JPS6145817B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improved dry imaging material in which the resulting image is black in color. The imaging method using silver halide, which has traditionally been most widely practiced, is a wet method in which several liquids are used for development and subsequent stabilization. Therefore, it has the disadvantage that it involves many complicated processing steps and requires considerable skill in handling. In response, dry methods that do not require liquid processing have been studied, and silver salt image forming materials have been proposed that allow images to be obtained only by dry processing. These include redox-imaging combinations consisting of a non-photosensitive organic silver salt oxidizing agent, such as long-chain fatty acid silver, saccharin silver, benzotriazole silver, and a suitable reducing agent, with halogen as a photosensitive catalyst therefor. It is a photosensitive material that is developed using heat, such as silver oxide. However, it is a well-known fact among those in the field that sufficiently clear images cannot be obtained with such dry image forming materials unless a so-called toning agent is used. One such toning agent is, for example, phthalazinone, which is described in US Pat. No. 3,080,254. but,
Of the toning agents that have been proposed, phthalazinone has the most favorable properties, but has the drawback of not providing good black images with sufficient optical density. Furthermore, phthalazinone has drawbacks such as being prone to bleeding and being easily sublimed. The present invention overcomes the above-mentioned drawbacks by using a combination of phthalazinone and an organic base to provide a dry imaging material with a black tone and very high sensitivity. That is, the present invention provides a non-photosensitive organic silver salt oxidizing agent,
b a reducing agent for the silver ion, c a photosensitive silver compound or a photosensitive silver compound generating component, d at least one phthalazinone compound, and e phthalazinepyridazine, quinoline, isoquinoline, quinazoline,
It is characterized by containing five components of at least one compound selected from cinnoline. As the non-photosensitive organic silver salt oxidizing agent of component (a) used in the dry image forming material of the present invention, silver salts of long chain fatty acids are particularly suitable. For example, silver behenate, silver stearate, silver palmitate, silver myristate, silver laurate, silver oleate, etc. are effective. Other suitable silver salt oxidizing agents include silver saccharin, silver benzotriazole, silver 5-substituted salicylaldoxime, silver phthalazinone, silver 3-mercapto-4-phenyl-1,2,4-triazole, and silver perfluoroalkanesulfate. Examples include silver fluoroate. As the reducing agent of component (b) used in the present invention,
An organic reducing agent is used that has a reducing power suitable for forming a silver image, reducing the non-photosensitive silver salt oxidizing agent when heated by the catalytic action of the silver halide in the exposed areas. . Suitable reducing agents include monohydroxybenzenes such as p-phenylphenol, p-methoxyphenol, 2,6-di-t-butyl-p-cresol; di- or polyhydroxybenzenes such as hydroquinone, t-
-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, catechol; naphthol and naphthylamines, such as α-naphthol, β-naphthol, 4-aminonaphthol; hydroxybinaphthyls, such as 1,
1'-dihydroxy-2,2'-binaphthyl, 4,
4′-dimethoxy-1,1′-dihydroxy-2,
2'-hinaphthyl; phenylene diamines; aminophenols, such as N-methyl-p-aminophenol, 2,4-diaminophenol; sulfonamide phenols, such as p-(p-toluenesulfonamide) phenol; 2,6-dibromo-4-(p-toluenesulfonamide)
Phenol; methylenebisphenols, such as 2,2'-methylenebis-(4-methyl-6-t-
butylphenol), 2,2'-methylenebis-
(4-ethyl-6-t-butylphenol), 2,
4,4-trimethylpentylbis-(2-hydroxy-3,5-dimethylphenyl-)methane; 3
-pyrazolidones, such as 1-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone; ascorbic acids. Two or more kinds of such reducing agents can also be used in combination. The amount of reducing agent used depends on the type of oxidizing agent used, the type of cyclic agent, other components in the element, etc., but it is usually 0.1 to 3 mol per 1 mol of silver salt oxidizing agent. . Component (c) used in the present invention is a photosensitive silver halide or a photosensitive silver halide forming component. Silver halides include silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chlorobromoiodide, silver iodide, or mixtures thereof. The silver halide catalyst may have coarse or fine particles, but extremely fine particles are particularly preferred. Emulsions containing light-sensitive silver halides can be made by any method known in the photographic art. Silver halide produced separately in this way may be used as a component of the photosensitive layer used in the present invention, but a catalytic amount of a halogen-containing compound may be coexisting as a silver halide-forming component to produce organic silver hydrochloride. It may be formed simultaneously with the curing agent. As the photosensitive silver halide forming component, there is a halogen-containing compound which acts on a part of the organic silver salt oxidizing agent to form silver halide. Examples of such halogen-containing compounds include hydrogen halides, metal halides, halogen molecules, and organic halides having active halogens. The amount of these photosensitive silver halides or silver halide forming components used is 0.001 to 1 mole of the organic silver salt oxidizing agent.
It is 0.3 mole. The phthalazinone component (d) is preferably a compound represented by the following general formula. (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, or a carbon-containing substituent having 1 to 20 carbon atoms.
M represents a hydrogen atom, a metal atom, a hydroxyalkyl group, a carbamoyl group having a carbon substituent having 1 to 18 carbon atoms, or an acyl group having 1 to 18 carbon atoms. ) Specific examples include phthalazinone, 4-methylphthalazinone, 4-phenylphthalazinone, 4(1
-naphthyl) phthalazinone, 4(2-naphthyl)
-phthalazinone, 4-hydroxymethylphthalazinone, 4-chlorophthalazinone, 4-(p-chlorophenyl)phthalazinone, 4-methoxyphthalazinone, 4-β-styrylphthalazinone, 4-dimethylaminophthalazinone , 4(P-methoxybenzyl)phthalazinone, 4-(benzylidenehydrazino)phthalazinone, 4(p-dimethylaminophenyl)phthalazinone, 4-benzylphthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone Radinone, 8-methylphthalazinone, 6
- Bromophthalazinone, 8-t-butylphthalazinone, 5-nitrophthalazinone, 8-aminophthalazinone, 8-hydroxyphthalazinone, sodium phthalazinone, potassium phthalazinone, lithium phthalazinone , (N-phenylcarbamoyl)-phthalazinone, (N-tolylcarbamoyl)phthalazinone, (N-cyclohexylcarbamoyl)-phthalazinone, (N-methylcarbamoyl)phthalazinone, N-acetyl phthalazinone, N-benzoyl phthalazinone, etc. can be mentioned. The preferred amount of these used is in the range of 0.01 to 10 mol based on the organic silver salt oxidizing agent. Component e of phthalazine, pyridazine, quinoline,
Isoquinoline, quinazoline, and cinnoline are used in an amount of 0.1 to 2 moles per mole of phthalazinone. Derivatives of these bases have similar effects. By adding component e, the sensitivity is improved compared to when phthalazinone is used alone, the development speed is increased, and the resulting image has a clear black tone. Furthermore, when comparing films with the same sensitivity, the light-sensitive material of the present invention has significantly less contamination due to sublimation of phthalazinone. In addition to the above-mentioned components, the dry image forming material of the present invention may optionally contain a binder, a chemical sensitizer,
Various known additives such as antifoggants, spectral sensitizing dyes, antihalation dyes, and background darkening inhibitors can be optionally added. As the binder, synthetic or natural polymeric substances such as polyvinyl butyral, polymethyl methacrylate, cellulose acetate, polyvinyl acetate, cellulose acetate propionate, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol, gelatin, etc. can be used. A suitable weight ratio of these amounts to the organic silver salt oxidizing agent is 10:1 to 1:10. Chemical sensitizers include, for example, sulfur, selenium or tellurium compounds or gold, platinum or palladium compounds. Suitable sensitization methods are described, for example, in U.S. Pat.
1623499 and 3297446. Examples of antifoggants include mercury acetate, N-
These include bromosuccinimide, benzotriazole, and cadmium chloride. These antifoggants are effective in preventing so-called thermal fog, in which unexposed areas become black when the dry image forming material of the present invention is thermally developed. Spectral sensitizing dyes are useful for sensitizing silver halides and include, for example, cyanines, merocyanines, styryls, and the like. Examples of the background darkening inhibitor include tetrabromobutane, hexabromocyclohexane, tribromoquinaldine, and the like. The heat-developable photosensitive layer and other layers used in the practice of this invention are coated on a variety of supports. Examples of these supports include polyethylene film, cellulose acetate film, poly(ethylene terephthalate) film, and paper. The composition described above is coated onto one of these supports together with a binder and a suitable solvent. The thickness of the coating after drying is 1 to 1000 microns, preferably 3 to 20 microns. Further, an overcoat layer may be formed to protect the heat-developable photosensitive layer or for other purposes. The applied film is dried in hot air or at room temperature before use. The obtained dry image-forming material can be image-exposed as a light-sensitive material and then heated for 1 to 60 seconds at a temperature usually in the range of 80 to 200 DEG C. to obtain a visible image. Hereinafter, specific examples of the present invention will be described based on Examples. Examples 1 to 14 Silver behenate suspensions were prepared by ball milling 4 parts of silver behenate and 20 parts of a methyl ethyl ketone-toluene mixture (2:1 weight ratio) for 24 hours. Using this suspension, the following composition was prepared and coated on a polyester film. [Coating emulsion] First layer silver behenate suspension 12.0 g Polyvinyl butyral 3.0 g Methyl ethyl ketone 12.0 g Mercury acetate 0.05 g Ammonium bromide 0.10 g Nitrogen-containing organic base Compound names and amounts added are shown in Table 1. 2nd layer Cellulose acetate 6.0g Acetone 80.0g Phthalazinone Shown in Table 1. 2,2'-methylenebis(6-t-butyl-4-
Ethylphenol) 3.5g The addition of the first layer followed the order described above.
After the first layer was applied and dried at room temperature, the second layer was applied and dried at 70°C. All operations were performed in the dark. The obtained film will fit the mask tightly.
It was exposed to light for 1/16 seconds using a 500W tungsten lamp and developed for 5 seconds at 120°C in an oil bath. The maximum optical density (ODmax) and minimum optical density (ODmin) of the obtained images are shown in Table 1.

【table】

[Table] Note that the images of the films of Examples 1 to 14 are all blacker than those of Comparative Examples 1 and 2. or,
The film of the present invention gave a black image even when developed using a hot roll, and did not contaminate the hot roll. Examples 15 to 19 Films were produced in the same manner as in Examples 1 to 14, except that the same weight of silver stearate was used instead of silver behenate, and 0.15 g of bufenyl tellurium and diromide were used instead of ammonium bromide. It was created. Table 2 shows the results of a similar evaluation.

【table】

Claims (1)

[Scope of Claims] 1 a non-photosensitive organic silver salt oxidizing agent, b a reducing agent for the above silver ions, c a photosensitive silver compound or a photosensitive silveride forming component, d at least one phthalazinone, and e Phthalazine, pyridazine, quinoline,
A dry image forming material characterized by containing five components of at least one organic base selected from isoquinoline, quinazoline, and cinnoline. 2 The phthalazinone of component d is in the range of 0.1 to 10 mol per mol of non-photosensitive organic silver salt,
2. The dry image forming material according to claim 1, wherein the organic base as component e is in a range of 0.1 to 2 moles per mole of phthalazinone.