KR790001430B1 - Luminous fluorescent composition - Google Patents

Abstract

A substance used for a fluorescent screen(5) of Braun tube in B/W TV, has characteristics that; (a) it is a compound of fluorescent substance of zinc sulfoselenide, emitting yellow or yellowish green, whose revival quantity of Au and Al is 10-6g to 10-4g and 5x10-7 to 5x10-3g respectively per 1g of zinc sulfoselenide whose formative formula is Zn(S1-a,Sea)(only 0.05<=a<=0.25), and of zinc sulfide, blue, whose revival quantity of Ag is 10-5g to 10-3g per 1g of zinc sulfide, and (b) the weight ratio of the latter to the former is 0.60 to 1.60.

Description

White light emitting phosphor

1 is Zn (S ₀ · 85, S _e0 · 15): a graph showing reflectances of Au and Al phosphors, and curve A is Au ^-10 / ³ / g / g, while curve B is Au Reflectance at ^-5 g / g,

2 is _a graph showing the relationship between the Se value a value of Zn (S _1-a , S _ea ): Au and Al phosphors used in the white light emitting phosphor of the present invention and the x value of the emission chromaticity point (curve A) and Se The relationship between the amount a value and the light emission luminance (curve B) is displayed.

3 shows the relationship between the Au reactivity amount in the Zn (S _1-a , _Sea ) Au and Al phosphors used in the white light-emitting phosphor of the present invention and the x value of the emission chromaticity point (straight line A) and the Au reactivity The relationship between the quantity and the light emission luminance (straight line B) is displayed.

4 is JEDEC standard, Zn (S _1-a , _Sea ) Au, Al phosphor and ZnS: Ag fluorescence constituting the white light emitting phosphor of the present invention and the fluorescent color of the brown tube for black and white television of the present invention The emission chromaticity point of the film (white light-emitting phosphor of the present invention) is indicated by a CIE colorimetric system.

5 is a schematic configuration diagram of a round tube for black and white television.

* Explanation of symbols for main parts of the drawings

1: Parnell 2: Neck

3: electron gun 4: screen

5: fluorescent film 6: aluminum vapor deposition film

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphor emitting white light by electron beam excitation and a round tube for televisions using the white light emitting phosphor as a fluorescent film. White light-emitting phosphors for black and white televisions, which are currently used, are not single phosphors, but two or three or more phosphors are mixed at a reasonable rate so as to emit substantially white light by electron beam excitation. Therefore, the emission color of the white light emitting phosphor for black and white televisions can be determined by the mixing ratio of the constituent phosphors, and the mixing ratio can be appropriately changed as needed. JEDEC (Joint Electron) surrounded by chromaticity points A (x = 0.273, y = 0.282), B (x = 0.267, y = 0.030), C (x = 0.286, y = 0.326) D (x = 0.290, y = 0.303) The device has a luminous chromaticity point within the standard or in the very near white region. Specifically, the white light emitting phosphor for black and white televisions of the present practical use

(1) consisting of a combination of yellow green to yellow luminescent gold and aluminum activated zinc luminescent phosphors (ZnS: Au, Al) and blue luminescent silver lubricated zinc phosphors (ZnS: Ag);

(2) In addition to the above-mentioned yellow green to yellow luminescent ZnS: Au, Al phosphors and blue luminescent ZnS: Ag phosphors, flow path product-inactivated yttrium phosphor (Y ₂ O ₃ : Eu) flow path product-activated yttrium phosphorate (YVO ₄ : there are two kinds of being Eu) from which the combination is added at least one red light-emitting phosphor of the: Eu) and the flow path width resurrection acid emulsion yttrium phosphor (Y ₂ O ₂ S.

However, the white light-emitting phosphor of (1) is sufficiently high in light emission luminance, but the white reproduction region does not completely contain the JEDEC standard, but is slightly biased on the short wavelength side (i.e., the green side). It is not preferable at the point of area. In the white light-emitting phosphor of (2), at least one red light-emitting phosphor of Y ₂ O ₃ : Eu phosphorus, YVO ₄ : Eu phosphor, and Y ₂ O ₂ S: Eu phosphor is added to the white light-emitting phosphor of (1). By mixing, the light emission color of the white light emitting phosphor of (1) is made longer and the reproduction area of white is made more complete, but since the light emission luminance is lower than that of the white light emitting phosphor of (1) because it contains a red light emitting phosphor of low luminous luminance, It is slightly lower and the red light-emitting phosphor contains a large amount of expensive rare earth elements, resulting in a phosphor that is more expensive than the white light-emitting phosphor of (1). The white light emitting phosphor of (2) which is more complete in the white reproduction area of the above-mentioned white light emitting phosphor of (1) and (2) is mainly used for the practical black and white television-type round tube.

An object of the present invention is to provide an inexpensive white light emitting phosphor having a high luminescence brightness, a perfect white reproducing area, and not using an expensive rare earth element and a round tube for black and white televisions using the white light emitting phosphor as a fluorescent film. .

0.30인 조건을 충족시키는 수다)로 표시되는 유세렌화 아연도체 1g에 대하여 금 및 알미늄 부활량이 각각 10^-4g내지 10^-2g의 범위 및 5×10^-5g내지 5×10^-3g의 범위에 있는 그 및 알미늄 부활 유세렌화 아연황녹색 내지 황색 발광형광체와 유화아연모체 1g에 대하여 은 부활량이 10^5-g내지 10^-3g의 범위에 있는 은, 부활유화아연 청색 발광형광체로부터 되는 혼합형광체이고 상기 황녹색 내지 황색 발광형광체에 대한 청색발광형광체의 중량비가 0.70 내지 1.60의 범위에 있는 백색 발광형광체를 발명하고 특허출원을 행하였다(특원소 51-20 309 호). 그러나 그 후의 연구결과 상기 백색 발광형광체를 구성하는 황녹색 내지 황색발광형광체 즉 Zn(S_1-a, S_ea) : Au, Al 형광체 (단 a는 0〈a

0.30인 조건을 충족시키는 수다)는 400㎜내지 500㎜의 가시영역의 흡수가 크고 따라서 상기 백색 발광형광체에 있어서 ZnS : Ag 형광체에 의한 청색발광은 Zn(S_1-a, S_ea): Au, Ag 형광체에 의하여 다분히 흡수되고 유효하게 이용되고 있지 않다는 것이 판명되었다.The inventors of the present invention, as a white light-emitting phosphor that achieves the above object, the composition formula is Zn (S _1-a , S _ea ) (where a is 0

Gold and aluminum activator amounts in the range of 10 ⁻⁴ g to 10 ⁻² g and 5 × 10 ⁻⁵ g to 5 × 10 ⁻³ g, respectively, for 1 g of unsintered zinc conductor, A mixture of silver and activated zinc zinc blue emitting phosphors in the range of ^105- g to 10 ^-3 g of silver with respect to those and aluminum-activated zinc-sulfurized green-yellow luminescent phosphors in the range and 1 g of an emulsified zinc matrix. A white light emitting phosphor having a phosphor and a weight ratio of the blue light emitting phosphor to the yellow green to yellow light emitting phosphor in the range of 0.70 to 1.60 was invented and patented (patent element 51-20 309). However, as a result of further research, yellow green to yellow luminescent phosphors constituting the white luminescent phosphor, that is, Zn (S _1-a , S _ea ): Au, Al phosphors (where a is 0 <a)

(A chatter that satisfies the condition of 0.30) has a large absorption in the visible region of 400 mm to 500 mm, and therefore, blue light emitted by the ZnS: Ag phosphor in the white light emitting phosphor is Zn (S _1-a , S _ea ): Au, It has been found that the Ag phosphor is absorbed to a large extent and is not effectively used.

Zn (S _1-a , S _ea ): In the Au and Al phosphors, absorption of the visible region of 400 mm to 500 mm is highly dependent on the Au reactivity amount, and the absorption rate gradually increases as the Au reactivity amount increases.

FIG. 1 is a graph showing the reflectances of Zn (S _{0 · 85} , S _{e0 · 15} ): Au, Al phosphors, and curve A shows the reflectance when Au reactivity is 10 ⁻³ g / g. In FIG. 1, it can be seen that the phosphor having an activating amount of 10 ^-3 g / g is significantly reduced in reflectance of 400 mm to 500 mm compared with the phosphor having an Au activating amount of 10 ^-5 g / g. That is, it can be seen that the water absorption of 400 mm to 500 mm is significantly increased. The absorption rate of 400 mm to 500 mm is also changed by the change of Se substitution, that is, the change of a value, and the absorption rate increases with the increase of a value, but the increment of absorption rate to the increment of a value is small and Zn (S _{1 -a} , S _ea ): It can be said that the absorption of 400 mm to 500 mm of Au and Al phosphors is mainly determined by the Au reactivity.

As described above, the inventors

1) Zn (S _1-a , S _ea ): Absorption of Au and Al phosphors 400mm to 500mm can be made smaller by reducing Au reactivity, and when Au reactivity is less than 10 ^-4 g / g, absorption becomes Significantly smaller. In addition to

2) Zn (S _1-a , S _ea ): Luminescence luminance of Au and Al phosphor decreases as the activator decreases in the region where Au reactivity is less than 10 ^-4 g / g, The lowering of the luminance shows high luminance emission even in the region where the Au reactivity is less than 10 ^-4 g / g,

3) "When the amount of Se replacement, i.e.

Zn (S _1-a , S _ea ): The emission color of Au and Al phosphors moves to the short wavelength side due to the decrease of Au reactivity in the area where Au reactivity is less than 10 ^-4 g / g, but the emission color for the decrease of Au reactivity The short wavelength of the light emission color in the region where the short wavelength of the is small and the Au reactivity is less than 10 ^-4 g / g can be prevented by increasing the a value. In light of this, the application of Zn (S _1-a , S _ea ): Au and Al phosphors with less than 10 ⁻⁴ g / g of Au _{reactivity was studied} .

As a result, Zn (S _1-a , S _ea ) with Au _reactivity less than 10 ^-4 g / g: Au and Al phosphors have Zn (S ₁ in the range of 10 ^-4 g / g to 10 ^-2 gg _-a , S _ea ): Compared with Au and Al phosphors, their own luminous luminance is low, but absorption of 400mm to 500mm is considerably smaller, so when combining white phosphors with ZnS: Ag blue phosphors The white luminance is almost equal to that when using Zn (S _1-a , S _ea ) Au, Al phosphor having Au _reactivity in the range of 10 ⁻⁴ g / g to 10 ⁻² g / g, and Au Zn (S _1-a , S _ea ) with less than 10 ^-4 g / g: The emission wavelength shortening due to the reduction of Au activity of Au and Al phosphors can be prevented by strict regulation of Se substitution value. Discovered and reached the present invention. That is, the white light emitting phosphor of the present invention has a composition formula

Zn (S _1-a , S _ea )

0.35인 조건을 충족하는 수다)로 표시되는 유세렌화 아연모체 1g에 대하여 Au 및 Al부활량이 각각 10^-6g이상 10^-4g미만 및 5×10^-7g이상 5×10^-5g미만에 있는 Zn(S_1-a, S_ea) : Au, Al 황녹색 내지 황색 발광형광체와 ZnS모체 1g에 대하여 Ag부활량이 10^-5g내지 10^-8g의 범위에 있는 ZnS : Ag 청색 발광형광체의 중량비가 0.60 내지 1.60의 범위에 있는 것을 특징으로 하는 것이다.(Where a is 0.05 <a

To more than 10 ^-6 g Au and Al, respectively with respect to the amount of resurrection campaign renhwa zinc 1g matrix represented by chat) to meet the conditions of 0.35 less than 10 ^-4 g, and less than 5 × 10 ^-7 g more than 5 × 10 ^-5 g Zn (S _1-a , S _ea ): Au, Al yellow-green to yellow luminescent phosphors and ZnS: Ag blue luminescent phosphors with Ag reactivity in the range of 10 ^-5 g to 10 ^-8 g per ¹ g of ZnS parent The weight ratio is in the range of 0.60 to 1.60.

Hereinafter, the white light emitting phosphor of the present invention will be described in detail. Zn (S _1-a , S _ea ): Au, Al phosphors (where a has the same definition as described above), for example, zinc selenide (ZnSe) or selenium oxide (SeO ₂ ) and zinc emulsion ( ZnS) is mixed at a rate of 1-a mole or 1 mole with respect to a mole of ZnSe or SeO _2, and again a gold compound such as gold chloride (HAuCl ₄ , 2H ₂ O) and aluminum sulfate [Al ₂ (SO _{4). 3} ) It is obtained by adding and mixing an aluminum compound such as 18H ₂ O] and baking for 1 hour to 5 hours at 900 ° C to 1,030 ° C in an emulsifying atmosphere, and the emission color is based on the Se amount (a value) and Au reactivity amount constituting the mother body. To change. In other words, as the amount of Se increases, the color of emission changes from green to red, and when the amount of Se is constant, the amount of Au is increased in the region where the amount of Au is less than 10 ^-4 g with respect to 1 g of the mother, and the color of emission gradually shifts to the longer wavelength side. . 2 is a constant (a relationship between Zn (S _1-a and S _ea ) when the Au _reactivity is 5 × 10 ⁻⁵ g relative to 1 g of the mother: the amount of Se of the Au and Al phosphors and the x value of the emission chromaticity point ( Curve A) and the relationship between the Se value and the luminance (curve B), and as shown in FIG. 2, the x value of the emission chromaticity point increases as the Se amount a value increases. In addition, the light emission luminance gradually decreases as the value of Se increases to 0.10, but gradually decreases as the value of a increases until the value of Se exceeds 0.10. Relationship between Au _{reactivity of} Zn (S _1-a , S _ea ): Au, Al phosphor [ie Zn (S _{0 · 85} , S _{e0 · 15} ): Au, Al phosphor] and x value of emission chromaticity point ( straight line a) and Au resurrection amount and the light emission luminance and the relationship (line B) the display of claim 10 the amount of Au relative to the parent resurrection 1g beating degree of the point x clear luminous colors, as in Figure 3 is to ^-4 g of Under a gradually increased to increase the amount of resurrection degree of increase is slight and, on the contrary, there is no method the amount of Au resurrection extremely small amount even if the luminescent color is greatly in the short wavelength, while the luminescence intensity against the amount of 10 g ^4- Au revived matrix 1g In the following, the Au reactivity is gradually increased, but the degree of increase is slightly as in the case of the above-described light emission color. On the contrary, even if the Au reactivity is extremely small, the luminance is not greatly reduced.

The Zn (S _1-a , S _ea ): Au, Al phosphors used in the white light-emitting phosphor of the present invention emit yellowish green to yellow, and the emission luminance is sufficiently high, and the Se amount a value is in the range of 0.05 to 0.35. Au reactivity is in the range of 10 ⁻⁶ g to 10 ⁻⁴ g (but not 10 ⁻⁴ g) per 1 g of the mother. More preferably, the Se amount a value range and the Au reactivity amount range are 0.10 to 0.25 and 5 × 10 ⁻⁶ g to 5 × 10 ⁻⁵ g, respectively. Zn (S _1-a , S _ea ): Au and Al phosphors having an Se amount a of 0.05 or less or 0.35 or more are not used because the emission color is not yellowish green or yellow and the emission luminance is low. In FIG. 4, chromaticity points Y ₁ (x = 0.380, y = 0.550), y ₂ (x = 0.415, y = 0.523), and Y ₃ (x = 0.457, y = 0.492) are 1 g of Au. It is to represent the emission chromaticity point of the Zn (S _1-a , S _ea ): Au, Al phosphor having 5 × 10 ^-5 g and Se amount a value of 0.05, 0.15 and 0.35, respectively. The emission chromaticity point of Zn (S _1-a , _Sea ): Au, Al phosphor is almost on the curve connecting the chromaticity points Y ₁ , Y ₂ , Y ₃ . In addition, Al is revived in the range of half the Au regeneration amount range. In other words, the Al resilience range is 5 × 10 ⁻⁷ g to 5 × 10 ⁻⁵ g (without 5 × 10 ⁻⁵ g not included) for 1 g of the mother, and the more preferred Al resilience range is 2.5 × for 1 g of the mother. It is ^10-6 g-2.5 * 10 ^-5 g

On the other hand, ZnS: Ag phosphors are used as the blue light-emitting phosphors constituting the white light-emitting phosphors of the present invention, such as the Zn (S _1-a , _Sea ): Au, Al phosphors, which are the above-mentioned yellow green to yellow light _- emitting phosphors. The ZnS: Ag phosphor is obtained by adding an appropriate amount of silver compound such as silver nitrate (AgNO ₃ ) to zinc emulsified raw material and firing at 900 ° C to 1,000 ° C for 1 to 5 hours in a weak reducing atmosphere. As it changes and generally the amount of Ag reactivity increases, the emission color gradually shifts toward the short wavelength side. The ZnS: Ag phosphor used in the white light-emitting phosphor of the present invention has an Ag reactivity in the range of 10 ^-5 g to 10 ^-3 g with respect to the parent ZnS 1g in terms of the emission color and the luminance, and particularly the Ag reactivity is the parent ZnS. A good white light emitting phosphor is obtained when a ZnS Ag phosphor in the range of 5 x 10 ^-5 g to 2 x 10 ^-4 g per 1 g is used. In FIG. 4, the chromaticity points B ₁ (x = 0.142, y = 0.110), B ₂ (x = 0.148, y = 0.050), and B ₃ (x = 0.142, y = 0.085) each represent Ag for ZnS 1g. The present invention shows the emission chromaticity point of 10 ^-5 g, 10 ^-3 g and 10 ^-4 g revived ZnS: Ag phosphors, and the Ag reactivity is in the range of 10 ^-5 g to 10 ^-3 g relative to 1 g of ZnS The luminescence chromaticity point of the ZnS: Ag phosphor used for the white luminescent phosphor of is almost on a curve connecting the chromaticity points B ₁ , B ₂ , and B ₃ .

The white light-emitting phosphor of the present invention is obtained by mixing the above-described Zn (S _1-a , S _ea ): Au, Al phosphors and ZnS: Ag phosphors, but not Zn (S _1-a , S _ea ): Au, Al phosphors. The mixed weight ratio of ZnS to Ag phosphors is in the range of 0.60 to 1.60. More preferred is the range of 0.80 to 1.30 and in particular the best white light emitting phosphor is obtained when in the range of 0.90 to 1.20. The white light-emitting phosphor of the present invention obtained by mixing Zn (S _1-a , _Sea ): Au, Al phosphors and ZnS: Ag phosphors in the above mixing ratio is sufficiently wide and complete in a white reproduction region. For example, in FIG. 4, it is evident that the JEDEC regulation and its peripheral region are completely contained between the straight line Y ₁ B ₁ and the straight line Y ₃ B ₂ . The white light-emitting phosphor of the present invention is also sufficiently high in luminance, and can be used as a phosphor for black and white televisions. In addition, the white light-emitting phosphor of the present invention does not contain a red light-emitting phosphor having an expensive rare earth element as a constituent and thus becomes a cheap phosphor compared to a white light-emitting phosphor containing a practical red light-emitting phosphor.

Next, a description will be given of the round tube for black and white television of the present invention, wherein the white light-emitting phosphor of the present invention described above is a fluorescent film.

The structure of the round tube for black and white television of the present invention is the same as that of the conventional black and white television round tube except for the fluorescent film as shown in FIG. In other words, the black-and-white television tube of the present invention has one electron gun 3 in the neck 2 of the panel 1 and a fluorescent film 5 formed on the entire surface on the screen 4 facing the electron gun 3. will be. Generally, the aluminum vapor deposition film 6 for preventing the charging front at the time of excitation is provided in the back surface of the fluorescent film 5.

In the round tube for black and white televisions configured as described above, the fluorescent film is characterized by the white light-emitting phosphor of the present invention described above. The fluorescent film is formed by the sedimentation coating method which is generally employed as a method for forming a fluorescent film of a round tube for black and white televisions. The phosphor amount of the fluorescent film is suitably in the range of 2.0 to 7.0 mg per cm 2 in terms of luminous luminance. More preferred is in the range of 2.5 to 6.0 mg per cm 2. The above-mentioned round tube for black and white television of the present invention is higher in luminance than the round tube for black and white television of the present practical use. In addition, since the white reproduction region of the white light emitting phosphor which can be used in the fluorescent film is wide, the selection tube has a wide selection range.

The present invention will be described by the following examples.

Example 1

ZnS: Ag phosphor (Ag / ZnS = 10 ^-4 g / g)

Zn (S _{0 · 85} , S _{e 0 · 15} ): Au, Al phosphor

[Au / Zn (S _{0 · 85} , S _{e 0 · 15} ) = 5 × 10 ^-5 g / g]

[Al / Zn (S _{0 · 85} , S _{e 0 · 15} ) = 2.5 × 10 ^-5 g / g]

The two kinds of phosphors were mixed in a weight ratio of ZnS Ag Zn (S _{0 .85} , S _{e 0} .15): Au, Al 0.85, 1.05 and 1.25 to obtain three mixed phosphors. Next, three 12-inch black-and-white television tubes for the three kinds of mixed phosphors as fluorescent films were produced by a conventional manufacturing method. In either case, the fluorescent film was formed by the sedimentation coating method, and the amount of the phosphor was 4.0 mg per cm 2. In either case, an aluminum deposition film was installed on the back of the fluorescent film and the vacuum degree in the tube was 10 ^-7 Torr. The emission chromaticity points when the fluorescent films of the three kinds of black and white televisions for the round tube are excited at a current density of 1.0 mA / cm 2 are shown in the following table and FIG.

[table]

In addition, the emission luminances of the above table are ZnS: Ag phosphor, ZnS Au, Al phosphor and Y ₂ O ₂ S: Eu phosphor, ZnS: Ag phosphor: ZnS: Au, Al phosphor: Y ₂ O ₂ S: Eu phosphor = 6: 4 : Current density value of 1.0 mA / cm 2 at the current practical value of the round tube for black and white televisions (the phosphor amount and vacuum degree per 1 cm 2 of the round tube size) of which the white light-emitting phosphor obtained by mixing at a weight ratio of 1 is used as a fluorescent film. The light emission luminance is expressed by a relative value of 100 (the same as in Example 2).

Example 2

ZnS: Ag phosphor (Ag / ZnS = 1.5 × 10 ^-4 g / g)

Zn (S _{0 · 90} , S _{e0 · 10} ): Au, Al phosphor

Au / Zn (S _{0 · 90} , S _{e0 · 10} ) = 5 × 10 ^-5 g / g

Al / Zn (S _{0 · 40} , S _{e0 · 10} ) = 2.5 × 10 ^-5 g / g

The two kinds of phosphors were mixed in a weight ratio of ZnS: Ag / Zn (S _{0 .90} , S _{e0 .10} ) = 1.05 and 1.15 to obtain two kinds of mixed phosphors. Next, two 12-inch black-and-white television tubes with the two kinds of mixed phosphors as fluorescent films were manufactured by a conventional manufacturing method. As in Example 1, all of the fluorescent films were formed by the sedimentation coating method, and the phosphor content thereof was 4.0 mg per cm 2. In either case, an aluminum vapor deposition film was provided on the back side of the fluorescent film, and the vacuum degree in the tube was 10 ^-7 Torr. The emission chromaticity points when the fluorescent films of the two kinds of black and white televisions for the round tube are excited at a current density of 1.0 mA / cm 2 are shown in the following table and FIG.

[table]

Claims (1)

Composition Zn (S _1-a , S _ea ) (Only 0.05

a

With respect to 1 g of zinc selenide matrix represented by 0.25), the activation amounts of gold and aluminum are respectively 10 ⁻⁶ g or more and less than 10 ⁻⁴ g and 5 × 10 ⁻⁷ g or more and 5 × 10 ⁻⁵ g The sulfur as a mixed phosphor comprising less than gold and aluminum-activated zinc-sulfurized green-yellow luminescent phosphors and a silver-activated zinc blue luminescent phosphor having a silver resilience amount of 10 ^-5 g or more and 10 ^-3 g or less with respect to 1 g of an emulsified zinc matrix. A white light emitting phosphor, wherein the weight ratio of the blue light emitting phosphor to the green to yellow light emitting phosphor is in the range of 0.60 to 1.60.

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