JPH0360415B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a diazo photosensitive composition that provides clear images. 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 light is irradiated through the original image having an image, that is, imagewise exposure is performed, development is performed using an alkaline developer containing a coupling component, and in the case of a two-component type, after imagewise exposure, Development is carried out using an alkaline developer, and during image exposure, the diazo compound and coupling component that remain undecomposed without being exposed to light or decomposed are removed under alkaline conditions. It is well known to those skilled in the art to couple with azo dyes to form azo dyes and thus obtain copies with dye images. Many compounds have been proposed and used as coupling components for diazo copying materials, which couple with diazo compounds to produce diazo dyes. Among these, the following general formula There is a hydrazone compound represented by This coupling component makes it possible to obtain a stable clear black image with a tinge of gray or blue even if the developing conditions vary slightly. However, this coupling component exhibits a pale yellow to deep yellow color, and has the disadvantage that the background area of the image recording is colored. The present invention has been made to eliminate the above-mentioned drawbacks. While synthesizing various formazan dyes, the present inventor focused on a hydrazone compound that is colorless and has good coupling properties, and arrived at the present invention. That is, the gist of the present invention is a photosensitive composition characterized by containing a hydrazone compound represented by the following general formula and a diazonium salt. (However, R ₁ , R ₂ :H, CH ₃ , C ₂ H ₅ may be the same or different. R ₃ :

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[Formula] n: an integer of 0 to 12) Typical examples of compounds having the above general formula used in the present invention are shown in Table 1.

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【table】

[Table] These hydrazone compounds can be easily obtained by reacting an aliphatic aldehyde compound and a hydrazine compound as shown in the reaction formula below. The method for synthesizing the hydrazone compound of the general formula according to the present invention is illustrated below. Synthesis method: (1) n-Laurylaldehyde-2-benzothiazolehydrazone (compound No. 18) 5.0g (0.0303mol) of 2-benzothiazolehydrazine and 100ml of ethanol were placed in a flask, and while stirring,
n-laurylaldehyde 5.78g (0.0303mol),
A solution of 10 ml of ethanol was added dropwise little by little. If stirring is continued for 1 hour after the dropwise addition, crystals will precipitate.
The crystals were redissolved in a water bath, gravity filtered, and the filtrate was recrystallized. The precipitated crystals were filtered off and recrystallized with ethanol repeatedly. Yield 6.5g
(yield 65%), colorless, wool-like needle-like crystals with a melting point of 99-101°C were obtained. (2) n-laurylaldehyde-2-pyridylhydrazone (compound No. 29) 2-hydrazinopyridine 4.0g (0.0367mol),
Add 40ml of ethanol and 0.5ml of glacial acetic acid to a flask, and add 6.8ml of n-laurylaldehyde while stirring.
g (0.0367 mol) in 10 ml of ethanol was added dropwise little by little. After continuing stirring for 1 hour, the precipitate was redissolved in a hot water bath, an appropriate amount of water was added so that no precipitate would come out, and gravity filtration was performed, and the filtrate was recrystallized. The precipitated crystals were filtered off and recrystallized repeatedly using an ethanol/water mixed solvent. Yield 8.2g (yield 82%)
Colorless, wax-like crystals with a melting point of 57-58.5°C were obtained. Other hydrazone compounds are also prepared by the same synthesis method as above, but when the alkyl of the aliphatic aldehyde is short, for example, when n-propyl aldehyde and 2-hydrazinobenzothiazole are reacted,
Adding a small amount of tetrahydrofuran to the alcohol will make the reaction go better. If the alkyl group of the aliphatic aldehyde is long, adding one drop of concentrated hydrochloric acid or about 1 ml of glacial acetic acid will improve the yield. Additionally, adding a small amount of zinc chloride to the reaction solution will increase the yield. 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-3-methoxyphenylpiperidine, 4-diazo-2,5-diethoxyphenylpyrrolidine, 4-Diazo-2,5-dipropoxyphenylpiperazine, 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. When a compound having the above general formula is used as a coupling component of a two-component copying material, naphthalene mono-, di- or tri-naphthalene may be used as an additive.
Sodium sulfonate, sulfosalicylic acid, urea, thiourea, sulfuric acid, tartaric acid, citric acid, malic acid, malonic acid, caffein, thiophyllin, saponin, etc. are used. Examples will be presented to explain the present invention in further detail. Examples 1 to 18 Photosensitive layer forming solutions 1 to 18 were prepared by mixing the following components. Citric acid: 2 g Sodium naphthalene-1,3,6-trisulfonate: 1 g Thiourea: 0.5 g Second hydrazone compound: 1 g 2-hydroxy-3-naphthoic acid nitroanilide
: 1 g 4-diazo-2,5-dibutoxy-N-phenylmorpholine BF ₄ 2 g Cellulose acetate 4 g Dioxane: 100 ml The above photosensitive layer forming solutions 1 to 18 were applied to a triacetate film and dried to form a photosensitive film. Obtained. This photosensitive film was divided into two parts, an original drawing with an image was superimposed on each part, and after exposure for 4 seconds to a 160W fluorescent light using commercially available diazo copying material,
Table 2 shows the results of developing images using a developer (a) obtained by mixing the following components and ammonia gas (that is, using a wet type copying machine and a dry type copying machine). Developer solution (a): Potassium carbonate: 2 g Potassium metaborate: 3 g Water: 100 ml

[Table] Examples 19-20 Hydrochloric acid gas was gently passed through a solution of 4 g of n-butyraldehyde-2-benzothiazole hydrazone No. 13 dissolved in 150 ml of ether for 30 minutes, and the precipitate was filtered out. A product obtained by quaternizing the nuclear nitrogen of thiazole No. 13 was obtained. This product had become water soluble. (This hydrazone is named No. 13 ⁺ ) Using No. 13 ⁺ and No. 13 hydrazone, the following compositions were mixed to prepare photosensitive layer forming solutions 19 to 20. Tartaric acid: 2 g Caffeine: 2 g Sulfosalcylic acid: 1 g Hydrazone from Table 3: 1.5 g 2-hydroxy-3-naphthoic acid ethanol
: 1 g 4-Diazo-2.5-diethoxy-N,N-dipropylaniline chloride 1/2ZnCl ₂ : 2 g Saponin: 0.1 g Water: 100 ml The above photosensitive layer forming liquids 19 to 20 were applied to white base paper for photosensitive paper. A photosensitive paper was obtained by coating and drying. This photosensitive paper
Images 19 to 20 are image-exposed using a wet copying machine, and developer (a′) is applied.
The results shown in Table 3 were obtained.

[Table] Regarding the coupling property, the image density of Example 19 was significantly higher than that of Example 20, and it was found that it is better to apply the photosensitive liquid in the form of a solution.

Claims (1)

[Scope of Claims] 1. A photosensitive composition comprising a hydrazone compound represented by the following general formula and a diazonium salt. (However, R ₁ and R ₂ : H, CH ₃ and C ₂ H ₅ may be the same or different. R ₃ : [Formula] [Formula] [Formula] [Formula] [Formula] or [Formula] [Formula] [Formula] [Formula] n: An integer from 0 to 12)