JPS59187340A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive composition giving a tough photosensitive film and capable of being developed with an aqueous developer by blending polyvinyl butyral, polyvinyl formula or polyvinyl acetate with an o-quinone diazide compound. CONSTITUTION:A photosensitive composition is obtd. by adding an o-quinone diazide compound to polyvinyl butyral having 10,000-230,000 average mol.wt. and 20-80mol% degree of butyral formation, polyvinyl formal having 9,000- 150,000 average mol.wt. and 20-80mol% degree of formula formation, or polyvinyl acetate having 15,000-270,000 average mol.wt. The amount of the o- quinone diazide compound added to the high molecular compound is 5-50wt%, preferably 10-30wt%. The photosensitive composition gives a tough film and a fine image having sharp relief, and since no org. solvent is used, the work efficiency is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive composition containing polyvinyl butyral, polyvinyl formal, or polyvinyl acetate and an orthoquinone diazide compound, and more particularly, the present invention relates to a photosensitive composition that has a strong photosensitive film and is suitable for aqueous development. The present invention relates to a photosensitive composition that can be developed with a liquid.

Photosensitive compositions containing a polymer compound and an orthoquinone diazide compound have been known for a long time, such as a phenol resin and 1,2-naphthoquinone diazide (2).
There is a combination of novolac esters of -4-sulfonic acid. These are used for applications such as photoresists and reliefs.

However, although these combinations can be developed with an alkaline aqueous solution, the photosensitive film is brittle and easily scratches, resulting in insufficient mechanical strength.

An object of the present invention is to solve these problems and provide a photosensitive composition which has a tough photosensitive film and can be developed with a wood-based developer.

As a result of intensive research in order to solve the above problems, the present inventors have discovered that when using a photosensitive composition containing polyvinyl butyral, polyvinyl formal, or polyvinyl acetate and an orthoquinone diazide compound, the I discovered that I could achieve my goal. The present invention has been made based on this knowledge.

The polymer compound used in the present invention is one or more selected from the group consisting of polyvinyl butyral, polyvinyl formal, and polyvinyl acetate. These polymer compounds can be used if they are soluble in organic solvents, but if their molecular weight is too small, the film strength will decrease, and if their molecular weight is too large, the photosensitive liquid will become highly viscous.
This is not preferable because the adjustment becomes difficult. If the degree of butyralization and the degree of formalization are too low, water resistance will deteriorate, and if it is too high, developability with an aqueous developer will decrease.

For the above reasons, polyvinyl butyral has an average molecular weight of 10,000 to 230,000 and a degree of butyralization of 20 to 80 mo1%, polyvinyl formal has an average molecular weight of 9,000 to 150,000 and a degree of formalization of 20 to 80 mo1%, and polyvinyl acetate has an average molecular weight of 9,000 to 150,000 and a degree of formalization of 20 to 80 mo1%. A polymer compound having an average molecular weight of 15,000 to 270,000 is preferred.

Further, as the orthoquinonediazide compound used in the present invention, 2-diazo-1-naphthol-5(4'
-methylphenylsulfone 1-), 2-diazo-1-
Naphthol-5-phenoxysulfonate, novolac ester of 1,2-naphthoquinone-siacid (2)-4-sulfonic acid 2,2'-dihydroxy-diphenyl-bis-(naphthoquinone-1,2-diazide-5-sulfonic acid ester) ), 2.3.4-1-lioxybenzophenone-bis(def1-quinone-1,2-diazide-5-
sulfonic acid esters), etc.

The amount of these orthoquinonediazide compounds to be added to the polymer compound is usually 5 to 50% by weight, and a preferable addition amount is 10 to 30%.

Furthermore, if necessary, dyes, pigments, etc. may be added. Depending on the purpose of use, if it is necessary to improve developability, corrosion resistance, etc., phenol resins, styrene-maleic acid copolymer resins, alkyd resins that are compatible with polyvinyl butyral, polyvinyl formal, or polyvinyl acetate may be used. , epoxy resin, etc. may be added in an amount equal to that of polyvinyl butyral, polyvinyl formal, or polyvinyl acetate.

The photosensitive composition of the present invention is generally used by dissolving it in an organic solvent and applying it to a substrate. Specific examples of organic solvents include acetin, methyl ethyl ketone, cyclohexanone, methyl alcohol, ethyl alcohol, propyl alcohol, toluene, xylene, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether, ethylene isbricol monoethyl ether, and dimethylpol 11. Examples include amides, etc., or mixtures of these organic solvents.

As the developer for the photosensitive composition of the present invention, an aqueous solution of an alkali metal salt compound of an aromatic carboxylic acid, an aromatic sulfonic acid, a phenol, or an alkyl sulfuric acid, and an alkali metal hydroxide and/or carbonate is used. can be used. Specific examples of these compounds include aromatic carboxylic acids such as P-chlorobenzoic acid, salicylic acid, and an-1-
Ranilic acid, etc., aromatic sulfonic acids such as 1-naphthol-4-sulfonic acid, phenols such as ethyl P-hydroxybenzoate, pentachlorophenol, etc., alkyl sulfates such as sodium, potassium, etc., lauryl sulfate, etc. Examples include metal salt compounds. Specific examples of hydroxides or carbonates of these alkali metals include sodium hydroxide and potassium hydroxide, and examples of the latter include lithium carbonate and potassium carbonate.

In view of the developability, stability, etc. of the developer, the most preferred developer is an aqueous solution of sodium P-chlorobenzoate, sodium salicylate, alone or in a mixture, and helium hydroxide, potassium hydroxide, alone or in a mixture. can be given. The concentration of the developer is usually 4 to 4.
It can be used as a 0% by weight aqueous solution, but for the purpose of improving developability, an organic solvent such as methyl alcohol is added to these developing solutions in an amount of 1 to 40% by weight.
% can also be added.

According to the photosensitive composition of the present invention, good images with strong films and sharp relief can be obtained, and workability is also good because no organic solvent is used.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 A film forming solution having the following composition was applied onto a polyethylene terephthalate film having a thickness of 100 μm so that the film thickness after drying was 10 μm and dried to form an alcohol-soluble polyamide layer.

Film-forming solution Next, a photosensitive solution having the following composition was applied onto the above polyamide layer so that the coating film after drying had a thickness of 3 μm, and dried to obtain a photosensitive film.

Photosensitive liquid: Bring this photosensitive film into close contact with the negative border line,
After exposure for 40 seconds from a distance of 1 m using a 2 kW ultra-high pressure mercury lamp, the photosensitive layer can be developed and the polyamide layer etched with one solution by processing with the following developer. A negative film was obtained.

Comparative Example of Developer Solution 1 Polymer compound for binder of photosensitive solution of Example 1...
Instead of polyvinyl butyral resin, phenolic resin (
A photosensitive film was prepared according to Example 1 using Gunei Chemical Industry Co., Ltd. (trade name: MP120HH), and a developed negative film was obtained.

The processed negative film was almost the same as in Example 1, except that the photosensitive film was not folded or
When the photosensitive film of Comparative Example 1 was strongly rolled into a cylindrical shape, cracks appeared, and grooves of the same type were formed in the soluble polyamide layer during the development process, but no abnormality was observed in the photosensitive film of Example 1. There wasn't.

Example 2 A 0.1 μm aluminum film was provided on one side of a 100 μm polyethylene terephthalate film by vacuum evaporation, and a photosensitive solution having the following composition was applied thereon so that the dried coating had a thickness of 3 μm, and then dried.

Photosensitive solution A positive original was brought into close contact with this film and exposed for 2 minutes from a distance of 1 m using a 2 kW ultra-high pressure mercury lamp, and then developed using the following developer. Next, aluminum was etched with a 50% by weight aqueous phosphoric acid solution. The photosensitive layer in the exposed area sufficiently functioned as a resist, and a clear aluminum positive image with high image light-shielding properties was obtained.

Developer Comparative Example 2 A photosensitive film was made according to Example 2 using a phenol resin (part name: MP120HH, manufactured by Gungaku Kagaku Kogyo Co., Ltd.) in place of the polyvinyl acetate used in the photosensitive solution of Example 2. Ta.

When both the films of Example 2 and Comparative Example 2 were bent and rolled tightly before development, the film of Comparative Example 2 showed cracks, and during the development and etching process, the aluminum in the cracked areas was dissolved and a good image was obtained. I couldn't.

No abnormalities were observed in the film of Example 2.

Example 3 A photosensitive solution having the following composition was applied onto a 100 μm thick polyethylene terephthalate film and dried to obtain a photosensitive film having a 3 μm thick colored photosensitive layer.

This photosensitive film was brought into close contact with a positive original, exposed for 60 seconds from a distance of 1 m using a 2 kW ultra-high pressure mercury lamp, and then treated with the developer of Example 1 to obtain a clear blue positive image.

Agent: Patent Attorney Moritani - Yu Procedure correction band type) %formula% 1.Display of the incident Patent Application No. 140907/1982 2. Name of the invention photosensitive composition 3. Person who makes corrections Relationship to the case Patent applicant Kimoto Co., Ltd. 4. Agent〒1.03 3-9-5 Nihonbashi Honmachi, Chuo-ku, Tokyo 5. Date of amendment order April 24, 1982 -21(

Claims (1)

[Scope of Claims] 1. A photosensitive composition characterized by containing one or more polymeric compounds selected from the group consisting of polyvinyl butyral, polyvinyl formal, or polyvinyl acetate, and an orthoquinone diazide compound. thing. 2. Polyvinyl butyral has an average molecular weight of 10,000 to 230,000 and a degree of butyralization of 20 to 80 mo.
1% of the photosensitive composition according to claim 1. 3. Polyvinyl formal has an average molecular weight of 19,000 to 150,000 and a degree of formalization of 20 to 80 m.
1% of the photosensitive composition according to claim 1. 4. Polyvinyl acetate has an average molecular weight of 115,000 to 27
0000. The photosensitive composition according to claim 1. 5. The photosensitive composition according to any one of claims 1, 2, 3, or 4, wherein the amount of the orthoquinone diazide compound added to the polymerized metal is 5 to 50 weight percent. thing. 6. A photosensitive composition containing one or more polymeric compounds selected from the group consisting of polyvinyl butyral, polyvinyl formal, or polyvinyl acetate and an orthoquinone diazide compound is exposed, and then developed with an aqueous developer. A method for developing a photosensitive composition, characterized by: 7o Claim 6, wherein the aqueous developer is an aqueous solution of an alkali metal salt compound of aromatic carboxylic acid, aromatic sulfonic acid, phenols, or alkyl sulfuric acid, and an alkali metal hydroxide and/or carbonate. The development method described in .