JPH09330661A - Forming method of graphite film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a forming method of a graphite film which prevents resticking of the graphite film once separated from a glass panel. SOLUTION: In the first spray developing, first, pure water is sprayed for only about 12sec. to a glass panel 2 from a nozzle 5. Thereafter, by sequence control, a pump 22 is operated, a surfactant solution is sprayed to flow in the glass panel 2 as a rinse liquid from a nozzle 21 by about 500cc for about 5sec. Further, the glass panel 2 is moved to a position of the next spray developing by a carrier 1, again similar spray developing is performed. In this way, on a graphite film in an internal surface of the glass panel 2 and a fine piece of the separated graphite film, a surfactant is respectively applied to act, between the glass panel 2 and the graphite film formed in its surface and the fine piece separated therefrom, electrical repulsion force is accelerated, the fine piece of the graphite film can be prevented from resticking.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a graphite film forming method for forming a mosaic graphite film on a glass panel used for a cathode ray tube or the like.

[0002]

2. Description of the Related Art On a glass panel such as a cathode ray tube, a black matrix made of a graphite film having a mosaic shape is formed in order to enhance the contrast of an image. Traditional,
Each step of forming the graphite film will be described.

The inside surface of the glass panel (image side) of the cathode ray tube is washed, coated with photoresist, dried, and then exposed to a predetermined pattern and developed to form a mosaic pattern of the photoresist. On the inner surface of the glass panel where the mosaic pattern of photoresist is formed,
A graphite solution, which is a light absorbing substance, is applied. Then, after the graphite film is dried, it is treated with an etching solution containing an oxidizing agent such as hydrogen peroxide solution, and further spray development is performed in which the cleaning solution is strongly sprayed in a shower shape. By this spray development, the graphite film coated on the photoresist is removed together with the photoresist, and a mosaic-shaped light absorption pattern of the graphite film is completed on the inner surface of the glass panel through a series of subsequent steps.

4 to 6 are cross-sectional views showing respective devices for forming a mosaic graphite film (black matrix) on a glass panel, and a series of steps will be described in more detail with reference to these drawings. .

In the spray developing device shown in FIG.
Is a glass panel rotatably held by a carrier 1, and a plurality of nozzles 5 connected to a pure water tank 3 via a pump 4 are arranged at positions facing the inner surface of the glass panel 2. . A mosaic pattern of a resist film and a graphite film are sequentially formed on the inner surface of the glass panel 2, and the photoresist is treated with an etching solution that acts on the resist film, and then strong spray development described below is performed.

In this developing process, while the glass panel 2 is held by the carrier 1, the pure water 6 supplied by the pump 4 is sprayed from its numerous nozzles 5 on its inner surface at a pressure of 5-6 kg / m ^2. To be done. The mosaic-shaped resist film loses its adhesive force to the glass surface due to the etching treatment with hydrogen peroxide solution, and the graphite film applied on the resist film by spraying pure water 6 together with the resist film is a glass panel. Knocked off from 2. As a result, the graphite film remains on the glass panel 2 in a mosaic pattern.

Next, the skirt region 2a on the inner surface of the glass panel 2 is shaped (trimmed). In this trimming step, the extra graphite film applied and formed on the skirt region 2a is removed.

Here, the trimming device shown in FIG. 5 is used. The trimming device is configured by integrally attaching a cam 8 and a nozzle 9 to the tip of the trimming arm 7, and the nozzle 9 moves together with the trimming arm 7 at a certain depth from the sealing surface of the skirt region 2a of the glass panel 2. . The cam 8 identifies an unnecessary graphite film region formed in the skirt region 2a, and is further ejected from the nozzle 9, for example, ammonium acid fluoride (NH ₄ HF ₂ ).
The glass surface is etched with the aqueous solution 10 of. Thus, the extra graphite film is removed from the skirt region 2a on the inner surface of the glass panel 2.

Finally, using the cleaning device shown in FIG.
The final cleaning of the inner surface and the outer surface of the glass panel 2 is performed by pouring the pure water 12 from the nozzle 11. The glass panel 2 that has been washed is sent to the final inspection step through the steps of high-speed shaking and drying. The above series of process schedules is generally executed by the sequence control of each automatic manufacturing apparatus.

The spray development shown in FIG. 4 is performed at two positions of about 30 seconds, and the trimming shown in FIG. 5 is 40-50.
4 positions in seconds (this time depends on the size of the glass panel), and the final wash shown in FIG.
It is processed in one position for 10 to 15 seconds.

[0011]

In the conventional method for forming a graphite film, a plurality of black dots are likely to occur in the light emitting region of the phosphor (formation region of the phosphor mosaic) on the inner surface of the glass panel 2, and the phosphor screen As a defect, there is a problem that the yield of the manufacturing process and the quality of the product are deteriorated. As shown in the partially enlarged view of the glass panel 2 in FIG. 7, the black dots are
On the inner surface of the glass panel 2, the graphite film particles 16 peeled off by spray development adhere to the area other than the graphite film area 13 which is the original black matrix.
The fine particles 16 remain as black dots 15 in the phosphor light emitting region 14 of the glass panel 2.

The above-mentioned problem is conventionally referred to as "scattering" caused by a defect in the spraying method in the developing process. Conventionally, it will be dealt with by changing the arrangement or angle of the developing nozzles, or the number of nozzles. I was trying. However, it was not possible to reliably prevent the reattachment of the graphite film particles 16 of "slag fly" only by such a treatment.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for forming a graphite film in which reattachment of graphite pieces once peeled from a glass panel is prevented. .

[0014]

In the method for forming a graphite film according to claim 1 of the present invention, a mosaic pattern of photoresist is formed on the inner surface of the glass panel, and then a light absorbing graphite film is formed on the entire surface of the glass panel. Then, the mosaic pattern of the photoresist is etched with an etching solution containing an oxidant, and the graphite film on the photoresist is removed by spray development together with the photoresist to form a mosaic graphite film on the inner surface of the glass panel. In the method of forming a film, a surfactant is allowed to act on the graphite film.

In the method for forming a graphite film according to the second aspect of the present invention, the surfactant is allowed to act on the graphite film in the step of removing the graphite film by spray development.

In the method for forming a graphite film according to the third aspect of the present invention, the surfactant is poured as a rinsing solution in the step of removing the graphite film by spray development to act.

The method for forming a graphite film according to claim 4 of the present invention is characterized in that the surfactant is an aqueous solution of polypropylene glycol polyethylene glycol ether-based nonionic surfactant having a concentration of 0.1% or less. It is what

A method for forming a graphite film according to a fifth aspect of the present invention is a polypropylene glycol polyethylene glycol ether-based nonionic surfactant of 0.01%.
It is characterized in that it is spray-developed with an aqueous solution having a concentration of not more than%.

In the method for forming a graphite film according to claim 6 of the present invention, a mosaic pattern of photoresist is formed on the inner surface of the glass panel, and then a light absorbing graphite film is formed on the entire surface of the glass panel, and then an oxidizing agent is added. By etching the photoresist mosaic pattern with an etching solution containing, by removing the graphite film on the photoresist with it by spray development,
In the method for forming a graphite film for forming a mosaic graphite film on the inner surface of the glass panel, an inorganic coagulant is allowed to act on the graphite film in a shaping step of removing the graphite film formed on the skirt region of the inner surface of the glass panel. is there.

In the method for forming a graphite film according to a seventh aspect of the present invention, the inorganic coagulant is an aqueous solution of aluminum sulfate, and the aqueous solution is poured onto the inner surface of the glass panel to act.

In the method for forming a graphite film according to the eighth aspect of the present invention, after the graphite film is removed from the skirt region on the inner surface of the glass panel, the graphite film remaining in the glass panel and attached in a washing step of washing the glass panel with water. The piece is treated with a surfactant and then washed with water.

[0022]

BRIEF DESCRIPTION OF THE DRAWINGS FIG.
An embodiment of the present invention will be described.

Embodiment 1 FIG. 1 is a diagram showing a graphite film spray developing apparatus for carrying out the first invention method. According to the method of the present invention, during spray development for removing a graphite film by a spray method, a surfactant is caused to act on each of the graphite film formed on the inner surface of the glass panel and the separated pieces of the graphite film, so that the inner surface of the glass panel is treated. Preventing reattachment of graphite film particles to the phosphor emission region of the glass panel by promoting electrical repulsion between the graphite film formed on the glass and the particles separated from it. It is a thing.

In FIG. 1, the glass panel 2 fixed to the carrier 1 is spray-developed with pure water sprayed from a plurality of nozzles 5. Here, parts corresponding to those of the conventional device shown in FIG. 4 are designated by the same reference numerals. Different from the one shown in FIG. 4, a nozzle 21 for a surfactant is provided separately from the nozzle 5. The nozzle 21 is connected to a tank 23 via a sequence-controlled pump 22, from which a surfactant solution is jetted onto the glass panel 2.

For the surfactant solution, a 0.1% aqueous solution of polypropylene glycol polyethylene glycol ether such as Epan 450 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) can be used as the nonionic surfactant.

Although the spray development is processed in two positions, in the first spray development, pure water is first sprayed from the plurality of nozzles 5 onto the glass panel 2 for 12 seconds as in the conventional case. After that, the pump 22 is controlled by sequence control.
Is operated for 5 seconds, and about 500 cc of the surfactant solution is poured from the nozzle 21 to the glass panel 2 as a rinse liquid. Further, the glass panel 2 is moved to the next spray developing position by the carrier 1 and the same spray developing is performed again. Thereby, the glass panel 2
The surface of the graphite film formed on the glass panel 2 or the surface of the graphite film and the fine particles exfoliated from the glass panel 2 are electrically acted on by the surfactants acting on the inner surface of the glass film and the small pieces of the exfoliated graphite film. Repulsive force is promoted.

It should be noted that the reason why the pouring of the surfactant solution is carried out immediately after the completion of spraying at the first position is
This is because it takes about 5 seconds to move between positions by the carrier 1, and the transition period of 5 seconds ensures the action of the surfactant on the graphite pieces.

As described above, by causing the surfactant to act on the graphite film in the step of removing the graphite film,
The conventional defective rate due to the residual graphite pieces was 0.1% to 0.3% on average, and was 1% or more when the number of occurrences was high, which can be greatly reduced. For example, when the method of the present invention was applied to a line for forming a graphite film (with an index time of 22 seconds) on a glass panel of a 25-inch color CRT, the defect rate could be suppressed to 0.02% or less. In addition, the occurrence of sudden defects was eliminated and it became possible to form a stable graphite film.

In the method of the first embodiment described above, it is not always necessary to act the surfactant at the first spray developing position. Since normal spray development is performed in two positions, the surfactant solution can be poured directly after the spray development in the second position by simply changing the sequence control schedule. The same effect can be obtained if the operation is performed at any position. Further, there are many kinds of surfactants other than the above Epan 450 as the surfactants for promoting the electric repulsive force on the graphite pieces peeled from the glass panel. Just select it.

Embodiment 2 FIG . In the method of the second embodiment, the conventional spray developing device is used as it is, and the graphite film is removed by spraying an aqueous solution of a surfactant instead of spray developing with pure water. .

That is, in the spray developing apparatus for carrying out the conventional method shown in FIG. 4, the surfactant solution is added to the pure water in the tank 3, and the surfactant solution is supplied from the nozzle 5 to a predetermined pressure. Spray the inside of the glass panel with. Then, the graphite film on the glass panel 2 is knocked off together with the photoresist, and at the same time, the surfactant acts on the separated graphite pieces. Therefore, since the electric repulsive force of the graphite particles is promoted, the graphite film particles can be reliably removed without reattachment to the light emitting region of the glass panel 2. In addition, this method is advantageous in terms of cost because existing equipment can be diverted as it is.

For the aqueous surfactant solution, Epan 450, which is a nonionic surfactant, can be used as in the first embodiment. In that case, use as an aqueous solution diluted to about 0.01%. When preparing the surfactant solution in the tank 3, if an automatic surfactant stock solution adding device is added to the tank 3, its concentration can be easily controlled.

Embodiment 3 FIG. 2 is a diagram showing a graphite film trimming apparatus for carrying out the third inventive method. According to the method of the present invention, in the trimming process of the graphite film, the graphite particles are subjected to an interfacial chemical action to promote the mutual aggregation of the particles, so that the graphite particles are dispersed in the light emitting region of the glass panel. It prevents reattachment.

In the trimming device of FIG. 2, the glass panel 2 is fixed to the carrier 1 and its skirt area 2a.
The graphite film formed at 1 is shaped by the cam 8 and the nozzle 9 at the tip of the trimming arm 7. Here, parts corresponding to those of the conventional device shown in FIG. 5 are designated by the same reference numerals. Unlike the one in FIG. 5, the nozzle 2
4 is provided at a position higher than the trimming arm 7, and an inorganic coagulant solution is supplied to the nozzle 24 from a tank (not shown). The inorganic coagulant solution 25 is flown from the nozzle 24 to the glass panel 2 to promote the cohesive action of the graphite pieces.

Here, the nozzle 24 is provided separately from the nozzle 9 of the trimming arm 7, and the inorganic coagulant solution, instead of the surfactant solution, is poured from here to shape the skirt region 2a. This is because it does not interfere. That is, when an aqueous solution of ammonium acid fluoride (NH ₄ HF ₂ ) is used as an etching solution for etching the graphite film near the cam 8, if a surfactant solution is used, it acts on the etching solution. As a result, the etching proceeds to the effective image surface of the glass panel 2, and the desired shaping in the skirt region 2a becomes impossible. Therefore,
In the third embodiment, instead of the surfactant solution, an inorganic coagulant solution such as aluminum sulfate (Al ₂ (S
An 8% aqueous solution of O ₄ ) ₃ ) is used.

Trimming is performed in four positions, but in the first position of the trimming process, the etching liquid is discharged from the nozzle 9 to the skirt region 2a of the glass panel 2 at the same time as in the conventional case, and at the same time, about 10 times from the nozzle 24.
A flocculating agent solution of about cc is poured onto the glass panel 2 as a rinse solution. After that, the glass panel 2 is moved to the next trimming position by the carrier 1.

In the third embodiment, in order to uniformly flow the inorganic coagulant solution 25 from the nozzle 24 onto the entire inner surface of the glass panel 2, the tip end portion of which is extremely thin is used. Then, for example, by spending a full index time of 17 seconds, by pouring a predetermined amount of the coagulant solution 25 onto the glass panel 2, the graphite pieces are aggregated and separated, and the same degree as in the first and second embodiments. It was possible to reduce the defective rate.

The method of the third embodiment described above uses only a small amount of an aqueous solution of aluminum sulfate having a strong aggregating action as the inorganic aggregating agent solution in the first trimming position. However, since the normal trimming process is executed in four positions, the same effect can be obtained even if the coagulant solution is poured over in any position by changing the sequence control schedule. it can. In addition, there are many types of inorganic coagulants that give a surface chemical cohesive action to the graphite pieces peeled from the glass panel, and there are many kinds of inorganic coagulants that are selected according to the conditions for producing the graphite film. Then, the same effect can be obtained.

Fourth Embodiment FIG. 3 is a view showing a graphite film cleaning apparatus for carrying out the fourth invention method. According to the method of the present invention, in the step of washing the glass panel with pure water after the step of trimming the graphite film, the surface of the glass solution is preliminarily poured to promote the electric repulsive force of the exfoliated particles, and It is designed to reliably remove the graphite particles remaining on the panel.

In the cleaning apparatus shown in the figure, the inner surface of the glass panel 2 fixed to the carrier 1 is usually cleaned with pure water from the nozzle 11. Here, parts corresponding to those of the conventional device shown in FIG. 6 are designated by the same reference numerals. Differently from the one shown in FIG. 6, a nozzle 21 for a surfactant is provided in addition to the nozzle 11, and this nozzle 21 is connected to a tank 23 via a pump 22 which is sequence-controlled, from which a surfactant solution is added to the glass. It is configured to be supplied to the panel 2.

As the surfactant solution, the same 0.1% aqueous solution of Epan 450 as the nonionic surfactant used in Embodiment 1 can be used. In that case, prior to cleaning with pure water, the pump 22 is operated for about 5 seconds by sequence control to flow the surfactant solution from the nozzle 21 onto the glass panel 2. After that, the glass panel 2 is 10-15
After a second washing process, the product is sent from the drying process to the final inspection process.

In order to reliably remove fine particles of the graphite film of the glass panel 2, the nozzle 1 for pure water is used.
It is preferable that 1 is a spray or a shower spray.

[0043]

As described above, according to claims 1 to 4 of the present invention.
According to the method for forming a graphite film, since the surfactant is allowed to act on the graphite film, redeposition of the graphite pieces in the developing step of the graphite film is reliably prevented, and defects on the fluorescent screen are eliminated. The yield of the manufacturing process and the quality of the product can be improved.

According to the method for forming a graphite film of claim 5 of the present invention, instead of pure water used for removing the graphite film by spray development, a polypropylene glycol polyethylene glycol ether-based nonionic surfactant is used as a surfactant. By using an aqueous solution of a surfactant having a concentration of 0.01% or less, it is possible to effectively utilize the existing equipment and form a graphite film while preventing the graphite pieces from reattaching.

Further, according to the method for forming a graphite film of claims 6 and 7 of the present invention, the inorganic coagulant acts on the graphite film in the shaping step of removing the graphite film formed in the skirt region of the inner surface of the glass panel. By doing so, it is possible to reliably prevent the redeposition of the graphite pieces in the step of shaping the graphite film.

Further, according to the method of forming a graphite film of claim 8 of the present invention, after the graphite film is removed from the skirt region of the inner surface of the glass panel, it remains on the glass panel in a washing step of washing the glass panel with water, It is possible to reliably prevent the reattachment of the graphite pieces by applying a surfactant to the attached graphite pieces and then washing with water.

[Brief description of drawings]

FIG. 1 is a view showing a graphite film spray developing apparatus for carrying out the method of the first embodiment.

FIG. 2 is a diagram showing a graphite film trimming apparatus for carrying out the invented method of the third embodiment.

FIG. 3 is a diagram showing a graphite film cleaning apparatus for carrying out the method of the fourth embodiment of the invention.

FIG. 4 is a sectional view showing a spray developing apparatus for forming a mosaic graphite film in a conventional method.

FIG. 5 is a cross-sectional view showing a trimming device for forming a mosaic graphite film in a conventional method.

FIG. 6 is a cross-sectional view showing a cleaning device for forming a mosaic graphite film in a conventional method.

FIG. 7 is a diagram showing defects on a phosphor screen that occur on a glass panel in a conventional method.

[Explanation of symbols]

1 carrier, 2 glass panel, 3 pure water tank, 4 pump, 5 nozzle (pure water), 7 trimming arm, 8 cam, 9 nozzle (trimming), 11 nozzle (final cleaning), 13 graphite film area, 14 phosphor Emitting area, 15 black dots,
16 fine particles of graphite film, 21 nozzle for surfactant, 22 pump, 23 tank, 24 nozzle (coagulant), 25 inorganic coagulant solution.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03F 7/32 G03F 7/32 501 501 7/40 521 7/40 521 G02B 1/10 Z

Claims (8)

[Claims] 1. A mosaic pattern of photoresist is formed on the inner surface of the glass panel, and then a light-absorbing graphite film is formed on the entire surface of the glass panel, and the mosaic pattern of the photoresist is etched with an etching solution containing an oxidant. By removing the graphite film on the photoresist together with the photoresist by spray development,
A method of forming a graphite film, wherein a mosaic graphite film is formed on the inner surface of the glass panel, wherein a surfactant is allowed to act on the graphite film. 2. The method for forming a graphite film according to claim 1, wherein the surfactant acts on the graphite film in a step of removing the graphite film by spray development. 3. The method for forming a graphite film according to claim 2, wherein the surfactant is poured as a rinsing liquid to act in the step of removing the graphite film by spray development. 4. The formation of a graphite film according to claim 3, wherein the surfactant is an aqueous solution of a polypropylene glycol polyethylene glycol ether-based nonionic surfactant having a concentration of 0.1% or less. Method. 5. A polypropylene glycol polyethylene glycol ether-based nonionic surfactant of 0.01
The method for forming a graphite film according to claim 2, wherein spray development is performed with an aqueous solution having a concentration of not more than%. 6. A mosaic pattern of photoresist is formed on the inner surface of the glass panel, and then a light-absorbing graphite film is formed on the entire surface of the glass panel, and the mosaic pattern of the photoresist is etched with an etching solution containing an oxidant, By removing the graphite film on the photoresist together with the photoresist by spray development,
In the method for forming a graphite film for forming a mosaic graphite film on the inner surface of the glass panel, an inorganic coagulant is allowed to act on the graphite film in a shaping step for removing the graphite film formed on the skirt region of the inner surface of the glass panel. Of forming a graphite film. 7. The method for forming a graphite film according to claim 6, wherein the inorganic coagulant is an aqueous solution of aluminum sulfate, and the aqueous solution is poured onto the inner surface of the glass panel to act. 8. The method according to claim 1, wherein after the graphite film is removed from the skirt region on the inner surface of the glass panel, a glass panel is washed with water to remove the graphite film from the skirt region, and the interface with the graphite pieces remaining on the glass panel. A method of forming a graphite film, which comprises rinsing with an activator and then washing with water.