JPH10273653A - Composition for forming fluorescent film and formation of fluorescent film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of suppressing fogging phenomena of a fluorescent film, by adding a quaternary ammonium group- containing compound to a fluorescent film-forming composition dispersing at least a fluorescent substance into a dispersion medium. SOLUTION: This composition is obtained by dispersing a fluorescent substance and a quaternary ammonium group-containing compound (especially preferably a quaternary ammonium group-containing metal alkoxide) into a dispersion medium. Preferably, the composition is compounded with a photocurable resin. A slurry for a fluorescent substance coating as the composition is applied to the inside of a face plate which is a fluorescent substance forming substrate and a fluorescent film can be formed through an exposure and a developing processes known as an optical printing method. When fluorescent films of various displays are formed from the composition, fogging occurrence can be suppressed, packing degree of the fluorescent substance in the fluorescent film can be raised and a fluorescent film having high brightness and improved color purity can be formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cathode ray tube (PD) having a fluorescent film which emits light by being excited by an electron beam, ultraviolet light or the like.
The present invention relates to a composition for forming a fluorescent film used for producing various displays such as P, FED, and fluorescent display tube, and a method for forming the fluorescent film. In particular, optical printing, screen printing,
When forming a fluorescent film for a display by applying it by an electrodeposition coating method, etc., the phosphor filling degree of the fluorescent film is improved to achieve high brightness and to provide an image with good color purity, contrast, etc. What you want to do.

[0002]

2. Description of the Related Art In forming a phosphor screen in the manufacture of various displays, for example, a color cathode ray tube (hereinafter, simply referred to as "CRT"), a face plate (usually a glass panel) is previously formed in order to improve the contrast. A black matrix (BM) layer made of a black non-luminous substance is provided on the inner surface, and a pre-coat film made of polyvinyl alcohol (hereinafter, referred to as “PVA”) is formed thereon so that the face plate and the phosphor slurry can be well blended. To do.

[0003] Then, on a pre-coat film, an aqueous dispersion medium containing PVA, dichromate and a surfactant is mixed with G
(Green), B (blue), and R (red) are prepared by preparing phosphor coating slurries of three colors in which phosphors emitting light of respective colors are dispersed, and sequentially applying the slurries for each color. )so,
The fluorescent film is formed by applying the coating to a dot having a predetermined diameter or a stripe having a predetermined width.

After the formation of the three color phosphor films, a slurry made of an acrylic emulsion or the like is applied to form a filming film in order to impart smoothness to the surface of the phosphor film, and then aluminum is deposited thereon. A display tube is obtained by forming a reflective film (hereinafter, metal back layer). After that, a cathode ray tube is completed by disposing an electron gun and the like.

When the fluorescent film is formed as described above, there is a problem that a fogging phenomenon occurs and the color purity and contrast of the fluorescent screen of the display tube are deteriorated. The fogging phenomenon refers to a phenomenon classified as follows.

1) BM fog: A phenomenon in which, when a pre-coat film, a BM and a fluorescent film are sequentially formed, a phosphor for forming a fluorescent film remains on and adheres to the BM, thereby deteriorating the contrast of an image. 2) Fogging on the glass surface: Since another fluorescent film is formed on the pre-coated film formed at a place where a specific fluorescent film is to be formed, the previously applied phosphor remains and adheres. Phenomenon that deteriorates the color purity of the fluorescent film. 3) Other color surface fog: The phosphor applied later remains and adheres on the phosphor film formed by applying the phosphor first,
A phenomenon that deteriorates the color purity of the previously formed fluorescent film.

[0007] Further, when a fluorescent film for a PDP is formed (see Japanese Patent Application Laid-Open No. 8-203439), and in some cases, a fluorescent film for a cathode ray tube is formed (see Japanese Patent Publication No. 61-23231). An ink composition for forming a fluorescent film, in which a phosphor is kneaded in a dispersion medium composed of an organic resin such as an acrylic resin or a cellulose resin, is directly printed on a substrate such as glass by a printing method such as a screen printing method or an offset printing method. A method of applying a desired pattern and drying it to obtain a fluorescent film has been carried out. It was difficult to obtain a fluorescent film completely free of fogging. Therefore, it is desired to obtain a phosphor film which has less fog than the conventional method, has excellent color purity and contrast, and maintains the luminance of the phosphor film without lowering the degree of filling of the phosphor in the phosphor film. I was

Conventionally, there has been proposed an improvement in a method for forming a fluorescent film for a display. For example, when a fluorescent film is formed on a cathode ray tube, a contact with the fluorescent material is made on the phosphor surface or a precoat layer in order to suppress the fogging phenomenon. Of a positively charged substance and a negatively charged substance adhered or mixed (Japanese Patent Publication No.
JP-A-3-66876) to prevent the phosphor film from being missing,
An example in which a resin having a specific degree of polymerization is used in a precoat layer in order to obtain a fluorescent film having a small decrease in luminance and a good phosphor packing density (see Japanese Patent Application Laid-Open No. 62-193034), unevenness of the fluorescent film of a cathode ray tube A method of adding a resin having a specific film-forming temperature to a phosphor coating slurry in order to eliminate color mixing and color (see Japanese Patent Publication No. 1-5737),
In water emulsion, the minimum constant film forming temperature is higher than this,
A method for preventing peeling of a metal back formed on a fluorescent film after the fluorescent film is formed by using a filming emulsion to which an organic substance / water emulsion incompatible with an acrylic / water emulsion is added (Japanese Patent Application Laid-Open No. Hei 2 (1994)). -215
840) have been proposed, but they have not been able to simultaneously achieve the intended purpose.

[0009]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and a composition for forming a fluorescent film capable of suppressing the fogging phenomenon of the fluorescent film without lowering the filling degree of the fluorescent material in the fluorescent film. An object and a method for forming a fluorescent film are provided.

[0010]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies mainly on additives to be added to the composition for forming a fluorescent film. By adding a compound containing a quaternary ammonium group to the fluorescent film forming composition dispersed in a medium, the affinity between the fluorescent film, the precoat film, and the filming film can be adjusted. By forming the film, the fogging phenomenon was suppressed, and the filling degree of the phosphor in the phosphor film was successfully maintained.

These additives are added to a coating slurry for forming a pre-coat layer and a coating slurry for forming a filming film, which are applied on and under the fluorescent film when forming the fluorescent film on the substrate. The above effects can be further enhanced.

The configuration of the present invention is as follows. (1) A composition for forming a fluorescent film, comprising a phosphor and a compound containing a quaternary ammonium group mixed in a dispersion medium.

(2) The compound having a quaternary ammonium group is a metal alkoxide.
The composition for forming a fluorescent film according to the above.

(3) The compound for forming a fluorescent film as described in (1) above, wherein the compound containing a quaternary ammonium group is polydiaryl containing a quaternary ammonium group or polyvinyl alcohol containing a quaternary ammonium group. Composition.

(4) The composition for forming a fluorescent film as described in any one of (1) to (3) above, wherein a photocurable resin is blended in the dispersion medium.

(5) A phosphor characterized in that the phosphor of the composition for forming a phosphor film according to any one of the above (1) to (4) is applied to the surface of a substrate to form a phosphor film. Method of forming a film.

(6) The substrate is a CRT face plate, a slurry for forming a pre-coat layer is applied on the face plate to form a pre-coat layer, and the fluorescent film is formed on the pre-coat layer. And above
(6) The method for forming a fluorescent film according to the above.

(7) The method for forming a fluorescent film according to the above (6), wherein a compound containing a quaternary ammonium group is added to the slurry for forming a precoat layer.

(8) The fluorescent film as described in any one of (5) to (7) above, wherein a filming film forming slurry is applied on the fluorescent film to provide a filming film. Method of forming a film.

(9) The method for forming a fluorescent film according to the above (8), wherein a compound containing a quaternary ammonium group is added to the slurry for forming a filming film.

(10) The substrate is a cathode-ray tube face plate, and a slurry for forming a pre-coat layer is applied on the face plate to form a first pre-coat layer.
A phosphor film having a first emission color is formed on the pre-coat layer, a slurry for forming a pre-coat layer is applied thereon again to form a second pre-coat layer, and a second pre-coat layer is formed on the second pre-coat layer. A method for forming a fluorescent film having a luminescent color, wherein a compound containing a quaternary ammonium group is added to each precoat layer forming slurry.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. Phosphor applied in the present invention, for example,
ZnS, a phosphor for CRT which emits light when excited by an electron beam:
Blue phosphor such as Ag, Al, ZnS: Ag, Cl, ZnS: Zn, red phosphor such as Y ₂ O ₃ : Eu, Y ₂ O ₂ S: Eu, ZnS: Cu, Al, ZnS: Cu, Au , A
l, etc., known phosphors for cathode rays, phosphors for plasma display tubes (PDP) that emit light by excitation with vacuum ultraviolet rays, and phosphors for lamps that emit light with ultraviolet rays (Ba, Eu) MgAl ₁₀ O ₁₇ , (Zn, M
The present invention can be applied to any phosphor without particular limitation, including n) SiO ₄ , (Y, Gd, Eu) BO ₃ phosphor.

The compound containing a quaternary ammonium group to be added to the composition for forming a fluorescent film of the present invention includes polyvinyl alcohol having a quaternary ammonium group and poly (di) having a quaternary ammonium group. Aryl, fourth
Metal alkoxides having a quaternary ammonium group, such as Si, Ti, and Zr, can be used.

Among these, particularly, when a metal alkoxide containing a quaternary ammonium group, particularly a Si alkoxide, is added to a phosphor suspension coating slurry for forming a fluorescent film of a CRT, fog characteristics are particularly improved. Thus, a fluorescent film can be manufactured with a high yield in an industrial manufacturing process, and a display tube with high color purity, high contrast, and high luminance can be stably manufactured. When forming a CRT fluorescent film, by adding these metal alkoxides not only in the above-mentioned fluorescent film but also in the pre-coat layer and / or the filming film, the fluorescent film and the filming film can be formed. This is preferable because the loss can be prevented and the yield of the fluorescent film (cathode ray tube) can be further improved.

The reason is that, unlike other compounds, the fourth compound
The metal alkoxide containing a quaternary ammonium group is hydrolyzed to form a fine sol, which is stably and uniformly present in the fluorescent film, partially adsorbed on the phosphor surface in the fluorescent film, and / or
This is considered to be due to the presence in the precoat layer and the filming film.

As the metal alkoxide containing a quaternary ammonium group of the present invention, those represented by the following structural formula can be used. In the formula, R ₁ represents an alkyl group having 1 to 24 carbon atoms, R _{2 to} R ₄ represent an alkyl group having 1 to 4 carbon atoms, and M represents a group of Si, Ti and Zr. Represents a selected element, and n represents an integer in the range of 1 to 8.
Among M, Si is particularly preferable since a fluorescent film with less fogging can be obtained.

[0027]

Embedded image

The metal of the present invention containing a quaternary ammonium group
Alkoxides are available on the fluorescent film surface according to the molecular weight of the N atom side chain.
Since the hydrophilicity / hydrophobicity of the surface can be controlled,
Sometimes the molecular weight can be appropriately selected. Also,
Silicon source of alkoxide of silicon containing quaternary ammonium group
The alkoxyl group bonded to the child (Si) is hydrolyzed
To stabilize the characteristics,_Three, ー OC_TwoH_Five,
-OC_ThreeH₈, ー OC _FourH₉Is particularly preferred.

The amount of the compound containing a quaternary ammonium group is preferably added in the range of 10 to 10000 ppm of the composition for forming a fluorescent film to adjust the conformity of the film surfaces that come into contact with each other. Preferably, 100 to 3000 ppm, more preferably 300 to 800 ppm is added.

If the amount of the compound containing a quaternary ammonium group added to the composition for forming a fluorescent film is less than 10 ppm, the effect of preventing fog during formation of the fluorescent film cannot be obtained.
When the addition amount exceeds 10000 ppm, the effect of preventing fogging is sufficiently obtained, but the adhesion of the phosphor film to the substrate or the precoat layer is rather deteriorated, the phosphor film is peeled off, and the degree of filling of the phosphor in the phosphor film is sufficient. It is not preferable because it cannot be obtained.

In preparing the composition for forming a fluorescent film,
There is no particular limitation on the order of addition of the constituent materials, and the composition for forming a fluorescent film before the final
It is sufficient that a compound containing a quaternary ammonium group is contained, and the order of addition does not significantly affect the effect of improving the characteristics of the formed fluorescent film. The reason that the film characteristics are improved by using the composition for forming a fluorescent film of the present invention is that a suitable amount of a compound containing a quaternary ammonium group is contained in the fluorescent film, and the It is considered that the surface charges have the same polarity.

Next, the composition for forming a fluorescent film and the method of forming the fluorescent film of the present invention will be described by taking the formation of a fluorescent film of a CRT by an optical printing method as an example. First, a phosphor is poured into an aqueous dispersion medium to prepare a phosphor slurry. Next, the compound containing a quaternary ammonium group is added thereto, and the mixture is sufficiently stirred. PVA, ammonium bichromate (hereinafter referred to as “ADC”) and various nonionic surfactants (N-
SAA) and an anionic surfactant (A-SAA) are further added and sufficiently stirred to prepare a phosphor coating slurry, which is a composition for forming a fluorescent film of the present invention. This is applied to the inner surface of the face plate, which is the fluorescent film forming substrate, by slurry, and the fluorescent film of the present invention is formed through exposure and development steps known as optical printing.

In the case of the CRT, an aqueous solution containing PVA having the same degree of polymerization and saponification as the slurry for forming the fluorescent film is formed on the inner surface of the face plate on which the fluorescent film is formed or on the previously formed fluorescent film. The slurry for forming a pre-coat layer is usually applied to a thickness of about 0.1 to 1.0 μm to form a pre-coat layer, thereby improving the adhesion to the fluorescent film. Also, after forming a three-color fluorescent film on the inner surface of the face plate, a filming film forming slurry composed of an acrylic emulsion, a polystyrene emulsion, silica, or the like is applied to form a filming film, and then aluminum is evaporated. A reflection film (metal back layer) is formed. At this time, the compound containing a quaternary ammonium group is added to the slurry for forming a precoat layer or the slurry for forming a filming film, and the compound containing a quaternary ammonium group is contained in the precoat layer or the filming film. Incorporation further enhances the effect of preventing fogging during the formation of the fluorescent film.

In forming a fluorescent film for a flat panel display such as PDP and FED, a phosphor is kneaded with an organic resin and an organic solvent as a dispersion medium to prepare a paste-like composition for forming a fluorescent film. Then, this composition is printed and applied on a substrate such as glass in a specific pattern by screen printing or offset printing to form a fluorescent film. 4
By adding and kneading a compound containing a quaternary ammonium group, the above fogging can be prevented, the degree of filling of the phosphor in the phosphor film can be increased, and a dense phosphor film can be obtained.

[0035]

【Example】

(Example 1) G (green), B (blue), R (red) for CRT
A phosphor film made of a phosphor emitting light of each color was formed on the inner surface of the face plate of the CRT glass panel by the following method.

(Step of Forming Pre-Coated Film) First, 0.1% PV was applied to the inner surface of the face plate fixed to the spin coating machine.
A (Nippon Gosei Co., Ltd., EG-30) aqueous solution was poured and rotated at a predetermined number of revolutions to spread the film, and then dried with hot air so that the temperature of the panel became 45 ° C. and about 0.1%.
A precoat layer having a thickness of μm was formed on the inner surface of the panel.

(Formation of Fluorescent Film) Next, G and G were added to a water slurry in which PVA, dichromate and a surfactant were mixed.
Each of the phosphors B and R was separately added, and three types (3
After preparing a slurry for forming the fluorescent film of (color), the slurry is sequentially applied to the inner surface of the face plate on which the PVA precoat film is formed for each color, and is formed into a dot having a predetermined diameter by a conventionally known optical printing method (exposure and development). Was formed. The manufacturing method of the fluorescent film of each color is as follows.

(1) Formation of Green Phosphor Film A green phosphor (ZnS: Cu, A) having an average particle size of 7.5 μm.
l) 100 g was put into 125 g of pure water and stirred to form a slurry. Then, dimethyloctadecyl-3-trimethoxysilylpropylammonium chloride (XS70-241 manufactured by Toshiba Silicone Co., Ltd.), which is a silicon alkoxide containing a quaternary ammonium group, is hydrolyzed in pure water in advance, and 500 per phosphor
ppm was added and stirred.

Further, PVA, a nonionic surfactant (N-SAA) and an anionic surfactant (A-SAA) were added at the following slurry composition ratio, and a green phosphor film forming slurry was prepared. After the preparation, the pH of the slurry was adjusted to 7.5 and stirred for 1 hour.

(Slurry composition) PVA (EG-30, manufactured by Nippon Gosei Co., Ltd.) 7.5 wt% ADC (ammonium dichromate dihydrate) 0.5 wt% Nonionic surfactant (N-SAA) (No. Tween 20 (HLB17), manufactured by Ichi Kogyo Co., Ltd.) 0.25 wt% Anionic surfactant (A-SAA) (Tamol 731, manufactured by Rohm and Haas Co.) 0.10 wt%

Next, a slurry for forming a green phosphor film is injected into the inner surface of the face plate portion of the panel on which the precoat layer is formed, and the slurry is spread at a predetermined number of rotations. The resultant was dried with hot air to form a phosphor film made of a green light-emitting phosphor having a thickness of about 15 μm. After that, ultraviolet light is irradiated through a shadow mask having a pitch of 0.29 mmΦ, and after exposure, the phosphor film surface is washed with water by a shower method to dissolve and remove the unexposed portion of the phosphor film. Was formed on the face plate.

(2) Formation of Blue Phosphor Film Next, a blue phosphor for cathode ray tube (Z
100 g of (nS: Ag, Cl) was put into 125 g of pure water and stirred to form a slurry. Then, dimethyloctadecyl-3-trimethoxysilylpropylammonium chloride (manufactured by Toshiba Silicone Co., Ltd .: XS70-241), which is a silicon alkoxide containing a quaternary ammonium group, is hydrolyzed in pure water, and the above slurry is subjected to fluorescence. 750 ppm per body was added and mixed well to prepare a phosphor film forming slurry of a blue light-emitting phosphor, and thereafter, in the same manner as in the case of forming the above-described green phosphor film, a cathode ray tube having a green phosphor film already formed was formed. About 15μ on the face plate
A dot-shaped blue fluorescent film having a thickness of 5 mm was formed.

(3) Formation of Red Phosphor Film Further, 100 g of a red phosphor (Y ₂ O ₂ S: Eu) for a cathode ray tube having an average particle size of 7.5 μm was put into 125 g of pure water and stirred to form a slurry. . Then, dimethyloctadecyl-3-trimethoxysilylpropylammonium chloride (manufactured by Toshiba Silicone Co., Ltd .: XS70-241), which is a silicon alkoxide containing a quaternary ammonium group, is hydrolyzed in pure water, and the above slurry is subjected to fluorescence. 750 ppm per body was added and mixed well to prepare a phosphor film forming slurry of a red light-emitting phosphor, and thereafter, a green phosphor film and a blue phosphor film were formed in the same manner as in the case of forming the above-described green phosphor film. A dot-shaped red fluorescent film having a thickness of about 15 μ was formed on the face plate of the CRT.

(Step of Forming Filming Film and Metal Back) Then, a 13 wt% aqueous solution of an acrylic emulsion (Nippon Acrylic Co., Ltd., Primal B-74) is applied on the green, blue and red dot-shaped fluorescent films. After injection and rotation at a predetermined number of rotations to spread the film, the panel was dried with hot air so that the temperature of the panel became 45 ° C., thereby forming a filming film having a thickness of about 1 μm. Thereafter, aluminum was deposited to form a reflective film (metal back). Regarding the phosphor film created in this way, "clogging" of the phosphor film,
"Fog of fluorescent film" and "luminance" were measured, and the results are shown in Table 1.

(Example 2) In Example 1, the fourth component added to the green, blue and red fluorescent film forming slurries was used.
As the compound containing a quaternary ammonium salt,
Dimethyldecyl-3-trimethoxysilylpropylammonium chloride (XS-1028, manufactured by Chisso Corporation) was previously added to pure water in place of silicon alkoxide containing a tertiary ammonium group (XS70-241, manufactured by Toshiba Silicone Co., Ltd.). Except for decomposing and adding this, green, blue, and red fluorescent films were formed on the face plate of a cathode ray tube in the same manner as in Example 1 except that the phosphor films were added. Then, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

(Example 3) In Example 1, 0.1% of the precoated film was formed on the inner surface of the face plate.
Dimethyloctadecyl-3-trimethoxysilylpropylammonium chloride (Toshiba Silicone), which is the silicon alkoxide containing a quaternary ammonium group used in Example 1, in an aqueous solution of% PVA (EG-30, manufactured by Nippon Gosei Co., Ltd.) XS70-241) was previously hydrolyzed in pure water, and 750 ppm per phosphor was added and mixed to prepare a slurry for forming a precoat layer, and the slurry was applied to the inner surface of the face plate. In the same manner as in Example 1, green, blue and red fluorescent films were formed on the inner surface of the face plate. Then, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

Example 4 In Example 1, as a slurry for forming a filming film, a silicon alkoxide containing a quaternary ammonium group was used in a 13% aqueous solution of an acrylic emulsion (Nippon Acrylic Co., Ltd., Primal B-74). Certain dimethyloctadecyl-3-trimethoxysilylpropylammonium chloride (manufactured by Toshiba Silicone:
XS70-241) was previously hydrolyzed in pure water, and 750 ppm per phosphor was added and mixed to prepare a slurry for forming a filming film. Except that this coating solution was used, all were the same as in Example 1. Thus, phosphor films of three colors of green, blue and red were formed on the inner surface of the face plate. And
Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

Example 5 In Example 1, a silicon alkoxide containing a quaternary ammonium salt (XS70-241 manufactured by Toshiba Silicone Co., Ltd.) was added to the green, blue and red fluorescent film forming slurries for forming the fluorescent film. )Instead of,
Ammonium polydiaryl quaternary (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Sharol-902P) was previously dissolved in pure water, and this was dissolved in 50 parts per green, blue and red phosphors.
Except for adding 0 ppm, 750 ppm and 250 ppm, phosphor films of three colors of green, blue and red were formed on the inner face of the face plate in the same manner as in Example 1. Then, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example) In Example 1, except that the addition of the silicon alkoxide containing a quaternary ammonium salt was omitted in the slurry for forming the phosphor films of the green, blue and red light emitting phosphors. In the same manner as in Example 1, green, blue and red fluorescent films were formed on the inner surface of the face plate. Then, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

(Example 6) In Example 1, 0.1% of the precoat layer was formed on the inner surface of the face plate.
% PVA (manufactured by Nippon Gosei Co., Ltd .; EG-30) in an aqueous solution, dimethyl-3-trimethoxysilylpropylammonium chloride (manufactured by Chisso: XS-1028) which is a silicon alkoxide containing a quaternary ammonium group.
Was preliminarily hydrolyzed in pure water, added and mixed to prepare a precoat layer forming slurry, which was applied to the inner surface of the face plate to form a precoat layer.

Next, three kinds of slurries for forming a fluorescent film having respective emission colors of green, blue and red (the addition of the silicon alkoxide containing a quaternary ammonium salt was omitted) used in the comparative example were prepared. did. First, a slurry for forming a green phosphor film was applied to the inner surface of the face plate on which the above-mentioned pre-coat layer was formed to form a phosphor film made of a green light-emitting phosphor.

Thereafter, the slurry for forming a pre-coat layer is applied, a pre-coat layer is formed on the green light-emitting fluorescent film, and the slurry for forming a blue fluorescent film is further applied thereon to form a blue light-emitting phosphor. Was formed.
Then, a phosphor film composed of a precoat layer and a red light-emitting phosphor was similarly formed thereon to complete a three-color phosphor film.
The phosphor film thus prepared was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Example 7) In Example 1, except that the addition of a silicon alkoxide containing a quaternary ammonium salt was omitted only in the slurry for forming a blue fluorescent film in the slurry for forming a fluorescent film. Similarly, fluorescent films of three colors of green, blue and red were formed on the inner surface of the face plate. Example 1 of the phosphor film thus formed was used.
Table 1 shows the results.

The evaluation of "clogging", "fogging of the fluorescent film", and "emission luminance" of the fluorescent films of Examples 1 to 7 and Comparative Example was carried out by the following methods. (Clogging of fluorescent film) 3 formed on face plate
This is a measure of the degree of filling of the phosphor in the color phosphor film, and the formed phosphor film is irradiated with light from a light source, and the transmitted light is projected on a white screen. It was visually observed and evaluated in the following three stages.

A: The density of the projected image is high, and the degree of filling of the phosphor is extremely good as compared with the phosphor film obtained by the conventional method. Δ: The density of the projected image was not so high, the degree of filling of the phosphor was not particularly good, and was comparable to that of the phosphor film obtained by the conventional method. X: A phosphor film having a lower degree of filling of a phosphor than a phosphor film obtained by a conventional method.

(Fogging of Fluorescent Film) When a fluorescent film is formed, a pre-coated film formed on a face plate and green, blue, and red light-emitting fluorescent films are sequentially formed thereon. The number of undesired phosphors adhered on the sample was observed with a stereoscopic microscope. The larger the number, the more fog was evaluated. The higher the fog, the worse the color purity of the light emitted from the fluorescent film.

In the table, in the evaluation of fogging, the glass surface fogging refers to the fogging of the green phosphor (G) at the time of forming the green light-emitting fluorescent film formed first on the pre-coated film after the formation of the pre-coated film. B / G refers to the fog of the blue phosphor (B) on the surface of the green light-emitting fluorescent film formed first when the next blue light-emitting fluorescent film is formed. R / G refers to the fog of the red phosphor (R) on the surface of the green light emitting fluorescent film when the red light emitting fluorescent film is formed. R / B refers to the fog of the red phosphor (R) on the blue light emitting phosphor film surface when the red light emitting phosphor film to be formed later is formed.

The evaluation criteria are as follows. ：: the number of undesired phosphor particles was much smaller than that of a phosphor film obtained by a conventional method. ：: The number of undesired phosphor particles was slightly less fogged than in the case of a phosphor film obtained by a conventional method. Δ: The number of undesired phosphor particles was not much different from that of the phosphor film obtained by the conventional method. X: The number of non-predetermined phosphor particles was not much different from that of the conventional phosphor or was larger.

(Brightness of Phosphor Film Surface)
After forming a metal back layer on the phosphor layer
Cut the faceplate after king into rectangular pieces of about 30mm square
And the vacuum is 10 ^-6Stand in the Torr chamber
Irradiate an electron beam with an accelerating voltage of 12 kV,
Each fluorescent film when the light film is simultaneously illuminated and whitened
These transmitted lights were measured using a luminance meter, and the fluorescent film of the comparative example was measured.
The emission luminance was expressed as a relative value with 100 being assumed.

[0060]

[Table 1]

[0061]

According to the present invention, by adopting the above structure, when forming fluorescent films of various displays,
The occurrence of fog can be suppressed, the degree of filling of the phosphor in the phosphor film is increased, and the formation of a phosphor film with high luminance and good color purity is enabled.

Claims (9)

[Claims] 1. A composition for forming a fluorescent film, comprising a phosphor and a compound containing a quaternary ammonium group mixed in a dispersion medium. 2. The composition according to claim 1, wherein the compound containing a quaternary ammonium group is a metal alkoxide. 3. The composition for forming a fluorescent film according to claim 1, wherein a photocurable resin is blended in the dispersion medium. 4. A method for forming a fluorescent film, comprising applying the composition for forming a fluorescent film according to claim 1 to a surface of a substrate to form a fluorescent film. 5. The method according to claim 1, wherein the substrate is a CRT face plate, a slurry for forming a pre-coat layer is applied on the face plate to form a pre-coat layer, and the fluorescent film is formed on the pre-coat layer. The method of forming a fluorescent film according to claim 4. 6. A pre-coating layer forming slurry,
The method for forming a fluorescent film according to claim 5, wherein a compound containing a quaternary ammonium group is blended. 7. The method for forming a fluorescent film according to claim 5, wherein a filming film is formed by applying a filming film forming slurry on the fluorescent film. 8. The method for forming a fluorescent film according to claim 7, wherein a compound containing a quaternary ammonium group is added to the filming film forming slurry. 9. The method according to claim 1, wherein the substrate is a face plate of a cathode ray tube, a slurry for forming a pre-coat layer is applied on the face plate to provide a first pre-coat layer, and a first emission color is formed on the first pre-coat layer. A method for forming a phosphor film having a second emission color on a second pre-coat layer by applying a slurry for forming a pre-coat layer again thereon and forming a second pre-coat layer on the second pre-coat layer 3. The method for forming a fluorescent film according to claim 1, wherein a compound containing a quaternary ammonium group is added to each precoat layer forming slurry.