S: Bi, and the like have been used for a long time as phosphorescent phosphors, and zinc sulfide-based phosphors are particularly widely used. In recent years, phosphor-containing resin materials have attracted attention in light-emitting devices that emit white light by emitting light using ultraviolet LEDs or near-ultraviolet LEDs. The phosphorescent phosphor has the property of absorbing and exciting light such as sunlight and fluorescent lamps and emitting light for a long time. And since phosphorescent phosphors can repeat light energy absorption, phosphorescence, and light emission as many times as possible, disaster prevention and safety signs and signs that need to be recognized in the dark, signs and signs for automobile interiors, etc. It is widely used in a wide range of applications such as various guide signs in buildings, clock dials, accessories such as tie pins and pendants. Further, in the field of phosphorescent phosphors, phosphors having aluminate as a base crystal (hereinafter referred to simply as “aluminate”) whose emission luminance and afterglow time are significantly improved compared to zinc sulfide phosphors. Is sometimes known (referred to as Patent Documents 1 and 2).

  On the other hand, polycarbonate resin has many excellent properties and is therefore used in a large amount in a wide range of fields. In particular, it has been used for a long time for disaster prevention and safety signs and markings due to its excellent impact resistance, heat resistance and flame retardancy. From the above viewpoints, it is considered that if a phosphorescent phosphor is blended with polycarbonate resin, it can be used as a phosphorescent label having excellent impact resistance, heat resistance, and flame retardancy, and a phosphorescent indicator material. Proposals have also been made (see Patent Document 3).

A synthetic resin material in which a phosphorescent phosphor containing SrAl ₂ O ₄ as a mother crystal is blended as a resin material in which an aluminate phosphor is blended, and the phosphor has an average particle size of 5 to 75 μm, preferably The material which is 5-25 micrometers is well-known (refer patent document 4). However, no specific resin material based on polycarbonate resin is known for such materials. Such an average particle diameter is still not optimal when considering the thermal decomposition of the polycarbonate resin. That is, when an aluminate-based phosphor is blended with a polycarbonate resin, there is a problem that the polycarbonate resin is severely decomposed due to a thermal history during processing. Such decomposition deteriorates the hue of the resin, impairs the light emitting function of the phosphor, and lowers the impact resistance of the resin composition. In addition, resin materials containing aluminate-based phosphors have a problem that the aesthetics of the product are deteriorated due to darkening of the molded product.

  As a method for suppressing decomposition, a method of limiting the blending amount of the aluminate-based phosphor is conceivable. However, this reduces the phosphorescent performance and makes it impossible to obtain desired characteristics. In addition, a method has also been proposed in which a phosphorescent phosphor particle is provided with a protective layer to reduce the influence on the resin and suppress decomposition (see Patent Document 5). Because of this problem, it has not been put into practical use.

  As described above, although there is a demand for a polycarbonate resin composition excellent in thermal stability and a molded product made thereof, in which thermal decomposition is suppressed when an aluminate-based phosphor is blended, such a requirement is sufficiently satisfied. The present condition is that the resin composition is not yet obtained.

JP-A-8-127772 Japanese Patent Laid-Open No. 9-208948 Japanese Patent Laid-Open No. 6-345902 JP-A-8-183955 JP 9-316443 A

  An object of the present invention is to provide a polycarbonate resin composition excellent in thermal stability and hue during processing and effectively exhibiting the light emission performance of an aluminate-based phosphor, and as a result, a molded product comprising the same Is to provide.

  As a result of intensive studies to achieve the above object, the present inventor has blended polycarbonate resin with aluminate-based phosphor particles having a controlled particle size, thereby deteriorating thermal stability during processing and molding. It was found that the deterioration of the hue of the product can be greatly suppressed, and by this means, it was found that a polycarbonate resin composition excellent in luminous performance and excellent in heat stability and hue during processing and a molded product comprising the same can be obtained. The present invention has been completed through further extensive studies.

  The present invention comprises (1) 100 parts by weight of a polycarbonate resin (component A) and 0.01 to 100 parts by weight of phosphor particles (component B) having aluminate as a base crystal, the component B being 100 weights %, Particles having a particle diameter of less than 10 μm are contained in an amount of 40% by weight or less, and particles having a particle diameter of more than 50 μm are contained in a proportion of 10% by weight or less.

  According to the configuration (1), the light emission performance is high, and further, the decrease in physical property strength due to the decomposition of the resin during processing, the unstable fluidity, and the deterioration of the hue, which has been a problem in the past, are eliminated. A polycarbonate resin composition having very excellent molding stability and hue is provided. In particular, when the phosphor is a phosphorescent phosphor, the resin composition having the structure (1) provides a molded product having stable light emission performance over a long period of time. It has a very good advantage in applications where it is necessary to emit light for hours.

  One of preferred embodiments of the present invention is the above (1), further comprising 0.001 to 0.1 parts by weight of phosphite (C component) per 100 parts by weight of polycarbonate resin (component A). ). According to this configuration (2), a polycarbonate resin composition having further excellent thermal stability is provided.

  One of the preferred embodiments of the present invention is the above (1) to (3), further comprising (3) 0.01 to 10 parts by weight of an ultraviolet absorber (component D) per 100 parts by weight of the polycarbonate resin (component A). It is a polycarbonate resin composition as described in 2). According to this configuration (3), there is provided a polycarbonate resin composition that is excellent in light emission performance as a phosphor and also excellent in weather resistance and, as a result, can stably exhibit such light emission performance over a long period of time.

  One of the preferred embodiments of the present invention is (4) a molded product obtained by melt-molding the polycarbonate resin composition described in (1) to (3) above. According to the configuration (4), a molded article from a polycarbonate paper resin composition having excellent light emitting performance and extremely excellent thermal stability during processing is provided.

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

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

  In the present invention, in addition to bisphenol A-based polycarbonate, which is a general-purpose polycarbonate, it is possible to use a special polycarbonate produced using other dihydric phenols as the A component.

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

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

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

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

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

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

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

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

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

  In addition, the aromatic polycarbonate resin as the component A in the resin composition of the present invention is a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, a bifunctional alcohol (fatty acid). It may be a copolymerized polycarbonate copolymerized with a cyclic group) and a polyester carbonate copolymerized with such a bifunctional carboxylic acid and a bifunctional alcohol. Moreover, the mixture which blended 2 or more types of the obtained polycarbonate may be used.

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

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

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

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

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

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

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

A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salt and potassium salt of dihydric phenol; alkaline earth metal compounds such as calcium hydroxide, barium hydroxide and magnesium hydroxide; Nitrogen-containing basic compounds such as methylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, and triethylamine can be used. Further, alkali (earth) metal alkoxides, alkali (earth) metal organic acid salts, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds, etc., esterification reaction, transesterification The catalyst used for the reaction can be used. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is preferably selected in the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻³ equivalents, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalents, relative to 1 mol of dihydric phenol as a raw material. It is.

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

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

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

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

In addition, when measuring the viscosity average molecular weight in the resin composition of this invention, it carries out in the following way. That is, the resin composition is dissolved in 20 to 30 times its weight of methylene chloride, and the soluble component is collected by Celite filtration, and then the solution is removed and dried sufficiently to obtain a solid component soluble in methylene chloride. . A specific viscosity (η _SP ) at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride using an Ostwald viscometer, and the viscosity average molecular weight M is calculated by the above formula.

<About B component>
Although the phosphor having an aluminate as a mother crystal in the component B of the present invention is not particularly limited, calcium, strontium, and barium are preferably exemplified as the metal elements usually used together with aluminum in such a phosphor. 1 type or 2 types or more may be sufficient and the combination of calcium, strontium, and barium and magnesium is illustrated suitably. Further, such a phosphor is composed of a combination of a mother crystal and an activator as an atom that can be a luminescent center or a trap center for excited electrons or excited holes, and in some cases, a co-activator. As such an activator, europium is used. Further, the co-activator is preferably at least one selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin, and bismuth. One or more are illustrated. The activator is preferably in the range of 0.001 mol% to 10 mol% per 1 mol of metal element used together with aluminum in the aluminate, and the coactivator is 0.001 mol per 1 mol of such metal element. It is preferable that it becomes the range of% -10 mol%.

The phosphor according aluminate, for _{example, 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 (where R is Sr or Ba, which may be combined), SrAl ₂ O ₄ : Eu, SrAl ₂ O ₄ : Eu, Dy, SrAl ₁₄ O ₂₅ : Eu, SrAl ₁₄ O ₂₅ : Eu , Dy, and CaAl ₂ O ₄ : Eu, Nd are preferable examples.

Among the aluminate-based phosphors, M _1-x Al ₂ O _4-x (where −0.33 ≦ x ≦ 0.6, and M is made of Ca, Sr, and Ba) A phosphor composed of a mother crystal represented by at least one element selected from the group and further including Mg combined with such an element is preferable. More preferably, a phosphor composed of a mother crystal represented by MAl ₂ O ₄ and M ₄ Al ₁₄ O ₂₅ is preferable. As the activator and coactivator added to the mother crystal, those exemplified above can be used, and among them, dysprosium is preferable. In general, aluminate-based phosphors are composed of an oxide (metal oxide) containing an element that becomes an activator and a coactivator with respect to a compound (carbonate or the like) containing an element constituting alumina and a salt. And further, a flux for promoting crystallization is added and baked. Preferable examples of the flux in component B of the present invention include boric acid, sodium silicofluoride, ammonium fluoride, sodium fluoride, potassium fluoride, potassium chloride, sodium hydrogenphosphate, and zinc silicofluoride. Is done.

  In addition, a phosphorescent phosphor is suitable as the phosphor of the present invention. Here, phosphorescence refers to the property that afterglow is recognized with the naked eye for a considerable length of time (several tens of minutes to several hours) even after external energy application is stopped, and the afterglow time of a normal phosphor is external. When the application of energy is stopped, the light emission is quickly distinguished from that which is attenuated. Among them, it is preferable to use strontium aluminate because it has a long afterglow time compared to other phosphorescent substances, can be visually recognized almost overnight, and has excellent weather resistance.

  Furthermore, the B component of the present invention has a specific particle size distribution. Such a particle size is calculated by a particle size distribution measuring method of Stokes diameter. The Stokes diameter is a particle diameter obtained by the Stokes equation and means the diameter of spherical particles having the same density that settles in the same medium at the same speed as the sample particles. The measurement of the particle diameter of the present invention is performed by a centrifugal sedimentation method by an X-ray transmission method, and is measured by, for example, a centrifugal automatic particle size distribution measuring device “CAPA-500” manufactured by Horiba, Ltd.

  The B component of the present invention comprises particles having a particle size of less than 10 μm in a total amount of 100% by weight of 40% by weight or less (preferably 30% by weight or less, more preferably 20% by weight or less), and particles having a particle size of more than 50 μm. Is 10% by weight or less (preferably 5% by weight or less, more preferably 1% by weight or less). When the number of particles having a particle diameter of less than 10 μm exceeds the above range, the polycarbonate resin is severely deteriorated during melt processing such as extrusion and injection molding, and the strength, molding stability, and hue of the resin material are deteriorated. This is presumably because the reaction active site is greatly increased by the decrease in particle size. On the other hand, if the number of particles exceeding 50 μm exceeds the above range, the contact pressure in contact between a part of the particles and the screw surface and cylinder surface of the extrusion device or molding device during melt processing such as extrusion or injection molding will be increased. Since it increases further, it becomes easy to wear these surfaces. As a result, the screw or cylinder material, or the carbonized resin layer attached to the surface of the resin material or the molded product is mixed into the resin material or the molded product, the molded product is darkened, and the luminous performance of the phosphor tends to be hindered. Since it is inferior, it is not preferable.

  Further, in the component B, particles having a particle diameter of less than 10 μm or particles having a particle diameter of more than 50 μm can be substantially zero, but the proportion of particles having a particle diameter of less than 10 μm is 5 as a practically reasonable range. % By weight or more. On the other hand, in the B component of the present invention, the proportion of particles having a particle size in the range of 10 to 50 μm is 50% by weight or more, preferably 60% by weight or more in 100% by weight of the B component. Further, the proportion of particles in such a range is practically reasonable to be 90% by weight or less, and more preferably 80% by weight or less.

  Furthermore, in the particle diameter accumulation curve in which the logarithmic coordinate of the particle diameter is taken on the horizontal axis and the integrated value of the particle weight corresponding to the vertical axis is taken, the median diameter calculated as the 50% value on the vertical axis is the average particle diameter. The average particle size in the component B is preferably in the range of 10 to 20 μm, more preferably in the range of 10 to 17 μm. In the present invention, the weight ratio of less than 10 μm means the value of the vertical axis of the 10 μm portion when the vertical axis of the integrated curve is 100%, and the weight ratio of more than 50 μm is the value of the 50 μm portion of the integrated curve. Is subtracted from 100.

  Particles having a particle size in the above range can be produced by pulverizing aluminate produced by calcination and then classification. Here, the pulverization method is not particularly limited, and examples thereof include a high-speed rotary mill method such as a disk mill, a pin mill, and a screen mill, a ball mill method such as a rolling ball mill, a vibration ball mill, and a planetary mill, an annular mill, and the like. The medium stirring mill method, the jet mill method, and the like can be used. Furthermore, as classifiers, in addition to sieve type classifiers, impactor type inertial force classifiers (variable impactors, etc.), Coanda effect type inertial force classifiers (elbow jets, etc.), centrifugal field classifiers (multistage cyclone, microplex) , Dispersion separator, Accucut, turbo classifier, turboplex, micron separator, super separator, etc.). The pulverization may be wet pulverization or dry pulverization, and various pulverization aids may be used during the pulverization.

  The blending ratio of component B is as follows. It mix | blends by 0.01-100 weight part of B components with respect to 100 weight part of A components. More preferably, it is 0.1-50 weight part, More preferably, it is 0.5-30 weight part. If the component B is less than 0.01 part by weight, the light emission performance is low and sufficient light emission luminance cannot be obtained. On the other hand, when the component B exceeds 100 parts by weight, the amount of the component B becomes excessive and deterioration of the resin becomes significant even if the particle size is controlled.

<About component C>
In the polycarbonate resin composition of the present invention, a phosphite is further used in order to further stabilize the molecular weight and hue during molding and heat treatment. The resin composition having higher practicality is provided by the combination of the aluminate-based phosphor having a specific particle diameter of the present invention and such a phosphite.

  Examples of such phosphites include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, Diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris (diethylphenyl) Phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phos Ite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Examples thereof include bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.

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

  Among these, tris (2,4-di-tert-butylphenyl) phosphite is particularly preferable. Phosphites may be used alone or in combination of two or more. The proportion of the phosphite ester of component C is preferably 0.001 to 0.1 parts by weight, more preferably 0.005 to 0.08 parts by weight, and still more preferably 0.001 to 0.1 parts by weight per 100 parts by weight of component A. 01 to 0.07 parts by weight.

<About D component>
The polycarbonate resin composition of the present invention preferably further contains an ultraviolet absorber. The UV absorber suppresses deterioration of the polycarbonate resin composition of the present invention due to the light source in which the resin material is used or external UV rays, and as a result, provides a polycarbonate resin composition that can stably exhibit such light emission performance over a long period of time. To do.

  Examples of the ultraviolet absorber include 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, and bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane. Benzophenone compounds represented by

  Examples of the ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenylbenzotriazole, 2,2′methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], condensate with methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol The benzotriazole type compound represented by can be mentioned.

  Further, examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4,6-bis (2,4-dimethyl). And hydroxyphenyltriazine compounds such as phenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol.

  Further, examples of the ultraviolet absorber include 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) and 2,2′-m-phenylenebis (3,1-benzoxazin-4-one). And cyclic imino ester compounds such as 2,2′-p, p′-diphenylenebis (3,1-benzoxazin-4-one).

  Also, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6- Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetra Carboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl ) Imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane. Can also include hindered amine light stabilizers represented by, such light stabilizers in combination with the ultraviolet absorber and various antioxidants, exhibit better performance in terms of weather resistance.

  The ultraviolet absorber and the light stabilizer have a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbing monomer and / or the light stable monomer, an alkyl (meth) acrylate, etc. It may be a polymer-type ultraviolet absorber and / or light stabilizer copolymerized with the above monomer. The UV-absorbing monomer and light-stable monomer contain a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a hindered amine skeleton in the ester substituent of (meth) acrylic acid ester. The compound is preferably exemplified.

  In the composition of the present invention, if the ultraviolet absorber absorbs too much light necessary for excitation by the phosphor, the luminous efficiency of the phosphor decreases. It is preferable that the absorption efficiency of light in the ultraviolet region is higher. Therefore, in the distribution of the light absorption with respect to the wavelength, an ultraviolet absorber having a characteristic that does not absorb much light necessary for excitation of the phosphor and abruptly increases the light absorption ability at a shorter wavelength side than the light. As the ultraviolet absorber having such characteristics, a cyclic imino ester compound of the following formula (1) is suitable in the present invention. As a compound of following formula (1), the compound of the said illustration is shown, for example.

（式中、Ａｒは炭素数６〜１２の芳香族炭化水素の芳香環上の水素基を２つ引き抜いた残基であり、ヘテロ原子を含有してもよい。ｎは０または１を示す。）

(In the formula, Ar is a residue obtained by extracting two hydrogen groups on the aromatic ring of an aromatic hydrocarbon having 6 to 12 carbon atoms, and may contain a hetero atom. N represents 0 or 1. )

  The composition ratio of the ultraviolet absorber and the light stabilizer is preferably 0.01 to 10 parts by weight, more preferably 0.02 to 1 part by weight, and still more preferably 0.03, relative to 100 parts by weight of component A, respectively. -0.5 parts by weight.

<About antioxidants>
In the polycarbonate resin composition of the present invention, a phenolic antioxidant can be further used in order to further stabilize the hue at the time of melt processing of the composition. Such phenolic antioxidants are also effective in improving heat aging resistance and weather resistance during product use.

  Examples of such phenol-based antioxidants include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N -Dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis ( 4-ethyl-6-tert-butylphenol), 4,4′-methylenebis 2,6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2 2,2′-ethylidene-bis (4,6-di-tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-) 6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3- ert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1, 1, -dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis ( 3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4, 4′-di-thiobis (2,6-di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol) 2,2-thiodiethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ', 5'-di-tert-butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) Butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4 -Hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert- Examples include butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate and tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane. All of these are readily available. Among them, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl -4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tetrakis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionyloxymethyl] methane is preferred, in particular n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  The ratio of the hindered phenol antioxidant is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1 part by weight per 100 parts by weight of the component A.

<About other phosphors>
The present invention solves a technical problem when an aluminate-based phosphor is blended with a polycarbonate resin composition. Therefore, the resin composition in which such a problem has been solved is further combined with other resin other than the aluminate-based phosphor. Mixing the phosphor does not impair the effects of the present invention, and it is possible to mix such a phosphor as appropriate.

Examples of such phosphors include halogen compounds such as KCl and ZnF ₂ as mother crystals, sulfur compounds such as CaS, SrS, ZnS, and sulfur compounds of Zn and Cd, silicates such as CaSiO ₂ and Ba ₂ Si ₃ O ₈ , Illustrative are phosphates such as CaP ₂ 0 ₇ and tungstates such as CaWO ₄ . Furthermore, examples of the activator and coactivator include Bi, Ce, Co, Cu, Dy, Eu, Mn, Nd, Pb, Sb, Sm, and Ti.

More specifically, for example, X ₂ O ₂ S: Eu (X is one or more selected from La, Gd, and Y), 0.5 MgF ₂ .3.5MgO.GeO ₂ : Mn Y ₂ O ₃ : Eu, Y (P, V) O ₄ : Eu, YVO ₄ : Eu, ZnS: Cu, ZnO: Zn, Zn ₂ GeO ₄ : Mn, Zn ₂ SiO ₄ : Mn, X ₃ MgSi ₂ O ₈ : Eu, Mn (X is one or more selected from Sr, Ba, Ca), X ₁₀ (PO ₄ ) 6Cl ₂ : Eu (X is Sr, Ca, Ba, Mg, Ce) ZnS; Ag, Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Ca ₁₀ (PO ₄ ) ₆ F ₂ : Sb, X ₃ MgSi ₂ O ₈ : Eu (X is one selected from Sr, Ba and Ca, or Species or in _{which), SrMgSi 2 O 8: Eu} , Sr 2 P 2 O 7: Eu, X 10 (PO 4) 6 Cl 2: Eu (X is one or two kinds selected from Ba, Ca, Mg Sr ₂ Si ₂ O ₈ · 2SrCl ₂ : Eu, ZnS: Mn, ZnS: Cu, Mn, Co, KCL: Ti, CaS: Bi, and SrS: Sm. The range of 0.01-50 weight part is suitable for this other fluorescent substance per 100 weight part of A component, and 0.05-30 weight part is preferable.

<About other additive components>
In the polycarbonate resin composition of the present invention, in order to further stabilize the molecular weight and hue at the time of molding or heat treatment, other phosphorus stabilizers other than the above phosphite can be used. Examples of such other phosphorus stabilizers include phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof.

  Specifically, tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenylenedi Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite Tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite,

  Tetrakis (2,6-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis ( 2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, and tetrakis (2 , 6-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite,

  Examples include tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

  These may be used alone or in combination of two or more, and when used in combination with a phosphite stabilizer, a greater stabilizing effect can be obtained.

  Such other phosphorous stabilizer is 0.0001 to 1 part by weight, preferably 0.0005 to 0.8 part by weight, and more preferably 0.001 to 0.00 part by weight based on 100 parts by weight of the polycarbonate resin (component A). It mix | blends in 6 weight part. If it is less than 0.0001 part by weight, the effect as a heat stabilizer is insufficient, and it is not preferable because molecular weight lowering and hue deterioration are likely to occur during molding. , Hue deterioration is more likely to occur, which is not preferable.

  In the polycarbonate resin composition of the present invention, an antioxidant other than the above-mentioned phenolic antioxidant can be used in order to further stabilize the hue at the time of heat treatment of the molded product. Examples of such other antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), and glycerol-3-stearyl thiopropionate. The amount of these other antioxidants used is preferably 0.001 to 0.05 parts by weight with respect to 100 parts by weight of the A component polycarbonate resin.

  The polycarbonate resin composition of the present invention may further contain 0.05 to 3.0 ppm (weight ratio) of a bluing agent in the polycarbonate resin composition. The resin composition of the present invention is relatively yellowish, and the yellowness of the resin composition may further increase when an ultraviolet absorber is further blended. Therefore, the use of a bluing agent is effective for imparting a natural hue to the molded product and adjusting the hue.

  Here, the bluing agent refers to a colorant that exhibits a blue or purple color by absorbing orange or yellow light. In particular, a dye is preferable from the viewpoint of photoactivation of a luminous substance. By blending the bluing agent, the polycarbonate phosphorescent resin composition of the present invention achieves an even better hue. Representative examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR from Bayer, and Terrasol Blue RLS from Sand.

  Additives other than those described above can be blended in the resin composition and molded product of the present invention in order to further exhibit the effects of the present invention and to impart other effects. This point will be described below.

  Furthermore, since the polycarbonate resin composition of the present invention may have good transparency by adjusting the blending amount of the phosphor particles, the light diffusing function by blending the light diffusing agent, the light high reflection blending with the white pigment. The function and the design effect by blending special dyes such as fluorescent dyes are more effectively exhibited. Examples of the light diffusing agent include polymer fine particles such as acrylic crosslinked particles and silicone crosslinked particles, and inorganic fine particles such as glass powder, ultrathin glass flakes, and calcium carbonate particles. Examples of white pigments include titanium oxide, zinc oxide, and zinc sulfide, with titanium oxide being particularly preferred. Furthermore, titanium oxide surface-treated with an organic surface treatment agent such as a silicone compound typified by polyalkyl hydrogen siloxane is more preferable. Examples of fluorescent dyes include various fluorescent dyes represented by anthraquinone dyes, perylene dyes, coumarin dyes, thioindigo dyes, thioxanthone dyes, bisbenzoxazolyl-stilbene derivatives, and bisbenzoxazolids. Illustrative are fluorescent brighteners such as ru-naphthalene derivatives, bisbenzoxazolyl-thiophene derivatives, and coumarin derivatives. The said additive can be utilized with the known compounding quantity at the time of mix | blending with polycarbonate resin. For example, the light diffusing agent is preferably in the range of 0.005 to 20 parts by weight with respect to 100 parts by weight of the polycarbonate resin, and the white pigment is preferably in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the polycarbonate resin. The agent is preferably in the range of 0.0001 to 1 part by weight per 100 parts by weight of the polycarbonate resin.

  The polycarbonate resin composition of the present invention has a fatty acid ester compound for the purpose of improving the dispersion efficiency of the phosphor particles in the resin and reducing the concentration distribution, and for imparting releasability from the mold during molding. Can be used.

  Such a fatty acid ester is preferably a partial ester or a total ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Such partial esters or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol. Tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, and 2 -Ethylhexyl stearate, among others, stearic acid monoglyceride, stearic acid triglyceride, pen Pentaerythritol tetrastearate are preferably used. The amount of the fatty acid ester used is preferably 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

  In the polycarbonate resin composition of the present invention, a release agent can be used to the extent that the object of the present invention is not impaired in order to further improve the mold release property from the mold during melt molding. Examples of the mold release agent include the fatty acid esters, polyorganosiloxane, paraffin wax, and beeswax. The amount of the release agent used is preferably 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the A component polycarbonate resin.

  In the polycarbonate resin composition of the present invention, various dyes can be used in addition to the bluing agent as long as the effects of the invention are exhibited. In particular, a dye is preferable because it does not impair the transparency. On the other hand, a deeper color or a metallic pigment can be blended to obtain a better metallic color.

  As dyes, perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindo Examples thereof include linone dyes and phthalocyanine dyes. Furthermore, fluorescent whitening agents such as bisbenzoxazolyl-stilbene derivatives, bisbenzoxazolyl-naphthalene derivatives, bisbenzoxazolyl-thiophene derivatives, and coumarin derivatives can be used. The amount of these dyes and fluorescent brightening agent used is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, per 100 parts by weight of the polycarbonate resin of component A.

  In the polycarbonate resin composition of the present invention, an amount of flame retardant that does not impair the object of the present invention can be used. Examples of the flame retardant include brominated epoxy resin, brominated polystyrene, brominated polycarbonate, brominated polyacrylate, monophosphate compound, phosphate oligomer compound, phosphonate oligomer compound, phosphonitrile oligomer compound, phosphonic acid amide compound, sulfonate salt Organic acid metal salts other than these, silicone flame retardants, and the like can be used, and one or more of them can be used. Each of these flame retardants can be blended in a known amount relative to the polycarbonate resin.

  In the polycarbonate resin composition of the present invention, other resins and elastomers can be used in a small proportion within a range where the object of the present invention is not impaired.

  Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethylene, and polypropylene. And other resins such as polyolefin resin, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, phenol resin, and epoxy resin.

  As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate / styrene / butadiene) which is a core-shell type elastomer. Examples thereof include rubber and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.

  Various inorganic fillers, flow modifiers, antibacterial agents, photocatalytic antifouling agents, infrared absorbers, photochromic agents, and the like can be blended in the polycarbonate resin composition of the present invention.

<About the manufacturing method of a resin composition>
In producing the polycarbonate resin composition of the present invention, the production method is not particularly limited. However, since it is necessary for the phosphorescent substance to be uniformly dispersed in the polycarbonate resin in the molded article, the resin composition of the present invention is preferably produced by melt-kneading each component.

  Specific examples of the melt kneading method include a Banbury mixer, a kneading roll, and an extruder. Among them, an extruder is preferable from the viewpoint of kneading efficiency, and a multi-screw extruder such as a twin screw extruder is more preferable.

  A typical example of the twin screw extruder is ZSK (trade name, manufactured by Werner & Pfleiderer). Specific examples of similar types include TEX (trade name, manufactured by Nippon Steel Works, Ltd.), TEM (trade name, manufactured by Toshiba Machine Co., Ltd.), KTX (product name, manufactured by Kobe Steel, Ltd.), and the like. Can be mentioned. In addition, melt kneaders such as FCM (manufactured by Farrel, trade name), Ko-Kneader (manufactured by Buss, trade name), and DSM (manufactured by Krauss-Maffei, trade name) can be given as specific examples.

  Among the above, the type represented by ZSK is more preferable. In such a twin screw extruder, a more preferred embodiment is as follows. As the screw shape, one, two, and three screw screws can be used, and in particular, a two-thread screw that has a wide range of application in both the ability to convey the molten resin and the shear kneading ability can be preferably used.

  The ratio (L / D) of the screw length (L) to the diameter (D) in the twin screw extruder is preferably 20 to 40, more preferably 28 to 38. When L / D is large, uniform dispersion of the phosphorescent substance is easily achieved. On the other hand, when the L / D is too large, the resin may be decomposed due to thermal degradation, and physical properties such as impact resistance may be lowered.

  Various specifications are possible for the screw configuration of the twin screw extruder. The fact that such specifications can be changed arbitrarily is also a great advantage of the ZSK type. The screw must have at least one kneading zone composed of a kneading disk segment (or a kneading segment corresponding to the kneading segment) for improving kneadability. More preferred is an embodiment having two or three kneading zones composed of the segments.

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

  Furthermore, the method for supplying the component B phosphor particles to the extruder is not particularly limited, but the phosphor particles used in the present invention are relatively hard solids, and the quality may be deteriorated during extrusion due to moisture absorption. In such a case, the following method is also preferable. (I) A method in which the phosphor particles and the polycarbonate resin are heated and dried, and then supplied into the extruder separately from the polycarbonate resin using a side feeder or the like. (Ii) A method in which phosphor particles and polycarbonate resin powder are premixed using a mixer such as a super mixer and then supplied to an extruder. One of the methods is a method in which all necessary raw materials are premixed and fed to an extruder. In another method, a master agent containing a high concentration of a phosphorescent substance is prepared, and the master agent is separately or further premixed with the remaining polycarbonate resin or the like, and then supplied to an extruder. The master agent can be selected from either a powder form or a form obtained by compressing and granulating the powder. Other premixing means include, for example, a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. A high-speed stirring type mixer such as a super mixer is preferable. Still another premixing method is, for example, a method in which a polycarbonate resin and phosphor particles are uniformly dispersed in a solvent and then the solvent is removed. (Iii) A method of melting and kneading phosphor particles and polycarbonate resin in advance to form a master pellet.

  The resin extruded from the twin-screw extruder is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. Furthermore, when it is necessary to reduce the influence of external dust or the like, it is preferable to clean the atmosphere around the extruder.

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

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

  Thereby, in addition to excellent light emitting performance, a molded article of a polycarbonate resin composition having good hue and thermal stability is provided. That is, according to the present invention, it comprises 100 parts by weight of component A, 0.01 to 100 parts by weight of component B, 0.001 to 0.1 parts by weight of component C, and 0.01 to 10 parts by weight of component D. A molded article obtained by melt-molding a polycarbonate resin composition is provided.

  As the molded article of the present invention, when the B component is a phosphorescent phosphor, various safety signs (traffic signs, emergency light signs, etc.), vehicle members (reflectors, meter members, accessories, etc.), sheet-like shapes In addition to members (including film members, such as guardrails, display devices, outdoor signboards, vending machine covers, etc.), etc., parts for lighting lamp covers and game machines (pachinko machines, etc.) (circuit covers, chassis, pachinko balls) Conveyance guides, etc.) and OA equipment parts (computers, mobile phone housings, covers, etc.). In addition, it can be suitably used in a light emitting device that uses white light as ultraviolet light (preferably by an ultraviolet LED) or near ultraviolet light (preferably by a near ultraviolet LED).

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

  The polycarbonate resin composition of the present invention is excellent in thermal stability and hue during processing, and effectively exhibits the light emitting performance of aluminate-based phosphors. As a result, a polycarbonate resin composition having high practicality is provided. Because it is possible, it is widely useful in various fields such as buildings, building materials, agricultural materials, marine materials, vehicles, electrical / electronic equipment, machinery, etc. Especially for light-emitting devices and safety signs such as safety signs The present invention provides extremely useful molded articles for members, building materials and other molded articles, sheets, and film members. Therefore, the industrial effect exhibited by the present invention is extremely great.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above-mentioned requirements. More specifically, the resin compositions described in the examples described later are exemplified. Of course, such a composition is an example, and the present invention is not limited to these forms.

The following examples further illustrate the present invention. The evaluation was based on the following method.
(1) Particle size distribution of phosphor particles: The particle size distribution of each phosphor particle sample was measured using a centrifugal automatic particle size distribution measuring apparatus “CAPA-500” manufactured by Horiba, Ltd.
(2) Luminous performance of the molded article: A test piece (length 70 mm × width 50 mm × thickness 2 mm) having a thickness of 2 mm is irradiated with light from the standard light source D65 at a brightness of 200 ± 10 lux for 4 minutes, and 120 seconds after the end of irradiation. The emission luminance (mcd / m ² ) after minutes was measured using a BN-8 luminance meter manufactured by TOPCON. The light emission luminance was an average value of three molded products.
(3) Molecular weight of molded product: When molding the test piece of the evaluation (2), the molding cycle was continuously set to 60 seconds by extending the cooling time, and the molding of the 40th shot from the start of molding was stable. The molded product was collected and its viscosity average molecular weight was measured by the method described in the text. It shows that it is inferior to shaping | molding heat stability, so that a value is small.
(4) Hue of molded product: The appearance of the test piece of the evaluation (2) was visually observed on the upper surface, the lower surface, and the side surface, and the hue was evaluated. The evaluation results were classified as follows.
○: Hue deterioration or coloring of the molded product is not observed. Δ: Slight hue deterioration or coloring is observed in the molded product. X: Severe hue deterioration or coloring is observed in the molded product. Property: About the test piece of thickness 2mm obtained by the said method, a sunshine weather meter (Suga Test Instruments Co., Ltd. product: WEL-SUN: HC-B) was used, black panel temperature 63 degreeC, and humidity 50 %, The viscosity average molecular weight of the molded product after 1000 hours of treatment with water spraying for 18 minutes and no spraying for 102 minutes for a total of 120 minutes as one cycle, and the viscosity average molecular weight of the molded product without such treatment The difference was obtained by subtracting the latter from the former and was calculated as “Δ molecular weight”. For the measurement of the viscosity average molecular weight of the molded article, three sheets were measured both before and after the treatment, and the average value was used as the viscosity average molecular weight.

[Examples 1-7, Comparative Examples 1-3]
Phosphors and other additives listed in Table 1 are added to the polycarbonate resin powder at the blending ratios listed in Table 1, and the mixture is uniformly mixed with a blender. The mixture was melt kneaded to obtain pellets. In addition, about the phosphite ester stabilizer and the ultraviolet absorber, a preliminary mixture with a polycarbonate resin powder was prepared in advance with a concentration of 10 times the blending amount as a guide, and then the whole was mixed by a blender. The vent type twin-screw extruder used was TEX30XSST (completely meshed, rotating in the same direction, double thread screw) manufactured by Nippon Steel Works. The kneading zone was of one type before the vent opening. Extrusion conditions were a discharge rate of 22 kg / h, a screw rotation speed of 120 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 270 ° C. from the first supply port to the die part.

  The obtained pellets were dried in a hot air circulation dryer at 120 ° C. for 5 hours, and then using an injection molding machine, a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., and a firing speed of 60 mm / sec, a molding cycle of 35 A test piece (a plate-like test piece having a length of 70 mm, a width of 50 mm, and a thickness of 2 mm) was molded under the condition of seconds. The injection molding machine used was Mitsubishi Heavy Industries, Ltd .: 80MSP-SC. Samples after 10 shots after the start of molding were continuously taken as samples, and the required number was selected at random from the evaluation. The evaluation results are shown in Table 1.

  Moreover, after drying the obtained pellet by the same method, the safety sign board | substrate shown in FIG. 1 is injection-molded machine (SG260M by Sumitomo Heavy Industries, Ltd.) on the conditions of cylinder temperature 280 degreeC and mold temperature 80 degreeC. -HP). This safety sign board made with each composition of the example has a good appearance such as hue, and also has good phosphorescent performance, so it is visible even in situations where it is difficult to see from a distance such as a dark place or dense fog. It is a safety sign board with excellent properties.

In addition, the content of each component, such as the luminous fluorescent substance of a symbol description in the said Example explanatory note and Table 1, and a heat stabilizer, is as follows.
(Component A)
PC-1: Polycarbonate resin powder having a viscosity average molecular weight of 22,200 produced by an interfacial polycondensation method from bisphenol A and phosgene (manufactured by Teijin Chemicals Ltd .: Panlite L-1225WP)
PC-2: Viscosity average molecular weight 20,300 copolymer polycarbonate resin powder produced by the following production method PC-3: Viscosity average molecular weight 14,500 copolymer polycarbonate resin powder produced by the following production method

(Method for producing PC-2)
A reactor equipped with a thermometer and a stirrer was charged with 19580 parts by weight of ion-exchanged water and 3850 parts by weight of a 48.5% by weight aqueous sodium hydroxide solution, and 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene ( 1175 parts by weight (hereinafter referred to as “BCF”), 2835 parts by weight of bisphenol A (hereinafter referred to as “BPA”) and 9 parts by weight of hydrosulfite were dissolved, and then 1310 parts by weight of methylene chloride was added and stirred at 15 ° C. with vigorous stirring. Then, the reaction was carried out by blowing in 2000 parts by weight of phosgene for about 40 minutes. After completion of the phosgene blowing, the mixture was raised to 28 ° C. and emulsified by adding 94 parts by weight of p-tert-butylphenol and 640 parts by weight of sodium hydroxide, and then 6 parts by weight of triethylamine was added and stirring was continued for 1 hour to complete the reaction. . After completion of the reaction, the organic phase was separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase was almost the same as that of ion-exchanged water, the methylene chloride was evaporated in a kneader. Thus, 4080 parts by weight of colorless powder having a molar ratio of BCF and BPA of 20:80 was obtained. The polycarbonate resin powder had a viscosity average molecular weight of 20,300.
(Method for producing PC-3)
A reactor equipped with a thermometer and a stirrer was charged with 22600 parts by weight of ion-exchanged water and 2700 parts by weight of a 48.5% by weight aqueous sodium hydroxide solution, and was charged with 4,4 '-(m-phenylenediisopropylidene) diphenol (hereinafter referred to as "4. 2518 parts by weight (referred to as “BPM”), 2001 parts by weight of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter referred to as “BTC”) and 10 parts by weight of hydrosulfite are dissolved. After that, 14121 parts by weight of methylene chloride was added and 1631 parts by weight of phosgene was blown into the reaction at 25 ° C. for about 40 minutes with vigorous stirring. After the phosgene blowing, the temperature was raised to 28 ° C. and 90.0 parts by weight of p-tert-butylphenol was added for emulsification, and then 3 parts by weight of triethylamine was added and stirring was continued for 1 hour to complete the reaction. After completion of the reaction, the organic phase was separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase was almost the same as that of ion-exchanged water, the methylene chloride was evaporated in a kneader. Thus, 4600 parts by weight of colorless powder having a molar ratio of BPM and BTC of 53:47 was obtained. The aromatic polycarbonate powder had a viscosity average molecular weight of 14,500.

(B component)
B-1: Strontium aluminate-based phosphorescent phosphor “N Yoko Luminova G-300F” manufactured by Nemoto Special Chemical Co., Ltd. (particles having a particle size of less than 10 μm are 34% by weight of the total particles, and particles exceeding 50 μm are particles (The total particle size is 6% by weight and the average particle size is 15 μm)
B-2 (for comparison): Strontium aluminate-based phosphorescent phosphor “N Nocturnal Luminova G-300FF” manufactured by Nemoto Special Chemical Co., Ltd. (particles having a particle size of less than 10 μm account for 100% by weight of the total particle, average particle size) (The diameter is 4μm)
B-3 (for comparison): Nemoto Special Chemical Co., Ltd. strontium aluminate-based phosphorescent phosphor “N Nightlight Luminova G-300M” (particles having a particle size of less than 10 μm account for 19% by weight of the total particle, 50 μm (Exceeding particle is 24% by weight of the whole particle, and the average particle size is 29 μm)
B-4 (for comparison): phosphor in which B-2 and B-3 are mixed at a weight ratio of 1: 1 (particles having a particle size of less than 10 μm are 59% by weight of the total particles, and particles having a particle size exceeding 50 μm (The total particle size is 12% by weight and the average particle size is 16 μm)

(C component)
C-1: Tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite as a main component and about 10 tris (2,4-di-tert-butylphenyl) phosphite Stabilizer mixture containing wt% (Clariant Japan Co., Ltd .: Sandstub P-EPQ)

(D component)
D-1: Benzotriazole-based ultraviolet absorber (Kemipro Kasei Co., Ltd .: Chemisorb 79)
D-2: Cyclic imino ester ultraviolet absorber (2,2′-p-phenylenebis (3,1-benzoxazin-4-one), manufactured by Takemoto Yushi Co., Ltd .: CEi-P)

[Reference Example 1]
Pellets were obtained by the same method as in Example 1 except that the phosphorescent resin and other additives were not blended with the polycarbonate resin (PC) used in Example 1. The obtained pellets were molded in the same manner as in Example 1. The evaluation results of the obtained molded plate are shown in Table 1.

  As is clear from the above table, it can be seen that the resin composition of the present invention is excellent in phosphorescent performance, and a polycarbonate phosphorescent resin composition excellent in thermal stability during processing and a molded product thereof can be obtained. On the other hand, in the technique shown in the comparative example, either characteristic is not fully satisfied.

The molded article of the safety sign board | substrate shape | molded in the Example is shown. As shown, the lens has a dome shape. [1-A] is a front view (a figure projected onto a platen surface during molding. Therefore, such an area is the maximum projected area), and [1-B] is a cross-sectional view taken along line AA.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Safety sign board | substrate body 2 The dome-shaped part of a board | substrate 3 The outer peripheral part of a board | substrate 4 The gate of a molded product (width 30mm, thickness of a gate part 4mm)
5 Sprue (diameter 7mmφ of gate part)
6 Diameter of the outer periphery of the substrate (220mm)
7 Diameter of substrate dome (200mm)
8 Board dome height (20mm)
9 Thickness of substrate molding (4mm)

Claims (4)

  It consists of 100 parts by weight of polycarbonate resin (component A) and phosphor particles (component B) containing aluminate as a base crystal (0.01 to 100 parts by weight). A polycarbonate resin composition characterized by containing 40% by weight or less of particles and a particle having a particle diameter of more than 50 μm in a proportion of 10% by weight or less.   Furthermore, the polycarbonate resin composition of Claim 1 formed by containing 0.001-0.1 weight part of phosphorous acid ester (C component) per 100 weight part of A component.   The polycarbonate resin composition according to any one of claims 1 and 2, further comprising 0.01 to 2 parts by weight of an ultraviolet absorber (component D) per 100 parts by weight of component A.   The molded article formed by melt-molding the polycarbonate resin composition of any one of the said Claims 1-3.

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