JPH02204750A - Photosensitive composition and pattern forming method by using this composition - Google Patents

Abstract

PURPOSE:To improve the sensitivity of the compsn. by incorporating a photosensitive agent consisting of a copolymer contg. specific maleate as a monomer unit and a water-soluble high-polymer compd. into the compsn. CONSTITUTION:The copolymer contg. the maleate (A) for which azidebenzylidene acetophenone sulfonic acid, azidobenzylidene acetophenone carboxylic acid or the salt thereof as an ester group as a monomer unit and the water-soluble high-polymer compd. (B) are incorporated into the compsn. used for production of a black matrix color cathode ray tube. The unit expressed by the formula A or the like is usable for the component A and a compd. (e.g. acrylamide-diacetone acrylamide copolymer) which exhibits a reciprocity law failure characteristic when used together with the above- mentioned copolymer which acts as the photosensitive agent is preferably used for the component B.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a water-soluble photosensitive composition and a pattern forming method using the same, and particularly to a water-soluble photosensitive composition suitable for use in IM manufacturing of color cathode ray tubes. The present invention relates to a composition and a pattern forming method using the same.

[Conventional technology]

As an example of a conventional pattern forming method,
-90185. JP-A-50-33764 describes a method for producing a black matrix for color cathode ray tubes and a photosensitive composition used therein. This method uses a photosensitive composition having reciprocity law failure characteristics, for example, a composition consisting of a polymeric compound such as acrylamide-diacetone acrylamide co-y (combination) and a bisazide cross-linking agent, and then This is a method for forming small-area patterns.

This will be explained in detail. Black matrix color cathode ray tubes have red on the inside of the panel.

It has a structure in which it has a phosphor pattern such as blue or green phosphor dots or stripes, and the gaps between them are filled with a non-luminescent light-absorbing substance such as carbon.

Hereinafter, for convenience of explanation, a manufacturing method for dots will be described. First, a coating film of a photosensitive composition having the reciprocity law failure characteristic described above is formed on the inner surface of a color cathode ray tube face plate, and the positions where phosphor dots are to be formed are exposed to light through a shadow mask, and developed to coat the photosensitive composition. form a dot.

Carbon is applied on top of this, and the dots are removed together with the carbon on top using a stripping solution. Thus, holes in the black matrix are formed. Red, blue, and green phosphor drivers 1- are sequentially formed in this hole.

Since a photosensitive composition having reciprocity law failure characteristics is used, the area of the dots of the photosensitive composition, that is, the area of the phosphor dots, is substantially smaller than the area irradiated with light through the shadow mask. . Therefore, if a color cathode ray tube is completed using this shadow mask, the diameter of the electron beam irradiated through the holes in the shadow mask will be larger than that of the fluorescent dots. Therefore, the manufactured color cathode ray tubes are bright and have excellent contrast.

[Problem to be solved by the invention]

The above conventional technology does not take into account the need to increase the size of color cathode ray tubes, and when manufacturing large color cathode ray tubes, the exposure surface is separated from the light source, which reduces the illuminance on the light surface and requires a long time for #l light. The object of the present invention is to provide a highly sensitive photosensitive composition and a pattern forming method using the same.

[Means to solve the problem]

The above purpose is to use a copolymer containing maleic ester of azidobenzylidene acetophenone sulfonate (Structure I) as a monomer unit as a photosensitizer, and to use a photosensitive composition containing this copolymer and a water-soluble polymer compound. This is achieved by

C=O 0sNa (Structure 1) In particular, by using a polymer compound as a water-soluble polymer that destroys the reciprocity law failure property when it reacts with the above-mentioned photosensitizer, reciprocity law failure property can be imparted to the present photosensitive composition. Can be granted.

The photosensitive composition is applied onto a surface on which a desired pattern is to be formed, the coating film is exposed to light in the desired pattern under conditions in the presence of oxygen, and then the coating film is developed. It becomes possible to form a pattern with an area substantially smaller than the irradiated area. If this pattern forming method is carried out using the inner surface of the face plate of a color cathode ray tube as a substrate, a black matrix phosphor screen with excellent performance can be formed.

In the photosensitive composition of the present invention, in addition to a copolymer containing a maleate ester of azidobenzylideneacetophenone sulfonic acid as one of the heptad units, azidobenzylideneacetophenonecarboxylic acid and salts thereof may be used as a photosensitizer. can. These salts are sodium and potassium.

It is a salt consisting of lithium, ammonium, and tetraalkylammonium.

Tetraalkylammonium salts include tetramethylammonium and tetraethylammonium.

Tetrapropylammonium and tetrabutylammonium salts can be used. The mixing ratio of the photosensitizer to the water-soluble polymer is preferably in the range of 1 to 50 wt%, more preferably in the range of 5 to 30 wt%, relative to the water-soluble polymer.

As the water-soluble polymer used in the photosensitive composition of the present invention, those having excellent oxygen permeability such as polyvinylpyrrolidone, polyacrylamide, vinylpyrrolidone copolymer, and acrylamide-diacetone acrylamide copolymer are preferred.

The photosensitive composition of the present invention can also be used in combination with other water-soluble polymer compounds that are compatible with the water-soluble polymer compound described above, such as carboxymethyl cellulose. This is disclosed in the aforementioned Japanese Patent Application Laid-open Nos. 48-90185 and 50-33764.

Additionally, surfactants such as polyoxyethylene alkyl ether or ethylene glycol may be added to the photosensitive composition of the present invention in order to improve properties when used as a paint, and to improve adhesion to a substrate. The aforementioned publication also describes the addition of a coupling agent such as vinyltris(β-methoxyethoxy)silane to the photosensitive composition, and such a method can also be used in the present invention.

The pattern forming method of the present invention requires exposure to be performed under conditions where gaseous oxygen is present. Also, the value of the Schwarzschild constant p is O< P < 0, 7 Ei! @
Preferably, the exposure is carried out at The Schwarzschild constant and reciprocity law failure characteristics are described in the above publication.

[Effect]

The copolymer of the present invention particularly well absorbs light with a wavelength of 340 nm or 365 nm among excitation light emitted from an ultra-high pressure mercury lamp. Furthermore, this copolymer has a higher molecular weight than conventional bisazide compounds and has many azide groups in one molecule. Therefore, at the same exposure amount, the increase rate of the molecular weight after crosslinking with respect to the number of crosslinking points increases, so it is possible to use a photosensitive composition with high FA!
31i.

〔Example〕

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

Example 1 Synthesis of azidobenzylidene acetophenone sulfonic acid sodium maleate ester-vinyl methyl ether copolymer (1) will be described.

14 g of p-hydroxyacetophenone is dissolved in 500 mm of 1% caustic soda water. Add and dissolve 25 g of sodium 4-azidobenzaldehyde-2-sulfonate.
This was left at around 30-40°C for one day, and acetic acid was added to make it acidic. The precipitated crystals were filtered out and then recrystallized from hot ethanol. Sodium Ia4-hydroxymonoazidobenzylideneace1-phenonesulfonate was obtained.

6 g of poly(methyl vinyl ether/maleic anhydride) is dissolved in dry pyridine roomQ, and to this is added a solution obtained by dissolving 5 g of the purified 4-hydroxymonoazidobenzylideneace-1-phenone in 100 mm of pyridine. It was heated at 50-60°C with stirring. This reaction solution was poured into excess acetone to completely precipitate the azide polymer.

It was dried to obtain poly(methyl vinyl ether/azidobenzylidene acetophenone sulfonate]-lium maleate).

Example 2 Poly(ethylene/azidobenzylideneacetophenonesulfonic acid sodium maleate ester) was obtained from the condensation reaction of ethylene-maleic anhydride copolymer and sodium 4-hydroxymonoazidobenzylideneacetophenonesulfonate in the same manner as in Example 1. Ta. [■] Example 3 Using the copolymer having an azide group obtained in Examples 1 and 2,
A solution of a photosensitive composition having the following composition was prepared. This was spin-coated onto a glass plate in a 0.5-0.7 μm ivy and dried to form a coating film.

Composition Niacrylamide-diacetone acrylamide copolymer (
Copolymerization ratio: acrylamide 2 diacetone acrylamide 1) 2.0wt% azide polymer 〇, 44 ethylene glycol
2 Silane coupling agent 0.002 water
Table 1 shows a comparison of sensitivity when changing the residual azide polymer. As a comparative example, Table 1 shows an example in which a bisazide compound (disodium 4,4'-diazidostilbene-2,2'-disulfonate) was used in place of the azide polymer. Sensitivity is evaluated by irradiating light from an ultra-high pressure mercury lamp for 20 seconds, developing with warm water at about 40°C, and determining how much illuminance (W/ITr) is sufficient to obtain a pattern with a predetermined hole diameter (160 μm). went. In the case of the comparative example, an illuminance of 1.43 W/rrr is required, but if the azide polymers of Examples 1 and 2 are used, the illumination intensity is 0.
A pattern with the same hole diameter can be obtained with an illuminance of 95 W/rrl'.

Table 1 Example 4 The composition liquid described in Example 3 was spin-coated on a panel, and after drying, a shadow mask was attached, and an ultra-high pressure mercury lamp was used as a light source.
Using a rotating light source exposure table, sheath light was applied to the positions where the red, blue, and green phosphors were to be deposited in the presence of air at -atmospheric pressure. Spray developing with warm water for 2 minutes, drying, applying black carbon, drying again, immersing in etching solution at 50°C for 3 minutes, then spraying water to remove the dots along with the carbon on top, and remove the black matrix. Manufactured. The black matrix holes were substantially smaller in area than the exposed portions.

Thereafter, phosphor coating, aluminizing, frit baking, and tIt gun sealing were performed in the same manner as in the conventional method.
A black matrix color cathode ray tube was obtained. In the above process, the exposure time was shorter than when using conventional compositions.

〔Effect of the invention〕

The photosensitive composition of the present invention has high sensitivity and exhibits reciprocity law failure characteristics. Therefore, it can be used, for example, in the production of large-sized black matrix color cathode ray tubes, and can be exposed to light in a short time. Furthermore, even when used in the manufacture of high-definition black matrix color cathode ray tubes, it has the effect of compensating for the reduction in illuminance on the exposed surface due to the smaller hole diameter of the shadow mask.

Claims (1)

[Scope of Claims] 1. A copolymer containing a maleic acid ester using azidobenzylideneacetophenonesulfonic acid or azidobenzylideneacetophenonecarboxylic acid or a salt thereof as an ester group as a water-soluble photosensitive monomer unit, and a water-soluble highly A photosensitive composition characterized by comprising molecules. 2. A photosensitive composition characterized in that the water-soluble polymer exhibits reciprocity law failure characteristics when used together with the photosensitive compound according to claim 1. 3. 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 to the desired pattern in the presence of oxygen. A pattern forming method comprising the steps of: developing the coating film to form a pattern having an area substantially smaller than the light irradiation area. 4. A pattern forming method, wherein the surface on which the pattern is formed is an inner surface of a color cathode ray tube face plate.