JP2010159318A - Luminosity fluorescent polycarbonate resin composition and molded article - Google Patents

Abstract

The present invention provides a phosphorescent fluorescent resin composition having excellent light emitting characteristics and extremely high whiteness.
To 100 parts by mass of an A component (polycarbonate resin), a transparent or semi-transparent or semi-B component (incompatible with the A component and having a refractive index of 0.01 to 0.2 smaller than that of the A component). 0.1 to 100 parts by mass of transparent material) and C component (Eu, Ln activated silicate phosphorescent phosphor represented by the following formula (1) having an oxide composition as a base) 0.1 to 50 parts by mass A phosphorescent fluorescent polycarbonate resin composition characterized by comprising. And the phosphorescent fluorescent polycarbonate resin composition characterized by further containing 0.0001-0.1 mass part fluorescent whitening agent.
^{_{m (Sr 1-a M 1}} a O) · n (Mg 1-b M 2 b O) · 2 (Si 1-c Ge c O 2): Eu, Ln
... (1)
[Selection figure] None

Description

The present invention relates to a phosphorescent fluorescent polycarbonate resin composition and a molded product thereof, and more particularly, the phosphor of the molded product is excellent in hue and hue at the time of fluorescent light emission, and in particular, the phosphorescent fluorescence having high body color whiteness and excellent aesthetics. The present invention relates to a polycarbonate resin composition and a molded product formed by melt-molding this phosphorescent fluorescent polycarbonate resin composition.
The molded article of the present invention is useful as an electric signboard, liquid crystal backlight, illumination display, traffic sign, safety sign, night visibility improving member, sign board, screen and the like.

  Thermoplastic resins have a wide range of uses because they are lighter than inorganic glass, have high colorability and a high degree of freedom in the shape of molded products, and are excellent in productivity. Among them, polycarbonate resins, especially aromatic polycarbonate resins, are used in various fields because they are excellent in impact resistance, heat resistance, dimensional stability and transparency in addition to the above-mentioned characteristics of thermoplastic resins. . The polycarbonate resin is also suitably used as an electric signboard, lighting display, traffic sign, safety sign, night visibility improving member, sign board, screen, etc. by taking advantage of this feature and further improving the visibility. .

  Conventionally, mixing phosphors (luminescent pigments) is known as a method for improving the visibility of thermoplastic resins. However, the phosphor generally has a high hardness, and the surface of the mixer is worn when the synthetic resin and the phosphor are mixed, and the barrel and the screw surface are worn when the mixture is melt-kneaded by the extruder. And since the metal piece which generate | occur | produced by this abrasion mixes in resin, there are many problems that a resin composition often becomes dark brown or black, and the commercial value is remarkably lowered. As a method for solving this problem, Patent Document 1 discloses an alkaline earth aluminin as a phosphorescent phosphor that has excellent long persistence and does not cause darkening in a resin composition obtained by kneading with a resin. A phosphorescent phosphor having a specific particle diameter using an acid salt as a base crystal and a rare earth element as an activator has been proposed. Patent Document 2 discloses a resin composition comprising a polycarbonate resin and an aluminate-based phosphor having a specific particle diameter as a resin composition that is excellent in thermal stability and hue during processing and that effectively exhibits light emitting performance. Has been proposed. However, none of the resin compositions has yet been sufficiently effective in improving darkening (hue). Furthermore, Patent Document 3 discloses a thermoplastic resin and a formula M-Al (wherein M is a resin composition that exhibits melt flow stability and does not cause much graying (darkening) during compounding in an extruder. A phosphor having a aluminate matrix represented by one or more metal elements selected from the group consisting of calcium, strontium and barium, and Al is an aluminate group). Thermoplastic resin compositions have been proposed. However, a resin composition excellent in long-time persistence and fluorescent properties from blue to blue-green to green has not yet been proposed.

Patent Documents 4 and 5 propose a silicate phosphorescent phosphor whose base material is a specific oxide composition as a phosphor excellent in long-time persistence and fluorescence characteristics from blue to blue-green to green. .
However, according to the study of the present inventors, these phosphors, when mixed with a thermoplastic resin, particularly a polycarbonate resin commonly used in a resin composition containing the phosphor, and heated and melted, significantly deteriorate the polycarbonate resin. . Further, the hue of the resin composition obtained is not satisfactory.

  In order to solve this problem, the present inventor examined a method for preventing deterioration of the resin when the silicate phosphorescent phosphor described in Patent Documents 4 and 5 is mixed with a thermoplastic resin and melted by heating. As a result, by adding an organosilane compound and / or silicone compound together with this silicate phosphorescent phosphor to the thermoplastic resin, the resin will not deteriorate even when heated and melted, and the hue will be satisfactory. And previously filed a patent application (Patent Document 6, Japanese Patent Application No. 2008-059943, hereinafter referred to as “prior application”).

  According to the thermoplastic resin composition of the prior application, a phosphorescent fluorescent resin composition having a better hue than that of the conventional product is provided. Highly luminous phosphorescent resin composition is demanded. That is, a material with high whiteness is excellent in aesthetics and senses cleanliness, refreshment, freshness, and the like, and improvement in whiteness is desired in various decorative displays and the like.

  Conventionally, as a technique for increasing the whiteness of a general material, there is a method of blending a white pigment such as titanium oxide. However, when a white pigment is blended in a phosphorescent fluorescent resin composition, the pigment blocks light. As a result, the fluorescence emission becomes weak, and such a method is inappropriate.

JP-A-11-209753 JP 2005-82647 A JP 2005-528510 A JP-A-9-194833 Japanese Patent Laid-Open No. 9-241631 Japanese Patent Application No. 2008-059943

  The present invention has been made in view of the above-described conventional circumstances, and an object of the present invention is to provide a phosphorescent fluorescent resin composition having excellent light emitting characteristics and extremely high whiteness.

  As a result of intensive studies to solve the above problems, the present inventor has obtained a phosphorescent fluorescent polycarbonate resin composition obtained by blending a specific Eu, Ln activated silicate phosphorescent phosphor with a polycarbonate resin. By blending a transparent or translucent material that is incompatible and has a slightly lower refractive index than that of polycarbonate resin, the body color due to light scattering effect at the interface between polycarbonate resin and this low refractive index material It was found that the whiteness of can be improved. Furthermore, it discovered that a body color can be made into the whiteness which is not conventionally by mix | blending a fluorescent whitening agent.

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

[1] A phosphorescent polycarbonate resin composition comprising 0.1 to 100 parts by mass of the following B component and 0.1 to 50 parts by mass of the following C component with respect to 100 parts by mass of the following A component. object.
A component: polycarbonate resin B component: A transparent or translucent material (hereinafter referred to as “light”) that is incompatible with the A component and has a refractive index of 0.01 to 0.2 smaller than that of the A component. Sometimes referred to as "scattering component".)
C component: Eu, Ln activated silicate phosphorescent phosphor represented by the following formula (1) whose matrix is an oxide composition m (Sr _1-a M ¹ _a O) · n (Mg _1-b M ² _b O ) · 2 (Si _1-c Ge _c O ₂ ): Eu, Ln
... (1)
(Wherein M ¹ is one or more elements selected from Ca and Ba, M ² is one or more elements selected from Be, Zn and Cd, Ln is Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, B, Al, Ga, In, Tl, Sb, Bi, As, P, Sn, Pb, Ti, Zr, Hf, V, It represents one or more elements selected from Nb, Ta, Mo, W, Cr and Mn, where a, b, c, m and n represent the following numbers.
0 ≦ a ≦ 0.8
0 ≦ b ≦ 0.2
0 ≦ c ≦ 0.2
1.5 ≦ m ≦ 3.5
0.5 ≦ n ≦ 1.5)

[2] The phosphorescent fluorescent polycarbonate resin composition according to [1], wherein the following D component is contained in an amount of 0.5 to 13% by mass based on the C component.
Component D: Organosilane compound and / or silicone compound represented by the following formula (2) (R ¹ O) _p SiR ² _4-p (2)
(In the formula, R ¹ and R ² represent organic groups, and p represents an integer of 1 to 4.)

[3] In [1] or [2], the B component is selected from the group consisting of ABS resin, AES resin, AS resin, MBS resin, MS resin, PMMA resin, glass beads, acrylic fine particles, and silicone fine particles. A phosphorescent fluorescent polycarbonate resin composition characterized by being one or more kinds.

[4] In any one of [1] to [3], Ln, which is an activator of component C, is one or more elements selected from Dy, Nd, Tm, Sn, In, and Bi. A phosphorescent fluorescent polycarbonate resin composition.

[5] In any one of [2] to [4], R ¹ in formula (2) is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ² is an aromatic or fatty acid having 6 to 12 carbon atoms. A cyclic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbon group having an ethylenically unsaturated bond having 2 to 16 carbon atoms, or a hydrocarbon group having an epoxy group having 3 to 15 carbon atoms. A phosphorescent fluorescent polycarbonate resin composition, wherein p is an integer of 1 to 3.

[6] In any one of [2] to [5], as 100 parts by mass of A component, 0.1 to 100 parts by mass of B component, 0.5 to 30 parts by mass of C component, and D component A phosphorescent fluorescent polycarbonate resin composition comprising 1 to 10% by mass of the organosilane compound with respect to component C.

[7] In any one of [2] to [4], 0.1 to 100 parts by mass of B component, 0.5 to 30 parts by mass of C component, and 100% of the silicone as D component with respect to 100 parts by mass of A component A phosphorescent polycarbonate resin composition comprising 1 to 6% by mass of a compound relative to component C.

[8] The phosphorescent fluorescent polycarbonate according to any one of [1] to [7], further containing 0.0001 to 0.1 parts by mass of a fluorescent brightening agent with respect to 100 parts by mass of the component A. Resin composition.

[9] The phosphorescent fluorescent polycarbonate resin composition according to [8], wherein the fluorescent brightening agent is one or more selected from the group consisting of a benzoxazole-based compound and a coumarin-based compound.

[10] A phosphorescent fluorescent polycarbonate resin composition according to any one of [1] to [9], wherein the component C surface-treated with the component D is melt kneaded with other components.

[11] A molded product obtained by melt-molding the phosphorescent fluorescent polycarbonate resin composition according to any one of [1] to [10].

[12] A molded product formed by multicolor composite molding of the phosphorescent fluorescent polycarbonate resin composition according to any one of [1] to [11] and a thermoplastic resin composition containing no C component.

According to the present invention, the excellent long persistence derived from Eu, Ln activated silicate phosphorescent phosphor and the light emission characteristics of blue to blue-green to green are not impaired, and the hue of the molded article exhibits a remarkably good white color. A phosphorescent fluorescent polycarbonate resin composition can be provided.
Furthermore, the heat stability at the time of processing, a light emission characteristic, and a hue can also be improved further by mix | blending a specific component.

  The molded product of the present invention obtained by melt-molding the phosphorescent fluorescent polycarbonate resin composition of the present invention is excellent in hue and light emission characteristics, and is excellent in mechanical strength, heat resistance, and moist heat resistance (the hue is hardly changed by wet heat). Automotive parts such as electrical signs, liquid crystal backlights, lighting displays, luminaire covers, traffic signs, safety signs, night visibility improving members, sign boards, screens, reflectors, and meter parts It is suitable for OA equipment parts, as well as toys and ornaments.

  Hereinafter, embodiments of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

[Polycarbonate resin (component A)]
Examples of the polycarbonate resin (component A) that is a main component of the phosphorescent fluorescent polycarbonate resin composition of the present invention include aromatic polycarbonate resins, aliphatic polycarbonate resins, and aromatic-aliphatic polycarbonate resins. Specifically, a thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic dihydroxy compound with phosgene or a diester of carbonic acid is used.

  Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), tetramethylbisphenol A, α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, Resorcinol, 4,4′-dihydroxydiphenyl and the like can be mentioned. Further, as a part of the dihydroxy compound, when the above-mentioned aromatic dihydroxy compound is combined with one or more tetraalkylphosphonium sulfonates, or a polymer or oligomer containing both terminal phenolic OH groups having a siloxane structure, A highly flame-retardant polycarbonate resin can be obtained.

  Preferred examples of the polycarbonate resin (component A) used in the present invention include 2,2-bis (4-hydroxyphenyl) propane as a dihydroxy compound, or 2,2-bis (4-hydroxyphenyl) propane and other aromatics. A polycarbonate resin used in combination with a dihydroxy compound is exemplified. In the present invention, two or more polycarbonate resins may be used in combination as the component A.

  The molecular weight of the polycarbonate resin (component A) used in the present invention is usually 14,000 to 30,000 in terms of viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent. Preferably, those having a molecular weight of 15,000 to 28,000 are used. When the viscosity average molecular weight is within this range, a resin composition that gives a molded product having generally good moldability and high mechanical strength can be obtained. The most preferred molecular weight range of the polycarbonate resin is 16.000 to 26,000.

  The method for producing the polycarbonate resin is not particularly limited, and a polycarbonate resin produced by any of the phosgene method (interfacial polymerization method) and the melting method (transesterification method) can also be used. Moreover, it is also preferable to use the polycarbonate resin which performed the post-process which adjusts the amount of terminal OH groups to the polycarbonate resin manufactured by the melting method.

  Further, the polycarbonate resin (component A) used in the present invention may be not only a polycarbonate resin as a virgin raw material but also a polycarbonate resin regenerated from a used product, a so-called material recycled polycarbonate resin. Such polycarbonate resins include optical recording media such as optical discs, light guide plates, automobile window glass and automobile headlamp lenses, vehicle transparent members such as windshields, containers such as water bottles, glasses lenses, soundproof walls and glass windows, The thing reproduced from building materials, such as a corrugated sheet, is mentioned. In addition, a polycarbonate resin regenerated from a rejected product, sprue, runner or the like when a molded product is manufactured from the polycarbonate resin can be used.

  The refractive index of the polycarbonate resin is usually 1.5 to 1.6 although there is a slight difference depending on the molecular structure.

[Light scattering component (B component)]
The B component used in the present invention is a transparent or translucent material that is incompatible with the polycarbonate resin as the A component and has a refractive index of 0.01 to 0.2 smaller than that of the polycarbonate resin.

  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.

  This B component has a refractive index of 0.01 to 0.2 smaller than the polycarbonate resin of the A component. If the difference in refractive index between the B component and the polycarbonate resin component is less than 0.01, it is not possible to obtain a sufficient light scattering effect by blending the B 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 agent that can be recognized on the surface of the molded body is lowered. The component B preferably has a refractive index of 0.05 to 0.12 smaller than that of the polycarbonate resin.

  The B component may be any material that is incompatible with the A component, has a refractive index difference in the above range, and is transparent or translucent. The materials include organic materials, inorganic materials, and organic-inorganic composite materials. Any of these may 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 component B 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.
Olefins 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 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>
As resin fine particles suitable as the component B, acrylic fine particles (1.49), silicone fine particles (1.45), styrene fine particles (1.59), epoxy fine particles (1.60), 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 the component B 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 B component, you may use together 2 or more types of said resin material, resin microparticles | fine-particles, and inorganic material microparticles | fine-particles.

  In addition, when using the thing of a particulate form as B component, if the particle size is too small, handling property will be bad, and the transparency will be too good to make it look white. Conversely, if the particle size is excessively large, the moldability is impaired and the surface appearance may be inferior. Therefore, the average particle size of the B component fine particles is preferably 0.1 to 30 μm, particularly preferably 0.5 to 20 μm.

  In this invention, B component is 0.1-100 mass parts with respect to 100 mass parts of A component, Preferably it is 0.5-50 mass parts, More preferably, 1-30 weight part is mix | blended. If the amount of the B component is less than the above range, the effect of improving the whiteness due to the blending of the B component cannot be sufficiently obtained, and if it is too much, the scattering effect is large, and the luminous intensity is inhibited because the expression of the phosphorescent action is inhibited. Decreases.

[Eu, Ln-activated silicate phosphorescent phosphor (component C)]
The phosphorescent fluorescent polycarbonate resin composition of the present invention has excellent afterglow characteristics and emission characteristics from blue to blue-green to green, and is a phosphorescent phosphor (C component) that is chemically stable and excellent in weather resistance. Containing. The Eu, Ln activated silicate phosphorescent phosphor (C component) used in the present invention has an oxide composition and is represented by the following formula (1). The manufacturing method and light emission characteristics of this phosphor are described in detail in the above-mentioned Patent Documents 4 and 5.

^{_{m (Sr 1-a M 1}} a O) · n (Mg 1-b M 2 b O) · 2 (Si 1-c Ge c O 2): Eu, Ln
... (1)
(Wherein M ¹ is one or more elements selected from Ca and Ba, M ² is one or more elements selected from Be, Zn and Cd, Ln is Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, B, Al, Ga, In, Tl, Sb, Bi, As, P, Sn, Pb, Ti, Zr, Hf, V, It represents one or more elements selected from Nb, Ta, Mo, W, Cr and Mn, where a, b, c, m and n represent the following numbers.
0 ≦ a ≦ 0.8
0 ≦ b ≦ 0.2
0 ≦ c ≦ 0.2
1.5 ≦ m ≦ 3.5
0.5 ≦ n ≦ 1.5)

  Among the Eu and Ln activated silicate phosphors represented by the above formula (1), a phosphor in which Ln is one or more elements selected from Dy, Nd, Tm, Sn, In and Bi is preferable. . As the Eu, Ln activated silicate phosphorescent phosphor (C component), for example, a phosphor sold under the product name “P170 phosphor” by Kasei Optonics Corporation can be used.

  The particle diameter of the Eu, Ln activated silicate phosphorescent phosphor (component C) used in the present invention is such that the median particle diameter (sometimes expressed as D50 value) measured by the ISO 13320 laser method is less than 70 μm. preferable. When this particle size exceeds 70 μm, the tensile elongation at break, impact strength, appearance and the like of the obtained molded product are lowered. The particle size of the component C is preferably less than 50 μm, particularly preferably less than 35 μm. The lower limit of the particle size is not limited, but is usually 10 μm. In general, when the particle size of the phosphor is too small, the light emission characteristics tend to be lowered.

  In addition, as C component, it is also possible to use 2 or more types of things from which a composition and a particle size differ.

The Eu, Ln activated silicate phosphorescent phosphor as component C is 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 100 parts by weight of the polycarbonate resin of component A. 10 parts by weight are used.
If the amount of component C is too small, sufficient light emission characteristics cannot be obtained, and if it is too large, moldability, thermal stability, mechanical strength of the molded product, and the like are impaired.

  In the phosphorescent fluorescent polycarbonate resin composition of the present invention, since the above-mentioned B component is blended together, especially when the B component is in the form of fine particles, the total blending amount of the B component and the C component is A It is preferable that the amount is 50 parts by mass or less with respect to 100 parts by mass of the component in terms of ensuring moldability, surface smoothness, good appearance, and the like.

[Organic Silane Compound and / or Silicone Compound (Component D)]
The organosilane compound used in the present invention is represented by the following formula (2).
(R ¹ O) _p SiR ² _4-p (2)
(In the formula, R ¹ and R ² represent organic groups, and p represents an integer of 1 to 4.)

Examples of the organic group represented by R ¹ and R ² include various aliphatic, aromatic and alicyclic hydrocarbon groups. These hydrocarbon groups may have an ethylenically unsaturated bond, may contain an ether bond or an ester bond inside, and further have a reactive functional group such as an epoxy group or an amino group. You may have.

Preferably, R ¹ is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R ² is an aromatic or alicyclic hydrocarbon group having 6 to 12 carbon atoms, and an aliphatic hydrocarbon group having 1 to 12 carbon atoms. , A hydrocarbon group having an ethylenically unsaturated bond having 2 to 16 carbon atoms, or a hydrocarbon group having an epoxy group having 3 to 15 carbon atoms. Particularly preferred are those in which R ¹ is an aliphatic hydrocarbon group having 1 to 4 carbon atoms and R ² is an aliphatic hydrocarbon group having 1 to 12 carbon atoms.
This organosilane compound preferably has one or more of R ¹ and R ² , and therefore p is preferably 1 to 3.

  Examples of the aromatic or alicyclic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group and a cyclohexyl group. Examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms include a methyl group, an ethyl group, and a propyl group. , Butyl group, isobutyl group, decyl group and the like. Examples of the hydrocarbon group having an ethylenically unsaturated bond having 2 to 16 carbon atoms include vinyl group, allyl group, isopropenyl group, butenyl group, and methacryloxypropyl. Groups having an ester bond such as an acryloxypropyl group, and hydrocarbon groups having an epoxy group having 3 to 15 carbon atoms include 3,4-epoxycyclohexyl group, glycidoxypropyl group, etc. Is mentioned.

  Specific examples of the organic silane compound (component D) used in the present invention include trimethylsilane, trimethoxysilane, methyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, and trimethylmethoxy. Silane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane Γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane Emissions, and the like phenyltrimethoxysilane.

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

  The silicone compound (component D) used in the present invention may be any of polyorganohydrogensiloxanes and organopolysiloxanes. The molecular weight is not particularly limited, and may belong to any group of oligomers and polymers. More specifically, polyorganohydrogensiloxanes represented by the formulas (A) to (C) described in JP-B-63-26140 and JP-B-63-31513 are described. Hydrocarbon oxysiloxanes represented by the formula: The silicone compound used as component D is preferably selected from polyorganohydrogensiloxanes. For example, it is preferable to use a polysiloxane having the following formula (3) as a repeating unit and a compound represented by the following formula (4) or (5).

(R) _α (H) _β SiO (3)
(In the above formula, R is a linear or branched alkyl group having 1 to 10 carbon atoms, and the sum of α and β is 2.)

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

(In said formula, A and B are synonymous with each in said Formula (4), and t is an integer of 1-50.)

  As the silicone compound, commercially available silicone oil, for example, SH1107 (product of Toray Dow Corning Silicone Co., Ltd.) can be used.

These silicone compounds may be used individually by 1 type, and may use 2 or more types together.
Moreover, in this invention, you may use together an organosilane compound and a silicone compound as C component.

The D component is preferably used in an amount of 0.5 to 13% by mass, more preferably 1 to 10% by mass with respect to the Eu, Ln activated silicate phosphorescent phosphor that is the C component.
The D component exhibits the function of covering the active sites on the surface of the C component to prevent the deterioration of the resin. However, if the amount of the D component is too small, this effect cannot be obtained sufficiently and obtained. The thermal stability of the resin composition is lowered, and the mechanical strength, hue, heat resistance, and heat and humidity resistance are also lowered. Conversely, if the amount of component C is too large, gas is generated during melt-kneading, which tends to cause mold deposits.

  In general, the effect of a silicone compound is smaller than that of an organic silane compound, and therefore when the silicone compound is used as the D component, the amount is preferably 1 to 6% by mass relative to the C component.

[Fluorescent brightener]
The phosphorescent fluorescent polycarbonate resin composition of the present invention preferably further contains a fluorescent brightening agent in order to further improve the whiteness.
As the fluorescent whitening agent, various conventionally known fluorescent whitening agents such as benzoxazole, stilbene, benzimidazole, naphthalimide, rhodamine, coumarin, and oxazine can be used. In particular, a white fluorescent whitening agent selected from benzoxazole-based compounds and coumarin-based compounds having a molecular weight of 300 to 1,000 is preferable from the viewpoint of thermal stability. Also, for example, distyrylbiphenyl blue fluorescent material, arylethynylbenzene blue fluorescent material, quinkipyridine fluorescent material, sexiphenyl blue fluorescent material, dimesitylborylanthracene fluorescent material, quinacridone fluorescent material White organic light emitters and blue organic light emitters selected from materials and the like can also be used as compounds exhibiting a fluorescent whitening effect.

In the resin composition of the present invention, the amount of the fluorescent brightening agent is preferably 0.0001 to 0.1 parts by mass, and 0.001 to 0.05 parts by mass with respect to 100 parts by mass of the polycarbonate resin of component A. Is more preferable.
If the amount of fluorescent whitening agent is less than the above range, the effect of adding fluorescent whitening agent cannot be obtained sufficiently. If it is too much, the phosphorescent action (excitation effect) on the phosphorescent agent is inhibited, and the light is blocked. The emission luminance of the light is reduced.

  Specific examples of the benzoxazole-based compound as the optical brightener include 4- (benzoxazol-2-yl) -4 ′-(5-methylbenzoxazol-2-yl) stilbene, 4,4′-bis ( And benzoxazol-2-yl) stilbene, 2,5-thiophenediyl (5-tert-butyl-1,3-benzoxazole), 4,4′-bis (benzoxazol-2-yl) furan and the like. Of these, stilbene benzoxazole compounds such as 4,4'-bis (benzoxazol-2-yl) stilbene are preferable.

  Specific examples of the coumarin compound include 3-phenyl-7-aminocoumarin and 3-phenyl-7- (imino-1 ′, 3 ′, 5′-triazine-2′-diethylamino-4′-chloro). -Coumarin, 3-phenyl-7- (imino-1 ', 3', 5'-triazine-2'-diethylamino-4'-methoxy) -coumarin, 3-phenyl-7-naphthotriazole coumarin, 4-methyl- Examples include 7-hydroxycoumarin. Of these, phenylallyltriazolyl coumarin compounds such as 3-phenyl-7-naphthotriazole coumarin are preferred.

[Other additives]
The phosphorescent fluorescent polycarbonate resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Examples of such additives include flame retardants, anti-dripping agents, thermal stabilizers, antioxidants, ultraviolet absorbers, mold release agents, and colorants.

<Flame Retardant>
It is preferable to add a flame retardant to the resin composition of the present invention in order to impart flame retardancy. The flame retardant is not particularly limited as long as it 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 (6) is preferable.

(In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent an optionally substituted aryl group, and X represents a divalent aromatic group which may have a substituent. Y represents a number from 0 to 5.)

In the above formula (6), examples of the aryl group represented by R ^{11 to} R ¹⁴ include a phenyl group and a naphthyl group. Examples of the divalent aromatic group represented by X 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 y is 0, the compound represented by Formula (6) is a phosphate ester, and when y is greater than 0, it is a condensed phosphate ester (including a mixture).

  Specific examples of the compound represented by the above formula (6) 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)). These may be used alone or in combination of two or more.

  The content of the phosphoric acid ester compound for the flame retardant in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass with respect to 100 parts by mass of the component A. More preferably, it is 5-30 mass parts. 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. These may be used alone or in combination of two or more. You may do it. The metal constituting the organic sulfonic acid metal salt is preferably an alkali metal, an alkaline earth metal, etc., and the alkali metal and the alkaline earth metal include sodium, lithium, potassium, rubidium, cesium, beryllium, magnesium. , Calcium, strontium and barium.

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

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

  The content of these organic sulfonic acid metal salts in the resin composition of the present invention is preferably 0.01 to 5 parts by mass, and 0.02 to 3 parts by mass with respect to 100 parts by mass of component A. Is more preferably 0.03 to 2 parts by mass. 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.

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

<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, and 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 the polytetrafluoroethylene (PTFE) which has a fibril formation ability, For example, what is classified into the type 3 in ASTM standard 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.

  The content of the dripping inhibitor in the resin composition of the present invention is preferably 0.05 to 2 parts by mass and more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the component A. 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. If the content of the dripping inhibitor exceeds 2 parts by mass with respect to 100 parts by mass of the component A, it is not preferable because the stored fluorescent fluorescence before and after the heat resistance test is lowered.

<Heat stabilizer>
It is preferable to add a heat stabilizer to the resin composition of the present invention in order to improve the heat stability. Preferable heat stabilizers include phosphorus heat stabilizers such as phosphites and phosphates.

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

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

Among the above phosphorus-based heat stabilizers, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol phosphite, bis (2,6-di-tert-butyl-4) -Methylphenyl) pentaerythritol phosphite and tris (2,4-di-tert-butylphenyl) phosphite are preferred. Among them, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite and Tris (2,4-di-t-butylphenyl) phosphite is particularly preferred.
In addition, a heat stabilizer may be used independently and may be used in combination of 2 or more type.

  The content of the heat stabilizer in the resin composition of the present invention is preferably 0.005 to 0.2 parts by mass, and 0.01 to 0.1 parts by mass with respect to 100 parts by mass of component A. Is more preferable. It is preferable for the content of the thermal stabilizer to be in the above-mentioned range since the thermal stability can be improved without causing hydrolysis or the like.

<Antioxidant>
It is preferable to add an antioxidant to the resin composition of the present invention.
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-methyl Eniru) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-spiro [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.

  It is preferable that content of the antioxidant in the resin composition of this invention is 0.002-0.5 mass part with respect to 100 mass parts of A component. This range is preferable because the antioxidant property can be improved without inhibiting the effects of the present invention.

<Ultraviolet absorber>
It is preferable to add an ultraviolet absorber to the resin composition of the present invention. Molded articles made of the resin composition of the present invention tend to be yellowish by ultraviolet rays when exposed to light such as sunlight or fluorescent lamps for a long time, but by adding an ultraviolet absorber, It can prevent or delay that a molded article becomes yellowish. Examples of the ultraviolet absorber include benzophenone, benzotriazole, phenyl salicylate, and hindered amine.

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

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

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

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

  The content of the ultraviolet absorber in the resin composition of the present invention is preferably 0.01 to 2 parts by mass, and 0.05 to 1.5 parts by mass with respect to 100 parts by mass of the component A. More preferably, it is 0.1-1 part by mass. When the content of the ultraviolet absorber is in the above range, the luminance is not lowered due to the toning property and excitation light absorption of the silicate phosphor, and the bleedout or the like is not generated on the surface of the molded product. It is preferable because the weather resistance can be improved.

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

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

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

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

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

<Colorant>
The resin composition of the present invention is intended to give a white material, but depending on the application, a colorant can be added in order to enhance visibility. Examples of the colorant that can be used include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow, silicate pigments such as ultramarine blue, titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, and zinc-iron. -Based brown, titanium-cobalt green, cobalt-green, cobalt-blue, oxide-based pigments such as copper-chromium black, copper-iron-based black, chromic pigments such as yellow lead, molybdate orange, ferrocyans such as bitumen And pigments. Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green, azo dyes such as nickel azo yellow, thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, Examples thereof include condensed polycyclic dyes such as quinophthalone, anthraquinone, heterocyclic, and methyl dyes.

  The preferable range of the content of the colorant in the resin composition of the present invention is preferably 3 parts by mass or less, preferably 1 part by mass or less, and 0.3 parts by mass with respect to 100 parts by mass of the component A. It is even more preferable that: By using the resin composition of the present invention, it is also possible to obtain a molded product having a bright color or a light pastel phosphorescent fluorescent action as compared with a resin composition containing a general phosphorescent agent.

  The colorant may be used alone or in combination of two or more.

<Others>
The resin composition of the present invention includes, in addition to the above components, an antistatic agent, an antifogging agent, a lubricant / antiblocking agent, a fluidity improving agent, a plasticizer, as long as the object of the present invention is not impaired as necessary. , Dispersing agents, antibacterial agents and the like can be added. These may be used alone or in combination of two or more.
However, in the present invention, it is important that a colored additive that reduces the whiteness of the molded product is not blended and is not used.

[Thermoplastic resin composition containing no C component]
When a molded product using the phosphorescent fluorescent polycarbonate resin composition of the present invention is injection-molded, at the same time, a multicolor molded product using another thermoplastic resin composition not containing a C component is used, thereby providing a design property. Can be improved, and scratch resistance can be improved. For example, by making a two-color molded article in which a transparent polycarbonate resin is laminated on the surface layer of the phosphorescent fluorescent polycarbonate resin composition molded article of the present invention, the impact resistance that has been lowered due to the addition of the C component can be improved. At the same time, the appearance can have a glass-like luxury. Moreover, the scratch resistance of the phosphorescent fluorescent polycarbonate resin composition can be improved by forming a two-color molded article in which a transparent acrylic resin is laminated on the surface layer of the phosphorescent polycarbonate resin composition molded product of the present invention. At the same time, since it can have a glass-like high-quality appearance, it can be suitably used as a part around the key insertion port or the switch.

In this case, the thermoplastic resin constituting the main component of the thermoplastic resin composition not containing the C component is not particularly limited, but is the same polycarbonate resin as the A component or the transparent resin exemplified as the resin material of the B component. 1 type (s) or 2 or more types can be used. It is preferable to use a polycarbonate-based resin in order to improve adhesion between materials.
Also about the thermoplastic resin composition which does not contain this C component, B component, a fluorescent whitening agent, and other additives can be mix | blended similarly to the resin composition which concerns on this invention.

[Production method]
The resin composition of the present invention can be produced by mixing and melt-kneading each component by a conventionally known method. Specific mixing methods include polycarbonate resin (A component), light scattering component (B component), silicate phosphorescent phosphor (C component), organosilane compound and / or silicone compound (D component), and as required A method of weighing a predetermined amount of the fluorescent whitening agent and other additive components to be blended in accordance with the mixture and using various mixers such as a tumbler and a Henschel mixer can be used.

  Among them, the method of mixing the C component and the D component in advance and adhering the D component to the surface of the C component, and then mixing the A component, the B component, and an additive component blended as necessary is the surface of the C component. This is a more preferable mixing method from the viewpoint of effectively suppressing the activity and preventing unnecessary side reactions in the resin composition. Particularly preferred is a solution in which a D component such as an organosilane compound is dissolved in a solvent and a C component, and then the solvent is evaporated to coat the D component on the surface of the C component, and the A component, B component, and It is a method of mixing additive components blended as necessary.

  In this case, as the solvent for dissolving the component D, one or more organic solvents such as water or alcohol or acetone can be used. Further, in this solution, in order to promote the binding reaction of the D component to the C component surface, one or more acid components such as lactic acid, acetic acid and phosphoric acid are added at a concentration of 0.05 to 1% by mass. However, when an acid component is added, it is preferable to use a weak acid while paying attention to dissolution of the C component. The density | concentration of D component in D component solution is the range of 0.01-20 mass% normally, and is suitably adjusted according to the adhesion amount to C component. In order to evaporate the solvent, it may be heated to 40 to 100 ° C. At this time, the pressure may be reduced.

  Examples of the method of melt-kneading after the components are mixed in advance by the above method include a method using a Banbury mixer, roll, plastic appender, single-screw kneading extruder, twin-screw kneading extruder, kneader and the like.

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

  Further, as described above, a composite molded article can be formed by multicolor composite molding of the resin composition of the present invention and a thermoplastic resin composition containing no C component.

In the present invention, when an organosilane compound and / or a silicone compound (D component) is used, the D component is promoted by the presence of Eu, Ln activated silicate phosphorescent phosphor (C component). The thermal decomposition at the time can be suppressed, the mechanical strength and the heat resistance can be improved, and the change in hue due to heating can be reduced. The degree of thermal decomposition of the polycarbonate resin can be known from changes in fluidity, that is, changes in melt index (MI) and Q value. Q values of the resin composition of the present invention, B components, the standard resin composition containing no component C and component D Q value of the (A component and the kind and mixing ratio of the same other additives) (Q ₀₎ On the other hand, it is preferably within Q ₀ + 100%, more preferably within Q ₀ + 70%, and even more preferably substantially equal.
In addition, Q value is the outflow per unit time about the pellet-shaped resin composition dried using the Koka type flow tester (manufactured by Shimadzu Corporation) under the conditions of a temperature of 280 ° C. and a load of 160 kgf / cm ^2. The value measured as a quantity. The orifice used at this time is 1 mm in diameter × 10 mm in length.

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 Example and the comparative example is as follows.

(A) Polycarbonate resin: Mitsubishi Engineering Plastics Co., Ltd. product “trade name: Iupilon (registered trademark) S-3000”, viscosity average molecular weight 22,000, refractive index 1.585

(B-1) ABS resin: acrylonitrile / butadiene / styrene copolymer, Nippon A & L Co., Ltd. product “trade name: Santac (registered trademark) UT-61”, refractive index 1.53
(B-2) AES resin: polymer of acrylonitrile / ethylene propylene / styrene / methacrylate, product of MG ABS Co., Ltd. “trade name: Dialac WH10”, refractive index 1.54
(B-3) PMMA resin: copolymer of methyl methacrylate and methyl acrylate, Mitsubishi Rayon Co., Ltd. product “trade name: Acrypet VH (001)”, refractive index 1.49
(B-4) Acrylic fine particles: cross-linked poly (meth) acrylic ester, “trade name: Ganzpearl GM-0630H” manufactured by Ganz Kasei Co., Ltd., average particle size 6 μm, refractive index 1.49
(B-5) Glass beads: “Product name: EGB731” manufactured by Potters Ballotini Co., Ltd., average particle size 20 μm, refractive index 1.54

(C) Eu, Ln activated silicate phosphorescent phosphor: blue light-emitting phosphorescent pigment, “trade name: P170 phosphor” manufactured by Kasei Optonics Co., Ltd., average particle size 31 μm

(D) Organosilane compound: Decyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. “Product name: KBM3103”

(E) Thermal stabilizer: Cresyl diphenyl phosphate, “Product name: CDP” manufactured by Daihachi Chemical Industry Co., Ltd.
(F) Mold release agent: Pentaerythritol tetrastearate, manufactured by NOF Corporation “Product name: Unistar H476”

(G-1) Optical brightener: 3-phenyl-7- (2H-naphtho [1,2-d] -triazol-2-yl) coumarin, “trade name: Hackol PSR” manufactured by Hackol Chemical Co.
(G-2) Optical brightener: 4,4′-bis (benzoxazol-2-yl) stilbene, manufactured by Ciba Specialty Chemicals “trade name: UVITEX OB-ONE”

(H) White pigment: Titanium dioxide, “Ishihara Sangyo Co., Ltd.“ trade name: Taipei PC-3 ”, refractive index 2.71
(I) Additives other than component B: PTFE (polytetrafluoroethylene resin), “trade name: Polyflon F201L” manufactured by Daikin Industries, Ltd., refractive index 1.35

(J) Strontium aluminate phosphorescent phosphor other than C component: Green light-emitting phosphorescent pigment, Nemoto Special Chemical Co., Ltd. “trade name: N Nightlight Luminova G-300M”, average particle size 29 μm

The (C) Eu, Ln activated silicate phosphorescent phosphor and (J) strontium aluminate phosphorescent phosphor were used after being surface-treated with the above (D) organosilane compound as follows. .
First, 6 g of the above (D) organosilane compound was added to an aqueous solution dissolved in 20 g of ion-exchanged water so that lactic acid (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was 0.3% by mass, and stirred. An aqueous dispersion was obtained. Next, 100 g of the above (C) Eu, Ln activated silicate phosphor or (J) strontium aluminate phosphor is charged in a 1 L beaker, and this (D) organosilane is stirred with a magnetic stirrer. An aqueous dispersion of the compound was added. Next, the mixture was stirred and mixed on a hot plate at 100 ° C. to evaporate water, thereby (D) (C) Eu, Ln activated silicate phosphorescent phosphor surface-treated with an organosilane compound and (J) A strontium aluminate phosphorescent phosphor was obtained.

[Examples 1 to 6 and Comparative Examples 1 to 4]
Each compounding ingredient shown in Table 1 was mixed for 20 minutes with a tamper in the ratio shown in Table 1. The obtained composition was kneaded at a cylinder temperature of 260 ° C. and a screw rotation speed of 70 rpm with a single screw extruder with a screw diameter of 40 mm (“SV-40” manufactured by Isuzu Chemical Industries Ltd.) and extruded as a strand. The extruded strand was cut to produce a pellet.
The obtained pellets were dried at 120 ° C. for 5 hours, and then injection molded with an injection molding machine (“M150AII-SJ” manufactured by Meiki Seisakusho) under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 50 seconds. The Izod test piece and the 3 mm-thick flat plate were produced. The following evaluation was performed using this as a test piece.

  The evaluation results are shown in Table 1.

[Evaluation methods]
(1) Impact resistance (Izod impact strength) (unit: J / m):
In accordance with ASTM D256, Izod impact strength (unit: J / m) was measured at a temperature of 23 ° C. for a notched specimen having a thickness of 3.2 mm. The larger the value, the better the impact resistance.

(2) Phosphorescent fluorescence Luminescent test pieces having a thickness of 3 mm were stored in a dark place for 24 hours to completely quench the phosphorescent agent. Thereafter, using a D65 light source, the test piece was vertically irradiated at an illuminance of 200 lux for 20 minutes to excite the test piece. The hue of fluorescence emission after the light source was turned off was visually evaluated in the following four stages.
○: The color of fluorescent light emission is bright and beautiful.
Δ: Fluorescent color tone is slightly dark and yellowish.
X: The color tone of fluorescence emission is dark and yellowish is conspicuous.
-: No fluorescence emission.

(3) Photoluminescence fluorescence after heat aging test:
The test piece was stored in an air atmosphere at 80 ° C. for 500 hours, and the stored fluorescent fluorescence was evaluated by the same method as in (2) above, and used as a heat resistance index.

(4) Whiteness A flat plate having a thickness of 3 mm was used as a test piece, and the whiteness WB value and WI value measured with a SE-2000 type spectrocolorimeter manufactured by Nippon Denshoku Industries Co., Ltd. were evaluated. The WB value is a value calculated by WB = 100Z / 118.225 using XYZ defined in JIS-Z8701. Further, the whiteness WI value defined by JIS-L1015 is calculated by WI = 4B-3G, and B = WB and G = Y.

  From Table 1, according to the present invention, the B component, which is a light scattering component, is used in combination with a polycarbonate resin blended with Eu, Ln activated silicate phosphorescent phosphor, so that it is extremely white without impairing the light emission characteristics. It can be seen that a molded article having a high degree can be obtained, and that the whiteness can be further improved by using a fluorescent whitening agent in combination.

  On the other hand, in Comparative Example 1 in which no B component is blended, the whiteness is low. In Comparative Example 2 using titanium oxide which is a normal white pigment instead of the B component, the whiteness is improved as compared with Comparative Example 1, but the light emission characteristics are impaired. Further, in Comparative Example 3 using PTFE having a refractive index difference outside the range of the B component, the whiteness is improved as compared with Comparative Example 1, but the light emission characteristics are impaired. In Comparative Example 4 using a phosphorescent phosphor other than the present invention, it is clear that the whiteness is inferior.

  As described above, according to the present invention, the whiteness that can be used in the manufacture of molded articles such as electrical signs, liquid crystal backlights, illumination displays, traffic signs, safety signs, night visibility improving members, sign boards, and screens. It can be seen that a highly luminous fluorescent polycarbonate resin composition can be provided.

Claims (12)

A phosphorescent fluorescent polycarbonate resin composition comprising 0.1 to 100 parts by mass of the following B component and 0.1 to 50 parts by mass of the following C component with respect to 100 parts by mass of the following A component.
Component A: Polycarbonate resin Component B: Transparent or translucent material that is incompatible with component A and has a refractive index smaller than component A by 0.01 to 0.2 Component C: The matrix is an oxide composition Eu represented by the following formula (1), Ln activated silicate phosphorescent phosphor ^{_{m (Sr 1-a M 1}} a O) · n (Mg 1-b M 2 b O) · 2 (Si 1-c Ge _c O ₂ ): Eu, Ln
... (1)
(Wherein M ¹ is one or more elements selected from Ca and Ba, M ² is one or more elements selected from Be, Zn and Cd, Ln is Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, B, Al, Ga, In, Tl, Sb, Bi, As, P, Sn, Pb, Ti, Zr, Hf, V, It represents one or more elements selected from Nb, Ta, Mo, W, Cr and Mn, where a, b, c, m and n represent the following numbers.
0 ≦ a ≦ 0.8
0 ≦ b ≦ 0.2
0 ≦ c ≦ 0.2
1.5 ≦ m ≦ 3.5
0.5 ≦ n ≦ 1.5) 2. The phosphorescent fluorescent polycarbonate resin composition according to claim 1, wherein the following D component is contained in an amount of 0.5 to 13 mass% with respect to the C component.
Component D: Organosilane compound and / or silicone compound represented by the following formula (2) (R ¹ O) _p SiR ² _4-p (2)
(In the formula, R ¹ and R ² represent organic groups, and p represents an integer of 1 to 4.)   3. The component B according to claim 1, wherein the component B is selected from the group consisting of ABS resin, AES resin, AS resin, MBS resin, MS resin, PMMA resin, glass beads, acrylic fine particles, and silicone fine particles. A phosphorescent fluorescent polycarbonate resin composition characterized by being a seed or more.   4. The phosphorescent according to claim 1, wherein Ln, which is an activator of the C component, is one or more elements selected from Dy, Nd, Tm, Sn, In, and Bi. Fluorescent polycarbonate resin composition. In any one of claims 2 to 4, an aliphatic hydrocarbon group R ¹ is from 1 to 4 carbon atoms in the formula (2), aromatic R ² is C 6-12 or alicyclic hydrocarbon A hydrogen group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbon group having an ethylenically unsaturated bond having 2 to 16 carbon atoms, or a hydrocarbon group having an epoxy group having 3 to 15 carbon atoms, p Is an integer of 1 to 3, a phosphorescent fluorescent polycarbonate resin composition.   In any 1 item | term of Claim 2 thru | or 5, 0.1-100 mass parts of B components, 0.5-30 mass parts of C components, and the said organosilane compound as D component with respect to 100 mass parts of A components. A phosphorescent fluorescent polycarbonate resin composition containing 1 to 10% by mass with respect to component C.   In any 1 item | term of Claim 2 thru | or 4, with respect to 100 mass parts of A components, 0.1-100 mass parts of B components, 0.5-30 mass parts of C components, and the said silicone compound as C component C A phosphorescent fluorescent polycarbonate resin composition comprising 1 to 6% by mass based on the components.   The phosphorescent fluorescent polycarbonate resin composition according to any one of claims 1 to 7, further comprising 0.0001 to 0.1 parts by mass of a fluorescent brightening agent with respect to 100 parts by mass of the component A. .   The phosphorescent fluorescent polycarbonate resin composition according to claim 8, wherein the fluorescent brightening agent is one or more selected from the group consisting of a benzoxazole-based compound and a coumarin-based compound.   10. The phosphorescent fluorescent polycarbonate resin composition according to any one of claims 1 to 9, wherein the component C surface-treated with the component D is melt kneaded with other components.   A molded article formed by melt-molding the phosphorescent fluorescent polycarbonate resin composition according to any one of claims 1 to 10.   A molded product formed by multicolor composite molding of the phosphorescent fluorescent polycarbonate resin composition according to any one of claims 1 to 10 and a thermoplastic resin composition containing no C component.