JPH04306648A - Treatment of anti-static silver halide photosensitive material for photograph - Google Patents

Abstract

PURPOSE:To obtain the treating method for silver halide photo-sensitive material for photograph which possesses superior anti-static function by a treating liquid having a pH of 12.0 or more, with the superior adhesiveness. CONSTITUTION:The silver halide photosensitive material for photograph which has an electric conductive polymer layer between a supporting body and a back coated layer containing gelatine is treated by a treating liquid having a pH of 12.0 or more, and the electric conductive polymer consists of a copolymer of N-methylol (metha) acryl amide and stylene sulfuonic acid.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing antistatic silver halide photographic materials.

0002

[Prior Art] In silver halide photographic materials,
Films, paper, etc. with low conductivity are often used as supports, and various problems have been caused by static electricity. During the manufacturing process of silver halide photographic light-sensitive materials or during use, static charges are accumulated due to contact friction and peeling, and due to the discharge, the silver halide emulsion layer is exposed to light, electrostatic fog occurs, and halogen The commercial value of silver oxide photographic materials is significantly reduced.

[0003] Furthermore, when silver halide photographic light-sensitive materials are transported to equipment such as color scanners and computer phototypesetting output machines, which have become popular as image processing equipment in recent years, contact with transport rolls causes Static charges can accumulate and act on the equipment's control unit, causing system failures or transport failures. Furthermore, the electrostatic charge on the silver halide photographic light-sensitive material attracts dirt and dust, which may cause pinholes during exposure and photographic processing. In order to solve these problems, it is necessary to impart sufficient antistatic properties to silver halide photographic materials both before and after photographic processing.

In order to solve these problems, methods have been proposed to improve the conductivity of the support and coated surface of photographic light-sensitive materials. , polymers, etc. are disclosed. For example, U.S. Patent Nos. 2,882,157 and 2,972,53
No. 5, No. 3,062,785, No. 3,262,807
No. 3,514,291, No. 3,938,999, etc.; US Pat. No. 2,9
No. 82,651, No. 3,428,456, No. 3,55
2,972, 3,655,387, etc.; US Pat. No. 3,753,716;
Fluorine-containing polymers such as those described in Japanese Patent Application Laid-open No. 1986-143431 and Japanese Patent Application Laid-open No. 63-98656 are known. It is being

However, in these conventional techniques,
It has disadvantages such as adversely affecting photographic properties, losing its antistatic effect during photographic processing, losing its antistatic effect in low humidity conditions, and making the coated surface uneven due to agglomeration of the antistatic agent.

Generally, photographic developers have a pH of less than 12, and no major problems occur when processing antistatic silver halide photosensitive materials. However, when processing with a developer having a pH of 12 or more, the film may Adhesion problems often occur. In particular, silver halide photosensitive materials using antistatic polymers as an antistatic layer, typified by polystyrene sulfonic acid polymers known in the art, have a pH of 12
When processed with the above-mentioned developer, the antistatic layer is eluted into the developer, resulting in film peeling, which has the drawback of significantly lowering the commercial value.

[0007]

[Problems to be Solved by the Invention] The purpose of the present invention is to
The object of the present invention is to provide a silver halide photographic material that has excellent adhesive properties even when treated with a processing solution having a molecular weight of 12.0 or higher and has excellent antistatic properties.

Another object of the present invention is to provide a silver halide photographic material having excellent antistatic properties at a pH of 12.
An object of the present invention is to provide a processing method that ensures excellent adhesion when processing with a processing liquid of 0 or more.

[0009]

[Means for Solving the Problems] The present invention involves processing a silver halide photographic material having a conductive polymer layer between a backing layer containing gelatin and a support with a processing solution having a pH of 12.0 or higher. In the method of processing a silver halide photographic light-sensitive material, the conductive polymer is made of a copolymer of N-methylol (meth)acrylamide and styrene sulfonic acid.

The conductive polymer used in the present invention is N-
It is a copolymer of methylol (meth)acrylamide and styrene sulfonic acid, and is crosslinked by heating. The ratio of N-methylol (meth)acrylamide in the copolymer is preferably 5% by weight or more and 70% by weight or less,
More preferably, it is 10% by weight or more and 60% by weight or less.

[0011] The copolymer is preferably produced by dissolving a mixture of P-styrene sulfonic acid or its alkali metal salt and N-methylol (meth)acrylamide in a mixed solvent of alcohol/water, and converting the mixture into monomers. The polymerization is carried out in a system in which the polymer is dissolved in the medium, but as the polymerization progresses, as the polymer is produced, it becomes insoluble in the medium and precipitates. Particularly preferred are water/alcohol mixed solvent systems containing alcohol in a concentration of at least 40% by weight. When carrying out such polymerization, by making a soluble resin exist in the medium in advance, the precipitated polymer can be obtained in the form of fine particles. That is, in the presence of a polymer that acts as a dispersion stabilizer, polymerization is carried out under conditions such that the monomer state is soluble in the medium, but the polymer becomes insoluble.

Furthermore, in the present invention, in addition to styrene sulfonic acid or its alkali metal salt and N-methylol (meth)acrylamide, various monomers can be copolymerized as the third component, among which monomers having an acidic group are particularly suitable. By copolymerizing, the thermosetting properties of the film can be further promoted. As such monomers, copolymerization of acidic monomers such as (meth)acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid or maleic acid is particularly preferred. The copolymerization ratio of such acidic monomers is preferably in the range of about 0.5% by weight to 10% by weight.

The thermosetting antistatic polymer of the present invention is synthesized with the above-mentioned composition, and basically forms a water-resistant antistatic film with sufficient performance. Depending on the situation, monomers other than those mentioned above, such as styrene, derivatives thereof, and (meth)acrylic acid esters, may be copolymerized.

As counter ions for styrene sulfonic acid, alkali metal ions such as sodium ions and potassium ions are preferred.

The method for synthesizing the conductive polymer used in the present invention is described in Japanese Patent Application No. 2-245660.

The conductive polymer used in the present invention forms a film on a support by itself, and is completely crosslinked within several hours under heating conditions of, for example, about 50°C.

[0017] The conductive polymer used in the present invention preferably has a coating amount of 0.1 to 5 g/m2 in terms of solid content.

In the present invention, the conductive polymer layer may contain other binders as necessary.

The processing solution having a pH of 12.0 or more used in the present invention is a developer containing a developing agent (for example, hydroquinone, catechol, 1-phenyl-3-pyrazolidone),
Any activating solution that does not contain a developing agent may be used, but it should have a pH of 12.0 or more when used.

[0020] In contrast to the film formed by a general polystyrene sulfonic acid polymer, which easily dissolves into a treatment solution with a pH of 12.0 or more and causes film peeling, the film formed by the conductive polymer of the present invention The resulting film has excellent adhesion and does not peel off even in a treatment solution with a pH of 12.0 or higher. This is thought to be due to the self-crosslinking reaction of the N-methylol groups in the conductive polymer of the present invention, which suppresses elution into the alkali.

Examples of the support used in the present invention include cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, polystyrene film, polyethylene terephthalate film, polycarbonate film, and other laminates thereof. There are things etc. Further examples include paper coated or laminated with baryta or α-olefin polymers, particularly polymers of α-olefins having 2 to 10 carbon atoms, such as polyethylene, polypropylene, and ethylene butene copolymers.

The backing layer used in the present invention consists of gelatin as the main binder, and optionally contains matting agents, antihalation dyes, white and colored pigments, antistatic agents, surfactants, A hardening agent and the like can be included. By disposing this backing layer on the antistatic layer, a sufficient antistatic effect can be obtained even after photographic processing.

In the present invention, another antistatic agent can be used in combination with the protective layer or other layers of the photographic material, thereby making it possible to obtain more preferable antistatic properties. Such antistatic agents include U.S. Pat. No. 2,882;
No. 157, No. 2,972,535, No. 2,982,6
No. 51, No. 3,062,785, No. 3,262,80
No. 7, No. 3,428,456, No. 3,457,076
No. 3,454,625, No. 3,514,291, No. 3,552,972, No. 3,615,531,
No. 3,655,387, No. 3,753,716, No. 3,938,999, No. 4,070,189, No. 4
, No. 266,015, No. 4,891,306, etc.

The silver halide photographic material according to the present invention will be explained. Binders for the photographic constituent layers include proteins such as gelatin and casein, cellulose compounds such as carboxymethyl cellulose, hydroxyethyl cellulose, and dextran, agar, sodium alginate, sugar derivatives such as starch derivatives, and synthetic hydrophilic colloids such as polyvinyl alcohol and poly-N- Vinyl pyrrolidone, polyacrylic acid copolymer, polyacrylamide, or derivatives thereof and partial hydrolysis can also be used in combination.

As the light-sensitive silver halide emulsion layer, any one known in the art can be used, but preferably it is an emulsion layer used in high-sensitivity silver halide light-sensitive materials, silver halide light-sensitive materials for high-temperature rapid processing, etc. can be mentioned.

The composition of the photographic processing liquid, such as a developer, a development stopper, a fixer, etc. in the photographic light-sensitive material of the present invention, can be determined according to the purpose and the type of photographic material, and those known to those skilled in the art can be used. .

[0027]

[Examples] The present invention will be illustrated below with reference to Examples, but the present invention is not limited thereto.

Example 1 The following coating, which also served as a backing layer, was formed on a polyester film support which had been subjected to an aqueous subbing process with a subbing composition containing an epoxy compound disclosed in JP-A No. 60-213942 for the purpose of making it hydrophilic. Apply the antistatic layer as shown below.

[0029] Method for preparing antistatic coating liquid Water

40
0ml 10% by weight solution of polystyrene sulfonic acid with 30% by weight N-methylolacrylamide

500ml 10%S
NP-4N (manufactured by Nikko Chemicals)
Add 10ml water

The coating amount of 1000 ml was applied at a moisture coating amount of 20 ml/m2.

Method for preparing coating liquid for back coating Gelatin

40g water

200ml 10%SNP
-4N (manufactured by Nikko Chemicals)
20ml Dick Hercules E
PINOXP-9007Y
Add 15ml water

On top of this 1000 ml sample, a backing layer was applied at a moisture coverage of 50 ml/m2 to prepare sample 1. VER manufactured by Kanebo N.C.R. Co., Ltd. in place of a 10% by weight solution of polystyrene sulfonic acid with 30% by weight of N-methylol acrylamide in the antistatic coating liquid.
Comparative a was prepared in the same manner except that 500 ml of SA-TL 10% aqueous solution was used. Thereafter, each sample was heated at 40°C for 6 days.

[0031] After heating, the sample was cut and subjected to photographic development processing. As a developing solution, AC for Silver Master manufactured by Mitsubishi Paper Mills Co., Ltd., which is a commercially available processing liquid for silver complex diffusion transfer, was used, and as a stabilizer, ST for Silver Master manufactured by Mitsubishi Paper Mills was used. Photographic processing was performed using a P-460R processor manufactured by Mitsubishi Paper Mills. AC for Silver Master manufactured by Mitsubishi Paper Mills had a pH of 13.6.

[0032] The antistatic ability was determined by leaving the sample before and after treatment in an atmosphere of 25°C, 50% RH (relative humidity) for 2 hours, and measuring the surface with a Hiresta surface resistance meter model HT-210 manufactured by Mitsubishi Yuka Co., Ltd. The surface resistance value was measured using As for the surface resistance, the lower the resistance value, the better the antistatic property.

[0033] In addition, in order to evaluate film peeling, square scratches were made on the surface of the sample with a knife at 5 mm intervals.
After immersing it in the AC processing solution for silver master at 30° C. for 30 seconds and rinsing it with water for 1 minute, the surface was evaluated by rubbing it with a tissue. ○ for those that cannot be removed at all.
It was rated △ if it peeled off slightly, and × if it peeled off considerably. These results are shown in Table 1.

[0034]

[Table 1]

As is clear from Table 1, Comparative A has excellent antistatic properties, but the occurrence of film peeling is observed, and the adhesion is clearly inferior, whereas the dispersion of gelatin and polypyrrole compounds Sample 1 containing the compound has excellent antistatic properties, no peeling of the film, and a good level of adhesion. Therefore, embodiments of the invention are objects of the invention,
It has been revealed that a silver halide photographic material can be provided which has excellent adhesive properties and excellent antistatic properties even when treated with a processing solution having a pH of 12.0 or higher.

Example 2 In order to investigate the adhesion of Sample 1 of Example 1 and Comparative a, model alkaline solutions of pH 10.0, 11.0, 12.0, 13.0, and 14.0 were used. was prepared and evaluated in the same manner as in Example 1, and the results shown in Table 2 were obtained.

[0037]

[Table 2]

As is clear from the results in Table 2, the embodiments of the present invention are capable of processing a silver halide photographic material having excellent antistatic properties, which is the object of the present invention, with a processing solution having a pH of 12.0 or higher. It has now become clear that there is a need to provide a treatment method that ensures excellent adhesion.

[0039]

Effects of the Invention As is clear from the results of the examples, the embodiments of the present invention achieve the object of the present invention, which is to have excellent adhesion even when treated with a treatment solution having a pH of 12.0 or more. It has been revealed that the present invention provides a silver halide photographic material having excellent antistatic properties. It has become clear that a silver halide photographic material with excellent antistatic properties without humidity dependence can be provided.

In addition, the embodiments of the present invention provide excellent adhesion when processing a silver halide photographic material having excellent antistatic properties with a processing solution having a pH of 12.0 or higher, which is the object of the present invention. It has become clear that a processing method will be provided to ensure this.

Claims (1)

[Claims] Claim 1: Processing of a silver halide photographic material having a conductive polymer layer between a gelatin-containing backing layer and a support with a processing solution having a pH of 12.0 or higher. 1. A method for processing a silver halide photographic material, wherein the conductive polymer comprises a copolymer of N-methylol (meth)acrylamide and styrene sulfonic acid.