JPS6145822B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improved dry imaging material that uses a novel toning agent to produce a black image. The most widely practiced silver halide imaging method to date 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 can be used in 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, and as a photosensitive catalyst for the halogenated A photosensitive material that uses silver or the like and is developed by heating. However, it is a well-known fact among those in the field that sufficiently clear images cannot be obtained in such dry image forming materials unless a so-called toning agent is used. One such toning agent is, for example, US Pat. No. 3,080,254.
There is a phthalazinone listed in but,
Toning agents that have been proposed so far do not give images with good black tones, especially when raw photosensitive materials are stored for a long period of time, they cause a decrease in black tone, and during heat development, for example, phthalazinone This method had drawbacks such as the toning agent subliming and contaminating the heat developing machine. It is an object of the present invention to provide a dry image formation system that provides a good black tone to the image obtained after exposure and heat development, has excellent long-term shelf life, and does not contaminate a heat developing machine. The goal is to provide materials. In order to achieve the above object, the present inventors have conducted extensive studies and found that N-unsubstituted sulfonamide is excellent as a toning agent.
The present invention has been completed. In JP-A No. 53-28416, N-substituted sulfonamides have been proposed as sensitizers, but as is clear from the comparative examples described later, the present invention has the following general formula ():
Surprisingly, so-called N-unsubstituted sulfonamides have dramatically higher toning effects than N-substituted sulfonamides, showing effects that could not be expected from N-substituted sulfonamides. . That is, the present invention provides (a) a non-photosensitive organic silver salt oxidizing agent, (b) a reducing agent for silver ions, (c) a photosensitive silver compound or a component for forming a photosensitive silver compound, and (d) the following general A dry image forming material characterized by containing at least one N-unsubstituted sulfonamide represented by the formula (). Component ( _a ) used in _the dry imaging material of the present invention As the non-photosensitive organic silver salt oxidizing agent, silver salts of long chain fatty acids are particularly suitable. For example, silver behenate, silver stearate, silver valmitate, silver myristate, silver laurate, silver oleate, etc. are effective. Other suitable non-photosensitive organic silver salt oxidizing agents include silver saccharin, silver benzotriazole,
5-Substituted salicylaldoxime silver, phthalazinone silver, 3-merkaft-4-phenyl-1,2,4
- Silver triazole, silver perfluoroalkanesulfonate, etc. Component (b) used in the present invention is a reducing agent for silver ions, which reduces the non-photosensitive silver salt oxidizing agent when heated by the catalytic action of the silver halide in the exposed area. , an organic reducing agent having a reducing power suitable for forming a silver image is used. Suitable reducing agents include monohydroxybenzenes,
For example, p-phenylphenol, p-methoxyphenol, 2,6-di-t-butyl-p-cresol; di- or polyhydroxybenzenes,
For example, hydroquinone, t-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, catechol; naphthol and naphthylamines, such as α-naphthol, β-naphthol, 4-aminonaphthol, 4
-Methoxynaphthol; Hydroxybinaphthyls, such as 1,1'-dihydroxy-2,2'binaphthyl, 4,4'-dimethoxy-1,1'-dihydroxy-2,2'-binaphthyl;Phenylenediamines; Amino Phenols, such as N-methyl-p-aminophenols, 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,
For example, 1-phenyl-3-pyrazolidone, 4
-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone; Contains 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 reducing agent, other components in the element, etc., but it is usually 0.1 per mole of the non-photosensitive organic silver salt oxidizing agent (a). ~3 mol is suitable. Component (c) used in the present invention is a photosensitive silver compound or a photosensitive silver compound forming component. Examples of photosensitive silver compounds include silver chloride, silver bromide,
Examples include silver bromoiodide, silver chlorobromide, silver chlorobromoiodide, silver iodide, etc., and these may be used alone or in combination. Emulsions containing these photosensitive silver halides can be made by any method known in the photographic field.
In this way, a component prepared externally may be added and used as a component of the photosensitive layer used in the present invention, but if the component for forming a photosensitive silver compound is allowed to coexist with an organic silver salt oxidizing agent, A photosensitive silver compound may be formed internally by reacting with a part of the organic silver salt oxidizing agent. As the photosensitive silver compound forming component,
For example, halogenated water salts, metal halides,
Halogen molecules, organic halides containing organic halogens containing active halogens (for example,
80030), organic elemental halogen compounds (e.g., compounds such as bis(p-anisyl)tellurium dibromide as described in JP-A-52-732022). Can be mentioned. The amount of these photosensitive silver compounds or photosensitive silver compound forming components used is 0.001 to 0.3 per mole of the non-photosensitive organic silver salt oxidizing agent (a).
It is a mole. Component (d) used in the present invention is at least one type of N-unsubstituted sulfonamide represented by the general formula (). R-SO ₂ NH ₂ () (In the formula, R is an aryl group, an alkyl group, a cycloalkyl group, or an aralkyl group.) In the general formula (), the aryl group of R is a benzene skeleton. It is preferable to have a core or a naphthalene bone core. Various atomic groups can be attached to these bone rings. Typical examples of such atomic groups include alkyl groups, halogens, nitro groups, amino groups, dialkylamino groups, hydroxy groups, acyloxy groups, alkoxy groups, cyano groups, carboxyl groups, alkoxycarbonyl groups, carbamoyl groups, and sulfamoyl groups. It is mentioned as something. Furthermore, the alkyl group may be linear or branched. As a straight chain alkyl group,
1 carbon number, such as methyl, ethyl, propyl, heptyl, octyl, dodecyl, and octatecyl
It is from 18. This group also includes those that constitute secondary sulfonamides, such as isobropyl, 2-butyl, and 17-octadecyl. Branched alkyl groups include those having 4 to 6 carbon atoms. The cycloaloxy group has 4 to 12 carbon atoms, and among these, cyclopentanesulfonamide and cyclohexane sulfonamide each having 5 and 6 carbon atoms gave good results. Furthermore, the aralkyl group constitutes a sulfonamide having the following structure. R' is a straight chain or branched hydrocarbon group having 1 to 4 carbon atoms, and among these, benzyl and phenethyl each having 1 and 2 carbon atoms in R' are preferred. Specific examples of the compound represented by the above-mentioned general formula () are as follows, and the toning effect thereof is as shown in the evaluation test listed in the Examples. 1 benzenesulfonamide 2 o-toluenesulfonamide 3 p-toluenesulfonamide 4 mesitylenesulfonamide 5 p-chlorobenzenesulfonamide 6 p-bromobenzenesulfonamide 7 p-nitrobenzenesulfonamide 8 m-nitrobenzene Sulfonamide 9 p-dimethylaminobenzenesulfonamide 10 p-aminobenzenesulfonamide 11 p-hydroxybenzenesulfonamide 12 p-acetoxybenzenesulfonamide 13 m-carboxybenzenesulfonamide 14 p-acetylaminobenzene Sulfonamide 15 p-methoxybenzenesulfonamide 16 1.3-benzene-di-sulfonamide 17 p-butylbenzenesulfonamide 18 2.5-diglolobenzenesulfonamide 19 α-naphthalenesulfonamide 20 β-naphthalene sulfonamide Fuonami 21 4-Methylnaphthalenesulfonamide 22 5-Cyanonaphthalenesulfonamide 23 Naphthalene-1,5-di-sulfonamide 24 5-Hydroxynaphthalenesulfonamide 25 Methanesulfonamide 26 Ethanesulfonamide 27 Propane Sulfonamide 28 Isopropanesulfonamide 29 Pentanesulfonamide 30 Heptanesulfonamide 31 Dodecanesulfonamide 32 Octadecanesulfonamide 33 s-Butanesulfonamide 34 2,3-Dimethylbutanesulfonamide 35 Cyclopentanesulfonamide Amide 36 Cyclohexanesulfonamide 37 Phenylmethanesulfonamide 38 Phenylethanesulfonamide A dry image forming material containing at least one of these compounds listed as specific examples of the compound represented by the general formula () may be A good black tone image was obtained by heat development. These compounds also have excellent shelf life and do not contaminate thermal processing machines. Component (d) described above can be used in the dry imaging materials of the present invention in a wide range of concentrations.
The concentration of component (d) is 1 of the non-photosensitive organic silver salt oxidizing agent of (a).
It is 0.05 to 3 moles per mole. This amount varies depending on the type of toning agent, the number of various components in the material, the processing temperature, etc. The dry image forming material of the present invention includes the above (a) to (d).
In addition to the ingredients, binders, antifoggants, spectral sensitizers, antihalation dyes,
Various known additives such as a background darkening inhibitor can be optionally added. As the binder, for example, 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, and gelatin can be used. The weight ratio of these to the non-photosensitive organic silver salt oxidizing agent (a) is suitably 10:1 to 1:10. Examples of antifoggants include mercury acetate and benzotriazole. These antifoggants cause unexposed areas to become black when the dry image forming material of the present invention is thermally developed. This is effective in preventing so-called thermal fog. Spectral sensitizing dyes are useful for sensitizing silver halides and include, for example, cyanines, merocyanines, and styryls.
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, polyethylene terephthalate film, and paper. The compositions described above are coated onto these supports together with a binder and a suitable solvent. The thickness of the coating is 1 to 1000μ after drying, preferably 3 to 20μ
It is. 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 imagewise exposed as a photosensitive material and then heated for 1 to 60 seconds at a temperature of 80 to 200 DEG C. to obtain a visible image. Also, JP-A-48-80030, JP-A-52-
By selecting an appropriate material composition similar to that described in No. 73022 or Japanese Patent Application No. 52-280088, it can also be used as a non-photosensitive image forming material. in this case,
It is used in a format where it is preheated in a temperature range of 70 to 180 degrees Celsius, then exposed to light and heat developed. In the dry image forming material of the present invention, by utilizing a novel toning agent, the image obtained after development exhibits a good black tone and has excellent long-term storage stability. Furthermore, there is almost no problem that the toning agent sublimes during development and contaminates the developing machine. The details of the present invention will be explained below based on examples. Example 1 Toluene-acetone mixture (weight ratio 1:1) 10
Prepare in advance a solution in which 0.6 g of polyvinyl butyral is dissolved in g. Add this along with 3g of silver behenate to 8
A homogeneous silver behenate dispersion was prepared by ball milling for an hour. A coating composition is prepared by sequentially adding the following components to 1.5 g of this silver behenate dispersion. This composition was applied onto a polyethylene terephthalate film and dried at 70 to 90°C for several minutes to produce a dry image forming material with a dried coating film having a thickness of about 10 μm. Polyvinyl butyral-acetone solution (weight ratio 1:10) 0.5g Calcium bromide 5mg t-butylhydroxynone 15mg Toning agent 15mg Mercuric acetate 0.1mg Specific examples of compounds represented by general formula () as toning agents As mentioned above, among them, 1, 3,
The toning agents numbered 5, 8, 15, 19, 25, 32, and 36 were used (in the following examples, the toning agents are indicated by the numbers mentioned above). In addition, a blank was prepared without containing a toning agent, and for comparison, samples were prepared using benzenesulfonanilide and N-butyl-p-toluenesulfonamide as toning agents, respectively. A mask film having gradation properties was brought into close contact with these dry image forming materials and exposed to light for 1/4 second. Next, this photosensitive material was brought into contact with a metal hot plate at 120° C. for 3 seconds to develop it. Table 1 shows the ODmaxO.D.min of images for dry image forming materials containing various toning agents of the present invention.
As comparative examples, an example containing no toning agent (blank) and an example using benzenesulfonanilide and N-butyl-p-toluenesphonamide in place of the toning agent of the present invention were shown at the same time. From Table 1, the nine examples containing each toning agent gave a good black tone image, whereas the blank not only did not form an image, but also had an unexposed background that was light brown. Also, benzenesulfonanilide, N-
The examples using butyl-P-toluenesulfonamide, respectively, compared to the examples containing the toning agent of the present invention.
ODmax is extremely low. Therefore, it is clear that the toning agent of the present invention is superior to such N-substituted sulfonamides as a toning agent.

[Table] Example 2 3 g of silver behenate was added to 22 g of a toluene-methyl ethyl ketone mixture (weight ratio 1:2) and ball milled for 15 hours to prepare a silver behenate suspension of about 100 g. To 1.5 g of this silver behenate suspension, add a polyvinyl butyral-methyl ethyl ketone solution (weight ratio 1:
10) Prepare an emulsion by adding 1.0 g of benzyltrimethylammonium iodide, 5 mg of benzyltrimethylammonium iodide, and 0.1 mg of mercuric acetate, and then apply it on a polyethylene terephthalate film and dry it at room temperature of about 20°C for several minutes.
An emulsion layer having a thickness of about 8 μm after drying was obtained.
On this layer, about 2 g of a reducing agent layer consisting of the following components was applied as a second layer and dried at 70 to 90°C for several minutes. Polymethyl metal rylate 10g 2,2'-methylenebis-(4-methyl-6-t
-Butylphenol) 3.4g Toning agent 1.5g Acetone 80g In this way, a dry image forming material having a total thickness of about 15μ was prepared by combining the upper and lower two layers. This photosensitive material was exposed to light for 1/4 second with a mask film having gradation properties in close contact with the material. 100% of this photosensitive material
℃ for 5 seconds with a metal hot plate. ODmax, ODmin for photosensitive materials using various toning agents
The results of the measurements are shown in Table 2. As a comparative example, an example (blank) in which no test sample was used was also shown.

【table】

[Table] Eleven examples containing each toning agent gave images with good black tone, whereas no image appeared in the blank. Example 3 Compounds 3, 15, 27, 36, 38 described above as toning agents
A dry image forming material prepared in the same manner as in Example 2, except that phthalazinone was used in place of the above compound as a comparative example, was exposed to tungsten light for 1 second through an original having gradations, and then exposed to tungsten light for 1 second, and Heated at ℃ for 5 seconds. Heating was accomplished by passing the film through hot rolls. All six types of dry image forming materials containing each of these compounds gave good black images. However, in the case of using phthalazinone, a drawback was observed that when thermal development was carried out, a considerable amount of white powder due to sublimation adhered to a part of the developing machine. In addition, when the same image forming process was performed after leaving the product in a dark place at 20°C for 3 months, all of the five examples of using the compounds of the present invention still gave good black-toned images. In the case of using phthalazinone, a decrease in color tone was observed. Example 4 Exactly the same treatment as in Example 1 was carried out, using the same amount of silver stearate instead of silver behenate and selecting the following compound (Table 3) as a toning agent. The ODmax and ODmin of the obtained images are shown in Table 3 together with the results of the blank test.

【table】

[Table] The five examples containing each toning agent gave images with good black tone. The blank did not form an image and at the same time a light browning of the background was observed. Example 5 To 1.5 g of silver behenate suspension prepared in exactly the same manner as in Example 1, 1.0 g of polyvinyl butyral-methyl ethyl ketone solution (weight ratio 1:10), 5 mg of iodine, and 1 mg of mercuric acetate were added to form an emulsion. was prepared. Next, this was applied onto a polyethylene terephthalate film and left to dry sufficiently at room temperature of about 20°C. On the thus obtained silver behenate emulsion layer having a thickness of about 8 μm, a reducing agent layer of about 2 g consisting of the following components was applied as a second layer and dried for several minutes at room temperature. In this way, a dry image forming material having a thickness of about 15 μm was produced by combining the upper and lower two layers. As toning agents, compounds 3, 20, 24, 31,
36, and a blank was also prepared for comparison. Polymethyl methacrylate 10g 2,6-bis-(2-hydroxy-3-t-butyl-5-methyl-benzyl)-p-cresol 3.4g Toning agent 1.5g Acetone 80g The obtained dry image forming material was After preheating for 5 seconds at 0.degree. C., it was exposed to tungsten light for 1 second through a gradated mask film. Next, this photosensitive material was brought into contact with a metal hot plate for 3 seconds at 120° C. in the dark. ODmax, OD of the obtained image
min is shown in Table 4 together with the results of the blank test.

【table】

[Table] The five examples containing each toning agent all gave good black images, whereas the blank did not form any images.

Claims (1)

[Scope of Claims] 1 (a) a non-photosensitive organic silver salt oxidizing agent, (b) a reducing agent for silver ions, (c) a photosensitive silver compound or a component for forming a photosensitive silver compound, and (d) the following: A dry image forming material comprising at least one N-unsubstituted sulfonamide represented by the general formula. R-SO ₂ NH ₂ (In the formula, R is an aryl group, an alkyl group, a cycloalkyl group, or an aralkyl group.)