SU958413A1 - Process for purifying 1,2-naphthoquinonediazidesulfo esters of iodine-substituted 4,4'-dioxydiphenylpropane - Google Patents

Description

54) METHOD FOR CLEANING 1,2-NAFT.OHINONDIAZIDESULPHOEFRATES OF IODINE-SUBSTITUTED 4.4-DIOXYDIPHYNENYL PROPANE

This invention relates to a method for purifying an industrial photosensitive product 1,2-naphthoquinone diazium cisulfoesters of iodo-substituted 4,4-dioxidine diphenylpropane, which has found widespread use in positive-type photoresists.

The method of purification of 1,2-naphthoquinone diazids sulphoesters of iodosubstituted 4,4-dioxydiphenylpropane is not available. . Known is a method for preparing 1,2-naftohinondiazidsulfoefirov yodzameschennogo 4.4 -dioksidifenilpropana comprising iodination 4.4 -dioksidifenilpropana followed by acylation of the resultant 1,2-yodproizzodnogo naftohinondiazid- (2) -5-sulfonyl chloride with a disksane and diluting the reaction mass with water. The 1,2-naphthoquinone diazides sulpho ester of the iodosubstituted 4,4-dioxidiphenyl propane formed in the reaction was isolated from the solution in dioxane by adding 3% hydrochloric acid solution l.

The disadvantage of this method is that the reaction is carried out at, and the acylation time is several minutes. In this mode, a solution of 1,2-naphthoquinone diazidesulfonic esters of iodo-substituted 4,4-dioxydiphenylpropane in dioxane at a concentration of 1-50% is stable, and the component with low solubility in dioxane does not precipitate during the synthesis. In addition, the disadvantage of this method is the irreproducibility of sulphospheres by the degree of substitution of oxy groups for naphthoquinone diazide

10 residues and on the content of iodine in the molecule of iodo substituted 4,4-dioxydiphenylpropane in the target product, as a result of which the resulting photosensitive product represents

15 is a mixture of mono- and dyspirs mono-, DI- tri- and tetriodisubstituted 4,4-dioxydiphenylpropane. These sulfoester components differ in solubility in organic solvents. .

The use of such an unstable sulfoester composition as a photosensitive component in the composition leads to non-reproducibility of the technological characteristics of photoresists, as well as to an increase in the defectiveness of the film as a result of extremely crystallization of the sulfoester components with low solubility

30 both when storing the composition and

in the film during the formation of the photosensitive layer. The crystallization of the sulfoether from the composition and during the formation of the film leads to a decrease in the shelf life of the photoresist from b months to 2 weeks and to an increase in its defectiveness from 20 to 70 cm.

The purpose of the invention is to improve the quality of the target product.

This goal is achieved by the fact that according to the method of purification of 1,2-naphthoquinone diazidesulfonic esters of iodosubstituted 4,4-dioxidiphenylpropane 1,2-naphthoquinone diazides sulfone ester of iodosubstituted 4,4-dioxydiphenyl propane is treated with dioxane at 18–24 ° C for 24 h at a concentration of 4,4-dioxydiphenyl propane and treated with dioxane at 18–24 ° C for 24 h at 4–4-dioxydiphenylpropane treated with dioxane at 18–24 ° C for 24 h at 4–4-dioxydiphenylpropane treated with dioxane at 18–24 ° C for 24 h at 4 ° –dioxydiphenylpropane and treated with dioxane at 18–24 ° C for 24 h at 4 ° –dioxydiphenylpropane treated with dioxane at 18–24 ° C for 24 h at 4 ° –dioxydiphenylpropane treated with dioxane at 18–24 ° C for 24 h at 4 ° –dioxydiphenylpropane treated with dioxane at 18–24 ° C. 50 wt.%, Followed by precipitation of the desired product by adding ice water to the filtrate at pH 1-2

Cleaning is subjected to a technical product with the content of insoluble components from 2 to 70%.

In the purified product, the concentration of insoluble components with a low iodine content is reduced to 1%. This leads to an increase in the iodine content in the purified sulfoester to 41–49%, and the content of naphthoquinone azide (NCD) groups is 25–29%

Example 1. In a 500 ml thin flask, 210 g (42%) of an industrial 1,2-naphthoquinone diadeesulfone ester of iodo substituted 4,4-dioxydiphenylpropane is dissolved with%, | insoluble components 46; iodine 40.2, nitrogen 3.7 and NHD groups 30.5 in 300 ml of dioxane. The solution is left in the closed flask for a day at 182 4 s. Then the contents of the flask are filtered through a .1 layer of a nylon technology or laboratory filter paper on a Buchner funnel. The soluble sulfoester remaining in the Filtrate is separated from the solution by precipitation while pouring the filtrate on-cooled water with ice with vigorous continuous stirring. The volume of water is taken about 2.5 times the volume of the filtrate (the pH of the water is adjusted by adding concentrated hydrochloric acid to a value of 1-2 universal indicator paper). The precipitated sulfoester is filtered on a Büchner funnel through 1 base layer, technical nylon or filter paper. Then the product is thoroughly washed with chilled distilled water until neutral.

The washed sulfoester is dried on a Buchner funnel with the vacuum on (0.7–0.8 atm) for about 1 h, then dried in air for a day and in vacuum at 0.05 atm.ost. to constant weight. The light yellow, dried sulfoester contains:

insoluble, components 0., 5; iodine 42.7} nitrogen 3,4 NHD groups 27.5.

Example 2. In a flask with a thin section, 150 g of an industrial 1,2-naphthoquinone diazide sulfoether of iodo-substituted 4,4-dioxydiphenylpropane with a content,% t, of insoluble components 70; iodine 37.6 / nitrogen 3.9, NHD groups 33 and 340 ml of dioxane. The process is then carried out as in Example 1 at 20 ° C. Purified, dried sulfoester does not contain insoluble impurities, iodine 47.5%, nitrogen 3.3% and NHD groups 28.2%.

Example 3. In a flask with thin section, 250 g of an industrial 1,2-naphthoquinone diazide sulfoether yozameceinogr 4,4-dioxidiphenylpropane with% are dissolved; insoluble components 2; iodine 39.6 / nitrogen 3.9, NHD 35.7 and 243 ml of dioxane. The process is then carried out as in Example 1 with. Purified and dried sulfoester contains,%: insoluble impurities 0.1, iodine 49.7, nitrogen 3,4 NHD groups 28.6.

When using solutions of industrial 1,2-naphthoquinone di-sidho ester of yo-substituted 4,4-dioxydiphenyl propane with a concentration of sulfo ester in dioxane less than 30%, purification is ineffective. Thus, for the complete isolation of insoluble components from the technical sulfoester with a solution concentration of 8-10%, it is necessary to maintain the solution at room temperature for about 17 days. When the concentration of the solution is more than 50%, the industrial sulfoester begins to precipitate already in the process of its dissolution. As a result, the yield of the purified product is significantly reduced. Thus, a solution concentration of 30-50% is optimal.

At elevated temperature of the solution (), insoluble components of the sulfoester are not precipitated from the solution. At temperatures below room temperature (for example, at + 10 ° C) partial precipitation from the solution and soluble components of the sulfoester occurs, which reduces the yield of the main product. Therefore, the prepared solution should be maintained at 18-24 C.

The proposed purification method of the industrial 1,2-naphthoquinone diazide sulfoether of iodosubstituted 4,4-dioxydiphenylpropane makes it possible to obtain a photosensitive product with high solubility in organic solvents due to the absence of insoluble components in the sulfoether. The stability of the composition prepared on the purified product, not less than 10-12 months, the defectiveness of the film

0.2–0.5 cm. For a composition on a crude sulfoester, the stability of the composition is 0.5–2 months, the film is defective, 20–70 cm.

Claims (1)

1. USSR author's certificate No. 687066, cl. C 07 C 143/68, 1979 (prototype).