JPH05323523A - Treatment of silver halide photographic material - Google Patents

Abstract

PURPOSE:To eliminate troubles such as development unevenness, fixing uneven ness, fixing defects, etc. by forming a hydrophilic colloidal layer, which contains a specified compound, on both sides of a support. CONSTITUTION:A photographic material has at least one hydrophilic colloidal layer, which contains a compound having a formula I and a compound having a formula III, on both sides of a support wherein (n) stands for natural number of l-10; M for hydrogen atom or an alkali metal; R for C5-C15 alkyl or a group having a formula II; R1 for C5-C15 alkyl, Cl, or OH; R2 for C1-C3 alkyl, hydrogen group, halogen atom. The addition amount of these surfactant is preferably 0.1-10g per 1 litre of a coating liquid and especially preferably 0.5-5.0g.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material processed by an automatic processor,
The present invention relates to a method for processing a silver halide photographic light-sensitive material which does not cause unevenness in fixing processing.

[0002]

2. Description of the Related Art In recent years, high-temperature rapid processing has become widespread in the development processing of photographic light-sensitive materials using silver halide. In the case of processing using an automatic processor, the processing speed is faster, and the shorter the processing time, the larger the number of processed sheets per unit time, which is a great economic effect. Therefore, manufacturers of photosensitive materials are making efforts to increase the processing temperature for development and fixing so that processing can be performed in a shorter time. However, since the processing is carried out in a short time, the conveying speed of the photographic light-sensitive material in the automatic developing machine is also increased, so that development unevenness in the development processing, fixing unevenness in the fixing processing, fixing failure and the like are likely to occur.

Each of these phenomena significantly impairs the commercial value and, in some cases, makes the commercial value completely lost.
It is also one of the very troublesome problems that is noticed only after the development processing. In order to solve these problems, as a measure for the automatic developing machine, a method of completely submerging the transfer roller in the processing liquid and an effort to eliminate the transfer roller above the liquid surface using a guide are made. However, there are many problems in transportability, and it is difficult to speed up further.

It is known that a surfactant containing a polyethylene group or a polyglycerol group is used as a means for eliminating uneven development in a light-sensitive material. , There was no concrete solution.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for processing a photographic light-sensitive material which is free from processing troubles such as uneven development, uneven fixing and poor fixing when being processed at high temperature by an automatic processor. Especially.

[0006]

The above object of the present invention is to provide at least one hydrophilic colloid layer containing a compound represented by the following chemical formula 4 and a compound represented by the following chemical formula 6 on both sides of a support. And a method of processing a silver halide photographic light-sensitive material.

[0007]

[Chemical 4]

(In the formula, n is a natural number of 1 to 10, M is hydrogen or an alkali metal, R is a C _{5 to} C ₁₅ alkyl group or compound 5, R ₁ is a C _{5 to} C ₁₅ alkyl group, R ₂ is C ₁
To C ₃ alkyl groups, hydrogen and halogen atoms are shown. )

[0009]

[Chemical 5]

[0010]

[Chemical 6]

(In the formula, R ₁ and R ₂ are Cl or OH, and M is hydrogen or an alkali metal.)

The present invention will be described in more detail below.

The surfactant, alkyl (aryl) polyether sulfonate, used in the present invention is described in US Pat.
No. 26,201 is described for the purpose of improving the coatability, but nothing is mentioned about the improvement of the stability of the processing by the automatic processor.

In the chemical formula 4, n is preferably 10 or less. 1
If it is 1 or more, the coatability is poor and it is not practical, especially 3
-9 are preferable. R is an alkyl group or a substituted aryl group C ₅ -C _15. If it is C ₄ or less, it does not serve as a surfactant. If it is C ₁₆ or more, the lipophilic property is too strong, causing uneven coating. In particular C ₈ -C ₁₂ are preferred. R ₁ is also a group of C ₅ -C _15. M is hydrogen or an alkali metal, and R ₂ is a C _{1 to} C ₃ alkyl group, hydrogen or a halogen atom. The addition amount of these surfactants is preferably 0.1 g to 10 g, and particularly preferably 0.5 g to 5.0 g per liter of the coating liquid. The timing of addition may be any time during the manufacturing process.

The addition positions of the compounds of Chemical formulas 4 and 6 used in the present invention are at least 1 on both sides of the support.
Hydrophilic colloid layer, such as a silver halide emulsion layer, a surface protective layer, an intermediate layer, an undercoat layer, a backing layer, etc., and when any one of them has a multilayer structure, any of them However, the surface layer is particularly preferable. A preferable example is to contain the compounds of Chemical formulas 4 and 6 in the silver halide emulsion layer, the surface protective layer and the backing layer, respectively.

Specific examples of the surfactant of Chemical formula 4 used in the present invention are shown below.

[0017]

[Chemical 7]

[0018]

[Chemical 8]

[0019]

[Chemical 9]

[0020]

[Chemical 10]

[0021]

[Chemical 11]

[0022]

[Chemical formula 12]

[0023]

[Chemical 13]

A typical example of the compound represented by the formula 6 used in the present invention is 2-hydroxy-4,6-.
Dichlorotriazine sodium is mentioned, and it is generally called triazine hardener. It is preferable to add 1 to 500 mg of triazine hardener in 1 g of gelatin,
Particularly, 10 mg to 100 mg is preferable. Addition just before coating enhances the effect of dura. It may be diffused into the emulsion layer in addition to the layer adjacent to the emulsion layer. The triazine hardener may be used alone or in combination with other hardeners.

The silver halide emulsion used in the practice of the present invention can be prepared by a known and conventional method. Silver halide formation and dispersion method, silver halide composition (eg silver chloride, silver bromide, silver iodobromide, silver chlorobromide, etc.), size and habit of silver halide grains, silver halide and gelatin The ratio, the pH and PAg of the silver halide emulsion, the type and amount of the chemical sensitizer, the type and amount of other additives, and the type and amount of gelatin and other binders are not limited.

As the support used in the silver halide photographic light-sensitive material of the present invention, in addition to a film made of a synthetic polymer such as cellulose acetate, polystyrene and polyethylene terephthalate, a high temperature and high speed automatic processor treatment such as RC photographic paper is used. Possible, especially if the support is water resistant.

Known developing solutions such as a developing solution and a fixing solution are used in the present invention. Specifically, a PQ developing solution, an MQ developing solution or a lith developing solution may be selected according to the purpose, and a fixing solution may be selected from a hard film type and a non-hard film type depending on the use.

[0028]

EXAMPLES The present invention will be further described below with reference to examples.

Example 1 (1) Preparation of Photosensitive Silver Halide Emulsion An appropriate amount of ammonia was added to a liquid containing gelatin, potassium bromide and water at 40 ° C., while keeping the PAg value at 7.60. The molar ratio of iridium to silver nitrate aqueous solution and silver is 1
A monodisperse silver bromide emulsion grain having an average grain size of 0.25 μm was prepared by adding a hexachloroiridium (III) salt-added potassium bromide aqueous solution so as to obtain 0 ⁻⁷ by a double jet method. After the emulsion was desalted, the pH was adjusted to 6.2 and the PAg was adjusted to 8.6 before the sensitizing dye (Chemical Formula 1
4) was added, followed by gold / sulfur sensitization using sodium thiosulfate and chloroauric acid to obtain Emulsion A.

[0030]

[Chemical 14]

In this emulsion A, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene aqueous solution as a stabilizer, 2-hydroxy-4,6-dichlorotriazine sodium as a hardener, and an interface The activators shown in Table 1 were used for the preparation.

[0032]

[Table 1]

(2) Preparation of surface protective layer of emulsion To a 6 wt% liquid of gelatin, an aqueous solution of sodium polystyrene sulfonate was added as a thickener, and 2-hydroxy-4,6-dichlorotriazine sodium as a hardener and a surface active agent. The agents shown in Table 1 were used as the agent, and the spherical agent of polymethylmethacrylate was used as the matting agent.

(3) Preparation of backing layer To a 6 wt% liquid of gelatin, an aqueous solution of sodium polystyrene sulfonate was added as a thickening agent, dyes (Chemical formula 1, Chemical formula 2, Chemical formula 3) were added, and 2-hydroxy- as a hardening agent. It was prepared by using 4,6-dichlorotriazine sodium, the surfactant shown in Table 1 and a spherical polymethacrylate as a matting agent.

[0035]

[Chemical 15]

[0036]

[Chemical 16]

[0037]

[Chemical 17]

(4) Preparation of coating sample The above-mentioned backing coating solution was coated on one side of the polyethylene terephthalate support so that gelatin was 4 g / m ² . Subsequently, a photosensitive silver halide emulsion was coated on the opposite side of the support at the same time so that the amount of silver was 3.0 g / m ² and a surface protective layer of the emulsion was 1.0 g / m ² of gelatin. These samples are 1 at 50.8 cm x 61.0 cm
I prepared 00 sheets.

(5) The compositions of the developing solution and the fixing solution are as follows. <Developer> Potassium hydroxide 17g Sodium sulfite 60g Diethylenetriaminepentaacetic acid 2g Potassium carbonate 5g Boric acid 3g Hydroquinone 35g Diethylene glycol 12g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.65g 5 Methylbenzotriazole 0. 6g Acetic acid 1.8g Potassium bromide 2g Adjust to 1l with water (adjust to pH 10.50)

<Fixer> Ammonium thiosulfate 140 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid / disodium dihydrate 25 mg Sodium hydroxide 6 g Water to 1 liter (pH = 4.95 adjusted with acetic acid)

The development processing was carried out by using an automatic developing machine LD-281Q manufactured by Dainippon Screen Co., Ltd., so that the processing time of Dry to Dry was 70 seconds, the development was set at 35 ° C. for 15 seconds, and the fixing at 33 ° C. for 15 seconds.

(6) Evaluation of Development Unevenness The sample film was exposed with a Macbeth densitometer so that the image density became 1.5, and the above-mentioned development processing was performed, and unevenness on the image was evaluated by the following four steps. evaluated. A: No development unevenness is observed. B: 〃 Somewhat acceptable. C: 〃 Quite acceptable. D: 〃 Approved on the whole surface.

(7) Evaluation of Fixing Unevenness and Fixing Failure 90 samples were continuously passed through the above-mentioned automatic developing machine, and after 1 hour, all 10 sheets were passed through without exposure. In particular, when the sample was passed through this 1 hour later, the first and second samples were apt to have poor fixing. Therefore, all the samples centered around the second sample were evaluated and evaluated in the following four grades. A: No uneven fixing and no fixing was observed. B: 〃 Somewhat acceptable. C: 〃 Quite acceptable. D: 〃 Approved on the whole surface.

[0044]

[Table 2]

As shown in Table 2, only the sample 16 in which the compound of the present invention was used for the emulsion surface and the backing surface was good without any development unevenness and fixing unevenness. Further, the one using the compound of the present invention only on the emulsion side is effective for the development unevenness, but it cannot be achieved for the fixing unevenness without using the compound of the present invention in the backing layer. it is obvious.

Example 2 (1) Preparation of photosensitive silver halide emulsion The silver halide emulsion A used in Example 1 was used as a stabilizer.
4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene aqueous solution was added, and the hardeners shown in Table 3 were used and the surfactant was adjusted with Chemical Formula 8. At this time, the amounts of various hardeners were changed and adjusted so that the samples had almost the same hardness.

[0047]

[Table 3]

[0048]

[Chemical 18]

[0049]

[Chemical 19]

[0050]

[Chemical 20]

[0051]

[Chemical 21]

(2) Preparation of surface protective layer of emulsion In the same manner as in Example 1, a 6 wt% gelatin solution was added with an aqueous solution of sodium polystyrene sulfonate to prepare a hardener.
Was used as the surfactant, and the amount of the hardening agent was adjusted so that the hardening degree was almost the same.

(3) Preparation of backing layer Gelatin, dye and matting agent were exactly the same as in Example 1, except that those shown in Table 3 were used as the hardener, and Chemical formula 8 was used as the surfactant. For the above, the amount of the hardening agent was adjusted so that the hardening degree was almost the same.

(4) The coating, developing treatment and evaluation were carried out in the same manner as in Example 1.

[0055]

[Table 4]

As shown in Table 4, when the combination of the triazine hardener as the surfactant of the present invention is used for the emulsion surface and the backing surface, there is no development unevenness or fixing unevenness, which is good. , Is not preferable in combination with other hardening agents.

Example 3 After processing 100 sheets of the sample Nos. 1, 6 and 11 used in Example 2, 10 sheets of the sample No. 16 are passed and further 1 hour later,
Throughout 0 sheets, the cleaning ability for fixing unevenness and fixing failure was tested. The results are shown in Table 5.

[0058]

[Table 5]

It can be seen that the fixing unevenness that occurred immediately afterward was eliminated by passing the sample of the present invention. That is, it is understood that the sample of the present invention has a cleaning ability.

[0060]

EFFECTS OF THE INVENTION It becomes possible to provide a processing method for silver halide photographic light-sensitive materials which is free from processing defects such as uneven development, uneven fixing, and poor fixing when high-speed rapid processing is carried out by an automatic processor.

Claims (1)

[Claims] 1. A silver halide photograph comprising, on both sides of a support, at least one hydrophilic colloid layer containing a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 3, respectively. Method of processing photosensitive material. [Chemical 1] (In the formula, n is a natural number of 1 to 10, M is hydrogen or an alkali metal, R is a C _{5 to} C ₁₅ alkyl group or Chemical formula 2,
₁ shows an alkyl group having C ₅ -C _15, alkyl group of R ₂ is C ₁ -C _3, hydrogen, a halogen atom. ) [Chemical 2] [Chemical 3] (In the formula, R ₁ and R ₂ represent Cl or OH, and M represents hydrogen or an alkali metal.)