JPH05197141A - Photosensitive composition and pattern forming method using the same - Google Patents

Abstract

(57) [Summary] [Structure] Maleic acid as a water-soluble non-photosensitive monomer unit,
Vinyl azidobenzylidene acetophenone sulfonic acid, vinyl azido benzylidene acetophenone carboxylic acid, vinyl azido cinnamylidene acetophenone sulfonic acid, as a monomer unit having an azide group and an electrolytic functional group,
Photosensitive composition using a photopolymerizable polymer containing at least one monomer unit selected from vinyl azidocinnamylidene acetophenone carboxylic acid and salts thereof as a photo-crosslinking agent and using a water-soluble polymer polyvinyl alcohol as a base polymer .. [Effect] The sensitivity can be increased.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition, a pattern forming method using the same, and a fluorescent screen forming method for a display device such as a color cathode ray tube.

[0002]

2. Description of the Related Art A photocurable photoresist composed of a water-soluble polymer and an alkali dichromate salt has been known for a long time.
It is used for photolithography, photolithography, photo-etching, and production of fluorescent screens for screen printing plate making display devices. This photoresist is described, for example, in Nagamatsu and Inui; "Photosensitive Polymer", pages 89 to 96 (1977) Kodansha.

An example of manufacturing a fluorescent screen of a color cathode ray tube using this photoresist will be described. Polyvinyl alcohol, a surfactant, ammonium dichromate, and a blue-emitting phosphor are mixed with water to form a slurry. On the other hand, a black matrix is formed on the inner surface of the color cathode ray tube face plate. The slurry is spin-coated on this to form a coating film. When ultraviolet rays are radiated through the shadow mask and developed with water, the exposed portions are insolubilized, so that blue-emitting phosphor dots are formed. Next, with respect to the red light emitting phosphor and the green light emitting phosphor, respective phosphor dots are sequentially formed by the same method. Then filming,
After aluminizing and panel baking, the face plate part and the funnel part are joined by frit baking, and an electron gun is attached to manufacture a cathode ray tube.

[0004]

The above-mentioned prior art has not sufficiently considered, for example, the enlargement or high definition of the color CRT. When the color cathode-ray tube becomes larger, when manufacturing phosphor dots, the exposed surface (coating surface)
However, there is a problem in that the illuminance on the exposed surface is lowered because it is separated from the light source, and it takes a long time for the exposure. Further, in order to improve the definition of the color cathode ray tube, it is necessary to make the phosphor dot diameter smaller. For this purpose, it is necessary to reduce the diameter of the rotating light source. As a result, there is a problem in that the illuminance on the exposed surface (coating surface) decreases, and it takes a long time for exposure.

An object of the present invention is to provide a highly sensitive photosensitive composition, a pattern forming method using the same, and a fluorescent screen forming method in which the exposure time is shortened. Another object of the present invention is to provide a photosensitive composition capable of forming a highly precise pattern, a pattern forming method using the same, and a fluorescent screen forming method.

[0006]

[Means for Solving the Problems] (1) A maleic acid alkali salt is used as a water-soluble non-photosensitive monomer unit, and a vinyl azidobenzylideneacetophenone sulfonic acid alkali salt is used as a monomer unit having an azide group and an electrolytic functional group. High photosensitivity containing at least one monomer unit selected from salt, vinyl azidobenzylidene acetophenone carboxylic acid alkali salt, vinyl azido cinnamylidene acetophenone carboxylic acid alkali salt, and vinyl azido cinnamylidene acetophenone carboxylic acid alkali salt A photosensitive composition characterized by comprising a molecule as a photo-crosslinking agent, and a polyvinyl alcohol which is a water-soluble polymer as the base polymer, and (2) the photosensitive composition of (1) above is coated on a substrate. , The step of forming a coating film, and the desired coating on the coating film of the photosensitive composition. Pattern exposure method, which comprises a step of exposing the coating film and a step of developing the coating film to form a pattern, (3) the photosensitive composition and the phosphor powder according to (1) above. And a step of forming a phosphor coating film by applying an aqueous suspension paint to the inner surface of a face plate of a color cathode ray tube, exposing the coating film to a desired pattern, and forming a pattern by development. This is achieved by a method for forming a fluorescent screen of a color cathode ray tube, which is characterized in that

In the present invention, the copolymer as the photo-crosslinking agent is a water-soluble non-photosensitive first monomer unit of a maleic acid alkali salt (Chemical Formula 1), a second group having an azide group and an electrolytic functional group. Monomer unit of vinyl azidobenzylidene acetophenone sulfonic acid alkali salt (Chemical formula 2, x = SO ₃ H),
Vinyl azidobenzylidene acetophenone carboxylic acid alkali salt (Chemical formula 2, x = COOH), vinyl azido cinnamylidene acetophenone sulfonic acid alkali salt (Chemical formula 3,
x = SO ₃ H), vinyl azidocinnamylidene acetophenonecarboxylic acid alkali salt (Chemical Formula 3, x = COOH), and at least one monomer unit. The monomer unit refers to a structure when the monomer is polymerized, and means the same structure as the structure where the monomer having the substituent is polymerized. Such a monomer unit can be obtained by polymerizing a monomer having the above-mentioned substituent or by polymerizing another monomer and then bonding the substituent by a chemical reaction.

[0008]

[Chemical 1]

[0009]

[Chemical 2]

[0010]

[Chemical 3]

The copolymer as the photocrosslinking agent of the present invention may contain a third monomer unit in addition to the first and second monomer units. The third monomer unit may be of one type or of two or more types.

The photosensitive composition of the present invention, as described above,
It comprises the photocrosslinking agent and polyvinyl alcohol which reacts with the photocrosslinking agent to form a pattern of the photoinsolubilized polymer. The ratio of the two is preferably such that the amount of the photocrosslinking agent is in the range of 1 to 50 wt% with respect to polyvinyl alcohol,
It is more preferably in the range of 5 to 30 wt%. Further, in order to improve the properties when used as a paint, a surfactant such as polyoxyethylene alkyl ether or ethylene glycol is added to the photosensitive composition, and vinyl tris (β A coupling agent such as -methoxyethoxy) silane can also be added to the photosensitive composition.

[0013]

The photocrosslinking agent of the present invention well absorbs the excitation light emitted from the ultra-high pressure mercury lamp, especially the light having a wavelength of 340 nm or 365 nm. In addition, this photocrosslinking agent is a polymer compared to the conventional dichromate alkali salt compound, which has many photocrosslinking groups in one molecule, and the photocrosslinking agent is a polymer. A "entanglement" phenomenon occurs between the polymer and the polyvinyl alcohol, and the crosslinking efficiency of the photolyzed photocrosslinking group to polyvinyl alcohol increases, so that the photosensitive composition has high sensitivity.

[0014]

EXAMPLES The present invention will be described in detail below with reference to examples.

Example 1 Sodium maleate-4-vinylmonoazidobenzylideneacetophenone sodium sulfonate copolymer (Chemical formula 4) as a photo-crosslinking agent was synthesized as follows.

Poly (styrene-maleic anhydride copolymer: 75% styrene, molecular weight: 1900, polyscience,
16 g (produced by Ink Co., Ltd.) was dissolved in a mixed solvent of 50 ml of chloroform and 50 ml of carbon disulfide. This solution was put into a solution prepared by dissolving 25 g of acetyl chloride and 43 g of anhydrous aluminum chloride in a mixed solvent of 100 ml of chloroform and 100 ml of carbon disulfide at room temperature while stirring. Then, it was heated and refluxed with stirring for 2 hours. After allowing to cool, it was filtered and the insoluble matter was dried. This was pulverized, treated with a large amount of water, washed thoroughly with water, and then dried. The obtained polymer is a maleic acid-4-vinylacetophenone copolymer (Chemical formula 5). However, the styrene unit was about 10%, that is, 7.5% of the whole copolymer remained unreacted.

Next, 1 g of this copolymer (Chemical Formula 5), 4-
Sodium azidobenzaldehyde-2-sulfonate 2
g, caseiso-da 0.3 g ethyl alcohol 40 ml
And 40 ml of water dissolve in a mixed solvent. Then, the mixture was allowed to stand at room temperature for 2 days, acidified with acetic acid, and the deposited precipitate was separated by filtration to obtain a sodium maleate-4-vinylmonoazidobenzylideneacetophenone sodium sulfonate copolymer (Formula 4). This copolymer consists of 25 mol% sodium maleate units, 7.5 mol% styrene units, 50.5 mol% vinylacetophenone units, and 17 mol% sodium vinylmonoazidobenzylideneacetophenonesulfonate units.

[0018]

[Chemical 4]

[0019]

[Chemical 5]

<Example 2> Sodium maleate-4-
The vinyl monoazidocinnamylidene acetophenone sodium sulfonate copolymer (Chemical Formula 6) was synthesized as follows.

Maleic acid-4-vinylacetophenone copolymer (Chemical formula 5) (1 g), sodium 4-azidocinnamaldehyde-2-sulfonate (2 g), sodium hydroxide (0.3 g), ethyl alcohol (40 ml) and water (4) were synthesized.
Dissolve in 0 ml of mixed solvent. Then, the mixture was allowed to stand at room temperature for 2 days, acidified with acetic acid, and the deposited precipitate was separated by filtration to obtain a sodium maleate-4-vinylmonoazidocinnamylideneacetophenone sodium sulfonate copolymer (Formula 6). This copolymer has a sodium maleate unit of 25 mol%, a styrene unit of 7.5 mol%, a vinylacetophenone unit of 50.5 mol%, a vinyl monoazidocinnamylidene acetophenonesulfonate unit of 1
It consists of 7 mol%.

[0022]

[Chemical 6]

Example 3 Using the photo-crosslinking agent copolymers obtained in Examples 1 and 2, solutions having the following compositions were prepared. This was spin-coated on a glass plate to a thickness of 0.5 to 0.7 μm and dried to form a coating film. Composition: Polyvinyl alcohol 2.0 wt% Copolymer having azide group 0.2 Silane coupling agent 0.002 Water Residual Table 1 shows a comparison of sensitivity when a copolymer having an azide group is changed. As a comparative example, the same Table 1 shows an example in which a sodium dichromate salt compound is used instead of the copolymer having an azide group. The sensitivity was evaluated by exposing the light from the ultra-high pressure mercury lamp with a constant illuminance for a certain period of time and then determining how much exposure time was required to obtain a pattern having a predetermined dot diameter. When the exposure time in the case of the comparative example is 1, and when the photo-crosslinking agents of Examples 1 and 2 are used, a pattern having the same dot diameter can be obtained in an exposure time of 1/2.

[0024]

[Table 1]

Example 4 Using the photo-crosslinking agent copolymer obtained in Example 1, a slurry solution having the following composition was prepared. Slurry composition: Phosphor powder 12.5 wt% Polyvinyl alcohol 1.25 Surfactant 0.0125 Photo-crosslinking agent copolymer 0.125 Silane coupling agent 0.00125 Water Residual This slurry composition is applied to a color cathode ray tube panel. After spin coating on the inner surface and drying, a shadow mask was attached, and light was exposed to the position where the fluorescent substance was adhered, using an ultra-high pressure mercury lamp as a light source.
Spray development was performed with warm water for two minutes to form phosphor dots.
This process was performed for each red, blue, and green phosphor powder to produce a phosphor screen on the inner surface of the panel. Thereafter, in the same manner as in the conventional method, after performing filming, aluminizing and panel baking, the face plate and the funnel were combined and frit baked, and an electron gun was attached to manufacture a color CRT.

After filming, aluminizing, and panel baking, the face plate and funnel are combined and frit baked, and an electron gun is mounted to manufacture a cathode ray tube. The exposure time in this process was shorter than with conventional compositions.

[0027]

The photosensitive composition of the present invention exhibits high sensitivity.
Therefore, for example, there is an effect that exposure can be performed in a short time when used for manufacturing a large color CRT. Further, even when it is used for manufacturing a high-definition color cathode ray tube, it is possible to compensate for the decrease in illuminance on the exposed surface due to the smaller hole diameter of the shadow mask.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location H01L 21/027 (72) Inventor Nobuaki Hayashi 1-280, Higashi Koikeku, Kokubunji, Tokyo, Hitachi, Ltd. Central Inside the research institute (72) Masato Ito 1-280 Higashi Koigokubo, Kokubunji, Tokyo Inside Hitachi Central Research Laboratory (72) Inventor Masahiro Nishizawa 3300 Hayano, Mobara-shi, Chiba Inside Hitachi Mobara factory (72) Inventor Saburo Nonogaki 1-280, Higashi Koigokubo, Kokubunji, Tokyo Inside the Central Research Laboratory, Hitachi, Ltd.

Claims (4)

[Claims] 1. A water-soluble, non-photosensitive monomer unit having maleic acid, an azide group and a monomer unit having an electrolytic functional group, vinyl azidobenzylidene acetophenone sulfonic acid, vinyl azido benzylidene acetophenone carboxylic acid, vinyl azidocinnamylidene acetophenone sulfone. Acid, vinyl azidocinnamylidene acetophenonecarboxylic acid and a photosensitive polymer containing at least one monomer unit selected from salts thereof as a photo-crosslinking agent, and using a water-soluble polyvinyl alcohol as a base polymer. A characteristic photosensitive composition. 2. A step of forming a coating film of the photosensitive composition according to claim 1 on a surface on which a desired pattern is to be formed, and exposing the coating film of the photosensitive composition with a desired pattern. A method of forming a pattern, which comprises a step of performing and a step of developing the coating film to form a pattern. 3. A step of applying a water-based suspension paint of the photosensitive composition according to claim 1 and phosphor powder to the inner surface of a face plate of a color cathode ray tube to form a phosphor coating film. A method for forming a fluorescent screen of a color CRT including a step of exposing a desired pattern and a step of forming a pattern by development. 4. The photosensitive composition according to claim 1, wherein the salt of the photocrosslinking agent-containing copolymer having an azide group is an ammonium salt, an alkali metal salt or an alkaline earth metal salt.