JPS6140977B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a diazo copying method using a compound having the following general formula as a coupling component in diazo copying. In the above formula, R is

【formula】

【formula】 or

[Formula] R ₁ is

[expression] or

[Formula], and R ₂ is an alkyl group having 1 to 4 hydrogen carbon atoms, a halogen, a substituted amino group or a sulfone group. Diazo copying materials include one-component copying materials in which a diazo compound is supported on the surface of a support such as paper, and two-component copying materials in which a diazo compound and a coupling component are supported on a support. In the case of a two-component type, after irradiating light through an original image with an image, that is, performing image exposure, it is developed using an alkaline developer containing a coupling component. , developed using an alkaline developer, and during image exposure, the remaining undecomposed diazo compound and coupling component are removed without being exposed to light and therefore without being decomposed, using an alkaline developer. It is well known to those skilled in the art to couple under conditions to form azo dyes and thus obtain copies with dye images. The compound having the above general formula can be used as a coupling component in one-component type and two-component type copying materials as described above, and can be coupled with a diazo compound to produce a yellow azo dye. The above compounds can form excellent black dye images when used together with a coupling component capable of forming a blue-violet azo dye. Many compounds have been proposed and used as coupling components that couple with diazo compounds to produce azo dyes. For example, coupling components that produce blue to purple azo dyes include naphthols, those that produce yellow to red azo dyes include phenol derivatives and resorcinol, and those that produce yellow azo dyes include active methylene groups. compounds that have Various combinations of such coupling components have been proposed in order to obtain copies with black dye images in diazo copying materials. However, when two or more types of coupling components are used in combination, it is difficult to obtain a clear black image because the coupling speeds differ. As coupling components for obtaining black dye images, phenol derivatives, acetoacetanilide, and 2-methylresorcinol among resorcinols have been used together with naphthols that produce blue to purple azo dyes, but these have been used satisfactorily. It is not possible to obtain a clean black dye image like this. The present invention was made in order to eliminate such defects, and by using a compound of the above general formula in place of the above acetoacetanilide and 2-methylresorcinol, a compound of the above general formula is used. A black dye image can be easily formed. Typical specific examples of the coupling component of the present invention represented by the above general formula are as follows. 2,4-dihydroxybenzaldehyde phenylhydrazone, 2,4-dihydroxy-3-methylbenzaldehyde phenylhydrazone, 2,4-dihydroxy-5-chlorobenzaldehyde phenylhydrazone, 2,4-dihydroxybenzaldehyde-2-
Benzothiazolylhydrazone, 2,4-dihydroxybenzaldehyde-2-
Naphthylhydrazone, 2-hydroxy-1-naphthaldehyde phenylhydrazone, 2-hydroxy-8-dimethylamino-1-naphthaldehyde phenylhydrazone, 2-hydroxy-6-sulfonate sodium-
1-naphthaldehyde phenylhydrazone, 2-hydroxy-1-naphthaldehyde benzothiazolylhydrazone. The coupling component of the present invention is obtained by reacting a hydrazine compound and an aldehyde compound as shown below. The method for synthesizing the coupling component of the present invention is illustrated below. Synthesis method: 1 2,4-dihydroxy-3-methylbenzaldehyde phenylhydrazone Phenylhydrazine 10.8g (0.1 mol), 2.
15.2 g (0.1 mol) of 4-dihydroxy-3-methylbenzaldehyde and 200 ml of ethanol were placed in a flask, and the reaction was carried out with stirring at a temperature of 40°C to 50°C for 1 hour, then poured into water 1 to remove the precipitate. After filtering and drying, recrystallize using 300 ml of toluene. Yield 17.7g (yield 73.1%) mp130.5℃~131.5℃. 2 2-Hydroxy-1-naphthaldehyde phenylhydrazone Phenylhydrazine 10.8g (0.1 mol), 2-
Hydroxy-1-naphthaldehyde 17.2g
(0.1 mol) and 500 ml of ethanol are placed in a flask and reacted for 1 hour with stirring at a temperature of 70°C to 80°C, then poured into 2 ml of water, and the precipitate is filtered off and dried. Yield 24.3g
(Yield 92.8%) mp199℃~200℃. As the diazo compound used with the coupling component of the present invention, any of the diazo compounds used in ordinary diazo copying materials can be used, but typical ones are as follows. 4-Diazo-2,5-dimethoxyphenylmorpholine, 4-diazo-2,5-diethoxyphenylmorpholine, 4-diazo-2,5-dipropoxyphenylmorpholine, 4-diazo-2,5-di Butoxyphenylmorpholine, 4-diazo-2,5-dibutoxy-N-benzyl-N-ethylaniline, 4-diazo-2,5-dibutoxy-N,N-dibutylaniline, 4-diazo-2,5-dibutoxy -N-benzyl-N-hydroxyethylaniline, 4-diazo-2,5-dibutoxyphenylpiperidine, 4-diazo-2,5-diethoxyphenylpyrrolidine, 4-diazo-2,5-dipropoxyphenyl enylpiperazine, 4-diazo-N/N-dimethylaniline, 4-diazo-N/N-diethylaniline, 4-diazo-N-ethyl-N-hydroxyethylaniline, 4-diazo-N/N-dipropylaniline , 4-diazo-phenylmorpholine, 4-diazo-phenylpyrrolidine, 4-diazo-2-methylphenylpyrrolidine. Diazo copying materials employing the coupling component of the present invention may contain additives such as sodium naphthalene mono-, di- or tri-sulfonate, sulfosalicylic acid, urea, thiourea, sulfuric acid, tartaric acid, citric acid, malic acid, caffeine, Theophylline, saponin, etc. are used. Examples of diazo copying materials using the coupling component of the present invention are shown below. Example 1 A photosensitive layer forming liquid (2) was prepared by mixing the following components. Photosensitive layer forming liquid () Tartaric acid 2 g Caffeine 2 g Sulfosalicylic acid 1 g 2,4-dihydroxy-3-methylbenzaldehyde phenylhydrazone 1.5 g 2-hydroxy-3-naphthoic acid ethanolamide 1 g 4-diazo-2.5 -Diethoxy-N・N-dipropylaniline chloride 1/2 ZnCl ₂ 2 g Saponin 0.1 g Water 100 ml The above photosensitive layer forming solution () is applied to white base paper for photosensitive paper and dried to obtain a two-component diazo copying material. (No.1) was obtained. This copying material was divided into two parts, an original drawing with an image was superimposed on each part, and after being exposed to a 160W fluorescent lamp for about 4 seconds using a commercially available diazo copying machine, a developed product was obtained by mixing the following components. Each was developed using ammonia gas and ammonia gas (i.e., using a wet copier and a dry copier), both yielding copies with sharp black dye images. Developer solution (): Potassium carbonate 2g Potassium metaborate 3g Water 100ml Examples 2 to 4 Example 1 except that photosensitive layer forming solutions (), (), and () prepared by mixing the following components were used.
Two-component diazo copying materials (No. 2 to No. 4) were obtained using exactly the same procedure as in Example 1, and using the same copying machine and the same developing method as in Example 1. Then, exposure and development were carried out to obtain copies with clear black dye images. Photosensitive layer forming liquid () Citric acid 2 g Caffeine 2 g Sodium naphthalene-1,3,6-trisulfonate 1 g 2,4-dihydroxybenzaldehyde-2-benzothiazolylhydrazone 1 g 2-hydroxy-3-naphthoate Acid morpholinopropylamide 1 g 4-diazo-2.5-diethoxy-N.N-dibenzylaniline chloride 1/2ZnCl ₂ 2.5 g Saponin 0.1 g Water 100 ml Photosensitive layer forming liquid () Malic acid 3 g Theophylline 2 g Sodium dehydroacetate 1 g Urea 0.5 g 2,4-dihydroxy-5-chlorobenzaldehyde phenylhydrazone 1 g 2-hydroxy-3-naphthoic acid hexylamide
1 g 4-Diazo-2,5-dibutoxy-N/N-methylbenzylaniline chloride 1/2ZnCl ₂ 2 g Saponin 0.1 g Water 100 ml Photosensitive layer forming liquid () Sulfuric acid 3 g Caffeine 2 g Naphthalene-1,3 -Sodium disulfonate
1 g Thiourea 0.5 g Sodium 2-hydroxy-6-sulfonate-1
-Naphthaldehyde phenylhydrazone 0.7 g 2-hydroxy-3-naphthoic acid ethanolamide 1 g 4-diazo-N.N-dipropylaniline chloride
1/2ZnCl ₂ 2 g Saponin 0.1 g Water 100 ml Example 5 The following components were mixed to prepare a photosensitive layer forming solution (). Photosensitive layer forming liquid () Citric acid 2 g Sodium naphthalene-1,3,6-trisulfonate 1 g Thiourea 0.5 g 2-hydroxy-1-naphthaldehyde benzothiazolylhydrazone 1 g 2-hydroxy-3-naphthoate Acid nitroanilide 4-diazo-2,5-dibutoxy-N-phenylmorpholine BF ₄ 2 g Dioxane 100 ml The above photosensitive layer forming solution () was applied to a triacetate film and dried to form a two-component diazo photosensitive film ( No.5) was obtained. Using this photosensitive film, image exposure was carried out using a dry copying machine and development was carried out using ammonia gas, and a clear black dye image was formed. The density of the dye image obtained as described above was measured using a Masbeth densitometer and was found to be 1.1 to 1.3. Furthermore, this dye image was irradiated with light for 3 hours using a fade meter to check for fading, and it was found that there was almost no fading. Further, the two-component diazo copying material and photosensitive film obtained as above were heated at 50°C and 50%RH.
After forced aging by leaving them in an atmosphere of (relative humidity) for one week, they were exposed and developed as shown in Example 1, but the density of the dye images was lower than that before aging. It was only a slight decline. Comparative Examples 1-2 2 of the photosensitive layer forming liquid () used in Example 1
Acetoacetanilide was used in place of 4-dihydroxy-3-methylbenzaldehyde phenylhydrazone, and in place of 2,4-dihydroxybenzaldehyde-2-benzothiazolylhydrazone in the photosensitive layer forming solution () used in Example 2. ,
Comparative diazo copying materials (No. 1-1 and No. 2-1) were obtained by repeating the procedure used in Example 1, except that 2-methylresorcinol was used, and exposed as in Example 1. and developed to obtain a copy. The image density of this copy was measured as described above, the fading condition was checked using a fade meter, and a forced aging test was conducted. Diazo copying materials No. 1 to No. 5 prepared by the method of the present invention and diazo copying materials for comparison as described above.
The results of measurements performed on the copies obtained from No. 1-1 and No. 2-1 are shown in the table below.

[Table] As can be seen from the above results, when the compound represented by the above-mentioned general formula is used as a coupling component for forming a black dye image of a diazo copying material, it has been found that To form an excellent black dye image compared to the case of using an active methylene compound such as acetoacetanilide or a compound such as 2-methylresorcinol which is used as a component for forming a dye image. I can do it.

Claims (1)

[Claims] 1. The following general formula [In the above formula, R is [Formula] [Formula] or [Formula] R ₁ is [Formula] or [Formula] (R ₂ is hydrogen, an alkyl group having 1 to 4 carbon atoms, a halogen, a substituted amino group, or a sulfone group) as a coupling component in diazo copying.