JPS5981832A - Pattern forming method - Google Patents

Abstract

PURPOSE:To form black matrix through simple and easy process by performing pattern exposure on a film of photo-viscous compound then adhering specific powder and exposing entirely thereafter adhering ferrite compound powder. CONSTITUTION:Photo-sensitive compound film exhibiting viscosity through exposure while containing water soluble aromatic diazonium salt is formed on a substrate. Then said film is chemically exposed with specific pattern and contacted with specific powder to adhere the powder at least one time. Thereafter chemical radiation is applied entirely on the film to contact ferrite compound powder to adhere said powder on the portion where specific powder pattern is not formed yet. Said ferrite powder is shown by general formula M<2>Fe2O4 (Where M<2> is metal ion of more than one kind of Ni<2+>, Co<2+>, Ba<2+>, Mn<2+>, Zn<2+>, Cu<2+>, Sr<2+>, Pb<2+>, Mg<2+>, Ca<2+>).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a pattern forming method applicable to black matrices of color picture tubes, copying of optical figures, lithography, and the like.

[Prior art]

Conventionally, the black matrix of a color picture tube is produced through the following steps: applying a photosensitive resin liquid to the inner surface of the face plate, drying, exposing, developing, drying, applying a carbon dispersion, drying, peeling off the photosensitive resin film, and drying. It is formed. This method has problems such as the complicated process and the need for a large amount of water for developing and peeling off the photosensitive resin.

Some of the inventors of the present invention previously published
In No. 1, a thin layer containing an aromatic diazonium salt that becomes sticky upon exposure to light was applied to the substrate surface, based on the idea that the photodecomposition products of the aromatic diazonium salt have no ability to accept powder particles. After forming the powder particles on top of the thin layer and bringing the powder particles into contact with the thin layer so that the powder particles are received in the area where the adhesiveness has occurred, the remaining powder particles are removed from the thin layer. We have proposed a method of forming a pattern-shaped powder coated layer of desired powder on the surface of a substrate by repeating it once or twice or more.

Forming a siblack matrix by this method is
After exposing the inner surface of a color cathode ray tube face plate to light using the method described above and applying phosphors to each of the three types of phosphors, the entire surface of the coating film is exposed to light, and graphite, which is a light-absorbing substance, is brought into contact with the coating film. It is possible by

However, although black-2 matrix can be formed using this method, it has become clear that the luminance of the fluorescent surface is low. The reason for this is that the average particle size of the phosphor particles is relatively large, about 3 to 18 μm, and the phosphor layer formed on the inner surface of the face plate has unevenness corresponding to the above particle size. This is because, since the powder is fine, some people will be crowded between the uneven surfaces. The fluorescent surface of the well-known conventional color cathode ray tube is aluminized. This is because the light emitted from the phosphor not only travels forward, that is, toward the glass substrate, but also travels backward. This is to improve the brightness of the phosphor surface by reflecting the light traveling backwards forward by the πha surface formed by the aluminizing. However, as mentioned above, when fine graphite powder is present on the phosphor layer, part of the light is absorbed by it, and the light reflected in the direction of the aluminum evaporation is reduced by that amount, resulting in a reduction of the entire phosphor surface. The brightness will decrease.

[Purpose of the invention]

An object of the present invention is to provide an improved method of pattern formation using a photosensitive composition that becomes tacky upon exposure to light.

[Summary of the invention]

The pattern forming method of the present invention involves forming a photosensitive adhesive composition containing a water-soluble diazonium salt on a substrate as a coating film, exposing selected portions of a predetermined pattern to actinic radiation, After adhering powder of the substance to the exposed portion at least once, the entire surface of the substrate is exposed to actinic radiation, and the powder of the black sintered body is made to adhere to the areas other than those to which the predetermined substance has adhered. shall be.

At this time, the substrate is the inner surface of the face plate of a cathode ray tube, and a shadow mask for the cathode ray tube is used to partially expose the substrate to light in the shape of dots or stripes, and the phosphor powder is attached to the exposed portions. By repeating the process once or twice, the fluorescent surface of the color picture tube can be formed.After the process is repeated, if black sintered powder is applied to form a black film, a black mask can be formed. )
It is possible to form a fluorescent surface of a color picture tube having an IJ box.

As described above, according to the present invention, blackma) I
In the formation of the light-emitting surface of a color picture tube having a Jx, or in application to copying and lithography of similar optical figures, it is possible to form a pattern in a process that is significantly simpler and easier than the process using conventional technology. .

The black sintered body used in the present invention has the general formula M”F
e2O4, M”Fe5/204, M”Fe1201G
A ferrite compound represented by either of these is used. Here, examples of M2+ include metal ions such as 1, nickel, cobalt, barium, manganese, zinc, copper, strontium, lead, magnesium, and calcium. Examples of M+ include lithium, sodium, potassium, rubidium, cesium, copper, and silver. Also,
Ferrite compounds containing two or more of the above metal ions, such as manganese-zinc ferrite and cobalt-zinc ferrite, can also be used.

When a ferrite compound becomes a small particle of around 1 to 2 μm, it becomes close to the size of a unit magnetic domain of a magnetic material, so it shows magnetism and aggregates with each other. It becomes an aggregate of about 10 μm. If the particle size exceeds a certain level, it will not exhibit magnetism and will not aggregate. Therefore, since fine particles rarely exist alone, it becomes difficult for ferrite particles to penetrate into the previously formed phosphor layer.

On the other hand, such a phenomenon is not observed in black materials other than ferrite compounds. That is, the particle sizes of these substances exhibit a certain diachronic distribution, and it is difficult to remove fine particles. Furthermore, if the average particle size is made too large, the number of fine particles decreases, but gaps are likely to be formed between particles in the area where the black matrix is formed, which is not preferable because the degree of coverage of the black substance decreases.

With ferrite compounds, the particle size of the sintered body produced can be freely controlled by changing the particle size of the raw material powder, calcination temperature, and time. You can easily get the powder.

The particle size of the ferrite compound used is 0.5 to 40 μm
It is preferable that it is in the range of . Even if particles with a small average particle size are used, they aggregate as described above and act in the same way as particles of several μm to 10 μm.

Moreover, if the particle diameter exceeds 40 μm, gaps are likely to be formed between the particles when a black matrix is formed, resulting in a decrease in the degree of coverage of the black matrix. Most of the black substances of general inorganic compounds and organic compounds have an average particle size of 0.5 to 40 μm, but in the case of ferrite compounds, it can be easily Particle sizes within this range are sent.

If the magnetism of the ferrite compound is too strong when it becomes fine particles, it will aggregate strongly and act as a powder with a large mass as a whole, which will easily affect the previously applied phosphor layer. Therefore, when the particle size reaches about 10 μm, it is desirable that the particles exhibit no magnetism and do not aggregate. Particularly preferred ferrite compounds having such characteristics are barium ferrite, strontium ferrite, cobalt ferrite, manganese-zinc ferrite, zinc ferrite, and magnesium ferrite.

The ferrite compounds used in the present invention all have a specific gravity of 445 to 5.5 and a bulk specific gravity of 0.5 to 2.3, which is higher than that of graphite, which is a typical black powder, with a specific gravity of 1. 6 to 2.3, which is sufficiently heavy compared to the bulk specific gravity of 0.1 to 0.3. This means that when it is attached to a photoadhesive film, it can be contacted with stronger pressure than graphite powder, making it easier to adhere to the adhesive film. Furthermore, when attaching powder to a photoadhesive film, it is known to increase the adhesion density by shaking the powder on the film, but even with this method, the bulk specific gravity is large. As a result, it exhibits sufficiently satisfactory fluidity compared to graphite powder.

In the photoadhesive composition of the present invention, the practically useful diazonium salt is a stabilized aromatic diazonium salt, such as aromatic diazonium fluoroborate, aromatic diazonium sulfate, aromatic diazonium sulfonate,
These include aromatic diazonium chloride zinc chloride double salt. For specific compound names, please refer to the above-mentioned % Kosho 57-20
It is described in No. 651, etc.

Furthermore, as similarly described in Japanese Patent Publication No. 57-20651, examples of substances used in combination with diazonium salts include organic polymer compounds such as gum arabic, alginate propylene glycol ester, polyvinyl alcohol, polyacrylamide, Examples include poly(N-vinylpyrrolidone), acrylamide-diacetone acrylamide copolymer, and the like. These are water soluble, do not require the use of organic solvents, and are preferred materials for use in the present invention. Of course, it is also possible to mix two or more types.

The purpose of using these substances is to improve the coating properties when forming a thin layer of a photoadhesive composition containing a diazonium salt as a photosensitive component, to improve the uniformity of the thin layer, and to improve the uniformity of the thin layer. The purpose is to control the powder particle receiving capacity of the layer. In this way, when a small amount of the diazonium salt is mixed with the diazonium salt, it is preferable that the mixed substance is 0.5 to 500% of the diazonium salt.
It is more preferable that the weight ratio is 1 to 50. Furthermore, various surfactants can be added as appropriate to improve coating properties. It is a known method to add a surfactant to a composition in order to improve the coating properties of the composition, and the surfactant used in such known methods is also used in the present invention. I can't help it. The amount added is about 0.01 to 1% based on the diazonium salt, which is sufficient according to general usage.

[Embodiments of the invention]

Hereinafter, the present invention will be explained in more detail using Examples.

Example 1 An aqueous solution of a photosensitive adhesive composition having the following composition was prepared.

4-(dimethylamino)benzenediazonium chloride/zinc chloride...3.3g Alginic acid furopylene gellicol ester (Kimitsu Chemical, Gimiroid MV)...O,17g ionized pure water
...97 g of this aqueous solution was applied to the face plate of a 6-inch color cathode ray tube at a rotational speed of 11-6 Orp, and dried by infrared heating. Attach a shadow mask to this17, use an ultra-high pressure mercury lamp as the light source,
The portion corresponding to the color was exposed to ultraviolet light, and then the shadow mask was removed, and then a blue phosphor was sprinkled to form a blue phosphor film. Repeat the same operation, expose the parts corresponding to green and red to ultraviolet light, and attach the green phosphor and red phosphor. A film was formed.

After that, the entire inner surface of the plate is exposed to ultraviolet rays without using a shadow mask, and barium ferrite (manufactured by Hitachi Metals, MPB-380, particle size 1 to 2 () μm) is attached to the parts where the phosphor is not attached. A black film corresponding to a black matrix was obtained.

The light transmittance of the black film portion was 3 factors. In addition, in order to compare the degree of contamination of the black powder into the previously applied phosphor layer, 330 n of black powder was applied before and after applying the black powder.
The phosphor layer was excited with ultraviolet rays of rn, and the brightness was compared. A 2-3% decrease in brightness was observed in the blue and green phosphors and a 5% decrease in the red phosphor. On the other hand, for comparison, graphite powder (manufactured by Hitachi Powder Metallurgy,
When Hitazol GP-6O8, particle size of about 0.1 μm) was used, a 15-20% decrease in brightness occurred in each color phosphor.

Example 2 The same operation as in Example 1 was performed, except that strontium ferrite (manufactured by Hitachi Metals, MPf3-380H, particle size 2 to 15 μm) was used instead of barium ferrite in Example I, and the same black matrix was prepared. Obtained a fluorescent surface.

The light transmittance of the black coating portion and the reduction in brightness of each phosphor were also approximately the same as in Example 1.

Example 3 A similar black matrix fluorescent surface was obtained by carrying out exactly the same operation as in Example 1, except that cobalt ferrite was used in place of the barium ferrite in Example 1.

Cobalt ferrite was prepared by mixing cobalt carbonate and ferric oxide at a molar ratio of 1:2 and firing the mixture at 100 oc for 2 hours.

The light transmittance of the black coating portion and the reduction in brightness of each phosphor were also approximately the same as in Example 1.

Example 4 A similar black matrix fluorescent surface was obtained by carrying out exactly the same operations as in Example 1, except that manganese-zinc ferrite was used in place of the barium ferrite in Example 1.

The light transmittance of the black film portion was 2. However, in this case, some ferrite powder was also observed to be attached to the upper side of the phosphor film. When the luminance reduction of each phosphor was measured in the same manner as in Example 1, it was 5% for the blue and green phosphors and 8 to 10% for the red phosphor.

Example 5 A similar black matrix was obtained by carrying out exactly the same operation as in Example 1, except that lithium barium ferrite was used in place of the barium ferrite in Example 1. The light transmittance of the black coating portion was 5. Further, the luminance reduction of the blue and green phosphors was 5 mm, and that of the red phosphor was 8 to 10 φ.

Note that similar operations were performed using ferrites other than those used in the above examples, such as zinc ferrite, nickel ferrite, copper ferrite, lithium ferrite, and sodium ferrite, but all had almost the same results. Get the black matrix. The light transmittance of the black coating part is about 2 to 5 inches, and the reduction in brightness of each phosphor is about 2 to 5 inches.
It was 10chi.

〔Effect of the invention〕

As explained above, in the present invention, the coating film of the photosensitive composition is exposed to light in a predetermined pattern and powder is applied at least once, and then the cold surface of the coating film is exposed to light to adhere the ferrite compound. By doing so, the black powder can be deposited on other parts without substantially affecting the pattern.

Agent Patent Attorney Toshiyuki Usuda Tachi Seisakusho Mobara Factory 0 shots by Kiyoaki Miura 3300 Hayano, Mobara City Nippon Co., Ltd. Tachi Seisakusho Mobara Factory

Claims (1)

[Scope of Claims] 1. (a) A step of forming on a substrate a coating film of a photosensitive composition containing a water-soluble aromatic diazonium salt that exhibits tackiness upon exposure; (c) exposing the entire surface of the coating film to a pattern of actinic radiation, bringing a predetermined powder into contact with the atomized coating film, and adhering the powder to the exposed area at least once; exposure to chemical radiation;
A step of applying the ferrite compound powder to the coating film and attaching the ferrite compound powder to areas other than those where a predetermined powder pattern has already been formed. Pattern formation method. 2, -1=The fluorite compound has the general formula M"Fe20
4 (here M2+ is N i” + G O2” +
I3 a”, Mn”. Z n 2 + , Cu 2 + , S r 2
" , P b 2 ", M g 2+ and Ca2
The ferrite compound represented by the general formula (representing at least one metal ion selected from the group consisting of M2"F'e
t20t9 (here M2+ is N i2", CO2+
, B a2+ , 1vln”. z , 12+, CLI”, Br”, Pb”
2. The method for forming a nodules according to claim 1, which is a ferrite compound represented by + Mg2+ and Ca ij +. 4. The ferrite compound described in - has the general formula M"F es/
204 (here M+ is J-j” IN”IK”l P
5. The pattern forming method according to claim 1, wherein the substrate is a ferrite compound represented by: On the inner surface of the color cathode ray tube face plate, the above-mentioned prescribed powder is a fluorescent substance, and the above-mentioned (
The pattern forming method according to any one of claims 1 to 4, wherein step (b) is repeated three times for three types of phosphors. 6. The pattern forming method according to claim 5, wherein the pattern formed by the phosphor is striped. 7. The pattern forming method according to claim 5, wherein the pattern formed by the phosphor is dot-shaped.