JPH0511298B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, and more particularly, the present invention relates to a silver halide photographic light-sensitive material, and more particularly, it produces high contrast images when processed with a rapid processing developer containing a super-additive developing agent and a relatively high concentration of sulfite. The present invention relates to a silver halide photographic material (hereinafter abbreviated as "photosensitive material") that is improved in terms of properties and stability over time. (Prior Art) The photoengraving process includes the step of converting a continuous tone original into a halftone image, that is, the step of replacing the continuous tone density change with a set of halftone dots having an area proportional to the density; This process includes a step of converting the halftone dot image obtained in this step into a halftone dot image with better sharpness, that is, a turning step. It is essential that the photosensitive materials used in these processes have high contrast in order to obtain good halftone dot quality. Conventionally, as a method to obtain such characteristics, a photosensitive material consisting of a silver chlorobromide emulsion with relatively fine grains, a narrow particle size distribution, and a high silver chloride content is processed using an alkaline hydroquinone developer with a very low sulfite concentration. A processing method, the so-called lithographic development method, is known. However, when this method is used, the storage stability is extremely poor because the concentration of sulfite ions in the developer is low, and rapid processing is not possible because hydroquinone is used as a single active ingredient. Therefore, high contrast can be achieved by processing with a so-called PQ type or MQ type developer that contains a relatively high concentration of sulfite and contains a super-additive developing agent that has good storage stability and can be processed quickly. It is desired to develop a new photosensitive material that can provide the following. One of the features related to this new light-sensitive material is a technology in which an oxidizing agent such as a tetrazolium compound is contained in a hydrophilic colloid layer including a silver halide emulsion layer on a support, and this is processed with a superadditive type developer. are disclosed, for example, in JP-A-52-18317, JP-A-53-17719 and JP-A-53-17720. The method of obtaining a silver image with high contrast by processing photosensitive materials containing oxidizing agents such as tetrazolium compounds with oxidizing properties with a super-additive type developer is an extremely revolutionary technology compared to conventional technology. be. However, in the above technology, since the photosensitive material contains an oxidizing agent such as an oxidizing tetrazolium compound, the sensitivity fluctuates during long-term storage or under conditions such as high temperature and high humidity.
It also has the disadvantage that the contrast is significantly lowered. Further, when a document is photographed through an intersection screen or a contact screen, particularly high contrast is required, and since the above-mentioned techniques do not always provide a sufficiently satisfactory contrast, improvements have been desired. (Objective of the Invention) Therefore, the first object of the present invention is to provide a photosensitive material that has high contrast and has excellent processing stability and rapidity, and the second object is to improve sensitivity and contrast during storage. An object of the present invention is to provide a photosensitive material with improved deterioration. (Structure of the Invention) The object of the present invention is to provide a silver halide photographic light-sensitive material in which a hydrophilic colloid layer including a silver halide emulsion layer is coated on a support. This can be achieved by using a silver halide photographic light-sensitive material that contains gelatin and at least one of the hydrophilic colloid layers contains a tetrazolium compound having in its molecule at least one functional group that reacts with gelatin. The present invention will be explained in more detail below. The tetrazolium compound contained in any one hydrophilic colloid layer according to the present invention is a tetrazolium compound having at least one functional group that reacts with gelatin in its molecule. Examples of the functional groups that react with gelatin in the tetrazolium compound include active vinyl groups, epoxy groups, methanesulfonic acid groups, active halogen-containing groups, active ester groups, aldehyde groups, maleimide groups, acid halide groups, and azolide groups. can be mentioned. Further, as the above-mentioned tetrazolium compound referred to in the present invention, a compound whose cathode half-wave potential is more positive than -1.0V is preferable. In the tetrazolium compound according to the present invention having a functional group that reacts with gelatin in the molecule,
The functional group that reacts with gelatin may be located in the vicinity of the oxidizing group of the tetrazolium compound molecule, or may be separated by various bonding groups, and may further include one oxidizing group. It may have two or more gelatin-reactive functional groups. The above-mentioned tetrazolium compound used in the present invention can be represented by the following general formula [], and more preferably can be represented by the following general formula [] to []. General formula [] [(A) _q −(B) _o ] − _n (Q) _T −(R) _S General formula [] General formula [] General formula [] In the general formula [], A is -Z-CH=CH ₂
group (here Z represents each group -CO-, -NHCO-, -CS- or _-SO2- ),

[Formula] -OSO ₃ CH ₃ group, -COCH ₂ G group, -COOCH ₂ G group, -SO ₂ CH ₂ CH ₂ G
group, -COG group, _-SO2G group,

【formula】

【formula】

[Formula] (where G represents a halogen atom or a gas-driving group such as a tosyl group, and Y represents a hydroxy group or an alkoxy group),

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】 [Development processing conditions]

(Process) (Temperature) (Time) Development 30℃ 30 seconds Fixing 〃 20 seconds Water Wash Room temperature 20 seconds Developer solution (undiluted solution) Potassium bromide 2.5g EDTA-2Na 1g Potassium sulfite (55% aqueous solution) 90ml Potassium carbonate 25g Hydroquinone 10g 5-methylbenzotriazole 100mg 5-nitrobenzotriazole 100mg 1-phenyl-5-mercaptotetrazole
30mg 5-Nitroindazole 50mg 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.5g Diethylene glycol 60g Sodium hydroxide Amount to make PH=10.6 Add water to make 500ml (PH=10.6) Above when using Use by diluting 500ml of the stock solution with 500ml of water. Tests were conducted on each test sample immediately after application, and in order to observe changes over time, the test sample was conditioned to 25°C, 50% RH, sealed in photographic barrier packaging material, and heat treated at 50°C for 30 days. Summer.

【table】

[Table] In (Table 1), contrast is a value representing the slope between each point of the density curve from 1.0 to 2.5, and represents high contrast. As is clear from the results shown above (Table 1), test samples according to the present invention (No. 3 to
33) has good processing stability, has significantly higher contrast than comparative sample No. 2 containing a tetrazolium compound that does not have a gelatin-reactive functional group, and has significantly improved contrast deterioration over time. showed excellent results. In addition, test samples No. 1, No. 2, and No. 1 showed that the number of gelatin-reactive functional groups present in one molecule and the substitution positions do not affect this excellent effect.
3. It can be understood from the results of No. 4, No. 5, No. 32, and No. 33. Example 2 An aqueous solution of silver nitrate and an aqueous solution containing potassium bromide and sodium chloride were mixed into an aqueous gelatin solution with stirring using a controlled double jet method, and then this emulsion was subjected to gold-hyposensitization and chemically sensitized. A silver chlorobromide emulsion (containing 90 mol % of silver chloride per mol of silver) was prepared by ripening. Emulsion liquid _F2 for preparation was prepared using the above silver halide emulsion in the same manner as for the preparation liquid _F1 . Next, phthalated gelatin was used in place of gelatin in the _P1 solution as a preparation solution for a protective film for emulsion.
_P2 solution was prepared in the same manner as _P1 solution. The above emulsion _F2 and preparation _P2 were coated in the same manner as in Example 1 to prepare test samples Nos. 34 to 38 as shown in Table 2. Exemplary compound 1 according to the present invention for emulsion solution F ₂ and preparation solution P ₂ in the above test sample
The amount of 2,3,5-triphenyltetrazolium chloride added for comparison was equivalent to 1×10 ^-4 mol per mol of coated silver. The obtained test sample was treated in the same manner as in Example 1, and the results are shown in Table 2 below.

[Table] From the results shown above, samples No. 37 and 38 to which the tetrazolium compound according to the present invention was added showed excellent high contrast not only immediately after application but also when stored over time. It was also found that there is no difference whether it is added to the emulsion solution or the protective film solution. Example 3 An aqueous solution containing 2.0×10 ^-4 mol of hexachlororhodium sodium salt, sodium chloride, and potassium bromide per 1 mol of silver nitrate and an aqueous silver nitrate solution were mixed into an aqueous gelatin solution with stirring using a controlled double run method. A silver chlorobromide emulsion (containing 80 mol % of silver chloride per mol of silver) having an average grain size of 0.2 μm was formed. After washing with water, 12 mg of thiourea dioxide per mole of silver halide was added to this silver halide emulsion at 65° C. in an atmosphere of pH 7.4, and the emulsion was subjected to fog ripening until the highest performance was obtained. Using this fogging emulsion, a preparation emulsion _F3 was prepared in the same manner as the _F1 preparation.
Next, test samples Nos. 39 to 43 shown below (Table 3) were prepared in Example 1 using this F ₃ preparation solution and the emulsion protective film preparation P ₁ in Example 1.
It was applied in the same way. The above test samples include exemplified compounds 1, 5 and 29 and comparative compounds 2, 2 and 3 for emulsion coating solution.
3,5-Triphenyltetrazolium chloride was added and contained in an amount of 1.times.10.sup. ^-4 mol per mol of coated silver. The obtained test sample was treated in the same manner as in Example 1, and the results are shown below (Table 3).
It was shown to.

[Table] As shown in the above table, it was also found that samples containing the tetrazolium compound according to the present invention exhibited excellent high contrast properties, both in direct positive photosensitive materials, immediately after application, and when stored over time. . (Effects of the Invention) The photosensitive material of the present invention, in which the hydrophilic colloid layer contains the tetrazolium compound of the present invention having a functional group reactive with gelatin in its molecule, has good processing stability and It is stable and exhibits excellent contrast characteristics even during long-term storage.

Claims (1)

[Claims] 1. A silver halide photographic material in which a hydrophilic colloid layer including a silver halide emulsion layer is coated on a support, in which at least one of the silver halide emulsion layers contains gelatin, and the hydrophilic colloid layer contains gelatin. A silver halide photographic light-sensitive material characterized in that at least one of the layers contains a tetrazolium compound having at least one functional group in its molecule that reacts with gelatin.