JPH06239930A - Production of aqueous solution of water-soluble photosensitive resin - Google Patents

Abstract

PURPOSE:To produce an aqueous solution of a water soluble photosensitive resin having high sensitivity and excellent in releasability. CONSTITUTION:An aqueous solution of a water-soluble photosensitive resin is produced by reacting a copolymer of a polymerizable unsaturated group- containing water-soluble monomer and vinyl acetophenone with an azide group- containing aldehyde compound and acetaldehyde and then adding two kinds of alkali compounds of sodium hydroxide and ammonia to the reactional product.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a water-soluble photosensitive resin containing acetaldehyde as a raw material, and more particularly to a method for producing an aqueous solution of a water-soluble photosensitive resin useful for forming a black matrix of a color cathode ray tube.

[0002]

2. Description of the Related Art Conventionally, a water-soluble photosensitive resin has been used as a material for forming a pattern, and is particularly useful as a material for forming a fine matrix pattern in the production of a black matrix of a color cathode ray tube. . As an example of this water-soluble photosensitive resin, JP-A 1-3
No. 02348 describes a copolymer containing a water-soluble monomer unit containing a polymerizable unsaturated group and a monomer unit having an azide group and a functional group exhibiting ionicity in an aqueous solution. Among them, water-soluble photosensitive resins containing a maleic acid unit and vinyl azidobenzylidene acetophenone sulfonate and vinyl azidocinnamylidene acetophenone sulfonate units are among the ones which are excellent in characteristics and relatively easy to synthesize.

[0003]

The above water-soluble photosensitive resin has high sensitivity, but when the resin that is no longer needed after the pattern is formed is peeled off from the substrate, the releasability is not sufficient and the resin is completely removed. There was a problem that it could not be removed and remained on the substrate. The present invention provides a method for producing an aqueous solution of a water-soluble photosensitive resin that maintains high sensitivity and improves releasability.

[0004]

The present invention is directed to the reaction of a copolymer of a polymerizable unsaturated group-containing water-soluble monomer with 4-vinylacetophenone, an azide group-containing aldehyde compound and acetaldehyde, followed by addition of sodium hydroxide. The present invention relates to a method for producing a water-soluble photosensitive resin aqueous solution in which two types of alkalis of ammonia are added. This water-soluble photosensitive resin contains a polymerizable unsaturated group-containing water-soluble monomer unit and an azide group and a monomer unit having a functional group exhibiting ionicity in an aqueous solution.

The copolymer of the polymerizable unsaturated group-containing water-soluble monomer and 4-vinylacetophenone in the present invention is a known compound, for example, the copolymer of the polymerizable unsaturated group-containing water-soluble monomer and styrene is free. It is obtained by acetylation by the Delucrafts reaction. As the water-soluble monomer containing a polymerizable unsaturated group, maleic acid, acrylic acid, methacrylic acid, styrenesulfonic acid, 2-acrylamido-2
-Methyl-1-propanesulfonic acid and the like. As the azido group-containing aldehyde compound, an aldehyde compound having an azide group on the aromatic ring and a functional group showing ionicity in an aqueous solution can be used. Examples of this include sodium 4-azidobenzaldehyde-2-sulfonate, 4-
Azidobenzaldehyde-2-sulfonate potassium, 4
-Sodium azidobenzaldehyde-2-carboxylate and the like can be mentioned. It is preferable to react the azido group-containing aldehyde compound in a proportion of 0.5 to 2 equivalents and acetaldehyde in a proportion of 0.2 to 1 equivalent to 1 equivalent of the acetyl group of the above copolymer, and the product is water-soluble. It is preferable to use water because it has good properties, and the reaction temperature is preferably in the range of 30 ° C to 50 ° C in consideration of the stability of azide as a raw material.
Use acetaldehyde as undiluted solution, or
It can be used as a 20% by weight aqueous solution.

In the present invention, two kinds of alkalis, sodium hydroxide and ammonia, are used in combination as the alkali used for dissolving the above copolymer. The ratio of the two can be selected arbitrarily, but from the viewpoint of characteristics, sodium hydroxide 100
Ammonia is preferably in the range of 50 to 400 parts by weight with respect to parts by weight.

[0007]

The present invention will be described below with reference to examples. In addition,
In Examples and Comparative Examples, “part” means “part by weight” and “%” means “% by weight”. Comparative Example SMA-3000 [manufactured by ATOCHEM, styrene-maleic anhydride copolymer (75% styrene, molecular weight about 20
00)] 33 g was dissolved in 250 ml of chloroform.
This solution was added dropwise to a solution prepared by dissolving 50 g of acetyl chloride and 83 g of anhydrous aluminum chloride in 300 ml of chloroform while stirring at room temperature. Then, the mixture was heated and refluxed with stirring for 2 hours. After allowing this to cool, it was filtered and the insoluble material was dried and pulverized. This powder was washed with a large amount of water and dried to obtain a maleic acid-4-vinylacetophenone copolymer. 20 g of this copolymer, 10 g of sodium hydroxide, 20 g of sodium 4-azidobenzaldehyde-2-sulfonate and 3 g of acetaldehyde were sequentially dissolved in 1 liter of water at 40 ° C., and the mixture was stirred at 40 ° C. for 3 hours as it was. 240 g of sodium chloride was added to the solution, and suction filtration was performed. The residue was put into 1 liter of a 1.5% aqueous acid solution, stirred, and suction filtered. The filter cake was put in 1 liter of water and stirred at 40 ° C., 3 g of sodium hydroxide was added, and the mixture was stirred for 1 hour to be dissolved. To the solution was added 5 liters of ethyl alcohol to form a precipitate, which was filtered off and dried to give a co-weight of maleic acid, sodium 4-vinylmonoazidobenzylideneacetophenonesulfonate and sodium 4-vinylmonoazidocinnamylideneacetophenonesulfonate. A coalescence (A) was obtained.

Example 1 Maleic acid and 4-vinylmonoazidobenzylideneacetophenone were prepared in the same manner as in Comparative Example 1 except that 3 g of sodium hydroxide in Comparative Example 1 was changed to 2.5 g of sodium hydroxide and 2.5 g of 25% aqueous ammonia. A copolymer (B) of sodium sulfonate and sodium 4-vinylmonoazidocinnamylideneacetophenonesulfonate was obtained.

Example 2 3 g of the sodium hydroxide of the comparative example was mixed with 1.
A copolymer of maleic acid, sodium 4-vinylmonoazidobenzylideneacetophenonesulfonate, and sodium 4-vinylmonoazidocinnamylideneacetophenonesulfonate (C) in the same manner as in Comparative Example except that 5 g and 5 g of 25% ammonia water were used. ) Got.

The properties of the copolymers of Examples and Comparative Examples are shown in Table 1.
Shown in.

[Table 1]

* The sensitivity was evaluated by the following method. 0.3 parts of copolymer, 1.7 parts of PAD (acrylamide-diacetone acrylamide copolymer), and 98 parts of water were mixed and stirred, and spin-coated on a glass plate to a thickness of 0.5 to 1 μm, and 60 ° C. It is dried for 1 minute at 50 ° C to form a coating film, which is then irradiated with ultraviolet light for 20 seconds and then sprayed with hot water for development to 160 μm.
The minimum illuminance required to obtain the hole diameter pattern was investigated and the reciprocal was taken as the sensitivity. (Note that the values are expressed as relative sensitivities where the sensitivity of the comparative example (0.7 W / cm ² ) is set to 1.) Peelability was 5 after forming a pattern with a hole diameter of 160 μm using the same material. After treatment with a stripping solution consisting of 95% by weight hydrogen peroxide solution and 5 parts of sulfamic acid at 60 ° C. for 2 minutes, the stripping property was observed by developing with warm water. Peelability is
Expressed at the next level. ◯: Good product level Δ: Good product limit As shown in Table 1, it is possible to produce a water-soluble photosensitive resin having high sensitivity and improved releasability according to Examples.

[0012]

By the method for producing a water-soluble photosensitive resin according to the present invention, it is possible to produce an aqueous solution of a water-soluble photosensitive resin which maintains high sensitivity and is excellent in releasability. By using the aqueous resin solution of the present invention for producing, for example, a black matrix for a large color cathode ray tube, exposure time can be shortened and quality can be improved to improve productivity.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Nobuaki Hayashi Inventor Nobuaki Hayashi 1-280, Higashi Koigokubo, Kokubunji, Tokyo Inside the Central Research Laboratory, Hitachi, Ltd.

Claims (1)

[Claims] 1. A polymerizable unsaturated group-containing water-soluble monomer and 4
-A method for producing a water-soluble photosensitive resin aqueous solution, which comprises reacting a copolymer with vinylacetophenone, an azide group-containing aldehyde compound and acetaldehyde, and then adding two kinds of alkalis, sodium hydroxide and ammonia.