KR790001425B1 - 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 10-4g to 10-2g and 5x10-3g to 5x10-3g respectively per 1g of zinc sulfoselenide whose formative for mula is Zn(S1-aSea)(Only O,a<=0.30), 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 0.07 to 1.60.

Description

White light emitting phosphor

1 shows the relationship between the Se amount a value and the x value of the emission chromaticity point (curve A) and the Se amount in the Zn (S _1-a , Se a): Au and Al phosphors used in the white light emitting phosphor of the present invention. indicates the relationship between the value a and the luminance (curve B)

2 shows Zn (S _1-a , S _e a): Au relationship between Au activation amount and x value of emission chromaticity point (curve A) and Au loading in the white light emitting phosphor of the present invention. Relationship between the quantity and the luminance of light emitted (curve B),

The third turning JEDEC standard, the Zn constituting the white light-emitting phosphor of the invention _{(S 1-a, S e} a): Au, Al phosphor and ZnS: emission color of Ag phosphor dojeom and the fluorescent film of the cathode-ray tube for monochrome telrebijyon of the invention (Luminescent chromaticity point CIE colorimetric system of the white light-emitting phosphor of the present invention),

4 is a schematic configuration diagram of a CRT for a 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 deposition film

The present invention relates to a phosphor that emits white light by electron beam excitation.

The white fluorescent substance for black and white televisions currently used is not a single fluorescent substance, but is a mixture of two or three or more kinds of phosphors at an appropriate ratio to emit substantially white light by electron beam excitation. Therefore, the emission color of the white light emitting phosphor for black and white televisions is determined by the mixing ratio of the constituent phosphors, and the mixing ratio can be appropriately changed as necessary, but in general, the white light emitting phosphors for the black and white televisions of the present practical use are shown in FIG. JEDEC (Joint) surrounded by chromaticity points A (x = 0.273, y = 0.282), B (x = 0.267, y = 0.303), C (x = 0.286, y = 0.326), and D (x = 0.290, y = 0.303) Electron Device Engineering Councils) has its luminous chromaticity point in the white region or in its very close range. Specifically, the white light-emitting phosphor for black and white televisions of the present practical use

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

(2) ZnS: Au, Al phosphors of yellow-green to yellow light emission and ZnS: Ag phosphors of blue light emission, and europium-activated yttrium phosphor (Y ₂ O ₃ : Eu), europium-activated vanadine yttrium phosphor (YVO ₄ : Eu) and europium-activated yttrium phosphate (Y ₂ O ₂ S: Eu) species There are two kinds of combinations by adding at least one red light-emitting phosphor.

However, although the white light-emitting phosphor of (1) is sufficiently high in light emission luminance, the white reproduction region does not completely include the JEDEC standard, and is slightly biased on the short wavelength side (after all, the green side), which is preferable in view of this white reproduction region. I can't.

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 phosphorus and Y ₂ O ₂ S: Eu phosphor is added to the white light emitting phosphor of (1). By mixing, the emission color of the white light-emitting phosphor of (1) is made longer and the reproduction area of white is made more complete. However, since the white light-emitting body of (2) includes a red light-emitting phosphor having a low light emission luminance, the light-emitting luminance is slightly lower than that of the white light-emitting phosphor of (1), and the red light-emitting phosphor contains a large amount of expensive rare earth elements. Therefore, the white light emitting phosphor of (2) is more expensive than the white light emitting phosphor of (1). Currently, the white light-emitting phosphor of (2) is mainly employed in the CRT for commercial black-and-white televisions. The white light-emitting phosphor of the above-mentioned white light-emitting phosphors of (1) and (2) is more complete.

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

0.30)이나 또는 청색발광성분 형광체로서 ZnS : Ag 형광체가 사용된다. Zn(S_1-a, S_ea) : Au, Al(단 a는 상기와 같으며, 이하 모두 같다)는, 예를 들면 세렌화아연(ZnSe) 또는 산화세렌(SeO₂)와 유화아연(ZnS)과를 ZnSe 또는 SeO₂몰에 대하여 ZnS가 (1-a)몰 또는 1몰의 비율로 혼합하고, 또한 여기에 염화금(HAuCl₄-2H₂O)등의 금화합물 및 황산알미늄[Al₂(SO₄)₃-18H₂O] 등의 알미늄화합물을 첨가 혼합하여, 유화성(硫化性)분위기중에서 900°내지 1,030℃에서 1시간 내지 5시간 소성시켜서 얻어지는 입방정개의 것으로, 그 발광색은 모체를 구성하는 Se량 (a치)및 Au부활량에 의하여 변화된다. 즉 Se량이 증가함에 따라서, 발광색은 점차적으로 녹색에서 적등색까지 변화하며, 또한 Se량이 일정한 경우, Au 부활량이 증가함에 따라서 발광색은 차례로 장 파장측으로 이동하며, 또한 Au부활량이 증가하면 그 발광색은 재차로 단파장측으로 이동하는 것이다. 제 1 도는 Au부활량이 일정(모체 1g에 대하여 10^-3g)한 경우의 Zn(S_1-a, S_ea) : Au, Al형광체의 Se량과 발광체색도점의 x치와의 관계(곡선 A) 및 Se량과 발광휘도와의 관계(곡선 B)를 나타내는 것이며, 제 1 도에서 명확한 바와 같이, 발광색도점의 x치는 Se량 a치가 증가함에 따라서 증가한다. 즉 발광색은 Se량의 a치가 증가함에 따라서 순차로 장파장측으로 이동한다. 또한 발광휘도는 Se량 a치가 0.10까지에는 거의 일정하나, 0.10이상이 되면 a치가 증가함에 따라서 순차적으로 감소한다.The white light-emitting phosphor of the present invention is a mixed phosphor that is appropriately mixed with yellow-green to yellow light-emitting phosphor and blue light-emitting phosphor to emit light substantially white. Phosphor [Zn (S _1-a , S _e a): Au, Al (where a is 0 <a

0.30) or a ZnS: Ag phosphor as a blue light emitting phosphor. Zn (S _1-a , S _e a): Au, Al (where a is the same as above and all are the same below), for example, zinc selenide (ZnSe) or cerene oxide (SeO ₂ ) and zinc emulsion ( ZnS) is mixed with ZnS in a ratio of (1-a) moles or 1 mole to ₂ moles of ZnSe or SeO, and also gold compounds such as gold chloride (HAuCl ₄ -2H ₂ O) and aluminum sulfate [Al ₂ (SO ₄ ) ₃ -18H ₂ O] is a cubic crystal obtained by adding and mixing aluminum compounds such as ₃ -18H ₂ O and sintering at 900 ° to 1,030 ° C for 1 to 5 hours in an emulsifying atmosphere. It changes with Se amount (a value) and Au reactivity which comprise. In other words, as the amount of Se increases, the emission color gradually changes from green to red-red, and when the amount of Se is constant, the emission color shifts to the longer wavelength side as the Au activation amount increases, and when the amount of Au reactivity increases, the emission color again To move to the shorter wavelength side. 1 shows Zn (S _1-a , S _e a) when Au reactivity is constant (10 ^-3 g relative to 1 g of mother): the relationship between the Se amount of Au and Al phosphors and the x value of the luminescence chromaticity point ( The curve A) and the relationship between the Se amount and the emission luminance (curve B) are shown. As is clear from FIG. 1, the x value of the emission chromaticity point increases as the Se amount a value increases. That is, the light emission color sequentially moves to the long wavelength side as the a value of the Se amount increases. In addition, the light emission luminance is substantially constant until the Se amount a value is 0.10, but decreases sequentially as the a value increases when it is 0.10 or more.

Au resurrection amount of: [Au, Al fluorescent substance that is _{Zn (S 0.95, Se 0.0)} ]: The second turning of the case of _{Zn (S 1-a, S} e a) constant (a = 0.05) the amount of Se Au, Al fluorescent substance And the relationship between the x value of the emission chromaticity point (curve A) and the relationship between the Au reactivity amount and the emission luminance (curve B). As is apparent from FIG. 2, the x value of the emission chromaticity point Au amount is Up to about 3 × 10 ^-3 g of 1 g of the mother increases sequentially as the Au reactivity increases, but when the Au reactivity increases to about 3 × 10 ³ g or more with respect to 1 g of the mother, conversely decreases as the Au reactivity increases. do.

In other words, the light emission color gradually moves toward longer wavelengths when the Au reactivity was increased to about 3 × 10 ⁻³ g with respect to 1 g of the mother, but when Au reactivity was 3 × 10 ^3- g or more with respect to 1 g of the mother, Au was reversed. As the amount of revival increases, it gradually moves toward shorter wavelengths. The light emission luminance is almost in about 5 × 10 ^-4 g to 10 ^-3 g with respect to the amount of Au relative to the parent resurrection 1g 5 × 10 ^-4 g amount of one bit by bit thus increase, increasing the amount of Au Au resurrection revived matrix 1g When saturation is reached, when it is 10 ^-3 g or more, the Au reactivity is gradually decreased as it increases. It also decreases considerably rapidly if it exceeds 3 × 10 ⁻³ g. Zn (S _1-a , S _e a): Au and 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 0.30 or less, Au The amount of activation is in the range of 10 ⁻⁴ g to 10 ⁻² g with respect to 1 g of the mother. Better Se amount a value ranges and Au reactivity amount ranges are 0.01 to 0.20 and 3 × 10 ⁴ g and 3 × 10 ³ g, respectively. Se amount of Zn a value greater than _{0.30 (S 1-a, S} e a): Au, Al phosphor and the amount of Au resurrection 10 ^-4 g or less, or less than 10 ^-2 g _{Zn (S 1-a, S} e a): Au and Al phosphors can be used because the luminous luminance is low because the emission color is not yellowish green to yellow. In FIG. 3, chromaticity points Y ₁ (A = 0.406, Y = 0.555), Y ₂ (x = 0.436, y = 0.538) and Y ₃ (x = 0.480, y = 0.495) are Au reactivity and the mother 1 g Zn (S _1-a , S _e a): Au and Al phosphors having a concentration of 10 ^-3 g and a Se value of 0.01, 0.10 and 0.30, respectively, and are used for the white light emitting phosphor of the present invention. The emission chromaticity points of Zn (S _1-a , S _e a): Au and Al phosphors are almost on a curve connecting chromaticity points Y ₁ , Y ₂ and Y ₃ . In addition, Al is revived in the range of half the Au regeneration amount range. That is, the regeneration amount range is 5 × 10 ⁻⁵ to 5 × 10 ⁻³ with respect to 1 g of the mother, and a better Al reactivity amount range is 1.5 × 10 ⁻⁴ to 1.5 × 10 ⁻³ g with respect to 1 g of the mother.

On the other hand, phosphors are used as the blue light-emitting fluorescent substance constituting the white light-emitting fluorescent substance of the present invention together with the above-mentioned yellow green to yellow light-emitting fluorescent substance Zn (S _1-a , S _e a): Au, Al phosphors. The ZnS: Ag phosphor is a cubic crystal obtained by adding an appropriate amount of silver compound such as silver acetate (AgNO ₃ ) to a zinc emulsified component and firing at 900 ° C to 1,000 ° C for 15 hours in a weak reducing atmosphere, and the emission color is Zn (S _1-a , S _e a): As in the case of Au and Al phosphors, they change with the amount of Ag activity, and in general, as the amount of Ag activity increases, the emission color shifts to the shorter wavelength side. The ZnS: Ag phosphor used in the white luminescent phosphor of the present invention has an Ag reactivity in the range of 10 ^-5 to 10 ^-3 g with respect to the mother ZnS 1g in terms of luminescent color and luminescence brightness, and in particular, the activating amount is relative to the mother ZnS1g. When a ZnS: Ag phosphor in the range of 5 x 10 ^-5 to 2 x 10 ^-4 g is used, a good white light emitting phosphor is obtained. In FIG. 3, 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. 10 ^-5 g, 10 ^-3 g and 10 ^-4 g of the regenerated ZnS: Ag phosphor exhibits the emission chromaticity point, and Ag reactivity is in the range of 10 ^-5 to 10 ^-3 g relative to 1 g of ZnS ZnS used in the white light-emitting phosphor of light emission color fluorescent substance that is substantially Ag chromaticity point B _1: it is on the curve connecting, B ₂ and B _3.

The white light-emitting phosphor of the present invention is obtained by mixing Zn (S _1-a , _Se a): Au, Al phosphor and ZnS: Ag phosphor, but Zn (S _1-a , _Se a): Au The mixed weight ratio of ZnS: Ag phosphor to Al phosphor is in the range of 0.70 to 1.60. More preferably, the best white light emitting phosphor is obtained in the range of 0.90 to 1.40, particularly in the range of 1.00 to 1.30.

_{Zn (S 1-a, S} e a): Au, Al phosphor, ZnS: white light-emitting phosphor of the present invention as obtained by mixing the fluorescent material and Ag as the above mixture ratio is a reproduction area of the white is sufficiently large and complete. This is evident, for example, in FIG. 3 in that the JEDEC standard and its surrounding area are completely included between the straight line Y ₁ B ₁ and the straight line Y ₃ B ₃ . In addition, since the white light emitting phosphor of the present invention is sufficiently high in its light emission luminance, it 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 which contains an expensive rare earth element as a constituent, thereby making it a cheaper phosphor compared to a white light-emitting phosphor including a practical red light-emitting phosphor.

Next, a description will be given of the CRT for a black and white television according to the present invention, wherein the white fluorescent light emitter of the present invention described above is used as a fluorescent film. The configuration of the CRT for the black and white television of the present invention is completely the same as that of the CRT for the black and white television, except for the fluorescent film as shown in FIG. That is, the CRT for the black and white television according to the present invention has one electron gun 3 in the neck 2 of the panel 1, and a fluorescent film 5 on the front surface of the screen 4 facing the former magnetic gun 3 Formed. Generally, the aluminum vapor deposition film | membrane for preventing the charge up at the time of excitation is formed in the back surface of the fluorescent film 5.

In the CRT for a black and white television configured as described above, the electroluminescent 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 CRT 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 preferably, it is in the range of 2.5 to 6.0 mg per cm 2.

The CRT for the black and white television of the present invention described above is higher in luminance than the CRT for a black and white television for the present practical use. In addition, the CRT for the black and white television according to the present invention has a wide selection range of the emission chromaticity point of the CRT because the CRT has a wide white reproduction region of a white light emitting phosphor. The present invention will be described below with reference to examples.

Example 1

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

Zn (. _0.95 , Se _0.05 ) Al Phosphor

Au / Zn (S _0.95 , Se _0.05 ) 1.4 × 10 ^-3 g / g

[Al / Zn (S _0.95 , Se _0.05 ) = 7 × 10 ⁴ g / g]

The two phosphors are mixed in a weight ratio of ZnS: Ag / Zn (S _0.95 , S _e0.05 ): Au, Al = 0.90, 1.10 and 1.30 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 production method. Either one is formed by the sedimentation coating method, and the amount of the phosphor is 4.0 mg per cm 2. In addition, an aluminum deposition film is formed on the back side of the fluorescent film, and the vacuum degree in the tube is 10 ^-7 Torr.

The emission chromaticity points when the fluorescent films of the three kinds of monochrome tubes for monochrome televisions are excited at a current density value of 10 mA / cm 2 are shown in the following table and FIG.

In addition, the emission luminance of the table is ZnS: Ag phosphor, ZnS: Au, Al phosphor and Y ₂ O ₂ S: Eu phosphor, ZnS: Ag phosphor: ZnS: Au, Al phosphor and Y ₂ O ₂ S: Eu phosphor = 6: Light emission at the current density value of 1.0 mA / cm 2 of the current practical monochrome tube for black and white televisions using a white light-emitting phosphor obtained by mixing at a weight ratio of 4: 1 as a fluorescent film (amount of phosphor per 1 cm 2 of brown tube size and the same degree of vacuum) This is expressed by relative value with luminance as 100.

(Example 2 is also the same)

Example 2

ZnS: Ag (phosphor (Ag / ZnS = 7 × 10 ⁵ g / g)

Zn (S _0.90 , S _e0.01 ): Au, Al phosphor

[Au / Zn (S _0.90 , S _e0.10 ) = 10 ^-3 g / g]

[Al / Zn (S _0.40 , S _e0.10 ) = 5 × 10 ^-4 g / g]

The two kinds of phosphors are mixed in a weight ratio of ZnS: Ag / Zn (S _0.90 , S _e0.10 ): Au, Al = 1.10 and 1.20 to obtain two kinds of mixed phosphors. Next, two 12-inch black-and-white television sets for black and white televisions, each of which used two kinds of mixed phosphors as fluorescent films, were produced by a conventional production method. In the same manner as in Example 1, the fluorescent film was either formed by the sedimentation coating method, and the phosphor content thereof was 4.0 mg per cm 2. In addition, an aluminum vapor deposition film is formed on the back of the fluorescent film, and the vacuum degree in the tube is 10 ^-7 Torr. The luminescence chromaticity points when the fluorescent films of the two kinds of black and white television tubes are excited at a current density value of 1.0 mA / cm 2 are shown in the following table and FIG.

Claims (1)

Composition Zn (S _1-a , S _e a) (where a is 0 <a

0.30), 3 to 1 g of the zinc selenide matrix represented by the present invention, gold and aluminum activating amount of 10 ^-4 to 10 ^-2 g and 5 × 10 ^-5 to 5 × 10 | _-3 g yellow-green to gold and aluminum resurrection campaign renhwa zinc phosphor of yellow light in the range of and, of the oil in the range of blue zinc eunbu hwalryang 10 ^-5 to 10 ^-3 g with respect to 1g matrix light-emitting is revived emulsion A white phosphor comprising a mixed phosphor of a zinc phosphor, wherein a weight ratio of the silver-activated zinc phosphor to the gold and aluminum-activated zinc-ensulfated phosphor is in the range of 0.07 to 1.60.

Images