JPH10125252A - Color cathode-ray tube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color cathode-ray rube having a flouorescent film of no color by improving the color purity of luminescent color of a green phosphor layer using a green pigment layer which possesses an improved light transmission characteristics. SOLUTION: This cathode-ray tube includes a fluorescent film 4 wherein a red pigment layer 14R, a blue pigment layer 14B and a green pigment layer 14G are deposited on the inside surface of a panel face plate 1A, and wherein a red phosphor layer 15R, a blue phosphor layer 15B and a green phosphor layer 15G are respectively deposited on the red pigment layer 14R, the blue pigment layer 14B and the green pigment layer 14G. In this constitution, the green pigment layer 14G comprises a green pigment based on TiO2 .NiO.CoO.ZnO oxide, and a green pigment based on TiO2 .Cr2 O3 .CoO.Al2 O3 oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color cathode ray tube, and more particularly to a color cathode ray tube comprising a red pigment layer, a blue pigment layer, a green pigment layer, and a phosphor layer of the same color formed on the pigment layer. The present invention relates to a color cathode ray tube having a fluorescent film, a high purity emission color and a high contrast characteristic.

[0002]

2. Description of the Related Art In general, a color cathode ray tube has a dot or striped pixel made of a red phosphor, a blue phosphor, and a green phosphor, which emit red, blue, and green light, respectively, on an inner surface of a face plate of a panel portion. Are arranged regularly. In this case, the pixels of the three-color phosphor emit light when excited by three electron beams emitted from the electron gun in the neck of the color cathode ray tube, and the three electron beams respectively correspond to the three colors. A color selection electrode (shadow mask or aperture grid) is arranged between the phosphor film and the electron gun so as to project on the phosphor. The phosphor film of the color cathode ray tube has a three-color phosphor. Various colors are reproduced depending on the degree of light emission according to the intensity of the electron beam hitting the body.

In recent years, a color cathode ray tube has a fluorescent material between an inner surface of a face plate and a red phosphor, a blue phosphor, and a green phosphor in order to improve color purity and contrast of light emission in a phosphor film. Means for depositing and forming a pigment layer (pigment filter layer) of the same color as the optical body layer has come to be employed. When such a three-color fluorescent film with a pigment layer is used, when light emitted from the three-color fluorescent material passes through a pigment layer of the same color, extra light emission in the emission spectrum of each of the three-color fluorescent materials is obtained. The components are selectively and strongly absorbed, and the color purity of light emission is improved. In addition, since the external light is absorbed by the three color pigment layers, the reflection of the external light on the fluorescent film is reduced, and blackening of the display screen is improved. At the same time, in the three color pigment layers, compared to the ratio at which the reflection of external incident light is reduced,
Since the rate of absorption of light emitted from the three-color phosphor is small,
The decrease in emission luminance of the three-color phosphor is reduced, and as a result, the contrast is improved.

In order to form such a fluorescent film with a pigment layer, a manufacturing process as disclosed in, for example, JP-A-64-7457 is used.

The manufacturing process disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 64-7457 will be described as follows.

First, a slurry of a photocurable photosensitive resin in which pigment particles of a first color (for example, red) are dispersed is applied to the inner surface of a face plate of a color cathode ray tube to form a first color pigment layer (step S1). ).

Next, using the shadow mask as an exposure mask, only the pigment layer of the first color pigment layer at the position where the first color is to be formed is exposed to light and cured (step S2).

Next, the first color pigment layer is developed, the unexposed pigment layer is removed, and the first color pigment layer is formed at a position where the first color is to be formed (step S3).

Subsequently, the same processing as the processing performed in steps S1 to S3 is performed, and the second color (for example, blue) is processed.
A second color pigment layer is formed at the position where the pigment layer is to be formed (Steps S4 to S6).

Next, a process similar to the process performed in step S1 to step S3 or step S4 to step S6 is performed to coat a third color (for example, green) pigment layer at a position where a third color (for example, green) pigment layer is to be formed. The formation is performed (steps S7 to S9).

As described above, steps S1 to S
After 9, the first to third color pigment layers are formed.

Subsequently, a photosensitive slurry containing a first color (for example, red) phosphor is applied to the inner surface of the face plate on which the first to third color pigment layers are formed, and the first color phosphor layer is formed. Is formed (step S10).

Next, using the shadow mask as an exposure mask, only the phosphor layer at the position where the first color is to be formed in the first color phosphor layer is exposed and photo-cured (step S1).
1). Next, the first color phosphor layer is developed, the unexposed phosphor layer is removed, and the first color phosphor layer is coated on the first color pigment layer at the position where the first color is to be formed. (Step S1)
2).

Subsequently, steps S10 to S1
The same processing as that performed in step 2 is performed, and the second color (for example, blue) phosphor layer is formed on the second color pigment layer at the position where the phosphor layer is to be formed.
A color phosphor layer is formed (steps S13 to S15).

Further, steps S10 to S1
2 or a process similar to the process performed in steps S13 to S15 is performed to form the third color phosphor layer on the third color pigment layer at the position where the third color (for example, green) phosphor layer is to be formed. Adhesion is formed (Steps S16 to S18).

As described above, through steps S10 to S18, a phosphor film including the first to third color phosphor layers with the same color pigment layer is formed.

In general, a phosphor called P22 phosphor is used as a phosphor forming a phosphor film of a color cathode ray tube. For example, a red phosphor is coated with europium. Active yttrium oxysulfide phosphor (Y ₂ O ₂ S:
Eu), but the blue phosphor includes a silver-activated zinc sulfide phosphor (Z
nS: Ag), and green phosphors include copper and aluminum activated zinc sulfide phosphors (ZnS: Cu, Al), and gold and aluminum activated zinc sulfide phosphors (ZnS: Au, Al)
Alternatively, copper, aluminum, and gold activated zinc sulfide phosphor (ZnS: Cu, Al, Au) and the like are used, respectively.

Further, as described above, in order to improve the contrast of the fluorescent film, the surface of the three-color phosphor layer is coated with a pigment layer of the same color, respectively. For the pigment forming the pigment layer, an inorganic pigment that is not deteriorated by heat treatment during the manufacturing process of the color cathode ray tube is used. For example, in a red pigment, fine particles of ferric oxide are used in a blue pigment. Are fine particles such as cobalt aluminate, and the green pigment is TiO ₂ .Ni
O-CoO-ZnO-based oxide or TiO ₂ -Cr
Particles such as _{2 O 3 · CoO · Al 2} O 3 based oxide is used.

FIG. 5 is a characteristic diagram showing the emission spectrum of a P22 green phosphor used in a known color cathode ray tube and the light transmittance characteristics of various green pigment layers. The horizontal axis is nm. The vertical axis indicates the relative luminance of the emission spectrum expressed in% and the transmittance of the green pigment layer.

The P22 green phosphor has an emission spectrum that extends over a fairly wide wavelength range, as shown by the thick solid line in FIG. The emission spectrum has a peak light wavelength near 530 nm (green), but the short wavelength side reaches around 450 nm corresponding to the blue emission color, and the long wavelength side corresponds to 570 to 6 corresponding to the yellow to red emission color.
It has reached about 30 nm. For this reason, the emission color of the P22 green phosphor is a mixture of these colors, and the color purity as green is not very good.

When a green phosphor layer is formed using such a P22 green phosphor and a green pigment layer is formed between the green phosphor layer and the face plate, light emitted by the green phosphor is generated. When passing through the green pigment layer, it selectively absorbs light wavelength components that degrade the color purity of green, so the color purity of green phosphor emission is significantly improved compared to the case where no green pigment layer is used. I do. In addition, the red pigment layer and the blue pigment layer, including the green pigment layer, strongly absorb external incident light such as fluorescent lamps and sunlight, so that the reflectance of the fluorescent film with respect to the external incident light becomes small, and the fluorescent film becomes fluorescent. The blackness of the film increases. On the other hand, since the pigment layer of each color does not strongly absorb the main light component emitted by each color phosphor, the decrease in luminance is relatively small, and as a result, the contrast of the screen is improved.

[0022]

However, as in a known color cathode ray tube, a green pigment layer using a known green pigment is used in combination with a green phosphor layer using a P22 green phosphor. In other words, TiO _2.
NiO / CoO / ZnO based oxide green pigment or TiO
When using a _{2 · Cr 2 O 3 · CoO} · Al 2 O 3 based oxide green pigment alone, a problem with the described below as a point in its light absorption properties.

First, TiO ₂ .NiO.CoO.ZnO
A green pigment layer (hereinafter, referred to as “Dipirooxide Green # 3320” manufactured by Dainichi Seika)
When this is referred to as a TiNiCoZn-based green pigment layer), the light transmission characteristics thereof are such that the light at both tails of the peak light wavelength in the emission spectrum of the P22 green phosphor as shown by the thin curve b in FIG. Since it has a characteristic of absorbing a relatively large wavelength, the emission color purity of the green phosphor is improved, and at the same time, the contrast is improved because the TiNiCoZn-based green pigment layer absorbs external incident light.

However, while the TiNiCoZn-based green pigment layer has a relatively large ratio of absorption of light (blue component) on the short wavelength side, the ratio of absorption of light (yellow to red component) on the long wavelength side is comparatively large. The emission color of the green phosphor is
It tends to be yellowish green, and it is not possible to obtain a deep, vivid green. Further, as described above, since the emission color of the green phosphor is yellow-green, when the green pigment layer is attached to the green phosphor, the color of the phosphor film becomes yellowish. The color of the fluorescent film is generally called a body color, and it is preferable that the color is not colored (so-called achromatic color). The reason is that if the coloring of the fluorescent film is too strong, an unnatural color is added to the emission color or black (non-light-emitting portion), and the image quality is deteriorated. When the reflection colors of the three primary color pixels including the red phosphor layer, the blue phosphor layer, and the green phosphor layer are in a well-balanced state, the color of the phosphor film mixed with the three primary color pixels becomes almost achromatic. However, as described above, when the green phosphor layer approaches yellow-green, the color balance of the phosphor film mixed with the three primary color pixels is lost, and the color of the phosphor film becomes yellowish, which is an undesirable state. Will be shown.

Next, TiO ₂ .Cr ₂ O ₃ .CoO.A
A green pigment layer (hereinafter referred to as a TiCrCoAl-based green pigment layer) using an l ₂ O ₃ -based oxide green pigment (for example, dipyroxide green # 3330 manufactured by Dainichi Seika)
Is formed, the light transmission characteristic is represented by a thin curve c in FIG.
As shown in (2), the emission characteristics of the P22 green phosphor have a characteristic of absorbing a relatively large amount of light wavelengths at both tails of the peak light wavelength in the emission spectrum, so that the color purity of the emission of the green phosphor is improved, and Since the TiCrCoAl-based green pigment layer absorbs external incident light, the contrast is also improved.

However, the TiCrCoAl-based green pigment layer has a relatively large ratio of absorption of light components on the long wavelength side (yellow to red components), whereas the absorption ratio of light components on the short wavelength side (blue component) is relatively large. Is relatively small, the emission color of the green phosphor tends to be bluish green, and a deep and vivid green cannot be obtained as in the previous case. Further, as described above, when the green phosphor layer approaches blue green, the color balance of the phosphor film in which the three primary color pixels are mixed is lost,
The color of the fluorescent film becomes bluish, indicating an undesirable state.

The present invention solves these problems, and an object of the present invention is to use a green pigment layer having improved light transmission characteristics, improve the color purity of the green phosphor for the emission color, and achieve an achromatic color. An object of the present invention is to provide a color cathode ray tube capable of obtaining a near fluorescent film.

[0028]

In order to achieve the above object, a color cathode ray tube according to the present invention comprises a green pigment layer attached to a green phosphor layer and a TiO ₂ .NiO.CoO.ZnO.
-Based oxide green pigment and TiO ₂ .Cr ₂ O ₃ .CoO.
Means using a green pigment having a composition mainly composed of an Al ₂ O ₃ -based oxide green pigment is provided.

According to the above means, TiO ₂ .NiO.C
oO.ZnO-based oxide green pigment and TiO ₂ .Cr ₂ O
A color cathode ray tube equipped with a known phosphor film of this type having a green pigment layer by using a composition mainly composed of a material mixed with a ₃ · CoO · Al ₂ O ₃ oxide green pigment In comparison with the above, the absorption intensity on the short wavelength side and the absorption intensity on the long wavelength side of the light absorption spectrum are balanced, the emission color from the green phosphor layer is improved, and a bright green color with good color purity is obtained. An emission color is obtained.

[0030]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In a preferred embodiment of the present invention, a color cathode ray tube has a red pigment layer, a blue pigment layer, and a green pigment layer coated on the inner surface of a face plate of a panel, and the same color is formed on the pigment layer of each color. And a green pigment layer formed of TiO ₂ .NiO.CoO.
ZnO-based oxide green pigment and TiO ₂ · Cr ₂ O ₃ · C
It is composed of a green pigment having a composition mainly composed of an oO.Al ₂ O ₃ -based oxide green pigment.

In the embodiment of the present invention, the green pigment layer is composed of a TiO ₂ .NiO.CoO.ZnO-based oxide green pigment and TiO ₂ .Cr ₂ O ₃ .CoO.Al ₂ O ₃
The mixing ratio with the base oxide green pigment is selected so as to be in the range of 4: 1 to 1: 4.

In a preferred embodiment of the present invention, the green pigment layer is made of TiO ₂ .NiO.CoO.ZnO.
-Based oxide green pigment and TiO ₂ · Cr ₂ O ₃ · CoO · A
The mixing ratio with the l ₂ O ₃ -based oxide green pigment is 2: 1 to 1
They are chosen to be within the range of two.

According to the embodiment of the present invention, Ti
O ₂ .NiO.CoO.ZnO-based oxide green pigment;
Since a green pigment having a composition mainly composed of a mixture of an iO ₂ · Cr ₂ O ₃ · CoO · Al ₂ O ₃ -based oxide green pigment is used, a TiO ₂ · NiO · CoO · ZnO-based oxide is used. Green pigment or TiO ₂ · Cr ₂ O ₃ · CoO ·
Compared with a known color cathode ray tube using an Al ₂ O ₃ -based oxide green pigment alone, the absorption intensity on the short wavelength side and the absorption intensity on the long wavelength side of the light absorption spectrum are more balanced. As a result, the emission color from the green phosphor layer is improved, and a bright green emission color with good color purity can be obtained.

In this case, TiO ₂ .NiO.CoO.Z
nO-based oxide green pigment and TiO ₂ · Cr ₂ O ₃ · CoO
The mixing ratio with the Al ₂ O ₃ -based oxide green pigment is in the range of 4: 1 to 1: 4, preferably, the mixing ratio is 2: 1.
By selecting from the range of 1 to 2, the balance between the absorption intensity on the short wavelength side and the absorption intensity on the long wavelength side of the light absorption spectrum becomes good, and a bright green luminescent color with good color purity is obtained. Can be obtained.

Further, the reflection color of the fluorescent film becomes almost achromatic, thereby realizing a good body color and obtaining a color cathode ray tube exhibiting a good contrast.

[0036]

Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a sectional view schematically showing the structure of an embodiment of a color cathode ray tube according to the present invention.

In FIG. 1, 1 is a panel portion, 1A is a face plate, 2 is a neck portion, 3 is a funnel portion, 4 is a fluorescent film, 5 is a shadow mask, 6 is an internal magnetic shield,
7 is a deflection yoke, 8 is a purity adjustment magnet, 9 is a center beam static convergence adjustment magnet, 10 is a side beam static convergence adjustment magnet, 11 is an electron gun, and 12 is an electron beam.

The glass vacuum envelope (bulb) constituting the color cathode ray tube has a large-diameter panel portion 1 disposed on the front side, an elongated neck portion 2 accommodating an electron gun 11 therein, A substantially funnel-shaped funnel 3 connecting the panel 1 and the neck 2. The panel unit 1 has a face plate 1A on the front surface, a fluorescent film 4 is formed on the inner surface of the face plate 1A, and a shadow mask 5 is attached so as to face the fluorescent film 4. An internal magnetic shield 6 is provided inside a joint portion between the panel portion 1 and the funnel portion 3, and a deflection yoke 8 is disposed outside a joint portion between the funnel portion 3 and the neck portion 2 when used. Electron gun 11
The three electron beams 12 (only one is shown) emitted from the deflecting yoke 7 are deflected in a predetermined direction by the deflection yoke 7, and then are projected onto the fluorescent film 4 through the shadow mask 5.
A purity adjusting magnet 8, a center beam static convergence adjusting magnet 9, and a side beam static convergence adjusting magnet 10 are arranged outside the neck portion 2 side by side.

The operation of the color cathode ray tube having the above-described structure, that is, the image display operation is exactly the same as the image display operation of the known color cathode ray tube, and therefore the description of the image display operation of the color cathode ray tube is omitted. I do.

Next, FIG. 2 is a cross sectional view showing the structure of a part of the fluorescent film 4 used in the color cathode ray tube shown in FIG.

In FIG. 2, 13 is a black matrix (BM), 14R is a red pigment layer (red pigment filter layer), 14B is a blue pigment layer (blue pigment filter layer),
4G is a green pigment layer (green pigment filter layer), 15R is a red phosphor layer, 15B is a blue phosphor layer, 15G is a green phosphor layer, and other components shown in FIG. The same components are denoted by the same reference numerals.

In the panel section 1, a large number of black matrices 13 (only a part of which are shown in FIG. 2) are formed at predetermined intervals on the inner surface of the face plate 1A. A red pigment layer 14R, a blue pigment layer 14B, and a green pigment layer 14G are sequentially formed in a region between the black matrices 13, a red phosphor layer 15R above the red pigment layer 14R, and a blue phosphor layer above the blue pigment layer 14B. The green phosphor layer 15 is formed on the body layer 15B and the green pigment layer 14G.
G are respectively formed, and the face plate 1
The fluorescent film 4 is formed on the inner surface of A.

Next, FIGS. 3A to 3D and FIG.
(A) to (d) are cross-sectional configuration diagrams showing a manufacturing process for forming a three-color pigment layer on the inner surface of the face plate 1A of the panel unit 1 of the color cathode ray tube shown in FIG. Represents only a part of the pigment layer.

In FIG. 3, 16 is a shadow mask used as an exposure mask, 17 is an exposure light beam,
In addition, the same components as those shown in FIG. 2 are denoted by the same reference numerals.

Here, FIGS. 3A to 3D and FIG.
With reference to (a) to (d), the steps of manufacturing the three color pigment layers in the color cathode ray tube of the present embodiment are as follows.

First, as shown in FIG. 3 (a), a number of black matrices 13 are formed on the inner surface of the face plate 1A of the panel section 1 at a predetermined interval by well-known forming means.

Next, as shown in FIG. 3B, a green pigment slurry is applied to the inner surface of the face plate 1A on which the black matrix 13 is formed by a spin coating method to form a coating film. Is dried to obtain a green pigment layer 1
4G was deposited.

In this case, the green pigment slurry is made of TiO ₂
・ NiO / CoO / ZnO based oxide green pigment and TiO ₂
3% by weight of a green pigment having a mixing ratio of 1: 1 with a Cr ₂ O ₃ .CoO.Al ₂ O ₃ -based oxide green pigment, 2% by weight of polyvinyl alcohol, and 0.1 of an alkali dichromate salt
6% by weight, with the balance being pure water, was added and stirred to mix.

Then, as shown in FIG. 3C, the shadow mask 16 is used as an exposure mask, and only a predetermined portion of the green pigment layer 14G where the green pigment layer 14G is to be formed is exposed to ultraviolet light or the like. Exposure is performed with light 17 to cure the exposed portion of the green pigment layer 14G.

Subsequently, as shown in FIG. 3 (d), the exposed green pigment layer 14G is sprayed with hot pure water and developed, and the unexposed portion in the green pigment layer 14G is washed and removed. The green pigment layer 14G is formed only on the portion.

Next, as shown in FIG. 4A, a blue pigment slurry is applied on the inner surface of the face plate 1A on which the green pigment layer 14G is formed by a spin coating method to form a coating film. After drying the film, the blue pigment layer 14B
Was formed.

In this case, the blue pigment slurry is prepared by adding 8% by weight of a blue pigment composed of cobalt aluminate to a solution composed of 2% by weight of polyvinyl alcohol, 0.16% by weight of alkali dichromate, and the balance being pure water. Are prepared by stirring them.

Next, as shown in FIG. 4 (b), using the shadow mask 16 as an exposure mask, only a predetermined portion of the blue pigment layer 14B where the blue pigment layer 14B is to be formed is exposed to ultraviolet light or the like. Exposure is performed with light 17 to cure the exposed portion of the blue pigment layer 14B.

Subsequently, as shown in FIG. 4 (c), the exposed blue pigment layer 14B is sprayed with hot pure water and developed, and the unexposed portion in the blue pigment layer 14B is washed and removed. The blue pigment layer 14B is formed only on the portion.

Next, as shown in FIG. 4D, a red pigment slurry is applied to the inner surface of the face plate 1A on which the green pigment layer 14G and the blue pigment layer 14B are formed by a spin coating method to form a coating film. Then, the coating film is dried to form a red pigment layer 14R. At this time, the red pigment slurry was prepared by dissolving 1.5% by weight of a red pigment composed of ferric oxide in a solution composed of 1.5% by weight of polyvinyl alcohol, 0.1% by weight of alkali dichromate, and the balance being pure water. , And those prepared by stirring them are used. Thereafter, using the shadow mask 16 as an exposure mask, only a predetermined portion of the red pigment layer 14R where the red pigment layer 14R is to be formed is exposed to exposure light 17 such as ultraviolet light, and the exposed portion of the red pigment layer 14R is exposed. Let it cure. Further, the exposed red pigment layer 14R is sprayed with hot pure water and developed, and the unexposed portion in the red pigment layer 14R is washed away, and the red pigment layer 14R is formed only on the predetermined portion.

In this manner, as shown in FIG. 4E, the green pigment layer 14 is formed on the inner surface of the face plate 1A.
Thus, three color pigment layers 14G, 14B, and 14R each including G, a blue pigment layer 14B, and a red pigment layer 14R are formed.

Subsequently, as shown in FIG. 2, a green pigment layer, a green phosphor layer, a blue phosphor layer and a red phosphor layer are formed in a known color cathode ray tube by the same forming steps. A P22 green phosphor layer 15G is formed on 14G, a P22 blue phosphor layer 15B is formed on the blue pigment layer 14B, and a P22 red phosphor layer 15R is formed on the red pigment layer 14R. A fluorescent film 4 comprising three-color fluorescent layers 15G, 15B and 15R with pigment layers 14G, 14B and 14R was formed.

Thereafter, the color cathode ray tube on which the fluorescent film 4 has been formed is subjected to filming, aluminum backing, and other processes as in a known manufacturing process to complete the color cathode ray tube.

In the color cathode ray tube obtained in this manner, the green pigment layer 14G of the fluorescent film 4 is coated with TiO ₂ .NiO
・ CoO / ZnO-based oxide green pigment and TiO ₂・ Cr ₂
O ₃ .CoO.Al ₂ O ₃ -based oxide green pigment is one-to-one
As shown by the thin curve A in FIG. 5, the emission spectrum (thick solid line) of the P22 green phosphor layer 15G is different from that of the green pigment layer 14G as shown by the thin curve A in FIG.
In this light absorption spectrum, the intensity of absorption on the short wavelength side and the intensity of absorption on the long wavelength side in such an emission spectrum are balanced, whereby the emission color from the green phosphor layer 15G is improved, A bright green luminescent color with good purity can be obtained.

In the above embodiment, when forming the fluorescent film 4, the green pigment layer 14G is formed first, then the blue pigment layer 14B is formed, and finally the red pigment layer 14R is formed. However, the order of forming the three color pigment layers 14G, 14B, and 14R in the present invention is not limited to the order described above, and the order of formation may be changed as appropriate.

FIG. 6 shows the composition of the green pigment constituting the green pigment layer, that is, TiO ₂ .NiO.CoO.ZnO.
-Based oxide green pigment and TiO ₂ · Cr ₂ O ₃ · CoO · A
FIG. 4 is a characteristic diagram showing a change state of a light emission color and a reflection color when a mixing ratio with an l ₂ O ₃ -based oxide green pigment is changed.

In FIG. 6, the first three examples are three different examples (Example 1, Example 2, and Example 3) of the present invention including the aforementioned example (named as Example 1). The following three examples are known configuration examples (Comparative Example 1, Comparative Example 2, and Comparative Example 3) listed for comparison with each example of the present invention. ) Are shown.

As shown in FIG. 6, first, in the case of Comparative Example 1 in which the green pigment layer was not provided, only the green emission color from the P22 green phosphor layer contributed.
The green light emission color is inferior in color purity and becomes a yellowish green light emission color. The x and y chromaticity coordinates of the light emission color are such that the value of x is 0.
At 285, the value of y becomes 0.602. Also, the fluorescent film 4
Has a pale yellow-green reflection color.

Here, in the x and y chromaticity coordinates of the green emission color, the smaller the value of x and the larger the value of y, the more
The color purity of green is improved, and the color becomes deep and vivid green. On the other hand, when both the value of x and the value of y decrease, the emission color shifts in the blue direction, becomes a bluish green, and the color purity of the green decreases. Further, when both the value of x and the value of y increase, the emission color shifts in the yellow direction, becomes yellowish green, and similarly, the color purity of green decreases.

Next, the green pigment layer was formed of TiO ₂ .NiO.
In the case of Comparative Example 2 formed using only the CoO / ZnO-based oxide green pigment, the value of y in the x and y chromaticity coordinates of the emission color is 0.613, and the value of y in Comparative Example 1 is (0.
602) is slightly larger than the value of x, but the value of x is 0.
At 281, there is not much difference from the value of x (0.285) of Comparative Example 3, and the emission color becomes green with a yellowish color remaining, and the color purity of green also decreases. The reflection color of the fluorescent film 4 also exhibits a relatively strong yellow-green color.

Next, the green pigment layer was coated with TiO ₂ .Cr ₂
For _{O 3 · CoO · Al 2 O} 3 based oxide green pigment only to the used form and Comparative Example 2, the emission color of the values of x, y in the y chromaticity coordinates 0.611, Comparative Example Although the value of x is slightly larger than the value of y (0.602) of Comparative Example 3, the value of x is 0.260, which is smaller than the value of x of Comparative Example 3 (0.285). The color becomes green with a strong bluish color, and the color purity of green also decreases. In addition, the reflection color of the fluorescent film 4 also exhibits a relatively bluish green color.

On the other hand, the green pigment layer was formed of TiO _2.
NiO / CoO / ZnO based oxide green pigment and TiO ₂
In the case of Example 1 in which a mixture of a Cr ₂ O ₃ .CoO.Al ₂ O ₃ -based oxide green pigment is used at a ratio of 1: 1, the x and y chromaticity coordinates of the emission color are used. Since the value of x in Example 2 is 0.270 and the value of y is 0.616, the emission color becomes vivid green, and the color purity of green is improved. In addition, the reflection color of the fluorescent film 4 becomes an achromatic color that has almost no color.

Next, the green pigment layer was formed of TiO ₂ .NiO.
CoO / ZnO-based oxide green pigment and TiO ₂ · Cr ₂ O
_In the case of Example 2 in which a mixture of ₃ · CoO · Al ₂ O ₃ -based oxide green pigment is used in a ratio of 2: 1, the x and y of the luminescent color are represented by x and y. Value is 0.2
73, and since the value of y is 0.616, the luminescent color becomes bright green as in the case of the first embodiment.
Green color purity is improved. In addition, the reflection color of the fluorescent film 4 becomes an achromatic color that has almost no color.

Next, the green pigment layer was formed of TiO ₂ .NiO
・ CoO / ZnO-based oxide green pigment and TiO ₂・ Cr ₂
O ₃ .CoO.Al ₂ O ₃ oxide green pigment is 1: 2
In the case of Example 3 in which the mixture is formed using a mixture of the luminous colors at the x and y chromaticity coordinates of 0.
266, and the value of y becomes 0.615. Thus, as in the case of the first and second embodiments, the emission color becomes vivid green, and the color purity of green is improved. In addition, the reflection color of the fluorescent film 4 becomes an achromatic color that has almost no color.

In each of the above-described embodiments (Examples 1 to 3), the TiO 2 when the green pigment layer is formed is used.
_2. NiO / CoO / ZnO based oxide green pigment (the former)
When the mixing ratio of TiO ₂ .Cr ₂ O ₃ .CoO.Al ₂ O ₃ -based oxide green pigment (the latter) is 1: 1, 2: 1, 1: 2 between the former and the latter Was described as an example, but the mixing ratio of the former and the latter in the present invention is not limited to each of the above-mentioned cases, and the ratio between the former and the latter is within a range of 4: 1 to 1: 4. If present, Examples 1 to 3
It has been experimentally confirmed that almost the same results can be obtained.

As described above, according to the present embodiment, TiO
₂ · NiO · CoO · ZnO based oxide green pigment and TiO
_Since the green pigment layer 14G is formed using a green pigment obtained by mixing an appropriate ratio of a ₂ • Cr ₂ O ₃ • CoO • Al ₂ O ₃ -based oxide green pigment, the green color of the green phosphor layer 15G The color purity of the emitted light can be improved, and the reflected color of the fluorescent film 4 can be made almost achromatic.

[0073]

As described above, according to the present invention, TiO ₂ .NiO.C is used as a green pigment for forming a green pigment layer.
oO.ZnO-based oxide green pigment and TiO ₂ .Cr ₂ O ₃
Since a material obtained by mixing a CoO.Al ₂ O ₃ -based oxide green pigment in an appropriate ratio is used as a main component, compared to a known green phosphor layer of a fluorescent film of a known color cathode ray tube, In the absorption spectrum, the absorption intensity on the short wavelength side and the absorption intensity on the long wavelength side are balanced, the green emission color from the green phosphor layer is improved, and the bright green color with good color purity is improved. An emission color can be obtained, and the reflection color of the fluorescent film can be made almost achromatic.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a schematic configuration of an embodiment of a color cathode ray tube according to the present invention.

FIG. 2 is a cross-sectional view showing a configuration of a part of a fluorescent film used in the color cathode ray tube shown in FIG.

3 is a cross-sectional configuration diagram illustrating a first half of a manufacturing process for forming a three-color pigment layer on an inner surface of a face plate of a panel portion of the color cathode ray tube illustrated in FIG. 1;

FIG. 4 is a cross-sectional configuration diagram illustrating a second half of a manufacturing process for forming a three-color pigment layer on an inner surface of a face plate of a panel portion of the color cathode ray tube illustrated in FIG.

FIG. 5 is a characteristic diagram showing an emission spectrum of a P22 green phosphor used in a known color cathode ray tube and light transmittance characteristics of various green pigments.

FIG. 6 is a characteristic diagram showing a change state of the emission color and the reflection color when the composition of the green pigment constituting the green pigment layer is changed.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Panel part 1A Face plate 2 Neck part 3 Funnel part 4 Fluorescent film 5 Shadow mask 6 Internal magnetic shield 7 Deflection yoke 8 Purity adjustment magnet 9 Center beam static convergence adjustment magnet 10 Side beam static convergence adjustment magnet 11 Electron gun 12 Electron beam 13 Black matrix (BM) 14R Red pigment layer (red pigment filter layer) 14B Blue pigment layer (blue pigment filter layer) 14G Green pigment layer (green pigment filter layer) 15R Red phosphor layer 15B Blue phosphor layer 15G Green phosphor layer 16 Shadow mask used for exposure mask 17 Exposure light

Claims (3)

[Claims] 1. A fluorescent film having a structure in which a red pigment layer, a blue pigment layer, and a green pigment layer are applied to the inner surface of a face plate of a panel section, and a phosphor layer of the same color is applied on the pigment layer of each color. In the color cathode ray tube provided with:
It is characterized by comprising a green pigment having a composition mainly composed of an iO ₂ .NiO.CoO.ZnO-based oxide green pigment and a TiO ₂ .Cr ₂ O ₃ .CoO.Al ₂ O ₃ -based oxide green pigment. Color cathode ray tube. 2. The green pigment layer is made of TiO ₂ .NiO.
CoO / ZnO-based oxide green pigment and TiO ₂ · Cr ₂ O
Color cathode ray tube according to claim 1, characterized in _{that 3} · CoO · Al ₂ mixing ratio of O ₃ based oxide green pigment is within the range of 4: 1 to 1: 4. 3. The green pigment layer is made of TiO ₂ .NiO.
CoO / ZnO-based oxide green pigment and TiO ₂ · Cr ₂ O
The color cathode ray tube according to claim 1 or 2, characterized in _{that 3-mixing} ratio of CoO · Al ₂ O ₃ based oxide green pigment is within the range of 2: 1 to 1: 2.