JPS6023762B2 - Manufacturing method of photosensitive resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a photosensitive polymer having an aromatic azide group in its side chain.

Polymers having azide groups in their side chains have been well known and have been used as photosensitive resins. Until now, aromatic azide groups have been introduced into polymers using a reaction between an aromatic diazonium salt and sodium azide, but such a reaction requires a large amount of nitrogen to be introduced during the reaction. This requires a large reactor compared to the amount of product.Especially when converting a polymeric diazonium salt into an azide in a solution, the liquid volume expands due to foaming due to its high viscosity.
It was necessary to use a large reactor or to add the azide in portions. In addition, polymers with phenylazide groups modified with azidobenzoic acid, azidobenzaldehyde, etc.
Since the light absorption wavelength is short, 1-etropylene, 1,8
Aromatic nitro compounds such as -dinitropyrene are added as sensitizers, but some of these are carcinogenic and are therefore undesirable for use.

Recently, polyvinyl alcohol has been esterified with 2-chloro-5-nitro (or 3-nitro-4-chloro)benzoic acid chloride and then reacted with sodium azide to form 2-azido-5-nitro( Alternatively, a method has been proposed in which a photosensitive resin is produced by synthesizing a polyvinyl alcohol derivative containing a 3-nitro-4-azido)benzoic acid ester group, but this method requires a special solvent to remove the polyvinyl alcohol. Moreover, there are disadvantages such as the need to use the above-mentioned acid chloride, which is unstable and highly toxic.

In view of the above-mentioned current situation, the present invention can be easily produced without the need for a particularly large reactor or the need to add a substance having an azide group in portions, and the solvent can be selected from a wide range without being limited to special ones. The purpose of this work was to provide a method for producing a photosensitive resin that does not require the use of highly toxic substances. - After reacting chlorobenzoic acid with a polymer containing epoxy groups,
By reacting with sodium azide, 2
The present invention relates to a method for producing a photosensitive resin, which comprises producing a polymer containing an azido-5-nitrobenzoic acid ester group or a 3-nitro-4-azidobenzoic acid ester group.

The type of polymer containing an epoxy group used in the present invention is not particularly limited, but as a preferred example,
Examples include sidyl (meth)acrylate polymers, bisphenol-type epoxy resins, and epoxidized products of nopolac-type resins.

In order to produce a photosensitive resin using the method of the present invention, first, the above-mentioned epoxy group-containing polymer is reacted with 2-chloro-5-nitrobenzoic acid or 3-nitro-4-chlorobenzoic acid. This reaction is usually carried out by adding the above-mentioned benzoic acid to a solution in which the above-mentioned polymer is dissolved and heating the mixture under low temperature. is preferred. Next, the product resulting from the above reaction is removed from the reaction solution by a method such as precipitation and filtration, and the product is reacted with sodium azide. This reaction can be carried out by dissolving the above product in a suitable solvent such as dimethylformamide and adding sodium azide to the solution, and if necessary, the solution may be cooled to below room temperature. In this case, a predetermined amount of sodium azide can be added all at once without dividing it, and there is no need to use a particularly large reactor, and the reaction can be carried out easily. The reaction product produced by the above reaction is a polymer containing a 2-azido-5-nitrobenzoic acid ester group or a 3-nitro-4-azidobenzoic acid ester group in the side chain, and this reaction product can be obtained by precipitation from the reaction solution. etc., it can be easily taken out.

Since the polymer thus obtained exhibits the property of being sensitive to ultraviolet light due to the action of the ester group contained in its side chain, it is used as a photosensitive resin for various etching materials and photosensitive films. Since the present invention is a method as described above, the photosensitive resin does not require the use of a particularly large reactor, the addition of materials in portions, the use of highly toxic compounds, or the use of a special solvent. It can be easily manufactured without any damage.

Examples of the present invention will be described below. Example A mixture of 4 parts of glycidyl methacrylate, 16 parts of dimethylformamide, and 0.02 parts of azobisisobutyronitrile was stirred at 75°C for 5 hours, precipitated with methanol, taken out and dried.

Three parts of the dry polymer obtained above were dissolved in 20 parts of dimethylformamide, and 4 parts of 2-chloro-5-nitrobenzoic acid were dissolved.
3 evenings, trimethylbenzylammonium chloride 0.0
The mixture was stirred at 110°C for 2 hours to react.

The reaction mixture was precipitated in methanol and dried to give a powder of 6.6 kg. This was dissolved in 60 parts of dimethylformamide, 1.25 parts of sodium azide was added, and the mixture was stirred at 5°C for 2 hours to react.

The reaction mixture was then extracted in methanol and dried.

Infrared absorption spectra and elemental analysis revealed that the structure of this substance was one in which 2-azidonitrobenzoic acid was added to polyglycidyl methacrylate.
This resin was made into a 10% solution in dimethylformamide and applied to an aluminum plate to obtain a coating film with a thickness of 2.5 microns.

A non-standard mask for sensitivity measurement (trade name: Kodatsuta Step Tablet No. 2) was placed on top of this coating film, and a 400W high-pressure mercury lamp was irradiated with 3 inkstones from a distance of 15 arcs, and the film was immersed in dimethylformamide for 1 minute. When I checked the degree of photosensitivity, it was found that 7
Every step was exposed to light.

Claims (1)

[Claims] 1 2-chloro-5-nitrobenzoic acid or 3-nitro-
By reacting 4-chlorobenzoic acid with a polymer containing an epoxy group and then reacting with sodium azide, a 2-azido-5-nitrobenzoic acid ester group or a 3-nitro-4- A method for producing a photosensitive resin, which comprises producing a polymer containing an azidobenzoic acid ester group.