JPH0549210B2 - - Google Patents

Description

[Detailed description of the invention]

(a) Industrial Application This invention relates to diazo copying materials. More specifically, the present invention relates to a diazo copying material that contains a specific compound as a stabilizer, so that image deterioration of undeveloped film over time is reduced, and component bleeding does not occur on the surface of undeveloped or developed film. . (b) Conventional technology Conventional stabilizers for diazo copying materials include organic carboxylic acids such as citric acid and oxalic acid, organic sulfonic acids such as sulfosalicylic acid and p-toluenesulfonic acid, and inorganic stabilizers such as sulfuric acid and hydrochloric acid. protonic acid,
Inorganic Lewis acids such as boron trifluoride are known. In particular, organic sulfonic acids are widely used because they are less dangerous and have sufficient ability to prevent pre-coupling. The so-called bleed phenomenon, in which fine powder floats to the surface of the film, tends to occur, and an improvement has been desired. (c) Problems to be Solved by the Invention This invention was made in order to improve the above-mentioned drawbacks, and its purpose is to improve the stability of the undeveloped film over time by containing a specific compound as a stabilizer. It is an object of the present invention to provide a diazo copying material with little image deterioration and no component bleeding onto the surface of undeveloped or developed film. In order to achieve the above object, the present invention was achieved by conducting detailed studies on materials used in diazo copying materials. (d) Means for Solving the Problems According to the present invention, in a diazo copying material comprising a photosensitive layer on a support containing a diazo compound and a coupling component as main components, the stabilizer has the general formula (): A diazo copying material is provided, which contains at least one compound represented by the formula (wherein R is an alkyl group having 4 to 20 carbon atoms). As the stabilizer used in this invention, those represented by the above general formula () are used. Films using this type of stabilizer have little image deterioration over time in undeveloped films, and there is no component bleeding to the surfaces of undeveloped or developed films. Specific examples of the compound represented by the general formula () include n-butylbenzenesulfonic acid, tert-butylbenzenesulfonic acid, hexylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, hexadodecylbenzenesulfonic acid, eiko Examples include sacilbenzenesulfonic acid. The coupling components used in this invention are not particularly limited, and those conventionally used in diazo copying materials can be used as they are. For example, phenol, 2,6-ditertiarybutylphenol,
Resorcinol, 2-methylresorcinol, phloroglucinol, pyrogallol, benzotriazole, 4-chlorresorcinol, α-resorcinol, β-resorcinol, dianoacetate morpholino, acetoacetanilide, 1-hydroxy-4-
Methoxynaphthalene, 2-naphthol-3-carboxylic acid-anilide, 2-naphthol-3-carboxylic acid-2'-methoxyanilide, 2-naphthol-
3-carboxylic acid-2'-ethoxyanilide, 2-naphthol-3-carboxylic acid-4'-chloroanilide, 2-naphthol-3-carboxylic acid-3'N-morpholino-propylamide, 2-naphthol-3
-Carboxylic acid-ethanolamide, 2-naphthol-3-carboxylic acid-diethanolamide, 2-
Naphthol-3-carboxylic acid-α-naphthanilide, 2-naphthol-3-carboxylic acid-β-naphthanilide, 2-naphthol-3-carboxylic acid-
2'-methylanilide, 2-naphthol-3-carboxylic acid-3'-nitroanilide, 2-naphthol-
Examples include 3-carboxylic acid-2',5'-dimethoxyanilide. Similarly, the diazo compound used in the present invention is not particularly limited, and those conventionally used in diazo copying materials can be used as they are. . For example, 4-dimethylaminobenzeneazonium, 4
-diethylaminobenzenediazonium, 4-diisopropylaminobenzenediazonium, 4-
Dibenzylaminobenzenediazonium, 4-methylbenzylaminobenzenediazonium, 4-
Morpholino-2,5-diethoxybenzenediazonium, 4-morpholino-2,5-diisopropoxybenzenediazonium, 4-morpholino-
2,5-dibutoxybenzenediazonium, 4-
Pyrrolidino-3-methoxybenzenediazonium, 4-morpholinobenzenediazonium, 4-
Strong acid salts of diazo compounds (e.g. sulfuric acid,
boron tetrafluoride, phosphoric acid hexafluoride, etc.),
Also included are double salts of these diazo compounds and metal halides (for example, zinc chloride, tin chloride, cadmium chloride, etc.), but of course the salts are not limited to these. The support used in this invention is commonly used, such as polyester film, polyethylene film, polycarbonate film,
Examples include acetate film and paper. In the present invention, in addition to the above-mentioned materials, various materials added to ordinary diazo copying materials, such as thiourea and urea as antioxidants, can be used. Further, saponin or the like can be used as a dispersing agent, and caffein, theophylline, etc. can be used as a solubilizing agent. As the binder resin, polymers such as starch, casein, polyvinyl acetate, polyacrylic acid or sodium polyacrylate, and cellulose derivatives can be used. Furthermore, fine silica powder can be added as a matting agent. If necessary, a styrene-based, vinylidene chloride-based, etc. undercoat may be applied. To prepare the diazo copying material of this invention, the above components are dissolved or dispersed in a suitable solvent such as water or methyl ethyl ketone, and this solution is then spread onto a suitable support such as polyester, cellulose acetate film or paper. Apply and dry. On this occasion,
The molar ratio of the stabilizer to the diazo component is desirably 1:0.1-10, preferably 1:0.1-1. To develop an azo dye image on the film produced in this way, the image is printed using a fluorescent lamp or an ultraviolet mercury lamp, and then an ammonia gas or alkaline developer is used, as with general diazo copying materials. to form an azo dye image. (E) Effect Since the diazo copying material of the present invention has the above-mentioned structure, image deterioration of the undeveloped film over time is reduced, and component bleeding to the surface of the undeveloped and developed film is improved. (F) Examples The present invention will be explained in detail below using examples. Example 1 A photosensitive solution is prepared with the following composition. Methyl ethyl ketone 40.0g Methyl cellosolve 40.0g Cellulose acetate 15.0g Silica fine powder 1.0g Dodecylbenzenesulfonic acid 1.5g 4-morpholino-2,5-dibutoxybenzenediazonium・BF ₄ 2.0g 2-naphthol-3-carboxylic acid-α- Naphthylanilide 1.4g The above photosensitive solution was coated with a wire bar on a polyester film (thickness 75μ) whose surface had been previously treated with a 10% monochloroacetic acid aqueous solution at 90°C.
A diazo copying material having a photosensitive layer with a thickness of 10 μm was obtained. Example 2 A photosensitive solution is prepared with the following composition. Methyl ethyl ketone 40.0g Methyl cellosolve 40.0g Cellulose acetate 15.0g tert-butylbenzenesulfonic acid 1.5g 4-morpholino-2,5-dibutoxybenzenediazonium・PF ₆ 2.2g 2-hydroxynaphthalene-3-carboxylic acid-
α-Naphthylamide 0.8g The above photosensitive solution was coated on a polyester film (thickness 75μ) whose surface had been previously treated with a 10% monochloroacetic acid aqueous solution using a wire bar, and then heated to 90°C.
A diazo copying material having a photosensitive layer with a thickness of 10 μm was obtained. Example 3 A photosensitive solution is prepared with the following composition. Methyl ethyl ketone 40.0g Methyl cellosolve 40.0g Cellulose acetate 15.0g Eicosylbenzenesulfonic acid 1.2g 4-Toluylmercapto-2,5-diethoxybenzenediazonium PF ₆ 2.3g 2-Naphthol-3-carboxylic acid-2'-methoxyanilide 0.6g of the above photosensitive solution was applied using a wire bar onto a polyester film (thickness 75μ) whose surface had been previously treated with a 10% monochloroacetic acid aqueous solution, and then heated at 90°C.
A diazo copying material having a photosensitive layer with a thickness of 10 μm was obtained. Example 4 A photosensitive solution is prepared with the following composition. Acetone 40.0g Methyl cellosolve acetate 40.0g Cellulose acetate butyrate 15.0g Hexylbenzenesulfonic acid 0.5g 4-morpholino-2,5-diisopropoxybenzenediazonium・PF ₆ 1.8g 2-naphthol-3-carboxylic acid-ethanolamide 0.8 g Resorcinol 1.0g The above photosensitive solution was coated with a wire bar on a polyester film (thickness 75μ) whose surface had been previously treated with a 10% monochloroacetic acid aqueous solution, and then heated at 90°C.
A diazo copying material having a photosensitive layer with a thickness of 10 μm was obtained. Comparative Example 1 A photosensitive solution is prepared with the following composition. Methyl ethyl ketone 40.0g Methyl cellosolve 40.0g Cellulose acetate 15.0g Boron trifluoride/methanol complex
0.5g 4-dimethylaminobenzenediazonium BF ₄
1.4g 2-naphthol-3-carboxylic acid-2'-ethoxyanilide 0.9g The above photosensitive solution was applied using a wire bar onto a polyester film (thickness 75μ) whose surface had been previously treated with a 10% monochloroacetic acid aqueous solution. 90℃
A diazo copying material having a photosensitive layer with a thickness of 10 μm was obtained. Comparative Example 2 A photosensitive solution was prepared with the following composition. Methyl ethyl ketone 40.0 g Methyl cellosolve 40.0 g Cellulose acetate 15.0 g Sulfosalicylic acid 0.4 g 4-dimethylamino-3-chlorobenzene diazonium BF ₄ 0.9 g 2-naphthol-3-carboxylic acid-2'-ethoxyanilide 1.2 g After coating with a wire bar on a polyester film (thickness 75μ) whose surface was previously treated with a 10% monochloroacetic acid aqueous solution, the temperature was heated to 90°C.
A diazo copying material having a photosensitive layer with a thickness of 10 μm was obtained. Comparative Example 3 A photosensitive solution is prepared with the following composition. Methyl ethyl ketone 40.0g Methyl cellosolve 40.0g Cellulose acetate 15.0g Paratoluenesulfonic acid 1.0g 4-morpholino-2,5-dibutoxybenzenediazonium・BF ₄ 2.0g 2-naphthol-3-carboxylic acid-diethanolamide 0.9g Resorcinol 0.3g The above photosensitive solution was applied using a wire bar onto a polyester film (thickness 75μ) whose surface had been previously treated with a 10% monochloroacetic acid aqueous solution at 90°C.
A diazo copying material having a photosensitive layer with a thickness of 10 μm was obtained. Test film Example 1 prepared as above
4 and Comparative Examples 1 to 3, the following tests were conducted. The test method and results are shown below. 1 Image deterioration test Each specimen was heated at 60℃ and 90% relative humidity for 72 hours, and then the image was printed using a mercury lamp and completely processed using an ammonia developer (Daicel Chemical Industries, Ltd. Across automatic processor AP-26D). Let the color develop,
Measure the density of the image area and non-image area using a transmission densitometer (Macbeth transmission densitometer TD-904, using a visible filter). The measurement results are shown below. Concentration measurement results

[Table] As is clear from the above, discoloration in the image area and increase in density in the non-image area are observed in both Comparative Examples 1 and 2, whereas in Example and Comparative Example 3, there is almost no change in density and the image It can be seen that there is little deterioration. 2. Bleed test Test specimens are prepared from undeveloped and developed film, each specimen is heated and left at 60°C and 90% relative humidity for 72 hours, and the presence or absence of bleed on the surface is visually observed. However, the undeveloped film was developed using an ammonia developing machine before observation. Observation results

[Table] As is clear from the above, while component bleeding was observed in Comparative Examples 1 to 3, there was almost no component bleeding in the examples, indicating that the object of the present invention was achieved.

Claims (1)

[Scope of Claims] 1. A diazo copying material comprising a photosensitive layer on a support containing a diazo compound and a coupling component as main components, wherein the stabilizer has the general formula (): A diazo copying material characterized by containing at least one compound represented by the formula (wherein R is an alkyl group having 4 to 20 carbon atoms).