JPH1036834A - Phosphor composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phosphor compsn. which, after stopping of external stimulation, e.g. by a light source, emits significantly distinct light and permits the emission to persist for a long period of time by incorporating a predetermined amt. of a fluorescent brightener and/or an UV discoloration agent into a luminous phosphor. SOLUTION: This phosphor compsn. comprises: 100 pts.wt. (hereinafter referred to as 'pts.') luminous phosphor, pref. a sulfide luminous phosphor (e.g. ZnS:Cu) or a luminous phosphor comprising MAl2 O4 (wherein M represents Ca, Sr, or Ba) as a mother crystal; and incorporated thereinto 0.01 to 500 pts., pref. 0.01 to 100 pts., fluorescent brightener e.g. 2,5'-bis[5-t-butylbenzoxazolyl(2)]thiophene} and/or ultraviolet discoloration agent (e.g. Y2 O3 :Eu). If necessary, 0.001 to 500 pts. organic fluorescent dye (e.g. perylene dye) is further incorporated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a phosphor composition.

[0002]

2. Description of the Related Art Japanese Patent Application Laid-Open No. 4-51405 discloses a film or sheet formed by kneading a sulfide-based phosphorescent pigment into a resin, or by mixing the phosphorescent pigment into a paint and applying it to the surface. Wall coverings made of recycled paper, woven fabric, vinyl leather and the like are disclosed. Japanese Patent Application Laid-Open No. 7-247391 discloses a nocturnal resin composition in which a luminous pigment composed of a metal oxide and a rare earth element is blended in a vinyl chloride resin composition. Also, Japanese Patent Application Laid-Open No. 7-112
No. 50 discloses that a compound represented by MAl ₂ O ₄ , wherein M is at least one metal element selected from the group consisting of calcium, strontium and barium, was used as a mother crystal. A phosphorescent phosphor characterized as a feature is disclosed. However, in any case, the resin product gives an external stimulus such as a light source, and then emits light after the stimulus is stopped. However, it has not been fully satisfactory when used for nighttime danger prevention clothing, evacuation route guide plates, electric appliance switches, and the like.

[0003]

SUMMARY OF THE INVENTION The present invention emits a remarkably clear light after the external stimulus is stopped (excellent initial luminance),
Another object of the present invention is to provide a phosphor composition that maintains clear light emission for a long time.

[0004]

Means for Solving the Problems The present inventors have conducted various studies to solve the above problems. As a result, when the luminous phosphor and the fluorescent whitening agent and / or the ultraviolet discoloring agent are blended in the following predetermined amounts, surprisingly, after the external stimulus is stopped, it emits a remarkably clear light, and is over a long period of time. It has been found that a phosphor composition that maintains clear light emission can be obtained.
The above effect cannot be achieved only by the phosphorescent phosphor, but can be achieved only by blending the phosphorescent phosphor and the fluorescent whitening agent and / or the ultraviolet discoloring agent in a predetermined amount.

That is, the present invention relates to a phosphor containing (1) (A) 100 parts by weight of a phosphorescent phosphor and (B) 0.001 to 500 parts by weight of a fluorescent whitening agent and / or an ultraviolet discoloring agent. A composition.

In a preferred embodiment, (2) (B) a phosphor composition containing 0.01 to 100 parts by weight of a fluorescent whitening agent and / or an ultraviolet discoloring agent, and (3) (A) a phosphorescent phosphor, a)
Sulfide phosphorescent phosphor or phosphorescent phosphor containing (b) a compound represented by MAl ₂ O ₄ (M is at least one metal element selected from the group consisting of calcium, strontium and barium) as a mother crystal (1) or (2) above
The phosphor composition as described in (4), as the activator, 0.001 to 10 mol% with respect to the metal element representing europium as M.
And (5) lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin The phosphor composition according to (4), wherein the phosphor composition contains at least one element selected from the group consisting of bismuth and bismuth in an amount of 0.001 to 10 mol% based on a metal element represented by M; The dye is used in an amount of 0.00% by weight based on 100 parts by weight of the phosphorescent phosphor (A).
The phosphor composition according to any one of the above (1) to (5), which contains 1 to 500 parts by weight, (7) the resin (D),
100 to 10,000 per 100 parts by weight of the phosphorescent phosphor
The phosphor composition according to any one of the above (1) to (6), which contains 0 parts by weight, (8) the resin (D) is a polyolefin resin, a polyvinyl chloride resin, a polystyrene resin,
The phosphor composition according to the above (7), which is at least one resin selected from the group consisting of an acrylic resin, an acrylate resin, a methacrylic resin, a methacrylic ester resin, and a polycarbonate resin. )
(D) the phosphor composition according to the above (7), wherein the resin is a polyvinyl chloride-based plastisol;
The laminate having the phosphor composition layer according to any one of (9) and (11) the laminate according to the above (10), wherein the laminate is a film or a sheet.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) phosphorescent phosphor used in the phosphor composition of the present invention is preferably represented by (a) a sulfide phosphorescent phosphor or (b) MAl ₂ O _4. (M is at least one metal element selected from the group consisting of calcium, strontium, and barium) as a mother phosphor.

(A) Examples of the sulfide phosphorescent phosphors include calcium sulfide / bismuth [CaS: Bi (purple blue emission)] and calcium strontium / bismuth [CaSrS: Bi (blue emission)]. And zinc sulfide / copper [ZnS: Cu (green emission)], zinc sulfide / cadmium / copper [ZnCdS: Cu (yellow to orange emission)], and the like. As a commercial product, for example, RINKO-GSS
(Trademark, manufactured by Nemoto Special Chemical Co., Ltd.) or the like.

(B) A compound represented by MAl ₂ O ₄ (M
Is at least one metal element selected from the group consisting of calcium, strontium and barium), and preferably M is at least one metal selected from the group consisting of calcium, strontium and barium It is a compound composed of a plurality of metal elements further containing magnesium. Further, as an activator, europium can be preferably contained in an amount of preferably 0.001 to 10 mol% based on the metal element represented by M. More preferably, as a co-activator, at least one selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, disprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin, bismuth. The element can also be contained in an amount of preferably 0.001 to 10 mol% based on the metal element represented by M. As (b), for example, SrAl ₂ O ₄ : E
u, CaAl ₂ O ₄ : Eu, BaAl ₂ O ₄ : Eu and the like. As a commercially available product, for example, N night light (Lumi)
Nova) (trademark, manufactured by Nemoto Special Chemical Co., Ltd.), Super Luminescent Pigment (trademark, manufactured by Shinloich Co., Ltd.), LUMI
LUX (trademark, manufactured by Hoechst Japan KK) or the like can be used.

In the component (B) of the present invention, (B-1)
The fluorescent whitening agent is near ultraviolet (wavelength: 400 to 450 n
m) is a colorless to pale yellow dye having an absorption in m) and emitting purple-blue to blue fluorescence. Examples of the fluorescent whitening agent include diaminostilbene disulfonic acid derivatives, imidazole derivatives, coumarin derivatives, triazole derivatives, carbazole derivatives, pyridine derivatives, naphthalic acid derivatives, and imidazolone derivatives. Of these, diaminostilbene disulfonic acid derivatives, imidazole derivatives, and coumarin derivatives are preferred. As commercial products, for example, Blankophor (trademark, manufactured by Bayer AG), Uv
itex (trademark, Ciba-Geigy), Whitex
(Trademark, manufactured by Sumitomo Chemical Co., Ltd.), Kaycoll
(Trademark, manufactured by Nippon Soda Co., Ltd.), TBO (trademark, manufactured by Sumitomo Seika Kogyo Co., Ltd.) and the like.
ex OB (trademark, manufactured by Ciba Geigy) is preferably used.

The (B-2) ultraviolet discoloring agent is colorless under visible light (wavelength: 400 to 750 nm), red under ultraviolet light having a wavelength of 300 to 400 nm,
It shows colors such as green and blue. For example, wavelength 3
It emits with ultraviolet light of 00 to 400 nm and has an emission peak of 60
Examples thereof include a red light-emitting inorganic phosphor in a range of 0 to 660 nm, a green light-emitting inorganic phosphor having a light emission peak in a range of 490 to 560 nm, and a blue light-emitting inorganic phosphor having a light emission peak in a range of 390 to 460 nm. As the red light-emitting inorganic phosphor, for example, Y ₃ O ₃ : Eu (emission peak 61)
1 nm), YVO ₄ : Eu (emission peak 619 nm),
Y ₂ O ₂ : Eu (emission peak: 626 nm), 3.5 Mg
O.0.5MgF ₂ GeO ₂ : Mn (emission peak 660
nm), (Y · Cd) BO ₂ : Eu (emission peak 661)
nm). As a green light-emitting inorganic phosphor,
For example, ZnS: Cu · Al (emission peak 530 nm),
(Zn · Cd) S: Cu · Al (emission peak 530-5)
60 nm), ZnS: Cu. Au. Al (emission peak 5)
35 nm), Zn ₂ SiO ₄ : Mn (emission peak 525)
nm), ZnSiO ₄ : Mn (emission peak 525 n)
m), ZnS: Ag · Cu (emission peak 527 nm),
(Zn · Cd) S: Cu (emission peak 525 nm), Z
nS: Cu (emission peak: 530 nm), GdOS: Tb
(Emission peak 544 nm), LaOS: Tb (emission peak 544 nm), YSiO ₄ : Ce · Tb (emission peak 544 nm), ZnGeO ₄ : Mn (emission peak 533)
nm), GeMgAlO: Tb (emission peak 543n)
m), SrGaS: Eu ²⁺ (emission peak 535 nm),
ZnS: Cu · Co (emission peak 516 nm), MgO
NB ₂ O ₃ : Ge · Tb (emission peak 544 nm),
LaOBr: Tb · Tm (emission peak 544 nm), L
a ₂ O ₂ S: Tb (emission peak: 544 nm). As the blue light emitting inorganic phosphor, for example, ZnS: A
g (emission peak 530 nm), GaWO ₄ (emission peak 530 nm), Y ₂ SiO ₆ : Ce (emission peak 410)
nm), ZnS: Ag · Ga · Cl (emission peak 450)
nm), Ca ₂ B ₄ OCl: Eu ²⁺ (emission peak 450
nm), BaMgAl ₄ O ₃ : Eu ²⁺ (emission peak 45
4 nm). Commercial products of the ultraviolet discoloring agent include LUMILITECOLOR (trademark, manufactured by Shinloich Co., Ltd.).

The upper limit of the amount of the component (B) of the fluorescent whitening agent and / or the ultraviolet ray discoloring agent is 500 parts by weight, preferably 300 parts by weight, especially 300 parts by weight, based on 100 parts by weight of the component (A) phosphorescent substance. Preferably it is 100 parts by weight, and the lower limit is 0.0
01 parts by weight, preferably 0.01 parts by weight. If the amount is less than the above lower limit, the light emitting effect of the present invention cannot be obtained. If the amount exceeds the above upper limit, a remarkable increase in the light emitting effect due to an increase in the blending amount cannot be obtained. Further, when the fluorescent whitening agent exceeds the above upper limit, blooming occurs, and when blended with a transparent resin, there is a problem that transparency is impaired.

The phosphor composition of the present invention may further contain (C) an organic fluorescent dye as an optional component. The compounding amount of the component (C) depends on the amount of the component (A) phosphorescent phosphor 100
The upper limit is preferably 500 parts by weight, particularly preferably 300 parts by weight, and the lower limit is preferably 0.1 part by weight.
001 parts by weight, particularly preferably 0.01 parts by weight.
By mixing in the above range, the emission color of the component (A) phosphorescent phosphor can be changed. Here, component (C)
Is excited by the absorbed light to emit light of a longer wavelength, and is generally called a daylight fluorescent dye. As for the color of a normal dye, for example, an orange color emits light by reflecting light in an orange portion of incident light, and light in other portions is absorbed and disappears as heat. On the other hand, the daylight fluorescent dye emits, in addition to the reflected light in the orange portion, light absorbed in wavelengths such as blue, green, and yellow from the short-wavelength ultraviolet portion as the same orange light as the reflected light. Is an addition. The (C) includes, for example, Naphtalimid dyes, Peryl
and en-based dyes. As a commercially available product, for example, L
uogen COLOR (trademark, manufactured by BASF) and the like.

The phosphor composition of the present invention is preferably used by being included in the resin (D). The amount of the component (D) resin is based on (A) 100 parts by weight of the phosphorescent phosphor.
The upper limit is preferably 10,000 parts by weight, more preferably 3,000 parts by weight, and the lower limit is preferably 100 parts by weight, more preferably 150 parts by weight, and further preferably 25 parts by weight.
0 parts by weight, particularly preferably 350 parts by weight. If the upper limit is exceeded, the effect of the phosphor composition of the present invention cannot be sufficiently exerted. If the lower limit is less than the lower limit, the moldability of the composition in which the phosphor composition of the present invention is blended with the resin (D) is insufficient. It is not preferable because it deteriorates.

Here, the component (D) resin used is not particularly limited. Preferably, a thermoplastic resin is used.
For example, polyolefin resins such as polypropylene resins, polyethylene resins, ethylene / propylene / diene copolymers, etc., polyvinyl chloride resins, polystyrene resins such as acrylonitrile / butadiene / styrene copolymers, methacrylate / butadiene / styrene copolymers Copolymer, styrene / ethylene / propylene / styrene copolymer, styrene / ethylene / butadiene / styrene copolymer, acrylic resin, acrylate resin, methacrylic resin, methacrylic ester resin, polycarbonate resin And the like.

The method for producing the composition by blending the phosphor composition of the present invention with the resin (D) is not particularly limited. For example, the components of the phosphor composition and the resin are mechanically mixed,
It can be melt-kneaded by a conventional device such as an extruder, extruded, and pelletized. It can also be mixed / molded as a masterbatch.

The composition is preferably used as a film or sheet. For molding, any known method such as T-die molding and inflation molding can be used. Preferably, T-die molding is used.

In the production of films and sheets,
A method of applying the above composition on a base film or sheet can also be adopted. At this time, the component (D) resin is preferably a plastisol in order to facilitate application of the composition onto a film or sheet serving as a base. Particularly preferably, a vinyl chloride plastisol is used. Here, the resin constituting the base film or sheet is not particularly limited. For example, a polyester resin such as a polyvinyl chloride resin, a polycarbonate resin, a polyethylene terephthalate resin, and a polybutylene terephthalate resin is used. .

A film produced by any of the above methods,
Also in the sheet, if necessary, a resin layer having a high hardness made of an ultraviolet curable or electron beam curable resin may be provided as a surface layer. The hardness of the surface layer is preferably H or higher in pencil hardness.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0021]

EXAMPLES The components used in the examples are as follows. <Component (A) phosphorescent phosphor> ・ Sulfide phosphorescent phosphor (ZnS: Cu) RINKO
-Gss (trademark, Nemoto Co., Ltd.) (F-1) · MAl 2 O 4 compounds represented by the host crystal was phosphorescent phosphor _{(SrAl 2 O 4: Eu)} N Luminous (TM radically (Lumi Nova, manufactured by Tokushu Kagaku Co., Ltd.) <Component (B) Optical brightener (B-1)>-UVITEX OB (trademark, manufactured by Ciba Geigy)
2,5'-bis [5-t-butyl benzoxazolyl (2)] thiophene (KS-1) <Component (B) UV discoloration agent (B-2)> · Y 2 O 2: Eu system LUMILITE Blue (trademark, Shinroihi Co., Ltd.) (UV-1) · BaMgAl 4 O 3: Eu system LUMILITE Red (trademark, manufactured by Shinroihi Co., Ltd.) (UV-2) <component (C) organic fluorescent dye> · Perylen system Rumogen F Green 08
3 (trademark, manufactured by BASF) (YK-1)-Perylen Lumogen F Red 300
(Trademark, manufactured by BASF) (YK-2)-Perylen Lumogen F Orange 24
0 (trademark, manufactured by BASF) (YK-3) <Component (D) thermoplastic resin>-Polypropylene MT-455 (trademark, manufactured by Tokuyama Corporation) (PP-1)-Polystyrene resin LJ-1050N (trademark, (PS-1)-Polystyrene resin HH-31B (trademark, manufactured by Idemitsu Kosan Co., Ltd.) (PS-2)-Polymethyl methacrylate GF-1000 (trademark, manufactured by Kuraray Co., Ltd.) ( PM-1) ・ Polycarbonate E2000 (trademark, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) (PC-1) ・ Polyvinyl chloride resin sol Kobazole SH-1 (trademark, manufactured by Kobayashi Co., Ltd.) (PV-1) In Examples and Comparative Examples, each phosphor composition was mixed with a resin to evaluate the luminance.

[0022]

Examples 1 to 14 and Comparative Examples 1 to 9 In each of the examples and comparative examples, the components (parts by weight) shown in Tables 1 and 2 were premixed for 10 minutes using a tumbler mixer to obtain a uniform mixture. After that, using a 20 mmφ biaxial different direction rotary extruder,
Pellets were prepared by melting and kneading at a temperature of 180 to 300 ° C. The obtained pellets are supplied to a 50-ton injection molding machine, and a cylinder temperature of 180 to 300 ° C. and a mold temperature of 50 to
A flat plate of 90 mm × 50 mm × 3 mm was formed at 100 ° C. and subjected to luminance measurement.

The luminance was measured as follows. First, the flat plate was illuminated in a dark room with a surface illuminance of 1,700.
Daylight fluorescent lamp (D
65) for 30 minutes for excitation. Next, the flat plate after excitation is placed in a light-shielding frame, and an illuminometer (HIOKI 3) is set so that the distance from the flat plate surface to the sensor unit is 10 mm.
422, trademark, manufactured by Hioki Electric Co., Ltd.). 2 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30
Minutes, 45 minutes, 60 minutes, 90 minutes, 120 minutes, 180 minutes, 2
Each illuminance was measured after a lapse of 40 minutes and 300 minutes. From the illuminance value, the luminance was calculated using the following equation and evaluated.

[0024]

I = L × 10 ⁻⁴ B = (1 / cos θ) dI / dA (where, B indicates luminance (mcd / m ² ), A indicates area (m ² ) of luminous body, I is the luminous intensity (mc
d), L indicates the measured illuminance (lx), and θ indicates the angle between the normal of the illuminant and the observation direction. )

[0025]

Examples 15 to 18 and Comparative Example 10 First, a polyethylene terephthalate (HP 7, trade name, manufactured by Teijin Chemicals Ltd.) was used as a raw material and a thickness of 0.25 mm was obtained using a T die.
A base film was prepared. Next, the components shown in Table 3 (parts by weight) were mixed and stirred well to obtain a uniform mixture. The mixture is coated on the base film with a thickness of 10
After coating with a comma coater so that the thickness becomes 0 μm,
Heat at 60 ° C. for 2 minutes. The film was cut into the same dimensions as the flat plate of Example 1 described above, and then the luminance was measured under the same conditions.

The above results are shown in Tables 4 to 6.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

[0030]

[Table 4]

[0031]

[Table 5]

[0032]

[Table 6] Examples 1 to 4 are compositions in which the phosphorescent composition of the present invention comprising the components (A) and (B) is blended with the component (D) resin, and (B-1) a fluorescent brightener as (B). And the amount thereof was varied within the scope of the present invention.
Compared to Comparative Example 1 in which (B) was not blended, the initial luminance was significantly higher in all cases, and there was a tendency to maintain clear light emission for a long time. Also, when the blending amount of (B) was increased, the initial luminance was increased, and clear light emission was maintained for a longer time. In Examples 5 and 6, (B-2) an ultraviolet ray discoloring agent was used as (B). In each case, a good light emitting effect was obtained. In the seventh embodiment, the type of (A) is changed. The initial luminance was higher than Comparative Example 2 in which (B) was not blended under the same conditions. Example 8-
Reference numeral 11 denotes a different type of (D). Compared to the corresponding Comparative Examples 3 to 6, respectively, the initial luminance was remarkably high, and clear light emission tended to be maintained for a long time. It was also found that a good light emitting effect was obtained irrespective of the type of (D). Examples 12 to 14
The amount of (A) was changed within the scope of the present invention.
Compared to the corresponding Comparative Examples 7 to 9, the initial luminance was remarkably high, and there was a tendency that clear light emission was maintained for a long time. Also, when the blending amount of (A) is increased,
The initial luminance increased and a clear light emission was maintained for a longer time.

In Examples 15 to 18, the phosphor composition of the present invention was applied on a base film. As compared with Comparative Example 10 in which (B) was not blended, the initial luminance was remarkably high, and clear light emission tended to be maintained for a long time. Examples 16 to 18 were green,
Although the red and orange organic fluorescent dyes (C) were added, the same light emitting effect as that of Example 15 in which neither (C) was added was obtained. Further, the luminescent color could be changed by the addition.

[0034]

According to the present invention, there is provided a phosphor composition which emits remarkably sharp light after stopping external stimulus and maintains clear light emission for a long time.

Claims (4)

[Claims] 1. An amount of (B) a fluorescent whitening agent and / or an ultraviolet discoloring agent of 0.0100 parts by weight of (A) a phosphorescent phosphor.
A phosphor composition containing from 01 to 500 parts by weight. 2. A phosphor composition comprising (B) 0.01 to 100 parts by weight of a fluorescent whitening agent and / or an ultraviolet discoloring agent. 3. The compound (M) wherein (A) the phosphorescent phosphor is (a) a sulfide phosphorescent phosphor or (b) a compound represented by MAl ₂ O _4.
3. The phosphor composition according to claim 1, wherein the phosphor composition is a phosphorescent phosphor having, as a mother crystal, at least one metal element selected from the group consisting of calcium, strontium, and barium. 4. 4. The phosphor composition according to claim 1, wherein the organic fluorescent dye (C) is contained in an amount of 0.001 to 500 parts by weight based on 100 parts by weight of the luminous phosphor (A). Stuff.