JPH0470621B2 - - Google Patents

Description

[Detailed description of the invention]

(A) Industrial Application Field The present invention relates to a silver halide photographic material, particularly a method for developing a silver image using a silver halide photographic material for plate making. (B) Prior art and its problems Power reduction processing is a method of exposing and developing a silver halide photographic material and then dissolving the image silver with a silver oxidizing agent to reduce the dot area ratio. In particular, when obtaining a printing original plate using a silver halide photosensitive material for plate making, in order to obtain a halftone gradation suitable for the printing characteristics and to obtain better color reproduction, the above-mentioned photographic material for plate making is used. By applying force reduction treatment to the photosensitive material and reducing the halftone dot area,
Images are often partially or completely modified. Therefore, the power reduction property of the photosensitive material for plate making is a process that oxidizes and dissolves the silver image, and by applying the power reduction process to the halftone dot image, the halftone dot area is reduced. Therefore, the range in which a halftone dot image can be corrected by power reduction processing is limited by the degree of reduction in blackening density per halftone dot as the halftone dot area decreases. In other words, the reduction processing capacity is determined by how much the halftone dot area can be reduced while maintaining an appropriate density as a printing original plate. On the other hand, sulfites are often used in developing solutions used for developing silver halide photosensitive materials in order to improve the storage stability of the developing solution. In particular, in rapid access processing, which has been widely used in recent years, 0.1 mol/
The above high concentration of sulfite is contained in the developer. When a silver halide photographic light-sensitive material is processed with such a developer, a large amount of silver complex is eluted into the developer, and the eluted silver complex is reduced to form silver sludge. In particular, when silver halide photographic materials are continuously processed in large quantities using an automatic processor, silver sludge may adhere to the developing roller or tank wall, contaminating the surface of the silver halide photographic materials. As a result, quality deteriorates. In order to prevent such silver sludge, a method of adding a mercapto compound to the developer is known. (British Patent No. 940169, British Patent No. 1144481,
U.S. Patent No. 3173789, U.S. Patent No. 3628955, Japanese Unexamined Patent Publication No. 1987-
No. 13331, No. 56-24347, No. 56-72441, No. 57
(No. 26848, No. 57-116340) However, when a mercapto compound is added to the developer in this way, silver sludge is prevented, but the problem is that the reduction properties mentioned above do not reach the desired level. I found out something. (C) Purpose of the Invention The present invention relates to a development method for silver halide photographic light-sensitive materials, and more specifically to a method for developing silver halide photographic light-sensitive materials for plate making that prevents silver sludge and is suitable for printing characteristics. The present invention relates to a development processing method for imparting characteristics. (D) Structure of the Invention As a result of intensive research aimed at achieving the above object, the present inventor found that in a processing method in which a silver halide photosensitive material is imagewise exposed and developed with an alkaline processing solution, the general formula [ It has been found that these objects can be achieved by containing at least one compound each represented by ] and [ ].

【formula】

_{[ Formula ] _} Represents a ₁ to _C5 lower alkyl group. M represents a hydrogen atom, an alkali metal atom, or a cation such as an ammonium ion. Specific examples of these compounds are shown below, but the present invention is not limited thereto. Specific examples of compounds in []

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】 Specific examples of compounds in []

【formula】

[Formula] The amount of these compounds added is such that the amount of the compound [] does not exceed 2g/.
You can choose any amount of 20mg/or more. The mixing ratio of [] and [] is 100:1 ~
It can be arbitrarily selected within the range of 1:50 (weight ratio). The silver halide emulsion used in the present invention may be produced by any of the acid method, neutral method, and ammonia method. It can also contain polyvalent metals. The present invention also relates to the properties of silver halide photographic emulsions, such as the composition of silver halide (for example, silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide).
It can be carried out regardless of the crystal form, crystal habit, or size of the silver halide. The emulsion used in the present invention can contain various additives. For example, chemical sensitizers (e.g., yellow sensitizers such as thiourea, hypo,
Noble metal sensitizers such as gold, platinum, and iridium compounds, reduction sensitizers), organic desensitizers, etc. can also be used in combination. Also, spectral sensitizers, supersensitizers,
Stabilizers, antifoggants, surfactants, developers, development accelerators, hardeners, hardening accelerators, dye removal improvers,
It can contain a brightener, a thickener, a precursor thereof, and the like. Protective colloids for the silver halide emulsion used in the present invention include gelatin, modified gelatin, albumin, agar, gum arabic, natural products such as alginic acid, polyvinyl alcohol, polyvinylpyrrolidone, and copolymers of acrylamide, acrylic acid, and vinylimidazole. Water-soluble synthetic resins such as The silver halide photographic emulsion used in the present invention is
A suitable support such as glass, cellulose acetate film, polyethylene terephthalate film,
paper, baryta-coated paper, polyolefin (e.g.
(polyethylene, polypropylene, etc.) coated onto something like paper. These supports may be corona treated by a known method, and may also be undercoated by a known method if necessary. The silver halide photographic emulsion used in the present invention is coated with a protective layer, an intermediate layer, an ultraviolet absorbing layer, an undercoat layer or other silver halide emulsions, if necessary. As the aqueous alkaline developer used in the present invention, those having generally known compositions can be used. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone),
Aminophenols, ascorbic acid, etc. can be used alone or in combination. The amount added is 0.05 to 0.5 mol/. The aqueous alkaline developer used in the present invention contains a sulfite preservative to protect the developer from air oxidation. For example, sodium sulfite, potassium sulfite, potassium metabisulfite, sodium bisulfite, etc. are added. The preferred amount is
It is 0.25 to 1.00 mol/. The aqueous alkaline developer used in the present invention has a pH of
Potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, tribasic potassium phosphate, etc. can be included for adjusting. The aqueous alkaline developer used in the present invention can contain the necessary organic antifoggants to minimize fog formation and to obtain desirable photographic properties. Benzotriazole, 6-nitrobenzimidazole nitrate, 5-methylbenzotriazole,
1-phenyl-2-tetrazoline-5-thione,
5-phenyltetrazole, 1-phenyl-5-
Mercaptotetrazole and the like are common. The aqueous alkaline developer used in the present invention includes antioxidants such as ascorbic acid, diethanolamine, and kojic acid, water softeners such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, polyalkylene oxides, amino compounds, and organic solvents such as triethylene glycol and methanol. can be included. Many types of reducing fluids are known for use in the present invention. For example, permanganate,
Reducing fluids using reducing agents such as iron salts, ceric salts, red blood salts, persulfates, and dichromates are known. As the fixer, one having a generally well-known composition can be used. As the fixing agent, in addition to thiosulfate and thiocyanate, organic sulfur compounds known as fixing agents can be used. (E) Examples Example 1 Silver chlorobromide containing 95 mol % of silver chloride was mixed in a conventional manner and subjected to physical ripening to obtain an emulsion with an average grain size of 0.1 μm and a narrow particle size distribution. After desalting and redissolving this emulsion, 500 mg of pinacryptol yellow was added per mole of silver halide as an organic desensitizer, and a hardening agent and a surfactant were added to the polyester film to give a silver content of 3.5 g/m2. ² together with gelatin solution for the protective layer and dried. The above sample was subjected to contact exposure with 150 lines and 50% halftone dots using a printer using a high-pressure mercury lamp as a light source. Furthermore, six types of developers shown in Table 1 were prepared, and 38
The film was developed for 20 seconds, fixed, and dried.

【table】

[Table] In the table, sample No. (6) is a blank, and samples (7) and (8) are comparative examples. "〃" represents the same as on the left. Next, each sample was subjected to a reduction treatment using a commercially available reduction liquid. The processing conditions are 20℃ and the reduction time is from 10 seconds.
It was changed in 100 seconds. For each sample, the range of change in dot area ratio was determined under the condition that the dot density was 3.0 or higher. This is called the reduction width. (%) Table 2 shows the results of the force reduction width measured for each sample (1) to (8).

[Table] As can be seen from the results in Table 2, samples containing a mercapto compound represented by the general formula (), a compound represented by the general formula (), or one comparative compound [(1) to (5), ( 7) to (8)] show a slight improvement in force reduction ability compared to blank sample (6), but from the point of view of work efficiency, a wider range of force reduction characteristics is desired. Next, a 150-line 50% halftone image was printed on the same silver halide photosensitive material using the same method. Furthermore, four types of processing solutions shown in Table 3 were prepared, and after development (38 degrees for 20 seconds), fixing, drying, and force reduction treatment were performed, and the force reduction width was measured in the same manner.

【table】

【table】 Table 4 shows the measurement results of the force reduction width.

[Table] As can be seen from Table 4, general formulas [] and []
It can be seen that the force reduction ability is improved by combining these compounds. Example 2 The same emulsion as in Example 1 was coated with 150 lines in the same manner.
A 50% halftone image was printed. Furthermore, it was treated with five types of Lith developer as shown in Table 5 (20 degrees 2
After fixing and drying, a force reduction treatment was performed, and the force reduction width was measured in the same manner.

【table】 Table 6 shows the measurement results of the force reduction width.

[Table] Next, a 150-line 50% halftone image was printed on the same emulsion using the same method. Furthermore, the film was developed with four types of processing solutions shown in Table 7 (20 degrees for 2 minutes), and after fixing and drying, a force reduction process was performed, and the force reduction width was measured. The results are shown in Table 8.

【table】

[Table] From Table 8, the superadditivity effect of the compound in the present invention was confirmed also in the Lith developer. From the above results, the compound in the present invention []
It can be seen that adding and [] is an extremely useful method for improving force reduction characteristics.

Claims (1)

[Claims] 1. A processing method in which a silver halide photosensitive material is imagewise exposed and developed with an alkaline processing solution, in which at least one compound each represented by the general formulas () and [] is added to the development solution. 1. A method for processing a silver halide photosensitive material, the method comprising: [Formula] [Formula] X: hydrogen or C ₁ to C ₅ lower alkyl group Y: hydrogen, substituted or unsubstituted lower alkyl group,
The substituted or unsubstituted amino group R ₁ represents a 5- or 6-position nitro group, and R ₂ represents a hydrogen atom or a C ₁ -C ₅ lower alkyl group. M represents a hydrogen atom, an alkali metal atom, or a cation such as an ammonium ion.