JPS6023761B2 - Method for producing photosensitive polymer - 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 are well known and are used as photosensitive resins. Aromatic azide groups have so far been introduced into polymers by the reaction of aromatic diazonium salts and sodium azide, but since a large amount of nitrogen is generated during the reaction, a large reactor is required compared to the amount of product. In particular, when a polymeric diazonium salt is converted into an azide in a solution, the liquid volume expands due to foaming due to its high viscosity, so it is necessary to use a large reactor or to add the azide in portions. Furthermore, since polymers with phenylazide groups modified with azidobenzoic acid or azidobenzaldehyde have short light absorption wavelengths, aromatic nitro compounds such as 1-nitropyrene and 1,8-dinitropyrene are usually added as sensitizers. However, some of these are carcinogenic, making them undesirable for use.

In view of the above-mentioned current situation, the present invention provides a method for producing photosensitive polymers that does not require a particularly large reactor or the divisional addition of a substance having an azide group, and does not require the addition of a sensitizer to the obtained polymer. The purpose of this work was to provide polyvinyl alcohol with 2-chlorine o-5
Esterification with nitrobenzoic acid chloride or 3-nito-4-chlorobenzoic acid chloride followed by reaction with sodium azide produces a 2-azido-5-nitrophenylcarbonyloxychetylene structure or 4-azido-3-nitro The present invention relates to a method for producing a photosensitive polymer containing a phenylcarbonyloxyethylene structure.

2-chloro-5-nito, which is an intermediate product obtained by the production method of the present invention.

Phenyl carbonyloxythiolesopolymers have been found to react very readily with sodium azide in aprotic solvents such as dimethyl formaldehyde. In the present invention, to esterify polyvinyl alcohol with 2-chloro-5-nitrobenzoic acid chloride or 4-chloro-3-nitrobenzoic acid chloride, for example, the chloride is added to a hexamethylphosphoramide solution of polyvinyl alcohol. A method of adding either of these and pyridine to the mixture, leaving it in a flooded state for a suitable period of time, and then reacting it with tanol is being explored.

The 2-chloro-5-nitrobenzoic acid chloride or 4-chloro-3-nitrobenzoic acid chloride is synthesized, for example, by reacting the corresponding chloronitrobenzoic acid with an excess of thionyl chloride. Since the method for producing the photosensitive polymer of the present invention is as described above, the photosensitive polymer can be easily obtained without using a particularly large reactor or adding sodium azide in portions. Furthermore, the photosensitive polymer obtained by the method of the present invention is sensitive to ultraviolet rays without adding a sensitizer, and can be used as various etching materials and photosensitive films.

Examples of the present invention are shown below. Example 1 The solvent was purified according to conventional methods before use.

Polyvinyl alcohol (degree of saponification of about 80%, average degree of polymerization of about 500), sodium azide, and sodium N,N-jethyldithiocarbamate were used as they were. 2-chloro-5-nitrobenzoic acid was reacted with excess thionyl chloride to synthesize 2-chloro-5-nitrobenzoic acid chloride.

2.9% of polyvinyl alcohol was dissolved in 40% of hexamethylphosphoramide, and 15% of 2-chloro-5-nitrobenzoic acid chloride and 5.6% of pyridine were added to give 60% of polyvinyl alcohol.
The reaction mixture was stirred immediately at 0.0 °C for 1 hour, added to 500 °C of methanol, precipitated, dried, dissolved again in tetrahydrofuran (THF), precipitated with methanol, and dried.

The yield of the obtained ester [1} was 10.7 hours, the intrinsic viscosity was 1.8 d'/hour, and the degree of esterification was 99.8%. Ester (1' was a 2-chloro-5 nitrophenylcarponyloxyethylene polymer. The polymer {1
}1.1.40' dimethyl formaldehyde (D
MF), add 0.33 g of sodium azide,
Stir for 1 hour at 20oo. The reaction mixture was added to 500 g of water to precipitate and dry, then dissolved in THF, reprecipitated with methanol, and dried. The yield of dry matter is 0.7
Polymer '2 whose structural unit is 2-azido-5-nitrophenylcarbonyloxyhethylene in which 90.3 mol% of chlorine has been replaced with an azide group, according to the infrared absorption spectrum and chlorine content. It turned out to be '.

Incidentally, when irradiated with ultraviolet rays, the film of polymer (1) was crosslinked and became insolubilized.

Example 2 Add 4-chloro-3nitrobenzoic acid to excess thionylchloride.

4-chloro-3-nitrobenzoic acid chloride was synthesized by reaction with Lido. Borivinyl alcohol and 4-chloro-
3 nits.

A 4-chloro-3nitrophenylcarbonyloxychetylene polymer {3' was synthesized from benzoic acid chloride under the same conditions as 'li' in Example 1. The intrinsic viscosity was 0.5 d'/night, and the degree of esterification was 99.8%. After that, ■ of Example 1
Under the same conditions as above, a 4-azido-3nitrophenylcarbonyloxyhethylene polymer {4) was synthesized from a 4-chloro-3nitrophenylcarbonyloxycyethylene polymer {3'. In addition, the infrared absorption of the polymer {4) is 2130 Fox-1
, 1740hada-1 and 1540kitsune-1, and when irradiated with ultraviolet rays, the absorption intensity of 2130hada-11540hada-1 decreased. Ultraviolet irradiation was performed from a distance of 30 skin using a high-pressure mercury lamp (USH-25 dish manufactured by Ushio Electric).

Examples 3 and 4 Table 1 shows the results of synthesizing a 2-azido-5-nitrophenylcarbonyloxyethylene polymer under conditions different from those in Example 1.

table ·

Claims (1)

[Claims] 1 Polyvinyl alcohol is esterified with 2-chloro-5-nitrobenzoic acid chloride or 3-nitro-4-chlorobenzoic acid chloride and then reacted with sodium azide to produce 2-azide. - A method for producing a photosensitive polymer containing a 5-nitrophenylcarbonyloxyethylene structure or a 4-azido 3-nitrophenylcarbonyloxyethylene structure.