KR900001384B1 - White luminescent fluorescent substance having long after glow - Google Patents

White luminescent fluorescent substance having long after glow Download PDF

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KR900001384B1
KR900001384B1 KR1019860008080A KR860008080A KR900001384B1 KR 900001384 B1 KR900001384 B1 KR 900001384B1 KR 1019860008080 A KR1019860008080 A KR 1019860008080A KR 860008080 A KR860008080 A KR 860008080A KR 900001384 B1 KR900001384 B1 KR 900001384B1
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phosphor
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KR880000545A (en
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카즈히코 타카츠지
히로노리 타테이와
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미쯔이 긴조꾸 고오교오 가부시기가이샤
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract

A white fluorescent substance has a compsn. of formula Ca(1-x) AxS: aM (I), bM(II), cCu, dM(III), eM(IV). In the formula, A is at least one element of Mg, Sr or Ba; M(I) is at least one of Mn of Sm; M(II) is Li and/or Na; M(IV) is Ce, S6 and/or Eu; 5 X 10-6 <= a <= 1 X 10-1; 0 <= b <= 1 X 10-1; 1 X 10-5 <= c <= 1 x 10-1; 1 X 10-5 <= d <=1 1 x 10; 0 <= e <= 1 X 10-1; 1 <= x <= 0.1. The substance is used for prepg. a cathode ray tube for displays. The substance gives an afterglow of the same colour as luminescence.

Description

장잔광백색발광형광체Long afterglow white emitting phosphor

제1도는 실시예 1∼7의 형광체의 CIE 색도도.1 is a CIE chromaticity diagram of the phosphors of Examples 1 to 7. FIG.

제2도는 실시예 8∼11의 형광체의 CIE 색도도.2 is a CIE chromaticity diagram of the phosphors of Examples 8-11.

제3도는 실시예 2, 18∼20의 형광체의 CIE 색도도.3 is a CIE chromaticity diagram of the phosphors of Examples 2 and 18-20.

제4도는 본 발명의 형광체의 색재현 범위 및 실시예 21∼24의 형광체의 CIE 색도도.4 is a color reproduction range of the phosphor of the present invention and a CIE chromaticity diagram of the phosphors of Examples 21 to 24.

본 발명은 황화물 형광체에 관한 것으로서, 상세히는 주로 디스플레이용 브라운관에 적합한 고휘도이면서도 장잔광(長殘光)의 백색발광형광체에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to sulfide phosphors, and in particular, to high brightness and long afterglow white light emitting phosphors suitable for display CRTs.

최근, 디스플레이용 단색브라운관의 수요가 증가되고 있고, 녹색, 백흑, 황 혹은 오렌지색의 형광체가 사용되고 있으나, 금후는 보기 편하고, 눈의 피로도가 적다는 점에서 오렌지색 및 백흑 표시가 주류가 될 것으로 보여지고 있다.Recently, the demand for monochromatic CRTs for displays is increasing, and green, black, yellow, or orange phosphors are used. However, orange and white marks are expected to become mainstream because they are easy to see and have less eye fatigue. have.

그런데, 디스플레이용 브라운관에 요구되는 특성에는 발광색외에 밝기가 적당할 것, 어른거림이 없는 것등을 들 수 있다. 특히 디스플레이용 브라운관으로서 사용하는 경우에는, 텔레비젼용 브라운관보다 전자선의 스위프주파수가 낮게 됨으로 장잔광형광체를 사용하지 않으면 화면에 어른거림이 보여진다. 그러나, 일반적으로 형광체는 장잔광화하면 휘도가 현저히 저하하여, 고휘도이면서도 장잔광의 형광체를 얻는것은 어렵By the way, the characteristic required for the display tube is that the brightness is appropriate in addition to the emission color, there is no adultiness. In particular, when the display tube is used as a display tube, the sweep frequency of the electron beam is lower than that of the television tube tube, and therefore, when the long afterglow phosphor is not used, the flicker appears on the screen. In general, however, when the phosphor is long afterglowed, the luminance is remarkably decreased, and thus it is difficult to obtain a phosphor having a high brightness and long afterglow.

현재 알려져있는 디스플레이용 장잔광 백색발광형광체로서는 일본국 특개소 59-202283호 공보에 개시되어 있는 Zn(1-x)CdxS(0

Figure kpo00001
x0.2)계 형광체, 및 장잔광형광체를 성분으로하는 예를 들면 일본국 특원소 60-32841에서 게시된것과 같은 혼합 백색발광형광체가 있다.Currently known long afterglow white light emitting phosphors are Zn (1-x) CdxS (0 ) disclosed in Japanese Patent Laid-Open No. 59-202283.
Figure kpo00001
x0.2) -based phosphors, and mixed white light-emitting phosphors such as those disclosed in Japanese Patent Application Laid-Open No. 60-32841.

그런데, 상기한 일본국 특개소 59-202283호 공보에 개시되어있는 장잔광 백색발광 형광체는, Cd를 함유하기 때문에 엄중한 회수 시스템을 필요로하며, 또한 휘도가 낮다고 하는 결점이 있다. 또, 통상 사용되고 있는 혼합백색발광형광체는, 잔광특성이 일치하지 않은 보색관계에 있는 형광체를 성분으로 하고 있기 때문에, 전자선 여기(勵起)정지후의 감쇠과정에서 색얼룩이나 어른거림이 생긴다. 또한, 상기한 일본국 특원소 60-32841호에 개시한 백색형광체도 발광색이 다른 형광체를 조합혼합하여 사용하기 때문에 미소영역에서 색얼룩이 생기기 쉽고, 해상도도 나쁘다는 문제점이 있다.By the way, the long afterglow white light-emitting fluorescent substance disclosed in Japanese Unexamined Patent Publication No. 59-202283 has a drawback that a severe recovery system is required because it contains Cd and the luminance is low. In addition, since the mixed white light-emitting phosphor commonly used is composed of a phosphor having a complementary color relationship in which afterglow characteristics do not coincide, color spots and tingling occur during attenuation after electron beam excitation. In addition, the white phosphor disclosed in Japanese Patent Application Laid-Open No. 60-32841 also has a problem in that color spots are easily generated in a small area because the fluorescent substance having different emission colors is used in combination, and the resolution is also poor.

본 발명의 목적은, 상술한 종래형의 디스플레이용 브라운관에 사용되는 형광체가 가진 결점을 해소하고, 무해이고, 발광색이 다른 형광체의 혼합물이 아니고 단일의 백색형광체로서 구성되고, 잔광시의 색얼룩, 어른거림 및 미소영역의 색얼룩을 없앤 고휘도이고도 장잔광의 백색발광형광체를 제공하는데 있다.SUMMARY OF THE INVENTION An object of the present invention is to solve the drawbacks of the phosphors used in the above-described conventional display CRTs, which are harmless and are composed of a single white phosphor instead of a mixture of phosphors having different emission colors, The present invention provides a high-luminance, long-afterglow white light-emitting phosphor that eliminates flicker and color spots in small areas.

본 발명자등은 상기 목적에 따라서 검토한 결과, 아래 조성을 가진 형광체가 상기 목적을 충분히 달성하는 것을 발견하여 본 발명에 도달하였다.MEANS TO SOLVE THE PROBLEM As a result of having examined according to the said objective, the present inventors discovered that the phosphor which has the following composition fully achieves the said objective, and reached | attained this invention.

즉 본 발명은, 조성식이 Ca(1-x)AxS : αMI, βMII, γCu, δMIII, εMIV로 표시I II III IV -6

Figure kpo00002
α
Figure kpo00003
1×10-1, 0
Figure kpo00004
β
Figure kpo00005
1×10-1(단, MI이 Mn일때는 5×10-7
Figure kpo00006
β
Figure kpo00007
1×10-1의 범위)That is, the present invention is represented by the composition formula Ca (1-x) AxS: αM I , βM II , γCu, δM III , εM IV I II III IV- 6
Figure kpo00002
α
Figure kpo00003
1 × 10 -1 , 0
Figure kpo00004
β
Figure kpo00005
1 × 10 -1 (5 × 10 -7 when M I is Mn
Figure kpo00006
β
Figure kpo00007
1 × 10 -1 range)

1×10-5

Figure kpo00008
γ
Figure kpo00009
1×10-1, 1×10-5
Figure kpo00010
δ
Figure kpo00011
1×10-1,0
Figure kpo00012
ε
Figure kpo00013
1×10-1, X
Figure kpo00014
γ
Figure kpo00015
0.1의 범위에 있는 것을 특징으로 하는 장잔광백색발광형광체에 있다.1 × 10 -5
Figure kpo00008
γ
Figure kpo00009
1 × 10 -1 , 1 × 10 -5
Figure kpo00010
δ
Figure kpo00011
1 × 10 -1, 0
Figure kpo00012
ε
Figure kpo00013
1 × 10 -1 , X
Figure kpo00014
γ
Figure kpo00015
It is in the long afterglow white light-emitting phosphor which is in the range of 0.1.

이와 같은 조성으로 하므로서, 단일백색발광하여, 잔광색이 발광색과 동일하고, 또한 전자선여기시의 잔광시정수(殘光時定數) γ1/10이 γ1/10

Figure kpo00016
g15m sec의 범위로 되는 장잔광 백색발광 형광체를 얻게 된다.With such a composition, single-white light is emitted, the afterglow color is the same as the emission color, and the afterglow time constant γ1 / 10 at the time of electron beam excitation is γ1 / 10.
Figure kpo00016
A long afterglow white light-emitting phosphor in the range of g15m sec is obtained.

본 발명에서 사용하는 상기 조성을 가진 장잔광 백색발광 형광체를 얻기 위해서는, 상기 조성식이 되도록 탄산칼슘등의 칼슘화합물, 황산마그네슘등의 알카리토류금속화합물, 탄산망간등의 망간 혹은 사마륨의 화합물, 산화스칸듐등의 스칸듐, 이트륨, 알루미늄, 란탄, 비스무트, 혹은 디스프로슘의 화합물, 산화동등의 구리화합물, 탄tks나트륨의 알카리금속화합물, 산화세륨등의 세륨, 안티몬 혹은 유로퓸의 화합물을, 예를 들면 황화수소등의 황화성 분위기중에서 소성하므로서 얻어진다. 단, 나트륨등의 알카리금속은 소성중에 휘발손실이 많으므로 상기 조성내에 수납되도록 소성 조건에 따라서 첨가량을 제어한다. 본 발명에 있어서는, 오렌지로부터 적색발광하는 망간 혹은 사마륨의 농-6

Figure kpo00017
α
Figure kpo00018
1×10-1에 있는 것이 필요하고, 그 범위를 벗어나면 발광이 약하게 되어 바람직하지 못하다. 또, 농도 α는 바람직하게는 2×10-5
Figure kpo00019
α
Figure kpo00020
2×10-2, 더욱 바람직한 최적범위는 5×10-4
Figure kpo00021
α
Figure kpo00022
2×10-3가 좋다.In order to obtain a long afterglow white light-emitting phosphor having the composition used in the present invention, a calcium compound such as calcium carbonate, an alkali earth metal compound such as magnesium sulfate, a manganese or samarium compound such as manganese carbonate, scandium oxide or the like may be used as the composition formula. Compounds of scandium, yttrium, aluminum, lanthanum, bismuth or dysprosium, copper compounds such as copper oxides, alkali metal compounds of sodium tantks, cerium oxides such as cerium oxide, compounds of cerium, antimony or europium, such as hydrogen sulfide It is obtained by baking in an atmosphere. However, since alkali metals, such as sodium, have many volatilization losses during baking, addition amount is controlled according to baking conditions so that they may be accommodated in the said composition. In the present invention, the concentration of manganese or samarium, red-emitting from orange -6
Figure kpo00017
α
Figure kpo00018
It is necessary to be 1 × 10 −1 , and light emission becomes weak when it is out of the range, which is not preferable. Further, the concentration α is preferably 2 x 10 -5
Figure kpo00019
α
Figure kpo00020
2 × 10 -2 , more preferred range is 5 × 10 -4
Figure kpo00021
α
Figure kpo00022
2 x 10 -3 is good.

망간 혹은 사마륨의 발광을 장잔광화하는 스칸듐, 이트륨, 알루미늄, 란탄, 비스무트 혹은 디스프로슘의 농도 β(몰비)는 0

Figure kpo00023
β
Figure kpo00024
1×10-1에 있는 것을 필요로 한다. 또한, 이β의 값은 상기의 망간 혹은 사마륨의 부활제로서 망간만을 사용하는 경우에는, 5×10-7
Figure kpo00025
β
Figure kpo00026
1×10-1로 되지 않으면 안된다. β가 이 범위보다 작으면 잔광이 짧게 되고, 크면 형광체로서의 발광이 약하게 되기 때문이다. 또, 농도 β는 바람직하게는 0
Figure kpo00027
β
Figure kpo00028
2×10-2(MI이 Mn일때는 2×10-6
Figure kpo00029
β
Figure kpo00030
2×10-1), 더욱 바람직한 최적범위는 0
Figure kpo00031
β
Figure kpo00032
2×10-3(MI이 Mn일때는 5×10-5
Figure kpo00033
β
Figure kpo00034
2×10-3)이 좋다.The concentration β (molar ratio) of scandium, yttrium, aluminum, lanthanum, bismuth or dysprosium, which causes long afterglow of manganese or samarium emission
Figure kpo00023
β
Figure kpo00024
It needs to be at 1 × 10 −1 . In addition, the value of this β is 5 × 10 -7 when only manganese is used as the manganese or samarium activator.
Figure kpo00025
β
Figure kpo00026
It must be 1x10 -1 . It is because afterglow becomes shorter when (beta) is less than this range, and light emission as fluorescent substance becomes weak. Further, the concentration β is preferably 0
Figure kpo00027
β
Figure kpo00028
2 × 10 -2 (2 × 10 -6 when M I is Mn
Figure kpo00029
β
Figure kpo00030
2 × 10 -1 ), more preferably the optimal range is 0
Figure kpo00031
β
Figure kpo00032
2 × 10 -3 (5 × 10 -5 when M I is Mn
Figure kpo00033
β
Figure kpo00034
2 × 10 -3 ) is good.

또, Cu의 몰농도 γ(몰비)는 1×10-5

Figure kpo00035
γ
Figure kpo00036
1×10-1의 범위에 있는 것이 필요하며, 이 범위를 벗어나면 청색 성분의 발광이 약하게 되어 바람직하지 못하다. 또, γ의 범위는 바람직하게는 5×10-5
Figure kpo00037
γ
Figure kpo00038
1×10-2, 더욱 바람직한 최적범위는 3×10-4
Figure kpo00039
γ
Figure kpo00040
5×10-3이 좋다.In addition, the molar concentration γ (molar ratio) of Cu is 1 × 10 −5.
Figure kpo00035
γ
Figure kpo00036
It is necessary to be in the range of 1 × 10 −1 , and the light emission of the blue component is weakened outside this range, which is not preferable. Moreover, the range of gamma becomes like this. Preferably it is 5x10 <-5>.
Figure kpo00037
γ
Figure kpo00038
1 × 10 -2 , more preferred range is 3 × 10 -4
Figure kpo00039
γ
Figure kpo00040
5x10 -3 is good.

청색발광성분을 장잔광화하기 위하여 나트륨등의 알카리금속의 몰농도 δ(몰비)는 1×10-5

Figure kpo00041
δ
Figure kpo00042
1×10-1의 범위 위에 있는 것이 필요하며, 이 범위를 벗어나면 청색발-5
Figure kpo00043
δ
Figure kpo00044
5×10-3, 더욱 바람직한 최적범위는 3×10-4
Figure kpo00045
δ
Figure kpo00046
2×10-3이 좋다.The molar concentration δ (molar ratio) of alkali metals such as sodium is 1 × 10 -5 in order to make long afterglow blue light emitting component.
Figure kpo00041
δ
Figure kpo00042
It needs to be in the range of 1 × 10 -1 , and if it is outside this range, the blue color is -5.
Figure kpo00043
δ
Figure kpo00044
5 × 10 -3 , more preferred range is 3 × 10 -4
Figure kpo00045
δ
Figure kpo00046
2 × 10 -3 is good.

색도조절용의 녹색발광부활제 세륨, 안티몬 혹은 적색발광 부활제 유로품의 농도 ε(몰비)는 0ε

Figure kpo00047
1×10-1의 범위에 있는 것이 필요하며, 이 범위를 벗어나면 발광이 약하게 되어 바람직하지 못하다. 또, ε의 범위는 바람직하기는 0
Figure kpo00048
ε
Figure kpo00049
2×10-2, 더욱 바람직한 최적범위는 0
Figure kpo00050
ε
Figure kpo00051
3×10-4가 좋다.The concentration ε (molar ratio) of the green light activator cerium, antimony or red light activator flow path product for color adjustment is 0ε
Figure kpo00047
It is necessary to be in the range of 1 × 10 −1 , and light emission becomes weak outside this range, which is not preferable. In addition, the range of ε is preferably 0.
Figure kpo00048
ε
Figure kpo00049
2 × 10 -2 , more preferred range is 0
Figure kpo00050
ε
Figure kpo00051
3 x 10 -4 is good.

또, 칼슘이외의 알카리토류금속은 각 부활제의 발광스펙트럼을 시프트시키는 동시에 발광스펙트럼 폭을 넓히기 때문에, 색도점(色度點)의 조정용으로서 유효하다. 단, 칼슘 이외의 알카리토류금속의 조성비 X는 0

Figure kpo00052
X
Figure kpo00053
0.1의 범위에 있는 것이 필요하며, 0.1를 초과하면 화학적 안정성이 저하하므로 바람직하지 못하다. 또, X의 범위는 바람직하게는 0
Figure kpo00054
X
Figure kpo00055
0.04, 더욱 바람직한 최적범위는 0
Figure kpo00056
X
Figure kpo00057
0.02가 좋다.Alkaline earth metals other than calcium are effective for adjusting chromaticity points because they shift the emission spectrum of each activator and widen the emission spectrum. However, the composition ratio X of alkali earth metals other than calcium is 0.
Figure kpo00052
X
Figure kpo00053
It is necessary to be in the range of 0.1, and if it exceeds 0.1, the chemical stability is lowered, which is not preferable. Moreover, the range of X becomes like this. Preferably it is 0
Figure kpo00054
X
Figure kpo00055
0.04, more preferably 0
Figure kpo00056
X
Figure kpo00057
0.02 is good.

또한, 청색발광부활제 Cu의 농도 γ와, 오렌지로부터 적색발광하는 부활제의 농도 α와의 농도비 γ/α는 0.1

Figure kpo00058
γ/α
Figure kpo00059
100의 범위에 있으면 좋다. 또, 이γ/α의 범위는 바람직하기는 2
Figure kpo00060
γ/α
Figure kpo00061
20, 더욱 바람직한 최적범위는 5
Figure kpo00062
γ/α
Figure kpo00063
10이 좋다.The concentration ratio γ / α between the concentration γ of the blue light-emitting activator Cu and the concentration α of the activator emitting red light from orange is 0.1.
Figure kpo00058
γ / α
Figure kpo00059
It should be in the range of 100. In addition, the range of this γ / α is preferably 2
Figure kpo00060
γ / α
Figure kpo00061
20, more preferably 5
Figure kpo00062
γ / α
Figure kpo00063
10 is good.

오렌지로부터 적색발광하는 부활제의 농도 α, 청색발광부활제 Cu농도γ, 그 농도비 γ/α, 녹색발광 혹은 적색발광의 부활제의 농도ε및 발광스펙트럼을 시프트하는 알카리토류금속농도 X를 변경하므로서, 색도좌표를 대폭으로 변경할 수 있음으로, 청백색으로부터 온백색의 기호의 백색을 단일의 형광체로 얻을 수가 있다.By changing the concentration α of the activator emitting red from orange, the concentration of blue activating agent Cu, γ / α concentration thereof, the concentration ε of the green or red emitting activator, and the alkali earth metal concentration X shifting the emission spectrum. Since the chromaticity coordinates can be changed drastically, white of the blue-white to warm-white symbol can be obtained as a single phosphor.

이하, 실시예 에 의거하여 본 발명을 구체적으로 설명한다. 또한, 하기의 실시예Hereinafter, the present invention will be specifically described based on Examples. Also, the following examples

[실시예 1]Example 1

탄산칼슘 200g, 탄산망간 57.5mg, 산화스칸듐 8.3mg, 산화동 79.5mg, 탄산나트륨 200mg을 원료로하고, V믹서로 5시간 혼합한 후, 황화수소분위기중 1200℃의 온도로 3시간 소성하여, CaS : Mn(0.025몰 %), Sc(0.006몰 %), Cu(0.05몰 %), Na(0.06몰 %)의 조성을 가진 형광체를 얻었다. 또한, 각 부활제의 농도의 단위는 모체(여기서는 CaS)에 대한 몰비를 백분율(%)로 나타낸것이며, 또 Na의 농도는 염광분석(炎光分析)으로의 분석치이다. 이하의 실시예 에 있어서도 마찬가지다.200 g of calcium carbonate, 57.5 mg of manganese carbonate, 8.3 mg of scandium oxide, 79.5 mg of copper oxide, and 200 mg of sodium carbonate were mixed with a V mixer for 5 hours, and then calcined at a temperature of 1200 ° C. in a hydrogen sulfide atmosphere for 3 hours, followed by CaS: Mn. (0.025 mol%), Sc (0.006 mol%), Cu (0.05 mol%), and Na (0.06 mol%) were obtained. In addition, the unit of the concentration of each activator represents the molar ratio with respect to the mother (here CaS) as a percentage (%), and the Na concentration is the analysis value by the salt light analysis. The same applies to the following examples.

가속전압 27kV의 전자선으로 여기(勵起)한때의 이 형광체의 색도좌표는 (x,y)=(0.25,0.30), 발광효율은 16%, 잔광시정수 γ1/10는 17m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.25,0.30), the luminous efficiency was 16%, and the afterglow time constant γ1 / 10 was 17 m sec.

[실시예 2]Example 2

탄산칼슘 200g, 탄산망간 57.5mg, 산화스칸듐 8.3mg, 산화동 318mg, 탄산나트륨 200mg을 원료로하고, 상기 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.025몰 %), Sc(0.006몰 %), Cu(0.20몰 %), Na(0.06몰 %)의 조성을 가진 형광체를 얻었다.200 g of calcium carbonate, 57.5 mg of manganese carbonate, 8.3 mg of scandium oxide, 318 mg of copper oxide, and 200 mg of sodium carbonate were mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.025 mol%), Sc (0.006 mol) %), Cu (0.20 mol%) and Na (0.06 mol%) were obtained.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.30,0.35), 발광효율은 15%, 잔광시정수 γ1/10는 18m sec였다 :The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.30,0.35), the luminous efficiency was 15%, and the afterglow time constant γ1 / 10 was 18 m sec:

[실시예 3]Example 3

탄산칼슘 200g, 탄산망간 57.5mg, 산화스칸듐 8.3mg, 산화동 795mg, 탄산나트륨 200mg을 원료로하고, 상기 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.025몰 %), Sc(0.006몰 %), Cu(0.5몰 %), Na(0.05몰 %)의 조성을 가진 형광체를200 g of calcium carbonate, 57.5 mg of manganese carbonate, 8.3 mg of scandium oxide, 795 mg of copper oxide, and 200 mg of sodium carbonate were mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.025 mol%), Sc (0.006 mol) %), Cu (0.5 mol%), Na (0.05 mol%)

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.45,0.40), 발광효율은 14%, 잔광시정수 γ1/10는 17m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.45,0.40), the luminous efficiency was 14%, and the afterglow time constant γ1 / 10 was 17 m sec.

[실시예 4]Example 4

탄산칼슘 200g, 탄산망간 4.6mg, 산화스칸듐 0.7mg, 산화동 31.8mg, 탄산나트륨 200mg을 원료로하고, 상기 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.002몰 %), Sc(0.0005몰 %), Cu(0.02몰 %), Na(0.04몰 %)의 조성을 가진 형광체를 얻었다.200 g of calcium carbonate, 4.6 mg of manganese carbonate, 0.7 mg of scandium oxide, 31.8 mg of copper oxide, and 200 mg of sodium carbonate were mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.002 mol%), Sc (0.0005). A phosphor having a composition of mol%), Cu (0.02 mol%) and Na (0.04 mol%) was obtained.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.27,0.30), 발광효율은 16%, 잔광시정수 γ1/10는 17m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.27,0.30), the luminous efficiency was 16%, and the afterglow time constant γ1 / 10 was 17 m sec.

[실시예 5]Example 5

탄산칼슘 200g, 탄산망간 4.6mg, 산화스칸듐 0.7mg, 산화동 159mg, 탄산나트륨 200mg을 원료로 하고, 상기 실시예 1과 동일조건으로 혼합 및 소성하고, CaS : Mn(0.002몰 %), Sc(0.0005몰 %), Cu(0.10몰 %), Na(0.06몰 %)의 조성을 가진 형광체를 얻었다.200 g of calcium carbonate, 4.6 mg of manganese carbonate, 0.7 mg of scandium oxide, 159 mg of copper oxide, and 200 mg of sodium carbonate were mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.002 mol%), Sc (0.0005 mol) %), Cu (0.10 mol%), Na (0.06 mol%) to obtain a phosphor.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.20,0.23), 발광효율은 16%, 잔광시정수 γ1/10는 18m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.20,0.23), the luminous efficiency was 16%, and the afterglow time constant γ1 / 10 was 18 m sec.

[실시예 6]Example 6

탄산칼슘 200g, 탄산망간 28.8mg, 산화스칸듐 4.3mg, 산화동 795mg, 탄산나트륨 200mg을 원료로하고, 상기 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.0125몰 %), Sc(0.003몰 %), Cu(0.5몰 %), Na(0.07몰 %)의 조성을 가진 형광체를200 g of calcium carbonate, 28.8 mg of manganese carbonate, 4.3 mg of scandium oxide, 795 mg of copper oxide, and 200 mg of sodium carbonate were mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.0125 mol%), Sc (0.003 mol) %), Cu (0.5 mol%), Na (0.07 mol%)

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.23,0.33), 발광효율은 14%, 잔광시정수 γ1/10는 16m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.23,0.33), the luminous efficiency was 14%, and the afterglow time constant γ1 / 10 was 16 m sec.

[실시예 7]Example 7

탄산칼슘 200g, 탄산망간 1.15g, 산화스칸듐 166mg, 산화동 795mg, 탄산나트륨 200mg을 원료로하고, 상기 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.5몰 %), Sc(0.12몰 %), Cu(0.5몰 %), Na(0.07몰 %)의 조성을 가진 형광체를 얻었다.200 g of calcium carbonate, 1.15 g of manganese carbonate, 166 mg of scandium oxide, 795 mg of copper oxide, and 200 mg of sodium carbonate were mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.5 mol%), Sc (0.12 mol%). ), Cu (0.5 mol%), Na (0.07 mol%) to obtain a phosphor.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.46,0.38), 발광효율은 15%, 잔광시정수 γ1/10는 16m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.46,0.38), the luminous efficiency was 15%, and the afterglow time constant γ1 / 10 was 16 m sec.

이상은 실시예 1∼7의 결과를 종합하여 표1에 표시한다. 또, 제1도에 CIE색도도를 표시한다.The above is summarized in Table 1 by the result of Examples 1-7. 1 shows a CIE chromaticity diagram.

[표 1]TABLE 1

Figure kpo00064
Figure kpo00064

탄산칼슘, 탄산망간, 산화스칸듐을 출발원료로하고 소정량 혼합하여, 황화수소분위기중 1200℃로 3시간 소성한 CaS : Mn(0.05몰 %), Sc(0.012몰 %)의 조성을 가진 장잔광 오렌지색 형광체(이하, 형광체 A로 함)와, 탄산칼슘, 산화동, 탄산나트륨을 출발원료로하고 소정량 혼합하여, 유화수소 분위기중 1200℃로 3시간 소성한 CaS :A long afterglow orange phosphor having a composition of CaS: Mn (0.05 mol%) and Sc (0.012 mol%) calcined at 1200 ° C. in a hydrogen sulfide atmosphere by mixing a predetermined amount with calcium carbonate, manganese carbonate and scandium oxide as starting materials. (Hereinafter referred to as phosphor A), calcium carbonate, copper oxide, sodium carbonate as a starting material, a predetermined amount is mixed, CaS calcined at 1200 ℃ in hydrogen emulsion atmosphere for 3 hours:

이 형광체 A를 100g, 형광체 B를 100g, 또 Na2CO3200mg을 원료로하여 V믹서로 5시간 혼합한후, 황화수소분위기중 1200℃로 3시간 소성하여 CaS : Mn(0.025몰 %), Sc(0.006몰 %), Cu(0.20몰 %), Na(0.07몰 %)의 조성을 가진 형광체를 얻었다.100 g of the phosphor A, 100 g of the phosphor B, and 200 mg of Na 2 CO 3 were mixed with a V mixer for 5 hours, and then calcined at 1200 ° C. in a hydrogen sulfide atmosphere for 3 hours, followed by CaS: Mn (0.025 mol%), Sc (0.006 mol%), Cu (0.20 mol%), and Na (0.07 mol%) were obtained.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.30,0.35), 발광효율은 16%, 잔광시정수 γ1/10는 17m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.30,0.35), the luminous efficiency was 16%, and the afterglow time constant γ1 / 10 was 17 m sec.

[실시예 9]Example 9

상기의 실시예 8에서 사용한 것과 동일한 로트품인 형광체 A 및 형광체 B를 각각 100g, 또는 Na2CO3150mg을 원료로하고 V믹서로 5시간 혼합하여, 황화수소분위기중 1200℃로 3시간 소성하여 CaS : Mn(0.025몰 %), Sc(0.006몰 %), Cu(0.20몰 %), Na(0.05몰 %)의 조성을 가진 형광체를 얻었다.The same lot of phosphor A and phosphor B as in Example 8 were used as 100 g or 150 mg of Na 2 CO 3 , respectively, and mixed in a V mixer for 5 hours, and then calcined at 1200 ° C. in a hydrogen sulfide atmosphere for 3 hours to give CaS. : A phosphor having a composition of Mn (0.025 mol%), Sc (0.006 mol%), Cu (0.20 mol%), Na (0.05 mol%) was obtained.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.30,0.35), 발광효율은 16%, 잔광시정수 γ1/10는 18m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.30,0.35), the luminous efficiency was 16%, and the afterglow time constant γ1 / 10 was 18 m sec.

[실시예 10]Example 10

상기의 실시예 8에서 사용한 것과 동일한 로트품인 형광체 A 및 형광체 B를 각각 100g, 또는 Na2CO3100mg을 원료로하고 V믹서로 5시간 혼합하여, 황화수소분위기중 1000℃로 3시간 소성하여 CaS : Mn(0.025몰 %), Sc(0.006몰 %), Cu(0.20몰 %), Na(0.07몰 %)의 조성을 가진 형광체를 얻었다.100 g of phosphor A and 100 B of the same lot as in Example 8, respectively, or 100 mg of Na 2 CO 3 were used as raw materials, mixed for 5 hours in a V mixer, and calcined at 1000 ° C. in a hydrogen sulfide atmosphere for 3 hours to obtain CaS. : A phosphor having a composition of Mn (0.025 mol%), Sc (0.006 mol%), Cu (0.20 mol%), Na (0.07 mol%) was obtained.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는The chromaticity coordinates of this phosphor when excited with an electron beam of 27 kV acceleration

[실시예 11]Example 11

상기의 실시예 8에서 사용한 것과 동일한 로트품인 형광체 A 및 형광체 B를 각각 100g, 또는 Na2CO350mg을 원료로하고 V믹서로 5시간 혼합하여, 황화수소분위기중 900℃로 12시간 소성하여 CaS : Mn(0.025몰 %), Sc(0.006몰 %), Cu(0.20몰 %), Na(0.07몰 %)의 조성을 가진 형광체를 얻었다.100 g or 50 mg of Na 2 CO 3 , respectively, was used as a raw material for phosphor A and phosphor B, which are the same lot as those used in Example 8, and mixed in a V mixer for 5 hours, and calcined at 900 ° C. for 12 hours in a hydrogen sulfide atmosphere to give CaS : A phosphor having a composition of Mn (0.025 mol%), Sc (0.006 mol%), Cu (0.20 mol%), Na (0.07 mol%) was obtained.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.41,0.40), 발광효율은 16%, 잔광시정수 γ1/10는 16m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.41,0.40), the luminous efficiency was 16%, and the afterglow time constant γ1 / 10 was 16 m sec.

이상은 실시예 8∼11의 결과를 종합하여 제2표에 표시한다. 또, 제2도에 CIE색도도를 표시한다.The above is summarized in the 2nd table | surface by the result of Examples 8-11. 2 shows a CIE chromaticity diagram.

[표 2]TABLE 2

Figure kpo00065
Figure kpo00065

[실시예 12]Example 12

탄산칼슘 196g, 황산마그네슘 4.8g, 탄산망간 57.5mg, 산화스칸듐 8.3mg, 산화동 318mg, 탄산나트륨 200mg을 원료로하고, 상기 실시예 1과 동일조건으로 혼합 및 소성하여, Ca0.98Mg0.02S : Mn(0.025몰 %), Sc(0.006몰 %), Cu(0.20몰 %), Na(0.05몰 %)의 조성을 가진 형광체를 얻었다.196 g of calcium carbonate, 4.8 g of magnesium sulfate, 57.5 mg of manganese carbonate, 8.3 mg of scandium oxide, 318 mg of copper oxide, and 200 mg of sodium carbonate were mixed and calcined under the same conditions as in Example 1, and Ca 0.98 Mg 0.02 S: Mn ( A phosphor having a composition of 0.025 mol%), Sc (0.006 mol%), Cu (0.20 mol%), Na (0.05 mol%) was obtained.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.31,0.33), 발광효율은 16%, 잔광시정수 γ1/10는 17m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.31,0.33), the luminous efficiency was 16%, and the afterglow time constant γ1 / 10 was 17 m sec.

[실시예 13]Example 13

탄산칼슘 196g, 탄산스트론튬 5.9g, 탄산망간 57.5mg, 산화스칸듐 8.3mg, 산화동 318mg, 탄산나트륨 200mg을 원료로하고, 상기 실시예 1과 동일조건으로 혼합 및 소성하여, Ca0.98: Sr0.02S : Mn(0.025몰 %), Sc(0.006몰 %), Cu(0.20몰 %), Na(0.07몰 %)의 조성을 가진 형광체를 얻었다.196 g of calcium carbonate, 5.9 g of strontium carbonate, 57.5 mg of manganese carbonate, 8.3 mg of scandium oxide, 318 mg of copper oxide, and 200 mg of sodium carbonate were mixed and calcined under the same conditions as in Example 1, and Ca 0.98 : Sr 0.02 S: Mn (0.025 mol%), Sc (0.006 mol%), Cu (0.20 mol%), and Na (0.07 mol%) were obtained.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.31,0.34), 발광효율은 15%, 잔광시정수 γ1/10는 17m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.31,0.34), the luminous efficiency was 15%, and the afterglow time constant γ1 / 10 was 17 m sec.

[실시예 14]Example 14

탄산칼슘 196g, 탄산바륨 7.9g, 탄산망간 57.5mg, 산화스칸듐 8.3mg, 산화동 318mg, 탄산나트륨 200mg을 원료로하고, 상기 실시예와 동일조건으로 혼합 및 소성하여, Ca898, Ba802S : Mn(0.025몰 %), Sc(0.006몰 %), Cu(0.20몰 %), Na(0.06몰 %)의 조성을 가진 형광체를 얻었다.196 g of calcium carbonate, 7.9 g of barium carbonate, 57.5 mg of manganese carbonate, 8.3 mg of scandium oxide, 318 mg of copper oxide, and 200 mg of sodium carbonate were used as raw materials, and mixed and calcined under the same conditions as in the above example, and Ca 898 , Ba 802 S: Mn ( A phosphor having a composition of 0.025 mol%), Sc (0.006 mol%), Cu (0.20 mol%), Na (0.06 mol%) was obtained.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.31,0.34), 발광효율은 15% 잔광시정수 γ1/10는 16m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.31,0.34) and the luminous efficiency was 15% in the afterglow time constant γ1 / 10 for 16 m sec.

이상의 실시예 2, 12~14의 결과를 종합하여 표3에 표시한다.Table 3 summarizes the results of the above Examples 2 and 12 to 14.

[표 3]TABLE 3

Figure kpo00066
Figure kpo00066

[실시예 15]Example 15

탄산칼슘 200g, 탄산망간 57.5mg, 산화스칸듐 8.3mg, 산화동 318mg, 탄산리튬 130mg을 원료로하고, 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.025몰 %), Sc(0.006몰 %), Cu(0.20몰 %), Li(0.05몰 %)의 조성을 가진 형광체를 얻었다. 또한 Li의 농도는 염광분석으로의 분석치이다.200 g of calcium carbonate, 57.5 mg of manganese carbonate, 8.3 mg of scandium oxide, 318 mg of copper oxide, and 130 mg of lithium carbonate were mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.025 mol%), Sc (0.006 mol) %, Cu (0.20 mol%), and Li (0.05 mol%) were obtained. In addition, the concentration of Li is an analysis value by the salt light analysis.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.30,0.35), 발광효율은 15%, 잔광시정수 γ1/10는 16m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.30,0.35), the luminous efficiency was 15%, and the afterglow time constant γ1 / 10 was 16 m sec.

[실시예 16]Example 16

탄산칼슘 200g, 탄산망간 57.5mg, 산화스칸듐 8.5mg, 산화동 318mg, 탄산칼륨 2.76mg을 원료로하고, 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.025몰 %), Sc(0.006몰 %), Cu(0.20몰 %), K(0.04몰 %)의 조성을 가진 형광체를 얻었다. 또한 K의 농도는 염광분석으로의 분석치이다.200 g of calcium carbonate, 57.5 mg of manganese carbonate, 8.5 mg of scandium oxide, 318 mg of copper oxide, and 2.76 mg of potassium carbonate were mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.025 mol%), Sc (0.006) A phosphor having a composition of mol%), Cu (0.20 mol%) and K (0.04 mol%) was obtained. In addition, the concentration of K is an analysis value by the salt light analysis.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.30,0.35), 발광효율은 16%, 잔광시정수 γ1/10는 17m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.30,0.35), the luminous efficiency was 16%, and the afterglow time constant γ1 / 10 was 17 m sec.

이상의 실시예 2, 15, 16의 결과를 종합하여 표4에 표시한다.Table 4 summarizes the results of the above Examples 2, 15 and 16.

[표 4]TABLE 4

Figure kpo00067
Figure kpo00067

[실시예 17]Example 17

탄산칼슘 200g, 산화사마륨 704mg, 산화동 318mg, 탄산나트륨 200mg을 원료로하고, 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Sm(0.2몰 %), Cu(0.20몰 %), Na(0.06몰 %)의 조성을 가진 형광체를 얻었다.200 g of calcium carbonate, 704 mg of samarium oxide, 318 mg of copper oxide, and 200 mg of sodium carbonate were mixed and calcined under the same conditions as in Example 1, and CaS: Sm (0.2 mol%), Cu (0.20 mol%), Na (0.06 mol) A phosphor having a composition of%) was obtained.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.28,0.28), 발광효율은 13%, 잔광시정수 γ1/10는 15m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.28,0.28), the luminous efficiency was 13%, and the afterglow time constant γ1 / 10 was 15 m sec.

[실시예 18]Example 18

탄산칼슘 200g, 탄산망간 57.5mg, 산화스칸듐 8.3mg, 산화동 318mg, 탄산나트륨 200mg, 산화세륨 86mg을 원료로하고, 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.025몰 %), Sc(0.006몰 %), Cu(0.20몰 %), Na(0.05몰 %), Ce(0.025몰 %)의 조성을 가진 형광체를 얻는다.200 g of calcium carbonate, 57.5 mg of manganese carbonate, 8.3 mg of scandium oxide, 318 mg of copper oxide, 200 mg of sodium carbonate, 86 mg of cerium oxide were mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.025 mol%), Sc (0.006 mol%), Cu (0.20 mol%), Na (0.05 mol%), and Ce (0.025 mol%) were obtained.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.28,0.43), 발광효율은 15%, 잔광시정수 γ1/10는 15m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.28,0.43), the luminous efficiency was 15%, and the afterglow time constant γ1 / 10 was 15 m sec.

[실시예 19]Example 19

탄산칼슘 200g, 탄산망간 57.5mg, 산화스칸듐 8.3mg, 산화동 318mg, 탄산나트륨 200mg, 산화안티몬 500mg을 원료로하고, 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.025몰 %), Sc(0.006몰 %), Cu(0.20몰 %), Na(0.08몰 %), Sb(0.02몰 %)의 조성을 가진 형광체를 얻었다. 또한 Sb의 농도는 염광분석으로의 분석치이다.200 g of calcium carbonate, 57.5 mg of manganese carbonate, 8.3 mg of scandium oxide, 318 mg of copper oxide, 200 mg of sodium carbonate, and 500 mg of antimony oxide were mixed, and mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.025 mol%), Sc (0.006 mol%), Cu (0.20 mol%), Na (0.08 mol%), and Sb (0.02 mol%) were obtained. In addition, the concentration of Sb is an analysis value by the salt light analysis.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.27,0.36), 발광효율은 15%, 잔광시정수 γ1/10은 16m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.27,0.36), the luminous efficiency was 15%, and the afterglow time constant γ1 / 10 was 16 m sec.

[실시예 20]Example 20

탄산칼슘 200g, 탄산망간 57.5mg, 산화스칸듐 8.3mg, 산화동 318mg, 탄산나트륨 200mg, 산화유로튬 70.4mg을 원료로하고, 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.025몰 %), Sc(0.006몰 %), Cu(0.20몰 %), Na(0.06몰 %), Eu(0.02몰 %)의 조성을 가진 형광체를 얻었다.200 g of calcium carbonate, 57.5 mg of manganese carbonate, 8.3 mg of scandium oxide, 318 mg of copper oxide, 200 mg of sodium carbonate, 70.4 mg of eurotium oxide, were mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.025 mol%) A phosphor having a composition of Sc, 0.006 mol%, Cu (0.20 mol%), Na (0.06 mol%), and Eu (0.02 mol%) was obtained.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.39,0.33), 발광효율은 16%, 잔광시정수 γ1/10는 15m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.39,0.33), the luminous efficiency was 16%, and the afterglow time constant γ1 / 10 was 15 m sec.

이상의 실시예 2, 18∼20의 결과를 종합하여 표5에 표시한다. 또, 제3도에 CIE색도도를 표시한다.Table 5 summarizes the results of the above Examples 2 and 18 to 20. 3 shows a CIE chromaticity diagram.

[표 5]TABLE 5

Figure kpo00068
Figure kpo00068

[실시예 21]Example 21

탄산칼슘 200g, 탄산망간 4.6mg, 산화스칸듐 0.7mg, 산화동 159mg, 탄산나트륨 200mg을 원료로하고, 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.025몰 %), Sc(0.0005몰 %), Cu(0.10몰 %), Na(0.05몰 %)의 조성을 가진 형광체를 얻는다.200 g of calcium carbonate, 4.6 mg of manganese carbonate, 0.7 mg of scandium oxide, 159 mg of copper oxide, and 200 mg of sodium carbonate were mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.025 mol%) and Sc (0.0005 mol%). ), Cu (0.10 mol%), Na (0.05 mol%) to obtain a phosphor.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.20,0.17), 발광효율은 14%, 잔광시정수 γ1/10는 15m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.20,0.17), the luminous efficiency was 14%, and the afterglow time constant γ1 / 10 was 15 m sec.

[실시예 22]Example 22

탄산칼슘 192g, 황산마그네슘 9.6g, 탄산망간 1.15g, 산화스칸듐 166mg, 산화동 47.7mg, 탄산나트륨 200mg, 산화유로퓸 14mg을 원료로하고, 실시예 1과 동일조건으로 혼합 및 소성하여, Ca0.96Mg0.04S : Mn(0.5몰 %), Sc(0.12몰 %), Cu(0.03몰 %), Na(0.05몰 %), Eu(0.04몰 %)의 조성을 가진 형광체를 얻었다.192 g of calcium carbonate, 9.6 g of magnesium sulfate, 1.15 g of manganese carbonate, 166 mg of scandium oxide, 47.7 mg of copper oxide, 200 mg of sodium carbonate, 14 mg of europium oxide were mixed and calcined under the same conditions as in Example 1, Ca 0.96 Mg 0.04 S : A phosphor having a composition of Mn (0.5 mol%), Sc (0.12 mol%), Cu (0.03 mol%), Na (0.05 mol%), Eu (0.04 mol%) was obtained.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.58,0.32), 발광효율은 15%, 잔광시정수 γ1/10는 18m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.58,0.32), the luminous efficiency was 15%, and the afterglow time constant γ1 / 10 was 18 m sec.

[실시예 23]Example 23

탄산칼슘 200g, 탄산망간 115mg, 산화스칸듐 16.6mg, 산화동 795mg, 탄산나트륨 200mg, 산화세륨 137.6mg을 원료로하고, 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.05몰 %), Sc(0.012몰 %), Cu(0.5몰 %), Na(0.09몰 %), Ce(0.04몰 %)의 조성을 가진 형광체를 얻었다.200 g of calcium carbonate, 115 mg of manganese carbonate, 16.6 mg of scandium oxide, 795 mg of copper oxide, 200 mg of sodium carbonate, 137.6 mg of cerium oxide were mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.05 mol%), Sc (0.012 mol%), Cu (0.5 mol%), Na (0.09 mol%), and Ce (0.04 mol%) were obtained.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.37,0.54), 발광효율은 14%, 잔광시정수 γ1/10는 15m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.37,0.54), the luminous efficiency was 14%, and the afterglow time constant γ1 / 10 was 15 m sec.

[실시예 24]Example 24

탄산칼슘 200g, 탄산망간 23mg, 산화스칸듐 3.3mg, 산화동 795mg, 탄산나트륨 200mg, 산화세륨 137.6mg을 원료로하고, 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.01몰 %), Sc(0.0024몰 %), Cu(0.5몰 %), Na(0.08몰 %), Ce(0.04몰 %)의 조성을 가진 형광체를 얻는다.200 g of calcium carbonate, 23 mg of manganese carbonate, 3.3 mg of scandium oxide, 795 mg of copper oxide, 200 mg of sodium carbonate, and 137.6 mg of cerium oxide were mixed, and mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.01 mol%), Sc (0.0024 mol%), Cu (0.5 mol%), Na (0.08 mol%), and Ce (0.04 mol%) were obtained.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.23,0.43), 발광효율은 14%, 잔광시정수 γ1/10는 15m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.23,0.43), the luminous efficiency was 14%, and the afterglow time constant γ1 / 10 was 15 m sec.

이상의 실시예 21∼24의 결과를 종합하여 표6에 표시한다. 또, 제4도에 CIE색도도를 표시한다. 동도면의 사선부분이 금번 개발한 형과체의 색재현범위이다.Table 6 summarizes the results of the above Examples 21 to 24. 4, the CIE chromaticity diagram is shown. The slanted portion of the diagram is the range of color reproduction of the mold and body developed this time.

[표 6]TABLE 6

Figure kpo00069
Figure kpo00069

[실시예 25]Example 25

탄산칼슘 200g, 탄산망간 57.5mg, 산화이트륨 13.6mg, 산화동 318mg, 탄산나트륨 200mg을 원료로하고, 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.025몰 %), Y(0.006몰 %), Cu(0.20몰 %), Na(0.07몰 %)의 조성을 가진 형광체를 얻는다.200 g of calcium carbonate, 57.5 mg of manganese carbonate, 13.6 mg of yttrium oxide, 318 mg of copper oxide, and 200 mg of sodium carbonate were mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.025 mol%), Y (0.006 mol%) ), Cu (0.20 mol%) and Na (0.07 mol%).

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.29,0.34), 발광효율은 14%, 잔광시정수 γ1/10는 16m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.29,0.34), the luminous efficiency was 14%, and the afterglow time constant γ1 / 10 was 16 m sec.

[실시예 26]Example 26

탄산칼슘 200g, 탄산망간 57.5mg, 수산화알루미늄 9.4mg, 산화동 318mg, 탄산나트륨 200mg,을 원료로하고, 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.025몰 %), Al(0.006몰 %), Cu(0.20몰 %), Na(0.05몰 %)의 조성을 가진 형광체를 얻는다.200 g of calcium carbonate, 57.5 mg of manganese carbonate, 9.4 mg of aluminum hydroxide, 318 mg of copper oxide, 200 mg of sodium carbonate were mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.025 mol%), Al (0.006 mol) %), Cu (0.20 mol%), Na (0.05 mol%) to obtain a phosphor.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.31,0.37), 발광효율은 15%, 잔광시정수 γ1/10는 17m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.31,0.37), the luminous efficiency was 15%, and the afterglow time constant γ1 / 10 was 17 m sec.

[실시예 27]Example 27

탄산칼슘 200g, 탄산망간 57.5mg, 산화란탄 19.6mg, 산화동 318g, 탄산나트륨 200mg을 원료로하고, 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.025몰 %), La(0.006몰 %), Cu(0.20몰 %), Na(0.08몰 %)의 조성을 가진 형광체를 얻는다.200 g of calcium carbonate, 57.5 mg of manganese carbonate, 19.6 mg of lanthanum oxide, 318 g of copper oxide, and 200 mg of sodium carbonate were mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.025 mol%), La (0.006 mol%) ), Cu (0.20 mol%), Na (0.08 mol%) to obtain a phosphor.

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.30,0.36), 발광효율은 14%, 잔광시정수 γ1/10는 16m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.30,0.36), the luminous efficiency was 14%, and the afterglow time constant γ1 / 10 was 16 m sec.

[실시예 28]Example 28

탄산칼슘 200g, 탄산망간 57.5mg, 산화비스무트 1g, 산화동 318mg, 탄산나트Calcium carbonate 200g, manganese carbonate 57.5mg, bismuth oxide 1g, copper 318mg, sodium carbonate

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.31,0.35), 발광효율은 14%, 잔광시정수 γ1/10는 15m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.31,0.35), the luminous efficiency was 14%, and the afterglow time constant γ1 / 10 was 15 m sec.

[실시예 29]Example 29

탄산칼슘 200g, 탄산망간 57.5mg, 산화디스프로슘 22.4mg, 산화동 318mg, 탄산나트륨 200mg을 원료로하고, 실시예 1과 동일조건으로 혼합 및 소성하여, CaS : Mn(0.025몰 %), Dy(0.006몰 %), Cu(0.20몰 %), Na(0.05몰 %)의 조성을 가진 형광체를 얻는다.200 g of calcium carbonate, 57.5 mg of manganese carbonate, 22.4 mg of dysprosium oxide, 318 mg of copper oxide, and 200 mg of sodium carbonate were mixed and calcined under the same conditions as in Example 1, and CaS: Mn (0.025 mol%) and Dy (0.006 mol%). ), Cu (0.20 mol%) and Na (0.05 mol%).

가속전압 27kV의 전자선으로 여기한때의 이 형광체의 색도좌표는 (x,y)=(0.31,0.37), 발광효율은 15%, 잔광시정수 γ1/10는 16m sec였다.The chromaticity coordinates of this phosphor when excited with an electron beam of acceleration voltage of 27 kV were (x, y) = (0.31,0.37), the luminous efficiency was 15%, and the afterglow time constant γ1 / 10 was 16 m sec.

이상의 실시예 2 및 25∼29의 결과를 종합하여 표7에 표시한다.Table 7 summarizes the results of the above Examples 2 and 25 to 29.

[표 7]TABLE 7

Figure kpo00070
Figure kpo00070

[표시실험예][Display Experiment Example]

상기의 실시예 2, 9의 단일 백색발광 형광체를 14인치 브라운관 페이스 플레이트에 도포후, 45Hz의 스위프주파수로 디스플레이 표시하였다. 이 결과, 미소영역에 있어The single white light-emitting phosphors of Examples 2 and 9 were applied to a 14-inch CRT face plate and displayed on a sweep frequency of 45 Hz. As a result, in the micro area

이상의 실시예 1∼24의 백색발광 형광체를 가속전압 27kV의 전자선으로 여기한때의 CIE색도좌표를 플로트하여 각각의 발광영역을 제4도 표시한다.The CIE chromaticity coordinates when the white light emitting phosphors of Examples 1 to 24 were excited with an electron beam having an acceleration voltage of 27 kV are plotted to show respective light emitting regions.

이와 같이, 본 발명의 백색발광 형광체를 사용하므로서, 디스플레이용 브라운관에 있어서, 고휘도이고, 잔광색과 발광색이 동일하며, 또, 미소영역까지 색얼룩이 없는 청백색에서 온백색까지의 표시가 가능하다. 또한, 상기의 실시예 에서는 전자선 여기에 의한 발광에 대하여서만 설명했으나, 본 발명의 형광체는 거의 착색하고 있지 않으므로, 자외선 여기용 형광체로서도 사용할 수가 있다.Thus, by using the white light-emitting fluorescent substance of the present invention, the display CRT can display from blue-white to warm-white with high brightness, the same afterglow color as the light-emitting color, and no color speckling to a small area. In the above embodiment, only the light emission by electron beam excitation has been described. However, since the phosphor of the present invention is hardly colored, it can be used as a phosphor for ultraviolet excitation.

이상과 같은 본 발명의 장잔광 백색발광 형광체는 다음의 효과가 있다.The long afterglow white light-emitting phosphor of the present invention as described above has the following effects.

① : 본 발명으로 얻어지는 형광체는, 단일모체로 장잔광의 백색발광을 하고, 잔광색과 이 발색광색과 동일하다. 따라서 디스플레이용 브라운관 위에서, 미소영역까지 어른거림이 없는 균일표시로 할수 있다.(1): The phosphor obtained by the present invention emits long afterglow white light in a single matrix, and is the same as the afterglow color and this color light emission color. Therefore, it is possible to achieve uniform display without flickering up to a minute area on the display CRT.

② : 부활제의 종류, 농도, 농도비, 반응조건을 변경하므로서, 제4도에 표시한 것 같이 백색의 색도좌표를 정확히 제어할 수 있다.②: By changing the type, concentration, concentration ratio, and reaction condition of the activator, the chromaticity coordinates of white can be precisely controlled as shown in FIG.

③ : 본 발명으로 얻어지는 백색 형광체는 고휘도이다.(3): The white phosphor obtained by the present invention is high luminance.

④ : 유해물질을 함유하지 않기 때문에 환경오염이 없다. 또 유해물질의 회수시스템등도 불필요함으로 코스트메릿이 있다.④: There is no environmental pollution because it does not contain harmful substances. In addition, there is no cost merchandise because there is no need for recovery of harmful substances.

Claims (1)

조성식이, Ca(1-x) AxS : αMI, βMII, γCu, δMIII, εMIV로 표시되고, 식중, A는 Mg, Sr, Ba중 적어도 1종의 원소이고, MI은 Mn, Sm중 적어도 1종의 원소이며, MII는 Sc, Y, Al, La, Bi, Dy중 적어도 1종의 원소이고, MIII은 Li, Na, K중 적어도 1종의 원소이며, MIV은 Ce, Sb, Eu중 적어도 1종의 원소이고, 모체에 대한 각 부활제의 농도를 몰비로 표시한 α,β,γ, 및 δ및, 또 조성비 X가, 각각, 5×10-6
Figure kpo00071
α
Figure kpo00072
1×10-1, 0
Figure kpo00073
β
Figure kpo00074
1×10-1(단, MI이 Mn의 때는 5×10-7
Figure kpo00075
β
Figure kpo00076
1×10-1의 범위), 1×10-5
Figure kpo00077
γ
Figure kpo00078
1×10-1, 1×10-5
Figure kpo00079
δ
Figure kpo00080
1×10,0
Figure kpo00081
ε
Figure kpo00082
1×10-1, 1
Figure kpo00083
X
Figure kpo00084
0.1의 범위에 있는 것을 특징으로 하는 장잔광 백색발광 형광체.The composition formula is represented by Ca (1-x) AxS: αM I , βM II , γCu, δM III , εMI V , wherein A is at least one element of Mg, Sr, Ba, and M I is Mn, At least one element of Sm, M II is at least one element of Sc, Y, Al, La, Bi, Dy, M III is at least one element of Li, Na, K, and M IV is Α, β, γ, and δ, which represent at least one element of Ce, Sb, Eu, and the concentration of each activator to the mother in a molar ratio, and the composition ratio X is 5 × 10 −6 , respectively.
Figure kpo00071
α
Figure kpo00072
1 × 10 -1 , 0
Figure kpo00073
β
Figure kpo00074
1 × 10 -1 (5 × 10 -7 when M I is Mn
Figure kpo00075
β
Figure kpo00076
1 × 10 -1 range), 1 × 10 -5
Figure kpo00077
γ
Figure kpo00078
1 × 10 -1 , 1 × 10 -5
Figure kpo00079
δ
Figure kpo00080
1 × 10 , 0
Figure kpo00081
ε
Figure kpo00082
1 × 10 -1 , 1
Figure kpo00083
X
Figure kpo00084
Long afterglow white light-emitting phosphor, characterized in that in the range of 0.1.
KR1019860008080A 1985-06-19 1986-09-26 White luminescent fluorescent substance having long after glow KR900001384B1 (en)

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JPH0374909A (en) * 1989-08-16 1991-03-29 Nissan Motor Co Ltd Electronic control antenna system
JPH03220802A (en) * 1990-01-26 1991-09-30 Pioneer Electron Corp Microstrip antenna
DE10043757C1 (en) * 2000-09-06 2001-11-15 Bosch Gmbh Robert Automobile antenna device has antenna structure on inside of wing protected from electrostatic discharge by conductive screening wall coupled to conductive chassis
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