JP2907632B2 - Processing method of silver halide photographic material - Google Patents

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 which is processed by an automatic developing machine.
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 process of developing photographic light-sensitive materials using silver halide. In the case of processing using an automatic developing machine, the processing speed is high, and the shorter the processing time, the greater the number of processed sheets per unit time and the greater the economic effect. Therefore, photosensitive material manufacturers are making efforts to raise the processing temperature of development and fixing so that processing can be performed in a shorter time. However, since the processing speed is short, the conveying speed of the photographic photosensitive material in the automatic developing machine is also increased, so that the development unevenness during the development processing, the fixing unevenness during the fixing processing, the fixing failure and the like are likely to occur.

[0003] Each of these phenomena significantly impairs the commercial value, and in some cases, causes the commercial value to be 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 countermeasure in automatic developing machines, efforts have been made to completely immerse the transport rollers in the processing liquid and to eliminate the transport rollers above the liquid level using guides. However, there are many problems in transportability, and it is difficult to further increase the speed.

[0004] In the case of photosensitive materials, it is known to use a surfactant containing a polyethylene group or a polyglycerol group as a means for eliminating development unevenness. There was no specific 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 problems such as uneven development, uneven fixing and defective fixing when rapid processing is performed at a high temperature by an automatic developing machine. It is in.

[0006]

An object of the present invention is to provide at least one hydrophilic colloid layer containing a compound represented by the following formula (4) and a compound represented by the following formula (6) on both surfaces of a support. This has been achieved by a method for processing a silver halide photographic light-sensitive material, characterized by having:

[0007]

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Wherein 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 a chemical formula 5, R ₁ is a C _{5 to} C ₁₅ alkyl group, R ₂ is C ₁
To C ₃ alkyl, hydrogen, and halogen. )

[0009]

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[0010]

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

Hereinafter, the present invention will be described in more detail.

The surfactant, alkyl (aryl) polyether sulfonate, used in the present invention is disclosed in US Pat.
No. 26,201 describes for the purpose of improving coatability, but does not disclose anything that leads to improvement in the stability of processing in an automatic developing machine.

In the chemical formula 4, n is preferably 10 or less. 1
If it is more than 1, the coatability will be poor and not practical.
To 9 are preferred. R is an alkyl group or a substituted aryl group C ₅ -C _15. If it is less than C _4, it does not serve as a surfactant. If it is C ₁₆ or higher lipophilic character too strong causing uneven coating. In particular C ₈ -C ₁₂ are preferred. R _{1 is} also a C ₅ -C ₁₅ alkyl group. M is hydrogen or an alkali metal, and R ₂ is a C ₁ -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 solution. The timing of addition may be at any time during the production process.

The compound of the formula (4) and the compound of the formula (6) to be used in the present invention may be added in at least one position on each side of the support.
The layer is a hydrophilic colloid layer, for example, a silver halide emulsion layer, a surface protective layer, an intermediate layer, an undercoat layer, a backing layer, and the like. , But a surface layer is particularly preferred. One preferred example is that the silver halide emulsion layer, the surface protective layer and the backing layer contain the compounds of the formulas 4 and 6, respectively.

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

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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A typical example of the compound represented by formula 6 used in the present invention is 2-hydroxy-4,6-
Examples include sodium dichlorotriazine, which is generally called a triazine hardener. It is preferred to add 1 to 500 mg of triazine hardener in 1 g of gelatin,
Particularly, 10 mg to 100 mg is preferable. When added immediately before coating, the effect of the hardening is further enhanced. 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 another hardener.

The silver halide emulsion used in the practice of the present invention can be prepared by a known and commonly used method. Silver halide formation and dispersion method, silver halide composition (eg, silver chloride, silver bromide, silver iodobromide, silver chlorobromide, etc.), size and crystal habit of silver halide grains, and silver halide and gelatin The ratio, pH and PAg of the silver halide emulsion, types and amounts of chemical sensitizers, types and amounts of other additives, types and amounts 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, polyethylene terephthalate, etc., a high-temperature high-speed automatic processor such as RC photographic paper can be used. Possible, especially if the support is water resistant.

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

[0028]

The present invention will be further described with reference to the following examples.

Example 1 (1) Preparation of photosensitive silver halide emulsion A suitable amount of ammonia was added to a solution of gelatin, potassium bromide and water at 40 ° C., and the PAg value was maintained at 7.60. A silver nitrate aqueous solution and a molar ratio of iridium to silver of 1
0 such that the ^-7 to prepare a monodispersed silver bromide emulsion grains having an average grain size of 0.25μ were added by a double jet method and a potassium bromide aqueous solution was added hexachloroiridate (III) salt. After desalting this emulsion, the pH was adjusted to 6.2 and the PAg to 8.6, and then the sensitizing dye (Chem.
4) was added, followed by gold / sulfur sensitization using sodium thiosulfate and chloroauric acid to obtain Emulsion A.

[0030]

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An aqueous solution of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was used as a stabilizer in this emulsion A, sodium 2-hydroxy-4,6-dichlorotriazine was used as a hardener, Activators were prepared using those shown in Table 1.

[0032]

[Table 1]

(2) Preparation of Surface Protective Layer of Emulsion Sodium polystyrene sulfonate aqueous solution was added as a thickener to a 6 wt% solution of gelatin, sodium 2-hydroxy-4,6-dichlorotriazine was used as a hardener, and a surfactant was used. The agents shown in Table 1 were used as the agents, and polymethyl methacrylate spherical agents were used as the matting agents.

[0034] (3) sodium polystyrenesulfonate solution was added as a thickener to 6 wt% solution of the preparation of gelatin backing layer, a dye (Formula 15, Formula 1
6, of 17) was added 2-hydroxy as a hardener -
Sodium 4,6-dichlorotriazine, a surfactant shown in Table 1 as a surfactant, and a polymethacrylate spherical material as a matting agent were prepared.

[0035]

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[0036]

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[0037]

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

(5) The compositions of the developing solution and the fixing solution are as follows. <Developer> Potassium hydroxide 17 g Sodium sulfite 60 g Diethylenetriaminepentaacetic acid 2 g Potassium carbonate 5 g Boric acid 3 g Hydroquinone 35 g Diethylene glycol 12 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.65 g 5-methylbenzotriazole 0.0 g 6 g Acetic acid 1.8 g Potassium bromide 2 g Make up to 1 l with water (adjust to pH 10.50)

<Fixing Solution> Ammonium thiosulfate 140 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid disodium dihydrate 25 mg Sodium hydroxide 6 g Make up to 1 l with water (adjust to pH = 4.95 with acetic acid)

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

(6) Evaluation of Developing Unevenness A sample film was exposed to an image density of 1.5 using a Macbeth densitometer so that the density was 1.5, and the above-described developing process was performed. evaluated. A: No development unevenness is observed. B: ら れ る A little. C: 〃 Significantly recognized. D: 認 め It is recognized all over.

(7) Evaluation of Fixing Unevenness and Fixing Failure 90 samples were continuously passed through the automatic developing machine described above, and after 1 hour, all 10 samples were passed unexposed. In particular, since the first and second samples when passing the sample one hour later tend to cause poor fixing, all samples centered on the two samples were evaluated by the following four grades. A: Fixing unevenness / fixing defect is not recognized at all. B: ら れ る A little. C: 〃 Significantly recognized. D: 認 め It is recognized all over.

[0044]

[Table 2]

As shown in Table 2, only the sample 16 using the compound of the present invention on the emulsion surface and the backing surface was excellent with no development unevenness or fixing unevenness. Further, those using the compound of the present invention only on the emulsion surface are effective for development unevenness, but can not be achieved for fixing unevenness unless the compound of the present invention is used 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 those prepared as shown in Table 3 were used as hardening agents, and Chemical Formula 8 was used as a surfactant. At this time, the amounts of various hardeners were changed and adjusted so that the samples had almost the same hardening degree.

[0047]

[Table 3]

[0048]

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[0049]

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[0050]

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[0051]

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(2) Preparation of Surface Protective Layer for Emulsion In the same manner as in Example 1, an aqueous solution of sodium polystyrene sulfonate was added to a 6 wt% gelatin solution, and a hardener was prepared as shown in Table 3.
Was used as the surfactant, and the amount of the hardening agent was changed and adjusted so that the hardening degree was almost the same.

(3) Preparation of backing layer The gelatin, the dye and the matting agent were exactly the same as those in Example 1. The hardening agents shown in Table 3 were used, the surfactant was used as a chemical formula 8, and the hardening agent was used. Was adjusted by changing the amount of the hardener so that the hardening degree was almost the same.

(4) The same method as in Example 1 was used for coating, developing and evaluation.

[0055]

[Table 4]

As shown in Table 4, when a combination of a triazine hardener and a surfactant was used on the emulsion side and the backing side as the surfactant of the present invention, no unevenness in development and no unevenness in fixation was generated, and good results were obtained. It is not preferable in combination with other hardeners.

Example 3 After treating 100 sheets of Sample Nos. 1, 6, and 11 used in Example 2, 10 sheets of Sample No. 16 were passed, and one hour later,
In particular, the cleaning ability against non-uniform fixing and defective fixing was tested by passing 0 sheets. Table 5 shows the results.

[0058]

[Table 5]

It can be seen that the fixing unevenness that occurred immediately after 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]

According to the present invention, a method for processing a silver halide photographic light-sensitive material free of processing defects such as uneven development, uneven fixing and defective fixing can be realized when high-speed rapid processing is performed by an automatic developing machine.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/76 G03C 1/30

Claims (1)

(57) [Claims] 1. A silver halide photograph comprising at least one hydrophilic colloid layer containing a compound represented by the following chemical formula 1 and a compound represented by the chemical formula 3 on both surfaces of a support. Processing method of photosensitive material. Embedded image Wherein 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
₁ shows an alkyl group having C ₅ -C _15, alkyl group of R ₂ is C ₁ -C _3, hydrogen, a halogen atom. ) Embedded image (In the formula, R ₁ and R ₂ represent Cl or OH, and M represents hydrogen or an alkali metal.)