JPS59191035A - Method for simply processing photosensitive silver salt material - Google Patents

Abstract

PURPOSE:To enable drying without practically passing through a washing stage by carrying out development using ascorbic acid as a developing agent. CONSTITUTION:An alkali soln. of l-ascorbic acid is used as a principal developing soln. The proper concn. of l-ascorbic acid in the developing soln. is 0.2-20g/ lin case of development by immersion and 0.5-100g/l in case of development by coating. Simple processing giving an image whose shelf stability is hardly deteriorated can be carried out.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a simple processing method for developing silver salt photographic materials, and particularly to a simple processing method that does not significantly impair the storage stability of images.

From another perspective, the present invention relates to a technology for water-free, rapid processing of silver-saving photographic materials that uses less silver halide.

Although silver salt photographic materials have the advantages of high sensitivity and high image quality, their disadvantage is that the development process is a complicated chemical operation.
Various methods have been taken to solve this problem. For example, photo-developable or heat-developable silver halogen photographic materials are examples. However, these methods sacrifice the characteristics of silver halogenide, such as high sensitivity and high image quality, in exchange for simplified processing.

The diffusion transfer method is another example of a simple process, in which the image-receiving layer is separated from the photosensitive layer, eliminating the need for washing with water and simplifying the process, but this results in additional manufacturing costs. It has become.

The conventional development method, which supplies developing chemicals relatively uniformly and sufficiently in the form of an aqueous solution, greatly contributes to achieving the characteristics of high sensitivity and high image quality. In other words, conventional wet processing is advantageous in terms of maintaining sensitivity and image quality. Therefore, when it comes to specific means for simplifying the process without changing the form of the wet process, the first option is to omit and integrate processes. In particular, if the flushing step 3 is omitted, there are advantages such as no need for piping and porta-pull.

However, omitting the water washing step involves many technical difficulties. The most significant one is that stains occur over time in images after processing. This stain is caused by residual developing agent, silver salt, and other compositional factors in the photographic material.
The former is particularly attributable to this.

An object of the present invention is to develop a means for preventing the occurrence of staining over time when a developing process is performed that substantially eliminates the washing step 8.

In particular, Japanese Patent Publication No. 763237 by the present inventors,
Do-/g-171 and O-g-210! #lf
The purpose of this invention is to develop a simple developing method that does not cause staining over time and can be applied to the photographic image forming method of No. 1. Here, the meaning of ``substantially not involving water washing'' is a patent application filed by the present inventor. 2-/Tough 7 It is the same as described in Part 2, and there is no washing with water at all, or there is only rinsing or wiping to remove the attached salt, and the photosensitive layer (or image layer) of the photographic material layer is ignored. The present inventors have discovered that the object of the present invention can be achieved by using t-ascorbic acid as a developing agent. Ta. That is, when an alkaline solution of t-ascorbic acid is used as a developer and processed in a liquid bath or by smearing, the photographic image after the subsequent liquid bath or smear-type fixing or stabilization process. The increase in stain over time is significantly reduced even though there is substantially no water washing step.

The concentration of t-ascorbic acid in the developer can be used within a wide range depending on the purpose, and in the case of immersion type processing, it is 01.2.
~． 20ff/l, especially /~109/, and if it is a smear development type, θ, j~100ii'/t, especially 3--,! ;Of/l, especially 1O-30y/l is suitable. The p 1-1 of the processing solution can be selected from any pH within the range that can impart the activity of the developing agent, but it is preferably 10 to ≠ for the liquid bath type, and 10 to 1 for the 2-spray type. ///
~/g is preferred.

In addition to ascorbic acid, 3-pyrazolidones and p-aminephenols, such as /phenyl-3pyrazolidone and N-methyl-p-aminephenol, are used to the extent that their own oxide contribution to the stain is negligible, that is, /2/. The following can also coexist.

The present invention is disclosed in Japanese Unexamined Patent Application Publication No. 763,231
It is particularly effective for the light/heat conversion type photographic materials described in Torito No. 71 and No. FG-210 and No. GG. Among these, it is particularly effective for the photographic material described in Japanese Patent Application Laid-Open No. 10-12911/G2171. The reason for this is probably that in this type of photographic material, most of the stains that occur over time are due to oxides of the developing agent, and little staining is due to other causes.

The above-mentioned applications describe a technique in which a small amount of silver halide in a photographic material is imagewise exposed and developed, and the resulting developed silver is irradiated with high-intensity flash light to widen the image in a dry manner. It is being

At this time, any method can be used for the development to produce developed silver, but the method of the present invention, that is, using ascorbic acid, is extremely advantageous because no stain is generated even if washing with water is omitted.

Example 1 A silver halide photographic material - black-and-white film or black-and-white photographic paper - was subjected to metho--ascorbic acid development, and then >! Dispose of debris, remove adhering liquid with a rinse bath, and dry.

2 In the above, phenidone-ascorbic acid developer was used.

3 Phenidone 0.0% for the above photosensitive material. /~θ, do2/1
1 ascorbic acid/~209/l-, thiosulfate/~,
20 y/l pJ-f / /~/21 g after liquid bath treatment, rinse and dry.

4 In the previous paragraph, liquid bath treatment was changed to smearing. In this case, a more highly concentrated solution can also be used.

5 The coating amount of silver halide is /2/ or less, especially O1λ
? /1, and siphenidone 0.1 for the photographic material of JP-A-Kokai Shoyu Doichi/guri♂7g, which contains a combination of heat-sensitive coloring materials.
/~0. To? /l, 7 scorbic acid 3~! 0? /
Apply a developing solution consisting of t
! After applying a thiosulfate solution, it is dried, and then a flash color is applied.

6 Regarding the photographic materials mentioned in the preceding paragraph, 3. Adopts Benoζ one-bath developer fixer mentioned in ≠ section.

Example 1 (1) Bisphenol A dispersion bisphenol A (,2,,2-bis(/I-hydroxyphenyl)propane)/Ay is mixed with 30d of 10% Serafon solution, and further λ, j% A slurry-like solution containing 20 parts of a dode/sodium ruberzene sulfonate aqueous solution, d, and water was dispersed in a ball mill to prepare a fine particle suspension A.

(2) Leuco base dye precursor dispersion No(β-ethoxyethylamino)-3-chloro-6-diethylaminofluorane/Afwo/0tiselatin aqueous solution 20-
Mix and match; 2. j% sodium dodecylbenzenesulfonate aqueous solution 207,! : A slurry to which water JtO- was added was finely pulverized and dispersed using a ball mill to prepare a fine particle suspension B.

(3) Silver halide emulsion A gold and sulfur sensitized silver bromide emulsion was prepared, containing silver halide equivalent to 7 wt % in terms of silver, 70 parts gelatin, and about 7 parts moisture.

(4) Coating composition The above suspension A/37, BAq, silver halide emulsion/, guar, and 73 parts of a 10% gelatin aqueous solution were mixed, and 7 m of 3
Coating was carried out on an acetic acid cellulose support. The amount of steel in the coated sample is θ, /17m2.

(5) Creation of images Cut three sets of strips fc of the size of the sensitometric test from the coated sample, pass them through an optical wedge,
After exposure of 2 times≠K s o o CMS, the following processes (1) and (2) were performed, respectively.

■ Comparative sample -] This sample piece was washed with a commercially available PQ developer (manufactured by Fuji Photo Film,
The stock solution of Papitol (trade name) was diluted with water to 2:2 and developed for 2J°C 2θ seconds, followed by 20 seconds of acid dura fixing (using EK's published formula F-j).
After rinsing with water for 20 seconds, it was dried and irradiated with xenon flash light (radiant energy/100 J, flash time constant 3 milliseconds) at approximately 2 J/sub2. A darkened image with a blackish gradation was obtained.

(2) Comparative sample - 2° Pavitol from the previous section was not diluted, but was applied as a undiluted solution onto the sample. After 20 seconds, a 3% ammonium thiosulfate solution was applied, and after 10 seconds, it was dried with hot air for 10 seconds. This was irradiated with xenon flash light as in the previous section to obtain an image with the same black gradation as in the previous section.

(2) Samples processed by the method of the present invention A developing solution containing ascorbic acid having the following composition was applied to the sample piece, and after 10 seconds, a 3% ammonium thiosulfate solution was applied, and after 70 seconds, hot air drying was performed for 10 seconds. This was irradiated with xenon flash light as in the previous section, and an image with the same black gradation as in the previous section was obtained.

t-Ascorbic acid 30'j'Na2SO3
3o y N a 2 COa 30 f/
/-Phenyl-3-pyrazolidone 0.3fN a O
HI) Add adjustment water to H/1.03 to make total Hid.

(6) Comparison of the performance of images over time When samples ■ and ■ were stored for a week under conditions of ≠o 0cio%⇠H, ■ exhibited significant staining and was judged to have reached the end of its life as an image. . Another 4tO0
Even when using the CZO%l(, H/week device), there was only slight staining of approximately the same extent as in ■ and ■, and the stability of the images in both cases was judged to be at a practical level.In other words, when ascorbic acid was used When water washing was omitted, substantially the same stability was shown as in the treatment with water washing.

Example 2 An experiment similar to Example 2 was conducted using commercially available black and white photographic paper (fine grain silver chlorobromide) as a sample. However, the development time for each sample was extended by 5 seconds from Example/1, and flash light irradiation was not performed.

The obtained characteristic curves were not significantly different.

Temporal test conditions≠o 0c, go%l(, 1(, /week) The staining significantly increased in both ■ and ■, and it was judged that the life of the image had ended, but no staining was observed in the case of ■.

Claims (1)

[Claims] A simple method for processing silver salt photographic materials, which is characterized in that after development is performed using ascorbic acids as a developing agent, drying is carried out without substantially performing a water washing process.