JPH0133023B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for manufacturing a striped black matrix color picture tube, and more specifically to a striped black matrix film in which phosphor stripes do not cause a docking phenomenon. The present invention relates to a method of forming.

[Technical background of the invention and its problems]

A striped black matrix color picture tube has a fluorescent surface composed of a matrix of stripes of a non-coloring black material and phosphor stripes.

Generally, stripes of this non-coloring black material are formed by the following method. That is, first, a photosensitive resin liquid is thinly applied to the inner surface of the face plate of the picture tube and dried to form a resin film (Step A). Then, a point or linear light source is used to expose the desired phosphor coating position to light through a shadow mask (step B). The resin film at the desired phosphor coating position is photocured to become an insoluble photoresist layer, and other parts remain without being photocured. At this time, in order to generate a light trajectory during exposure that approximates the trajectory of the electron beam from an electron gun that is incorporated into the final product based on predetermined design specifications, the light source is placed at the center of deflection of the electron gun. A correction lens, usually made of glass or transparent plastic material, is interposed between the light source and the shadow mask.

Thereafter, the unexposed resin film is removed by hot water spray (Step C). At this time,
The inner surface of the panel face is exposed at the portion where the resin film has been removed.

In this state, a light-absorbing black material such as a graphite suspension is then applied over the entire surface and dried to form a non-coloring black material film (Step D). Next, a remover such as hydrogen peroxide is brought into contact with this area (E
process). At this time, the resin film photocured by the release agent swells and becomes brittle. After that, by applying hot water spray treatment, the brittle resin film and the non-coloring black material film laminated on it are removed, exposing this part of the panel face, and leaving the other parts as they are with the non-coloring black material film. Since the film remains, it becomes a striped black matrix. here,
The exposed panel face (striped) has
A phosphor is applied, and a prescribed exposure and development process is performed through a shadow mask to form phosphor stripes.

In the striped black matrix color picture tube manufactured in this way, the phosphor stripes (width) are adjusted to prevent the electron beam emitted from the electron gun from mislanding with respect to the phosphor stripes. It is necessary to make the slit hole narrower than the width of the slit hole in the shadow mask located in front of the electron gun to emit light.

To solve this problem, the first conventional measure is to create a fluorescent surface of a striped black matrix using a shadow mask with a narrow slit width in step B, and then adjust the shadow mask appropriately. This is a so-called post-etching method in which the slit width is made wider than the width of the phosphor stripe on the phosphor surface by etching with a suitable etchant, and the slit width is then incorporated.

However, with this method, the shape of the wall surface of the beam passage hole deteriorates due to side etching during etching of the shadow mask slit, the oxide film for heat dissipation that adheres to the surface of the shadow mask peels off, and after etching. The heat treatment causes disadvantages such as distortion of the shadow mask.

The second countermeasure is to reduce the area of the irradiation position when comparing a predetermined position of the photosensitive resin film with the O primary color light source in step B, so that the area (width) of the adjacent light-absorbing layer is widened. This is an optical method that exposes the image to the light.

However, due to the number of man-hours involved, this method usually involves continuous exposure with three primary color light sources and then development, which means that the light reaches the resin film in the position that should originally serve as the light absorption layer. The resin film is exposed to light and cured by a diffraction phenomenon, and as a result, the cured portions of the resin film are continuous, which has the disadvantage that a so-called docking phenomenon is likely to occur.

In order to eliminate this dotting phenomenon, recently,
A photosensitive resin film with reciprocity law failure is used, and in step B, the Schwart-Schult constant p is 0<p<
A method has been proposed in which a phosphor stripe with an area smaller than the actual light irradiation area is formed in the area where the phosphor is to be applied by exposing the area to light under the conditions of 0.76 (See No. 13913).

However, even with this method, it is still not possible to form striped black matrix-phosphor stripes with sufficient landing margin, and further improvements are currently desired.

[Purpose of the invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for forming a striped black matrix film that can prevent the docking phenomenon of phosphor stripes.

[Summary of the invention]

The method of the present invention includes the steps of forming a photosensitive resin film having reciprocity law failure characteristics on the inner surface of the face plate (first step); The light source position is shifted so that only a certain part of the resin film is irradiated with light, and the photocrosslinking agent in the resin film is exposed to photodecomposition without photocrosslinking the resin components in the resin film. a step (second step); a step (third step) of exposing a portion of the resin film at a desired position to be coated with phosphor so as to be photo-crosslinked;
step); and a development step (fourth step) of selectively removing the portion of the resin film located at the light absorption layer forming position.
(fifth step); applying a release agent; The present invention is characterized by comprising a step (sixth step) of selectively removing a portion of the resin film located at a desired position to be coated with the phosphor and the non-coloring black material thereon.

Each step will be explained in detail below.

First, the first step is to thinly apply a photosensitive resin having reciprocity failure characteristics to the inner surface of the face plate and dry it to form a resin film. The photosensitive resin used in the present invention includes polyvinyl alcohol,
4,4'-Diazidobenzalacetophenone-2- is added to commonly used resin components such as polyvinylpyrrolidone.
Sulfonic acid, 4,4'-diazidostilbene-2,
It contains a photocrosslinking agent such as a water-soluble bisazide compound such as 2'-disulfonic acid, 4,4'-diazidostilbene-α-carboxylic acid, and salts thereof. Such photosensitive resins can be used under a weak light intensity of 1.5 mW/cm ² or less in an oxygen atmosphere (enzyme concentration 70 to 100 vol%), a high temperature atmosphere (temperature 60 to 90°C), or a combination of both. When exposed to light, the photocrosslinking agent in the resin is photodecomposed, and the resin component has the property that it does not undergo photocrosslinking (photocuring).

The method of the present invention effectively utilizes the above-mentioned reciprocity law failure property, but in the case of the photosensitive resin used in the present invention, the weight ratio of the resin component to the resin component is 0.1 to 1.
It is preferable to use one containing 10% by weight of a photocrosslinking agent.

The resin film obtained in the first step is then transferred to the second step, where a treatment is performed to eliminate the photocrosslinkability of the portion of the resin film at the position where the desired striped black matrix is to be formed. will be carried out. That is, the position of the light source is shifted through a shadow mask, and only the resin film at the position where the light absorption layer of the black matrix is to be formed is continuously irradiated with light of a predetermined light intensity from the light source.

This step is carried out in an enzyme atmosphere or a high temperature atmosphere or a combination of both.
In the case of an enzyme atmosphere, the enzyme concentration is 70 to 100 vol%.
In the case of a high temperature atmosphere, it is preferable that
Preferably, the temperature is in the range of 60-90°C. If these conditions are not met, the exposed part of the resin film (the part where the light absorption layer should be formed)
is photocrosslinked (photocured) and the object of the present invention cannot be achieved.

In addition, the intensity of the irradiated light is 0.8 to 1.5 mW/cm ²
It is preferable that the light intensity is within the range of 0.8 m.
If the light intensity is less than 1.5 mW/cm ² , the photocrosslinking agent in the exposed portion of the resin film will photodecompose and it will take a long time for that portion to lose its photocrosslinking properties.
If it exceeds cm ² , the portion will be photo-crosslinked, making it difficult to achieve the object of the present invention.

Furthermore, in this step, it is necessary to displace the light source position in order to irradiate light only to the resin film portion at the position where the light absorption layer is to be formed. In other words, from the exposure position of the three primary color electron guns based on the predetermined design specifications, the P _H
L ₀ /6q (P _H : pitch in the width direction of the slit, L ₀ : distance between the light source and the surface of the resin film to be exposed, q: distance between the shadow mask and the resin film to be exposed, all units are the same) It is necessary to displace it by the calculated distance. Specifically, 1/2 of the slit width
Displace only. When exposed from this position, the light from each light source will be irradiated onto the light absorption layer forming position, and the light will be stronger at the center and weaker toward the periphery.

By being treated in the second step as described above, the photocrosslinking agent is photodecomposed in the portion of the resin film formed in the first step at the position where the light absorption layer is to be formed. The photocrosslinking agent disappears.

This is then transferred to the third step, where:
A portion of the resin film at a desired location to be coated with the phosphor is exposed to light at a predetermined intensity for photocrosslinking. In this case, the above-described atmospheric conditions or light source position conditions are canceled and exposure is performed. Specifically, the entire surface is exposed with the shadow mask removed, or the light source is returned to a predetermined position. In the case of full-surface exposure, the photocrosslinking agent in the resin film at the light absorption layer formation position has already been photodecomposed in the second step, so it is not photocrosslinked and the phosphor coating adjacent to each layer Only the portions of the resin film located at desired positions are photocrosslinked and rendered insolubilized.

The light intensity applied in this third step may be any intensity necessary to photo-crosslink the resin film at the desired location where the phosphor is applied, and is usually greater than 1.5 mW/cm ² .

The resin film that has been subjected to the two-step exposure process as described above is then developed in a fourth step by spraying, for example, hot water spray. The part of the resin film at the desired position for applying the phosphor is photo-crosslinked and insolubilized, so it remains as it is, and only the part of the resin film at the position where the light absorption layer is to be formed is selectively removed and the face plate is applied there. The surface is exposed.

The fifth step is a step of applying a suspension of the non-coloring black material over the entire surface thus obtained and drying it to form a film of the non-coloring black material. Here, the non-coloring black material is a material that does not develop color due to the electron beam emitted from the electron gun, and any known material can be used in the present invention. Specifically, graphite, manganese dioxide, etc. are used.

Next, the surface of the film obtained in the fifth step is brought into contact with an aqueous solution of a stripping agent consisting of a commonly used oxidizing agent such as hydrogen peroxide and sulfuric acid. In this sixth step,
The photo-crosslinked resin film (the resin film at the desired phosphor coating position) swells and becomes brittle due to the release agent. Here,
For example, by applying hot water spray treatment, the swollen and brittle resin film is selectively removed together with the non-coloring black material film formed thereon, and the face plate surface is exposed at that position. On the other hand, the non-coloring black material film applied to the face plate surface exposed in the fourth step is not removed in the sixth step. Therefore, a striped black matrix according to the present invention is formed here.

[Embodiments of the invention]

Example 1 A photosensitive resin liquid having the following composition was applied to the inner surface of the panel face of a 14-inch color picture tube to a thickness of 0.55μ,
After drying to form a film, the photosensitive resin film was exposed to light through a shadow mask with a slit width of 0.165 mm and a horizontal pitch P _H =0.6 mm in an air atmosphere at 80°C. The light source position is the distance L ₀ from the light source to the inner surface of the face plate (the surface of the resin film), and the distance from the shadow mask to the inner surface of the face plate q = 11.2 mm. [P _H・L ₀ /6q] than the exposure position of the surface, that is, the exposure position corresponding to the G, B, and R electron gun positions.
, respectively, and exposure was performed at each displaced position, so that only the position where a black stripe was to be formed was irradiated with light.

Composition of photosensitive resin Polyvinylpyrrolidone 4.7g 4,4'-diazidostilbene-2,2'-disulfonic acid disodium salt 0.47g Polyamine-based silane compound A-1106 (trade name, manufactured by Nippon Unicar Co., Ltd.) 0.35g Surfactant (nonion, manufactured by NOF Corporation) 0.075g Ethyl alcohol 1.1g Pure water 195.5g When performing exposure, the size of this exposure area is
Since the central part of the screen of the face plate is small, and it is necessary to make the peripheral part large, a light intensity correction filter was used for exposure. Specifically,
The light intensity at the center is 1.1mW/cm ³ and the light intensity at the periphery is
Exposure was carried out for about 6 seconds at a power of 1.3 mW/cm ² and a shadow mask size of 0.165 mm at the center and 0.155 mm at the periphery.

After exposure, the panel temperature was lowered to 35° C., the shadow mask was removed, and the entire inner surface of the panel was exposed to light for about 2 seconds at a light intensity of 2.1 mV/cm ² . After hot water development, a graphite suspension was applied to the entire inner surface of the panel and dried to form a graphite film. The sample was then immersed in a 15% aqueous sulfamic acid solution for about 60 seconds, and then treated with hot water spray. A good black matrix was formed with a stripe width of 0.14 mm at the center of the screen and a stripe width of 0.09 mm at the periphery.

Example 2 Exposure was performed in an atmosphere with an oxygen concentration of 80%, and after lowering the panel temperature to 35°C, the shadow mask was returned to the normal exposure position without removing it, and the light intensity was 2.0 mW/cm ² from that position. A black stripe was formed in the same manner as in Example 1, except that the R, G, and B phosphor positions were exposed for about 3 seconds. Similar results were obtained.

〔Effect of the invention〕

As is clear from the above description, the method of the present invention prevents the dotting phenomenon of phosphor stripes and forms a phosphor screen with a high degree of landing margin for electron beams, so its industrial value is extremely large.

Claims (1)

[Claims] 1. A step of forming a film of a photosensitive resin having reciprocity law failure characteristics on the inner surface of the face plate; Displacing the light source position so that only a portion of the film is irradiated with light, and exposing the resin film so as to photodecompose the photocrosslinking agent in the resin film without photocrosslinking the resin components in the resin film; a step of exposing to light so that a portion of the resin film located at a desired position to be coated with a phosphor is photocrosslinked; a developing step of selectively removing a portion of the resin film located at a position where the light absorption layer is to be formed; forming a film of a non-coloring black material over the entire surface of the resin film at the light absorption layer formation position and the desired position for applying the phosphor; applying a release agent and applying the phosphor; A method for manufacturing a striped black matrix color picture tube, comprising the step of selectively removing a portion of the resin film at a desired position and the non-coloring black material thereon.