JPH0361938B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming an image using a photosensitive composition containing polyvinyl butyral, polyvinyl formal, or polyvinyl acetate and an azide compound soluble in an organic solvent. relates to an image forming method using a photosensitive composition which has a strong photosensitive film and can be developed with an aqueous developer.

Photosensitive compositions containing a polymer compound and an aromatic azide compound are conventionally known, such as a combination of a cyclized rubber and an aromatic azide compound, a combination of an alkali-soluble formalin condensation resin and an aromatic azide compound, etc. be. These are used for applications such as photoresist and photorelief.

However, although the combination of cyclized rubber and aromatic azide compound has excellent corrosion resistance and adhesion,
Toxicity to the human body as it is developed using an organic solvent.
It cannot be said to be desirable from the viewpoint of work environment such as flammability.

Furthermore, a combination of an alkali-soluble formalin condensation resin and an aromatic azide compound can be developed with an alkaline aqueous solution, but the photosensitive film is brittle and easily scratched, resulting in insufficient mechanical strength.

An object of the present invention is to solve these problems and provide an image forming method using a photosensitive composition which has a strong photosensitive film and can be developed with an aqueous developer.

As a result of intensive research to solve the above problems, the present inventor used a photosensitive composition containing polyvinyl butyral, polyvinyl formal, or polyvinyl acetate and an azide compound soluble in an organic solvent. It has been discovered that the above objective can be achieved when 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 as long as they are soluble in organic solvents, but if their molecular weight is too low, the curing of the exposed areas will be weak and the exposed areas will swell or run out when developed, making them unsuitable for practical use. Moreover, the film strength also decreases. In addition, as the molecular weight increases, photocuring of exposed areas improves and resistance to aqueous developers improves, but solubility of unexposed areas in aqueous developers decreases, development time becomes longer, and extreme In such cases, development becomes impossible and the photosensitive solution becomes highly viscous, making preparation, coating, etc. difficult, which is not preferable. Regarding the degree of butyralization and formalization, if they are low, it will be insoluble in organic solvents and difficult to mix with azide compounds that are soluble in organic solvents, and the water resistance of the coating will be poor. When the temperature increases, the solubility in an aqueous developer decreases, and in extreme cases, development becomes impossible. For the above reasons, polyvinyl butyral has an average molecular weight of 10,000.
230,000, the degree of butyralization is 20 to 80 mol%, and the average molecular weight of polyvinyl formal is 9,000.
From 150,000, the degree of formalization is 20 to 80 mol%,
For polyvinyl acetate, the average molecular weight starts from 15,000.
270,000 is preferred.

In addition, examples of the azide compounds soluble in organic solvents used in the present invention include 4,4'-diazidochalcone, 2,6-di(4'-azidobenzal)-cyclohexanone, and 2,6-di(4'- Azidobenzal)
-4-methyl-cyclohexanone, 4,4'-diazidostilbene, 4,4'-diazidobenzophenone, P-phenylene diazide, 4,4'-diazidophenylmethane, etc. .

The amount of these organic solvent-soluble azide compounds added to the polymer compound is usually 1 to 60%, preferably 4 to 30%, by weight.

Furthermore, if necessary, an increaser for these azide compounds, a dye, a pigment, etc. may be added.
Depending on the purpose of use, if it is necessary to improve developability, corrosion resistance, etc., phenolic 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 acetone, methyl ethyl ketone, cyclohexanone, methyl alcohol, ethyl alcohol, propyl alcohol, toluene,
Examples include xylene, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dimethylformamide, and mixtures of these organic solvents.

As a 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 can be used. Specific examples of these compounds include aromatic carboxylic acids such as P-chlorobenzoic acid, salicylic acid, and anthranilic acid, aromatic sulfonic acids such as 1-naphthol-4-sulfonic acid, and phenols such as P-
Examples of alkyl sulfates include ethyl hydroxybenzoate and pentachlorophenol, lauryl sulfate, and alkali metal salts of these compounds such as sodium and potassium.
In view of the developability, stability, etc. of the developer, the most preferred are sodium P-chlorobenzoate and sodium salicylate. The concentration of the developer can usually be used as an aqueous solution with a concentration of 4 to 40% by weight, but in order to improve the developability, organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, benzyl alcohol, etc. are added to these developers. It is also possible to add 1 to 40% by weight.

According to the image forming method of the photosensitive composition of the present invention, a good image with a strong film 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. Note that the present invention is not limited to the following examples.

Example 1 A photosensitive solution having the following composition was coated on a polyethylene phthalate film having a thickness of 100 μm which had been subjected to corona discharge treatment so that the coating film after drying had a thickness of 3 μm, and then dried.

Photosensitive liquid Polyvinyl butyral Eslec BX-L
(manufactured by Sekisui Chemical Co., Ltd.) 10 parts by weight 4,4'-diazide chalcone 2 〃 Methyl ethyl ketone 50 〃 Toluene 40 〃 Butyl acetate 30 〃 Oil Blue 603 (manufactured by Hodogaya Chemical Co., Ltd.)
0.2〃 A negative original was brought into close contact with the photosensitive film obtained in this way and exposed for 1 minute from a distance of 1 m using a 2〓 ultra-high pressure mercury lamp, and then developed with the following developer to remove the unexposed areas. was removed and a clear positive image was obtained.

Developer Sodium salicylate 40 parts by weight Water 60 〃 Example 2 A 0.1μ aluminum film was provided on one side of a 100μ polyethylene phthalate film by vacuum deposition, and a photosensitive solution with the following composition was dried on top of it.
It was applied to a thickness of 3μ and dried.

Photosensitive liquid Polyvinyl acetate Gosenyl M35-X6 (35% methyl alcohol solution, Nippon Gosei Chemical Industry Co., Ltd.)
) 40 parts by weight Methyl ethyl ketone 60 Toluene 40 2,6-di(4'-azidobenzal)-4-methylcyclohexanone 3 A negative original was brought into close contact with this film and exposed to light from a distance of 1 m using a 2 kW ultra-high pressure mercury lamp. After exposure for one minute, development was carried out using the following developer. then
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 Sodium P-chlorobenzoate 20 parts by weight Water 80 〃 Example 3 A film forming solution with the following composition was applied onto a 100μ thick polyethylene terephthalate film so that the film thickness after drying was 10μ, and dried. An alcohol-soluble polyamide layer was formed.

Film forming liquid Alcohol-soluble polyamide/Ultramid
IC (manufactured by BASF) 10 parts by weight Red organic dye 3 Methyl alcohol 70 Toluene 20 Next, a photosensitive solution with the following composition was applied on the polyamide layer so that the coating film after drying was 3μ, and dried. A photosensitive film was obtained.

Photosensitive liquid Polyvinyl butyral Eslec BL-3 (manufactured by Sekisui Chemical Co., Ltd.) 4 parts by weight 2,6-di(4'-azidobenzal)-cyclohexanone 0.6 〃 Methyl ethyl ketone 60 〃 Toluene 40 〃 Use this photosensitive film as a positive original After bringing them into close contact and exposing them for 40 seconds from a distance of 1 meter using a 2 kW ultra-high pressure mercury lamp, the photosensitive layer can be developed and the polyamide layer can be etched with one solution by processing with the developer used in Example 2. A good negative film was obtained.

Example 4 A photosensitive solution having the following composition was applied onto a copper-clad laminate so that the coating film after drying had a thickness of 4μ, and dried.

Photosensitive liquid Polyvinyl formal vinylec K (manufactured by Chitsuso Corporation) 10 parts by weight 2,6-di(4'-azidobenzal)-4-methylcyclohexanone 1 〃 Toluene 45 〃 Methyl alcohol 20 〃 Ethylene glycol monomethyl ether
30 This was placed in close contact with a negative original and exposed for 2 minutes from a distance of 1 meter using a 2 kW ultra-high pressure mercury lamp. After developing with the developer used in Example 2, the film was immersed in a 40% by weight ferric chloride aqueous solution to etch the copper in the non-image areas, but the photosensitive layer in the exposed areas was not sufficiently exposed to the resist. fulfilled its function. Thereafter, the resist layer could be easily removed by immersion in dimethylformamide.

Example 5 The film that had been exposed in Example 1 was developed using the following developing solutions 1 to 3.
As in Example 1, clear positive images were obtained in all cases.

Developer 1 Sodium lauryl sulfate 25 parts by weight Water 75 〃 Developer 2 Sodium alkylnaphthalene sulfonate salt (34% or more of active ingredients manufactured by Perex NBL, Kao Atlas Co., Ltd.) 50 parts by weight Water 50 〃 Developer 3 P-hydroxy 36 parts by weight of η-propyl benzoate Sodium hydroxide 8 Water 100 Comparative example A known photosensitive liquid having the following composition was dried on the polyamide layer of the polyethylene terephthalate film having the alcohol-soluble polyamide layer produced in Example 3. The film was coated to a thickness of 3μ and dried to obtain a photosensitive film.

Photosensitive liquid Phenol resin MP-707 (manufactured by Gunei Kagaku Co., Ltd.) 4 parts by weight 2,6-di(4'-azidobenzal)-cyclohexanone 0.6 〃 Methyl ethyl ketone 60 〃 Toluene 40 〃 This photosensitive film is brought into close contact with a positive original After exposure was carried out for 1 minute and 30 seconds from a distance of 1 m using a 2 kW ultra-high pressure mercury lamp, the photosensitive layer was developed with a 1% by weight aqueous sodium hydroxide solution. Next, the polyamide layer was etched using the developer used in Example 2, but cracks appeared in the photosensitive layer, and the polyamide layer in the cracked areas was etched.
It was not possible to obtain a good negative film.

Claims (1)

[Claims] 1 As a polymer compound, average molecular weight from 10,000
Polyvinyl butyral with degree of butyralization from 20 to 80 mol% at 230000, average molecular weight from 9000
150,000 with a formalization degree of 20 to 80 mol%, or polyvinyl acetate with an average molecular weight of 15,000 to 270,000, and 1 to 60% by weight of the polymer compound. A photosensitive composition containing an azide compound soluble in an organic solvent is exposed to light and photocured,
An image forming method, which is then developed with an aqueous developer that is an aqueous solution of an alkali metal salt compound of aromatic carboxylic acid, aromatic sulfonic acid, phenols, or alkyl sulfuric acid.