JP2001172623A - Fluorescent substance and fluorescent lamp using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a blue to a bluish green light emitting fluorescent substance capable of manifesting a high luminous output under excitation by ultraviolet rays at 185 nm and 254 nm wavelengths and excellent in life characteristics and to provide a fluorescent lamp using the fluorescent substance. SOLUTION: This fluorescent substance is obtained by mixing a bivalent europium-activated alkaline earth chlorophosphate fluorescent substance substantially represented by general formula (M1-xEux)10(PO4)6.Cl2 (wherein M denotes at least one kind of element selected from Mg, Ca, Sr and Ba; and x is a number satisfying 0.001<=x<=0.10) with a bivalent manganese-activated alkaline earth aluminate fluorescent substance substantially represented by general formula (M1-yMny)O.zAl2O3 (wherein M denotes at least one kind of element selected from Mg, Ca, Sr and Ba; and y and z are each a number satisfying 0.01<=y<=0.35 and 4.5<=z<=8.0). The fluorescent lamp has a fluorescent screen containing the fluorescent substance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphor emitting blue to blue-green light and a fluorescent lamp using the same.

[0002]

2. Description of the Related Art In recent years, a three-wavelength band fluorescent lamp that satisfies both high color rendering and high efficiency has been widely used as a fluorescent lamp for general illumination. This three-wavelength band fluorescent lamp is different from a so-called ordinary white fluorescent lamp using a conventional calcium halophosphate phosphor, and emits three types of blue, green and red light having a relatively narrow band emission spectrum distribution. Is a fluorescent lamp that emits white or desired color light by appropriately mixing the above phosphors.

In recent three-wavelength-range fluorescent lamps, among the blue, green and red phosphors, the blue phosphor is a halophosphate phosphor activated by divalent europium or Aluminate phosphors activated with divalent europium or divalent europium and manganese are commonly used.

However, each of these phosphors has advantages and disadvantages. For example, halophosphate phosphors have excellent life characteristics, but have a somewhat insufficient luminance (total luminous flux). On the other hand, aluminate phosphors provide high luminance but have poor life characteristics. Also, the specific gravity of the halophosphate phosphor is around 4.2, while the specific gravity of the aluminate phosphor is around 3.8. Uses more body weight.

As described above, the conventional blue light emitting phosphors include:
There is a point to be improved in each case, and no one having sufficiently satisfactory characteristics has yet been obtained.

[0006]

As described above, a halophosphate phosphor or an aluminate phosphor is generally used as a blue light-emitting phosphor for a three-wavelength band light-emitting fluorescent lamp, but it is still excellent. There is no one that has both life characteristics and high brightness, and its development is desired.

[0007] The problem of the low brightness of the phosphor is that short-wavelength ultraviolet light (having a wavelength of 185 nm) peculiar to the halophosphate phosphor is used.
m) (color center generation) is considered to be the cause. In other words, the ultraviolet light emitted by the mercury discharge plasma, which is the excitation source of the fluorescent lamp, contains a small amount of ultraviolet light having a wavelength of 185 nm in addition to ultraviolet light having a wavelength of 254 nm. As a result, it is considered that the brightness of the halophosphate phosphor decreases.

For this reason, it has been studied to coat the surface of the phosphate phosphor particles with an absorbent that absorbs short-wavelength ultraviolet light that causes deterioration. However, it is difficult to balance the absorption of ultraviolet rays having a wavelength of 185 nm and the transmission of ultraviolet rays having a wavelength of 254 nm, so that the technology has not yet been established.

SUMMARY OF THE INVENTION The present invention has been made to address such a problem, and exhibits high emission output under ultraviolet excitation at wavelengths of 185 nm and 254 nm, and has excellent blue-to-blue-green fluorescence having excellent life characteristics. It is an object of the present invention to provide a body and a fluorescent lamp using such a phosphor.

[0010]

The phosphor of the present invention has the following general formula: (M ₁ -xE _x ) ₁₀ (PO ₄ ) ₆ .Cl ₂ (1) (where M is Mg, Ca, X represents at least one element selected from Sr and Ba, and x is 0.001 ≦ x ≦ 0.
Bivalent europium-activated alkaline earth chlorophosphate phosphor substantially represented by a number) satisfying the 10 general _{formula: (M 1-y Mn y} ) O · zAl 2 O 3 ... ( 2) (In the formula, M represents at least one element selected from Mg, Ca, Sr and Ba, and y and z are numbers satisfying 0.01 ≦ y ≦ 0.35 and 4.5 ≦ z ≦ 8.0, respectively. ) And a mixture with a divalent manganese-activated alkaline earth aluminate phosphor substantially represented by the formula (1).

The above-mentioned phosphor emits blue to blue-green light at a high output under excitation of ultraviolet rays having wavelengths of 185 nm and 254 nm, and has excellent life characteristics. This is presumably because the divalent manganese-activated alkaline earth aluminate phosphor absorbs ultraviolet light having a wavelength of 185 nm, which deteriorates the divalent europium-activated alkaline earth chlorophosphate phosphor.

In the present invention, as described in claim 2, the surface of the divalent europium-activated alkaline earth chlorophosphate phosphor particles substantially represented by the above formula (1) is provided on the surface of the above ( 2) It is desirable to coat the divalent manganese-activated alkaline earth aluminate phosphor particles substantially represented by the formula, and the wavelength is 185 nm and the wavelength is 254 nm.
Can further increase the light emission output under ultraviolet excitation.

In this case, as described in claim 3, 2
The particle size (primary particle size) of the divalent europium-activated alkaline earth chlorophosphate phosphor particles is 2 μm to 10 μm, and the particle size (primary particle size) of the divalent manganese activated alkaline earth aluminate phosphor particles (Diameter) is desirably 10 nm to 500 nm. The particle size referred to in the present invention is based on a so-called aeration method. Specifically, dibutyl phthalate is used as a manometer liquid, and air is applied to a measurement cell having a powder layer having a cross-sectional area of 64 mm ² and a thickness of 40 mm. And the specific surface area is calculated by the Kosenikaman equation.

Further, as described in claim 4, the coating amount of the divalent manganese-activated alkaline earth aluminate phosphor particles to the divalent europium-activated alkaline earth chlorophosphate phosphor particles is 0.01 to 0.01%. It is desirably from 3.0% by weight to 3.0% by weight.

According to a fifth aspect of the present invention, there is provided a phosphor containing a blue light-emitting component, a green light-emitting component and a red light-emitting component, wherein the above-mentioned phosphor is used as the blue light-emitting component. It is characterized by including.

Here, the green light-emitting component may be
As described in Item 6, the general formula: (Re_1-abTb_aCe_b)_TwoO_Three・_cSiO_Two ・_dP_TwoO_Five・_eB_TwoO_{Three … (3)} (Wherein, Re is a small number selected from Y, Gd and La
Each represents one element, and a, b, c, d and e
Are a> 0, b> 0, 0 <a + b <1, c> 0, d> 0, 2 × 10
^-Four≦ e ≦ 6 × 10^-3Is a number that satisfies
Phosphor, and a general formula: (Re_1-fgTb_fCe_g)_TwoO_Three・_hAl_TwoO_Three・_iSiO_Two・_jP_TwoO_Five・_kB _Two O_{3… (4)} (Wherein, Re is a small number selected from Y, Gd and La
Each represents one element, and f, g, h, i, j, and
And k are f> 0, g> 0, 0 <f + g <1, h ≧ 0, i ≧ 0, j
≧ 0, 1 × 10^-6≦ k ≦ 1.8 × 10^-Four, 0.8 ≦ h + i + j + k ≦
Which is a number that satisfies 1.30)
Use at least one phosphor selected from the group
Is desirable.

Further, as the red emission component, as described in claim 7, the general _{formula: (Re 1-p Eu p} ) 2 O 3 ... (5) ( wherein, Re is Y, the Gd and La It is preferable to use a phosphor substantially representing (at least one element selected and p is a number satisfying 0.01 ≦ p ≦ 0.06).

Further, a fluorescent lamp of the present invention is characterized in that it has a fluorescent film containing the phosphor of the present invention described above.

In such a fluorescent lamp, the wavelength 18
It emits blue to bluish green light with high output under ultraviolet excitation at 5 nm and wavelength of 254 nm, and contains a phosphor excellent in life characteristics, so that high luminance can be achieved and excellent life characteristics can be achieved. Become.

[0020]

Embodiments of the present invention will be described below.

The phosphor of the present invention has a general formula: (M _1-x Eu _x ) ₁₀ (PO ₄ ) ₆ .Cl ₂ (1) (where M is selected from Mg, Ca, Sr and Ba) Represents at least one element, and x is 0.001 ≦ x ≦ 0.
Bivalent europium-activated alkaline earth chlorophosphate phosphor substantially represented by a number) satisfying the 10 general _{formula: (M 1-y Mn y} ) O · zAl 2 O 3 ... ( 2) (In the formula, M represents at least one element selected from Mg, Ca, Sr and Ba, and y and z are numbers satisfying 0.01 ≦ y ≦ 0.35 and 4.5 ≦ z ≦ 8.0, respectively. ) And a mixture with a divalent manganese-activated alkaline earth aluminate phosphor substantially represented by (1).

X in the above equations (1) and (2),
The reasons for limiting the ranges of the values of y and z are as follows.

If the value of x, which indicates the content of divalent europium (Eu), is less than 0.001, the concentration of the activator in the phosphor becomes low, the luminous efficiency is reduced, and sufficient luminance is obtained. Can not. Conversely, when the value of x exceeds 0.10, the luminance is significantly reduced due to concentration quenching and the like. The value of x is 0.01 to 0.
More preferably, it is in the range of 05.

The value of y indicating the manganese (Mn) content is
If it is less than 0.01, the concentration of the activator in the phosphor becomes low, so that the luminous efficiency is reduced and sufficient luminance cannot be obtained. Conversely, if the value of y exceeds 0.35, the luminance is significantly reduced due to concentration quenching and the like. The value of y is more preferably in the range of 0.05 to 0.20.

If the value of z indicating the content of aluminum (Al) is less than 4.5 or 8.0 or more, the crystallinity is poor, and ultraviolet light having a wavelength of 185 nm is efficiently absorbed and light cannot be emitted. The value of z is more preferably in the range of 5.5 to 6.5.

The divalent europium-activated alkaline earth chlorophosphate phosphor efficiently absorbs ultraviolet light having a wavelength of 254 nm and emits blue to blue-green light efficiently. On the other hand, the divalent manganese-activated alkaline earth aluminate phosphor particles have an excitation spectrum as shown in FIG. 1, absorb ultraviolet rays having a wavelength of 185 nm, and emit blue to blue-green light. . Therefore, the phosphor mixed with these has a wavelength of 185 nm emitted by mercury discharge plasma.
And emits blue to blue-green light very efficiently under ultraviolet excitation at a wavelength of 254 nm.

In the present invention, the surface of the divalent europium-activated alkaline earth chlorophosphate phosphor particles is
It is desirable that the divalent manganese-activated alkaline earth aluminate phosphor particles be coated. As a result, the excitation light having a wavelength of 185 nm, which lowers the luminous efficiency of the divalent europium-activated alkaline earth chlorophosphate phosphor, is almost completely absorbed by the divalent manganese activated alkaline earth aluminate phosphor. Further, the emission output under the excitation of ultraviolet rays having wavelengths of 185 nm and 254 nm can be further increased.

In order to obtain a phosphor in which the surface of the divalent europium-activated alkaline earth chlorophosphate phosphor particles is coated with the divalent manganese activated alkaline earth aluminate phosphor particles, For example, first, divalent manganese-activated alkaline earth aluminate phosphor particles are charged into a container containing an acrylic resin aqueous solution of about 0.1% by weight, sufficiently stirred, and then divalent europium-activated alkaline earth. Chlorophosphate phosphor particles are added, stirring is further continued, and when a uniform suspension is obtained, filtration and drying may be performed.

In this case, divalent europium-activated alkaline earth chlorophosphate phosphor particles having a particle size (primary particle size) of 2 μm to 10 μm, and divalent manganese-activated alkali The earth aluminate phosphor particles preferably have a particle diameter (primary particle diameter) of 10 nm to 500 nm. More desirable particle size, divalent europium activated alkaline earth chlorophosphate phosphor particles 4μm ~ 6μ
m, divalent manganese-activated alkaline earth aluminate phosphor particles are in the range of 20 nm to 50 nm. If the particle size of the divalent europium-activated alkaline earth chlorophosphate phosphor particles is less than 2 μm, the crystallinity is insufficient and the luminous efficiency is reduced. Conversely, if the particle size exceeds 10 μm, a uniform phosphor screen is obtained. Becomes difficult. If the particle diameter of the divalent manganese-activated alkaline earth aluminate phosphor particles is less than 10 nm, the crystallinity is poor and the 185 nm ultraviolet rays cannot be efficiently absorbed and emitted, and conversely, 500 nm If it exceeds, it becomes difficult to coat the divalent europium-activated alkaline earth chlorophosphate phosphor particle surface. In the case of simple mixing as described above, the particle diameter of the divalent manganese-activated alkaline earth aluminate phosphor particles may exceed 500 nm. However, if it is too large, it has the effect of lowering the emission output of the fluorescent lamp.
It is desirable to set the range not to exceed m.

The amount of the divalent manganese-activated alkaline earth aluminate phosphor particles coated on the divalent europium-activated alkaline earth chlorophosphate phosphor particles is 0.01% by weight to 3.0% by weight. When the coating amount is less than 0.01% by weight, the effect of improving brightness cannot be sufficiently obtained.
On the other hand, when the content exceeds 3.0% by weight, the absorption of ultraviolet light having a wavelength of 254 nm of the divalent europium-activated alkaline earth chlorophosphate phosphor particles may be inhibited, and the emission luminance may be reduced. A more preferable range of the coating amount of the divalent manganese-activated alkaline earth aluminate phosphor particles is 0.05% by weight.
~ 1.0% by weight.

In the present invention, the phosphor can contain a green light-emitting component and a red light-emitting component. Such a phosphor is applied to a three-wavelength band fluorescent lamp. Here, the phosphors as the green and red light emitting components are not particularly limited, but have a wavelength of 254.
It is preferable to use a phosphor excellent in luminous efficiency by ultraviolet light of 185 nm and 185 nm.

For example, the green light-emitting component has the general formula: (Re_1-abTb_aCe_b)_TwoO_Three・_cSiO_Two ・_dP_TwoO_Five・_eB_TwoO_{Three … (3)} (Wherein, Re is a small number selected from Y, Gd and La
Each represents one element, and a, b, c, d and e
Are a> 0, b> 0, 0 <a + b <1, c> 0, d> 0, 2 × 10
^-Four≦ e ≦ 6 × 10^-3Is a number that satisfies
Phosphor, and a general formula: (Re_1-fgTb_fCe_g)_TwoO_Three・_hAl_TwoO_Three・_iSiO_Two・_jP_TwoO_Five・_kB _Two O_{3… (4)} (Wherein, Re is a small number selected from Y, Gd and La
Each represents one element, and f, g, h, i, j, and
And k are f> 0, g> 0, 0 <f + g <1, h ≧ 0, i ≧ 0, j
≧ 0, 1 × 10^-6≦ k ≦ 1.8 × 10^-Four, 0.8 ≦ h + i + j + k ≦
Which is a number that satisfies 1.30)
It is possible to use at least one phosphor selected from the group
desirable.

Further, as the red emission component, the general _{formula: (Re 1-p Eu p} ) 2 O 3 ... (5) ( wherein, Re is at least one element selected from Y, Gd and La And p is a number satisfying 0.01 ≦ p ≦ 0.06).

The mixing ratio of the blue light-emitting phosphor of the present invention to other green light-emitting components and the like can be appropriately set according to the target light emission color. When the particle diameter of the aluminate phosphor particles is about 1.0 μm or more, the blue light-emitting phosphor of the present invention is used in an amount of 10% by weight or less.
It is desirable that the content be contained by 60% by weight. If the content is outside this range, the effect of the present invention may not be sufficiently obtained. A more preferred range is from 15% to 40% by weight. In this case, the green light-emitting component is 15% by weight.
It is desirable that the red light emitting component be contained in an amount of 15 to 75% by weight.

[0035]

Next, specific examples of the present invention and evaluation results thereof will be described.

Example 1 8.20 mol of SrHPO ₄ , 0.50 mol of CaCO ₃ , Ba
_{Cl 2 1.50 mol, SrCl 2 4.00} mol, Eu 2 O 3
0.05 mol was accurately weighed and placed in a ball mill and mixed well. Next, this raw material mixture is put into an alumina crucible and placed in a reducing atmosphere (hydrogen 10% + nitrogen 90%) at 1500 ° C.
For 3 hours. The obtained fired product was pulverized, washed thoroughly with pure water, filtered and dried to obtain (Sr _0.82 Ba _0.12
A chlorophosphate phosphor (particle size: 4.5 μm) represented by Ca _0.05 Eu _0.01 ) ₁₀ (PO ₄ ) ₆ · Cl ₂ was obtained. The particle size was calculated by the aeration method described above, with the weight of the powder layer being 5.0 g.

In addition, BaCO_Three0.9 mol, MnCO_Three
0.1 mol, Al_TwoO_Three 6.0 mol, H _ThreeBO_Three1.3 mol
Accurately weighed and placed in a ball mill and mixed well. Next
Then, put this raw material mixture in an alumina crucible,
Fired at 1500 ℃ for 3 hours in an atmosphere (10% hydrogen + 90% nitrogen)
Was. The obtained calcined product was pulverized and pure and thoroughly washed
Then, it is filtered and dried, and (Ba_0.9Mn_0.1) Al₁₂O₁₉so
The obtained aluminate phosphor (particle size: 60 nm) was obtained. What
The particle size is determined by the weight of the powder layer in the aeration method described above.
It was calculated as 2.0 g.

Next, an acrylic resin aqueous solution of 800% by weight is used.
First, (Ba _0.9 M) in a container (capacity: 1000 cc)
n _0.1 ) _0.1 g of Al ₁₂ O ₁₉ phosphor was added, and after sufficiently stirring, (Sr _0.82 Ba _0.12 Ca _0.05 Eu _0.01 ) ₁₀ (P
100 g of O ₄ ) ₆ · Cl ₂ phosphor was added and stirring was continued.
When a uniform suspension was obtained, the suspension was filtered and dried to obtain a blue light-emitting phosphor according to the present invention. When this blue light emitting phosphor was observed with a scanning electron microscope (SEM),
(Sr _0.82 Ba _0.12 Ca _0.05 Eu _0.01 ) ₁₀ (PO ₄ ) ₆
(Ba _0.9 Mn _0.1 ) Al ₁₂ O _{19 on the} Cl ₂ phosphor surface
It was confirmed that the phosphor was uniformly coated.

Subsequently, the thus obtained blue light-emitting phosphor and (La _0.55 Ce _0.30 Tb _0.15 ) ₂ O ₃ · 1.01 P ₂ O ₅
A green-emitting phosphor represented by _{0.001B 2 O 3 · 0.002SiO 2 ·} , a (Y _0.96 Eu _0.04) and red-emitting phosphor represented by ₂ O _3, mixing ratio as shown in Table 2 Weigh as
Mix well. Using this mixed phosphor, according to a conventional method,
A three-wavelength fluorescent lamp was manufactured.

For comparison, (Sr _0.73 Ba _0.21
Three wavelengths were obtained in the same manner as in Example 1 using a blue light-emitting phosphor composed of only a chlorophosphate phosphor (particle diameter: 4.5 μm) represented by Ca _0.05 Eu _0.01 ) ₁₀ (PO ₄ ) ₆ .Cl _2. Type fluorescent lamp was produced. (Comparative Example 1) With respect to the fluorescent lamps obtained in Example 1 and Comparative Example 1, the brightness, the attached amount (total amount) of the phosphor, and the color temperature were measured. The results are shown in Table 2. Example 1
Are shown as relative values when the measured value in Comparative Example 1 is set to 100.

Example 2 The procedure of Example 1 was repeated, except that the starting materials were changed._0.69B
a_0.20Ca_0.10Eu_{0.0 1})_Ten(PO_Four)₆・ Cl_TwoRepresented by
Chlorophosphate phosphor (particle size 5.5 μm) and (Ba
_0.85Mn_0.15) Al₁₂O₁₉Aluminate fluorescence represented by
Body (particle size: 50 nm), and these are mixed to form
A blue light emitting phosphor according to the invention was obtained. This blue emission fluorescent light
When the body was observed by SEM, (Sr_0.69Ba_0.20C
a_0.10Eu _0.01)_Ten(PO_Four)₆・ Cl_TwoOn the surface of the phosphor
(Ba_0.85Mn_0.15) Al₁₂O₁₉Phosphor is coated
(Coating amount 0.3% by weight).

Next, the blue light-emitting phosphor thus obtained and (La _0.70 Ce _0.12 Tb _0.18 ) ₂ O ₃ · 1.05 P ₂ O ₅
A green-emitting phosphor represented by _{0.005B 2 O 3 · 0.008SiO 2 ·} , a (Y _0.98 Eu _0.02) and red-emitting phosphor represented by ₂ O _3, mixing ratio as shown in Table 2 Weigh as
Mix well. Using this mixed phosphor, according to a conventional method,
A three-wavelength fluorescent lamp was manufactured.

For comparison, (Sr _0.56 Ba _{0.33
Ca 0.10 Eu 0.01) 10 (PO} 4) chloro phosphate phosphor represented by ₆ · Cl ₂ (using blue-emitting phosphor consisting of particle size 5.5 [mu] m) only, in the same manner as in Example 2, three band Type fluorescent lamp was produced. (Comparative Example 2) With respect to the fluorescent lamps obtained in Example 2 and Comparative Example 2, the brightness, the amount of attached phosphor, and the color temperature were measured. The results are shown in Table 2. Note that the brightness and the amount of adhesion in Example 2 were 100
And the relative value when

Example 3 In the same manner as in Example 1 except that the starting materials were changed, (Sr_0.92B
a_0.05Ca_0.01Eu_{0.0 Two})_Ten(PO_Four)₆・ Cl_TwoRepresented by
Chlorophosphate phosphor (particle size 5.0 μm) and (Ba
_0.95Mn_0.05) Al₁₂O₁₉Aluminate fluorescence represented by
Body (particle size: 80 nm), and these are mixed to form
A blue light emitting phosphor according to the invention was obtained. This blue emission fluorescent light
When the body was observed by SEM, (Sr_0.92Ba_0.05C
a_0.01Eu _0.02)_Ten(PO_Four)₆・ Cl_TwoOn the surface of the phosphor
(Ba_0.95Mn_0.05) Al₁₂O₁₉Phosphor is coated
(A coating amount of 0.2% by weight).

Next, the blue light-emitting phosphor thus obtained and (La _0.50 Ce _0.40 Tb _0.10 ) ₂ O ₃ .1.00P ₂ O ₅
A green-emitting phosphor represented by _{0.003B 2 O 3 · 0.010SiO 2 ·} , (Y 0.55 Gd 0.40 Eu 0.05) and red-emitting phosphor represented by ₂ O _3, mixing ratio as shown in Table 2 And weighed so that Using this mixed phosphor, a three-wavelength fluorescent lamp was produced in a conventional manner.

For comparison, (Sr _0.85 Ba _0.12
Using a blue light-emitting phosphor composed of only a chlorophosphate phosphor (particle diameter: 5.0 μm) represented by Ca _0.01 Eu _0.02 ) ₁₀ (PO ₄ ) ₆ .Cl ₂ , in the same manner as in Example 3, three wavelengths Type fluorescent lamp was produced. (Comparative Example 3) With respect to the fluorescent lamps obtained in Example 3 and Comparative Example 3, the brightness, the attached amount of the phosphor, and the color temperature were measured. The results are shown in Table 2. The brightness and the amount of adhesion in Example 3 were 100
And the relative value when

Example 4 (Sr)_0.97C
a_0.01Eu_0.02)_Ten(PO_Four)₆・ Cl_TwoBlack represented by
Phosphoric acid phosphors (particle size 4.0 μm) and (Ba_{0 .90}Mn
_0.10) Al₁₂O₁₉Aluminate phosphor (particle size
200 nm), and further, these are mixed to obtain the present invention.
This blue light emitting phosphor was obtained. This blue light emitting phosphor is represented by S
Observation by EM showed that (Sr_0.97Ca_0.01E
u_0.02)_Ten(PO _Four)₆・ (Ba) on the surface of Cl phosphor
_0.90Mn_0.10) Al₁₂O₁₉The phosphor is coated
It was confirmed (coating amount: 0.6% by weight).

Next, the blue light-emitting phosphor thus obtained and (La _0.55 Ce _0.25 Tb _0.20 ) ₂ O ₃ .1.0P ₂ O ₅
A green-emitting phosphor represented by _{0.003Al 2 O 3 · 0.020SiO 2 ·} 0.0001B 2 O 3 ·, (Y 0.40 La 0.50 Eu 0.10) 2
The red light-emitting phosphor represented by O ₃ was weighed so as to have a compounding ratio as shown in Table 2, and thoroughly mixed. Using this mixed phosphor, a three-wavelength fluorescent lamp was produced in a conventional manner.

For comparison, (Sr _0.88 Ba _0.08
Using a blue light-emitting phosphor composed only of a chlorophosphate phosphor (particle diameter: 4.0 μm) represented by Ca _0.01 Eu _0.02 ) ₁₀ (PO ₄ ) ₆ .Cl ₂ , in the same manner as in Example 4, three wavelengths Type fluorescent lamp was produced. (Comparative Example 4) With respect to the fluorescent lamps obtained in Example 4 and Comparative Example 4, the brightness, the attached amount of the phosphor, and the color temperature were measured. The results are shown in Table 2. The brightness and the amount of adhesion in Example 4 were 100
And the relative value when

Example 5 The procedure of (Sr _0.79 B
_{a 0.15 Ca 0.05 Eu 0. 01)} 10 (PO 4) 6 · Cl 2 chloro phosphate phosphor represented (particle size 4.5 [mu] m) and (Ba
An aluminate phosphor (particle diameter: 30 nm) represented by _0.80 Mn _0.20 ) Al ₁₂ O ₁₉ was obtained, and these were mixed to obtain a blue light-emitting phosphor according to the present invention. Observation of this blue light-emitting phosphor by SEM revealed that (Sr _0.79 Ba _0.15 C
a _0.05 Eu _0.01 ) ₁₀ (PO ₄ ) ₆ .Cl ₂ phosphor was confirmed to be coated on the surface with (Ba _0.80 Mn _0.20 ) Al ₁₂ O ₁₉ phosphor (coating amount: 0.05% by weight).

Next, the blue light-emitting phosphor thus obtained and (La _0.70 Ce _0.20 Tb _0.10 ) ₂ O ₃ .1.00 P ₂ O ₅
A green-emitting phosphor represented by _{0.010Al 2 O 3 · 0.050SiO 2 ·} 0.00003B 2 O 3 ·, and a red light-emitting phosphor represented by _{(Y 0.95 Eu 0.05) 2 O} 3, shown in Table 2 It was weighed so as to have such a mixing ratio and mixed well. Using this mixed phosphor, a three-wavelength fluorescent lamp was produced in a conventional manner.

For comparison, (Sr _0.68 Ba _0.26
Three wavelengths were obtained in the same manner as in Example 5 using a blue light-emitting phosphor composed of only a chlorophosphate phosphor (particle diameter: 4.5 μm) represented by Ca _0.05 Eu _0.01 ) ₁₀ (PO ₄ ) ₆ .Cl _2. Type fluorescent lamp was produced. (Comparative Example 5) With respect to the fluorescent lamps obtained in Example 5 and Comparative Example 5, the brightness, the amount of attached phosphor, and the color temperature were measured. The results are shown in Table 2. The brightness and the amount of adhesion in Example 5 were 100
And the relative value when

[0053]

[Table 1]

[0054]

[Table 2]

Example 6 (Sr _0.79 B
_{a 0.15 Ca 0.05 Eu 0.0 1)} 10 (PO 4) 6 · Cl 2 chloro phosphate phosphor represented (particle size 5.0 .mu.m) and (Ba
An aluminate phosphor (particle diameter: 2.5 μm) represented by _0.85 Mn _0.15 ) Al ₁₂ O ₁₉ was obtained.

Next, the thus obtained (Sr_0.79B
a_0.15Ca_0.05Eu_0.01)_Ten(PO _Four)₆・ Cl_TwoPhosphor
36.5% by weight, (Ba_0.85Mn_0.15) Al₁₂O₁₉Phosphor
5.0% by weight, (La_0.50Ce_0.35Tb_0.15)_TwoO_Three・ 1.0
2P_TwoO_Five・ 0.00005B_TwoO_Three.Green-emitting phosphors represented by
(Particle size: 4.0 μm) by 33.5% by weight, (Y_0.965Eu_0.035)_Two
O_Three30.0 weight of red light emitting phosphor (particle diameter 4.0μm) represented by
The mixture was homogeneously mixed in the ratio of% by volume. Using this mixed phosphor,
A three-wavelength fluorescent lamp was manufactured by a conventional method.

For comparison, (Sr _0.70 Ba _{0.24
Ca 0.05 Eu 0.01) 10 (PO} 4) 6 · Cl 2 chloro phosphate blue-emitting phosphor represented by (particle size 5.0 .mu.m) 38.5 _{wt%, (La 0.50 Ce 0.35 Tb} 0.15) 2 O 3 · 1.02P ₂ O ₅
0.00005 B ₂ O ₃ · green light-emitting phosphor (particle size 4.0 μm)
m) was uniformly mixed at a ratio of 28.0% by weight with a red light-emitting phosphor (particle size: 4.0 μm) represented by 33.5% by weight and (Y _0.965 Eu _0.035 ) ₂ O _3. By law,
A three-wavelength fluorescent lamp was manufactured. (Comparative Example 6) With respect to the fluorescent lamps obtained in Example 6 and Comparative Example 6, the brightness, the attached amount of the phosphor, and the color temperature were measured.
The brightness and the attached amount of the phosphor according to Comparative Example 6 were respectively measured.
When it was set to 100, the brightness and the attached amount of the phosphor in Example 6 were 102.0 and 96.0, respectively. Also,
The color temperature was 6500K in all cases.

As is clear from the above measurement results,
The brightness of the phosphor according to the example is improved although the amount of adhesion is smaller than that of the phosphor of the comparative example.

[0059]

As described above, according to the present invention,
Obtaining a blue-to-blue-green light-emitting phosphor exhibiting high emission output under ultraviolet excitation at wavelengths of 185 nm and 254 nm and having excellent life characteristics, and a high-luminance fluorescent lamp using such a phosphor Can be.

[Brief description of the drawings]

FIG. 1 is a diagram showing an excitation spectrum distribution of divalent manganese-activated alkaline earth aluminate phosphor particles used in the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C09K 11/81 CPR C09K 11/81 CPR H01J 61/44 H01J 61/44 N (72) Inventor Nobuyuki Sudo Kanagawa 7-1, Nisshin-cho, Kawasaki-ku, Kawasaki-ku, Toshiba Electronic Engineering Co., Ltd. (72) Inventor Kenji Terashima 8 Shinsugita-cho, Isogo-ku, Yokohama-shi, Kanagawa Prefecture Toshiba Yokohama Works Co., Ltd. (72) Inventor Tsuyoshi Iwasaki, Kanagawa 7-1-1 Nisshin-cho, Kawasaki-ku, Kawasaki-ku Toshiba Electronics Engineering Co., Ltd. (72) Inventor Masaaki Suzuki 7-1 Nisshin-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa F-term in Toshiba Electronic Engineering Co., Ltd. 4H001 CA05 CA07 X07 XA05 XA08 XA12 XA13 XA14 XA15 XA17 XA20 XA38 XA39 XA57 XA64 YA25 YA58 YA63 YA65 5C043 AA07 CC09 DD28 EB04 EC03 EC16

Claims (9)

[Claims] 1. A general _{formula: (M 1-x Eu x} ) 10 (PO 4) 6 ·
Cl ₂ (wherein M represents at least one element selected from Mg, Ca, Sr and Ba, and x is 0.001 ≦ x ≦ 0.
A divalent europium-activated alkaline earth chlorophosphate phosphor substantially represented by the following formula: (M ₁ -yM n _y ) O · zAl ₂ O ₃ (formula Wherein M represents at least one element selected from Mg, Ca, Sr and Ba, and y and z are each a number satisfying 0.01 ≦ y ≦ 0.35 and 4.5 ≦ z ≦ 8.0), respectively. A phosphor comprising a mixture with a divalent manganese-activated alkaline earth aluminate phosphor represented by the following formula: 2. The general formula: (M _1-x Eu _x ) ₁₀ (PO ₄ ) _6.
Cl ₂ (wherein M represents at least one element selected from Mg, Ca, Sr and Ba, and x is 0.001 ≦ x ≦ 0.
A divalent europium-activated alkaline earth chlorophosphate phosphor particle substantially represented by the following formula ( _10), and a general formula: (M _1-y) coated on the surface of the phosphor particle Mn _y ) O · zAl ₂ O ₃ (wherein M represents at least one element selected from Mg, Ca, Sr and Ba, and y and z are respectively 0.01 ≦ y ≦ 0.35, 4.5 ≦ z ≦ 8.0, which is a number that satisfies 8.0). The phosphor comprises divalent manganese-activated alkaline earth aluminate phosphor particles substantially represented by the following formula: 3. The phosphor according to claim 2, wherein the divalent europium-activated alkaline earth chlorophosphate phosphor particles have a particle size (primary particle size) of 2 μm to 10 μm, and are activated by divalent manganese. A phosphor characterized in that the particle size (primary particle size) of the alkaline earth aluminate phosphor particles is 10 nm to 500 nm. 4. The phosphor according to claim 2, wherein the divalent europium-activated alkaline earth chlorophosphate phosphor particles are coated with divalent manganese-activated alkaline earth aluminate phosphor particles. Is 0.01% by weight to 3.0% by weight. 5. A phosphor containing a blue light-emitting component, a green light-emitting component, and a red light-emitting component, wherein the blue light-emitting component is any one of claims 1 to 4.
A phosphor comprising the phosphor described in the above item. 6. The phosphor according to claim 5, wherein the green light-emitting component has a general formula: (Re)_1-abTb_aCe_b)_TwoO_Three・_cSiO_Two
 ・_dP_TwoO_Five・_eB_TwoO_Three (Wherein, Re is a small number selected from Y, Gd and La
Each represents one element, and a, b, c, d and e
Are a> 0, b> 0, 0 <a + b <1, c> 0, d> 0, 2 × 10
^-Four≦ e ≦ 6 × 10^-3Is a number that satisfies
Phosphor, and a general formula: (Re_1-fgTb_fCe_g)_TwoO_Three・ HAl_TwoO
_Three・ ISiO_Two・ JP_TwoO_Five・ KB _TwoO_Three (Wherein, Re is a small number selected from Y, Gd and La
Each represents one element, and f, g, h, i, j, and
And k are f> 0, g> 0, 0 <f + g <1, h ≧ 0, i ≧ 0, j
≧ 0, 1 × 10^-6≦ k ≦ 1.8 × 10^-Four, 0.8 ≦ h + i + j + k ≦
Which is a number that satisfies 1.30)
Characterized in that it contains at least one phosphor selected from the group
Phosphor to be featured. 7. A phosphor according to claim 5 or 6, wherein, as the red emission component, the general _{formula: (Re 1-p Eu p} ) 2 O 3 ( where, Re is selected from Y, Gd and La And at least one element, and p is a number satisfying 0.01 ≦ p ≦ 0.06). 8. The phosphor according to claim 5, wherein the blue light-emitting component is 10% to 60% by weight, the green light-emitting component is 15% to 55% by weight, and the red light is emitted. A phosphor comprising 15% to 75% by weight of a component. 9. A fluorescent lamp comprising a phosphor film containing the phosphor according to claim 1. Description: