JPH0611785A - Silver halide photographic sensitive material improved in physical property of binder - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material free from unevenness in coating and development by incorporating a compound comprising structural units of glucose, mannose, glucuronic acid, and their derivatives. CONSTITUTION:The compound to be added comprises the structural units of glucose, mannose, glucronic acid, and their derivatives and it can be given the thixotropic property that is lowered in viscosity by applying shearing stress. The photographic coating fluid containing it is easily applied to web and raised in viscosity by the shearing stress dropped immediately after coating and made difficult in flowing, thus permitting uniform coating finish to be attained. An extremely small amount of it can control the viscosity of the photographic coating fluid using gelatin as a binder and it does not adversely affect photographic performances, such as sensitivity and fog, and it does not deteriorate the speeds of development, fixation, rinsing, and the like.

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 using a novel anionic polysaccharide in a binder, and in particular, it improves the physical properties of the binder when various additives are added to the binder at high density. And a silver halide photographic light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION A silver halide photographic light-sensitive material generally comprises a photosensitive silver halide grain, various additives for controlling photographic characteristics of the grain, and a binder for holding these additives. Manufactured by applying on top.

However, in addition to this, more demands for high-level physical properties have been increased from the viewpoint of manufacturing or easiness of use (handling) of the light-sensitive material, so that more additives have been used.

For example, in a series of processes in which a photosensitive silver halide emulsion is coated on a support at a high speed, cut, packaged, and commercialized, a surface active agent for coating the emulsion uniformly is coated. A lot of additives such as a slipping agent or a matting agent for smoothly transporting the web, and an antistatic agent and a UV absorber for preventing the generation of static marks due to static electricity during the transportation of the film are used. The reality is that

From the convenience of using the photosensitive material, bending, crimping,
A physical action such as rubbing or pulling is also added. To improve the physical properties of the film, a binder physical property improving agent such as latex is further used. Gelatin and its derivatives are generally used as binders for holding these additives. It is no exaggeration to say that gelatin is commonly used because of its excellent protective colloid property and settability. However, as described above, when many additives are used in the emulsion liquid, the settability of gelatin at the time of coating is deteriorated, which causes deterioration of coating property.

As a result, serious troubles such as uneven coating or unevenness in the line image due to the finished development are brought about. Therefore, conventionally, a thickener for adjusting the viscosity of the emulsion coating solution and a gelling agent for improving the setting property are known.

For example, as a thickener, a copolymer of styrene and maleic acid, a copolymer of styrene sulfonic acid and maleic acid, polystyrene sulfonic acid, polyacrylic acid,
Examples thereof include polyacrylamide.

However, while these compounds increase the viscosity, they have drawbacks such as deterioration of scratch resistance of the emulsion film surface and deterioration of drying property during photographic processing.

Further, when an inorganic salt such as calcium or magnesium, which is known as a gelling agent, is added to cause gelation, there is a problem that a rapid aggregation occurs when the salt is added and the salt becomes insoluble. Technology was desired.

[0010]

SUMMARY OF THE INVENTION Therefore, a first object of the present invention is to provide a silver halide photographic light-sensitive material which is free from uneven coating and uneven development. A second object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in rapid processability without delay in developing fixability and drying property. A third object of the present invention is to provide a silver halide photographic light-sensitive material which is less susceptible to development stains even when processed with a large amount of developer and has scratch resistance. Other objects will be apparent from the following specification.

[0011]

The above-mentioned objects of the present invention have been accomplished by the following finding. That is, it is achieved by a silver halide photographic light-sensitive material characterized in that it contains at least one compound having a component containing glucose, mannose, glucuronic acid and derivatives thereof as a unit. Hereinafter, the present invention will be described in detail.

The compound of the present invention can impart a thixotropic property that the viscosity decreases when it is subjected to shearing. A photographic coating liquid containing this compound is easily applied to a web, and immediately after the coating, the shearing force is decreased to increase the viscosity and the liquid flow is less likely to occur, and as a result, a uniform coating finish is possible. .

The inventor of the present invention has searched for a compound having such a property, and although there are many compounds having this property, many of them have various drawbacks, and a compound suitable for a silver halide photographic light-sensitive material is extremely high. It was known to be few.

Therefore, it was surprising that the compound according to the present invention could not be expected to have the advantages as described below. That is, the compound according to the present invention can control the viscosity of a photographic coating liquid containing gelatin as a binder in a very small amount. Does not adversely affect photographic performance such as sensitivity and fog. It does not reduce the speed of development, washing with fixing water, and drying.

Further, residual color contamination does not occur on the processed light-sensitive material. The photosensitive material has features such as being less likely to be charged with static electricity and being excellent in scratch resistance.

The above-mentioned sugar compound according to the present invention can be easily obtained. For example, as a commercially available product, it is produced by Kelco, Inc. in the United States and is a polysaccharide produced by fermentation of Xanthomonas compestrii, and has a basic structure of a compound called xanthan gum. Fermentation of xanthan gum is described in "The journal of General Microbiology" 134 (4) 1.
055, 1988, the esterification of the carboxyl group of the compound can be easily performed by a general esterification method.

The general structure of the compounds of the present invention is shown below.

[0018]

[Chemical 1]

In the formula, R represents a lower alkyl group having 1 to 6 carbon atoms which may be substituted, or Na ⁺ , K ⁺ , 1 / 2Ca ⁺ .
n represents the degree of polymerization, and is preferably 1 to 1000.

The preferred amount of the compound used in the present invention is 0.2 to 0.001 g per 1 g of gelatin, but 0.2 to 0.001 g is particularly preferred.
It is preferably 0.01 g. To add to the coating solution, the compound can be dissolved in water and used.

The coating solution referred to in the present invention refers to a coating solution for various constituent layers of a silver halide photographic light-sensitive material, specifically, a light-sensitive emulsion layer containing silver halide grains, an antihalation layer and an intermediate layer. Coating liquids such as a protective layer, an antistatic layer, a UV absorbing layer, a filter layer and a backing layer. Among them, the coating solution for the photosensitive emulsion layer contains a large amount of various photographic additives, so that the application of the present compound according to the present invention is effective. When the compound of the present invention is used, it can be dissolved and used together with usual additives. For example, for the coating liquid for protective layer, a matting agent can be used by dispersing it in an aqueous solution of the compound of the present invention.
When preparing a photosensitive emulsion, a sensitizing dye, a desensitizing dye,
Stabilizers and the like can be dispersed in the compound of the present invention and added.

As another method, it is possible to add the compound as a solid after it is dispersed in this compound and then dried to obtain a dispersion in the form of fine particles. The silver halide composition of the silver halide photographic material to which the present invention can be applied is arbitrary such as silver chloride, silver bromide, silver chlorobromide and silver chloroiodobromide. Silver halide can be sensitized with a noble metal salt such as a sulfur compound or a gold salt. Further, it is possible to add performance according to the application by using a doping technique. For example, the contrast may be increased with a rhodium salt or the like, or the high illuminance sensitivity may be increased with an iridium salt or the like. Further, reduction sensitization can be performed, and these methods can be combined for sensitization.

The silver halide is dispersed in a hydrophilic colloid medium such as gelatin to prepare an emulsion solution, which is coated on a support such as polyethylene terephthalate base or triacetate cellulose base to prepare the silver halide photographic light-sensitive material of the present invention. Obtainable.

As a gelatin hardener, aldehydes such as glyoxal and mucochloric acid, cyanuric acid, aziridine or vinyl sulfone can be used.

For example, various antihalation dyes, safelight improving dyes, sensitizing dyes, antifoggants, matting agents, antistatic agents, development regulators, etc., which are contained in the silver halide photographic light-sensitive material of the present invention, can be used. The additive compound is
It can be appropriately selected and used according to the intended use performance. As the developing agent for the black-and-white developing solution used in the present invention, a combination of hydroquinone and its derivative, metol and its derivative, or phenidone and its derivative may be used. In particular, it is useful to use a combination of hydroquinone and a phenidone derivative. A sulfite salt can be used as the antioxidant of the developing solution, and for example, sodium sulfite, potassium sulfite, potassium metabisulfite and the like can be appropriately used. If 0.25 mol / l or more of sulfite ion is used, the effect of preventing oxidation is remarkable.

The developer is ethylenediaminetetraacetic acid,
A water softener such as nitriloacetic acid, potassium bromide or sodium chloride as an inorganic fog inhibitor, and benzotrizole or benzimidazole as an organic fog inhibitor can be used. Further, glycols such as diethylene glycol and triethylene glycol and amines such as diethanolamine and triethanolamine can be used. The alkaline agent used in the developer includes sodium hydroxide and potassium hydroxide, but is not particularly limited.

The form of the developing solution may be a mixture of solid components, an organic aqueous solution containing glycol or amine, or a viscous liquid in a semi-kneaded state with high viscosity. When used, it may be diluted or used as it is.

In developing the light-sensitive material of the present invention,
The developing temperature can be set within the usual range of 20 to 30 ° C or the range of high temperature processing of 30 to 40 ° C. Processing time is normal
It can be set in the range of 45 to 90 seconds or rapid processing of 5 to 45 seconds.

The compound of the present invention can be used in a photosensitive material for printing or medical purposes, and can also be used in various color silver halide photographic photosensitive materials.

Although a photosensitive material for printing is given as an example here, the present invention is not limited to this.

[0031]

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

Example 1 (Preparation of Photosensitive Material) As a silver halide photographic photosensitive material of the present invention, a bright room photosensitive material for plate making was taken as an example.

As the light-sensitive material, the silver halide emulsion and additives described in the examples of JP-A-63-230035 by the same applicant as the present invention were used. A silver chlorobromide emulsion containing 1 mol% of silver bromide having an average grain size of 0.13 μm was used as the silver halide emulsion.

The emulsion was coated with an emulsion layer and a protective layer for the emulsion layer on the opposite side of the support coated with an antihalation layer as a backing layer. The coating amount of each layer is shown below.
The latex and dyes used are described in JP-A-63-23003.
Using the same compound as described in Example of No. 5,
An appropriate amount of cyanuric acid was used as a hardener.

Emulsion protective layer 1.0 g / m ² with gelatin 1.0 g / m ² with latex 1.0 g / m ² Safelight improving dye 0.3 g / m ² Matting agent (SiO ₂ ) 0.01 g / m ² Emulsion layer with gelatin 2 g / m ² Latex amount 1.0g / m ² Silver amount 3.0g / m ² Backing layer with gelatin 1.0g / m ² Latex amount 0.3g / m ² Antihalation dye 0.4g / m ² Backing protective layer with gelatin Amount 1.0 g / m ² matting agent (SiO ₂ ) 0.01 g / m ² The compound of the present invention and the comparative compound are an emulsion layer, an emulsion protective layer,
Nine types of film samples shown in Table 1 were prepared by adding 5% by weight to the amount of gelatin in each of the photographic layers of the backing layer and the backing protective layer.

Film breakdown A No compound B Copolymer of styrene and maleic acid C Polystyrene sulfonic acid D Polyacrylic acid E Polyacrylic acid amide F Compound of the invention Xanthan gum sodium salt G 〃 Xanthan gum methyl ester salt H 〃 Xanthan gum ethyl ester salt I 〃 Xanthan gum propyl ester salt (treatment) The prepared film was developed, fixed, washed with water, and dried. In the processing, the developing temperature was 38 ° C., the developing time was 10 seconds, the fixing temperature was 34 ° C., the washing temperature was 25 ° C., and the drying temperature was 40 ° C. as standard processing conditions. The developer and fixer used had the following compositions. Developer composition Ethylenediaminetetraacetic acid sodium salt 1g Sodium sulfite 60g Hydroquinone 20g 1-Phenyl-3-pyrazolidone 0.5g Potassium carbonate 38g Potassium bromide 3g 5-Methylbenzotriazole 0.5g Add water containing 10% di-ethylene glycol 1 liter
The pH was adjusted to 10.8 with sodium hydroxide. Fixer composition Ammonium thiosulfate 174g Sodium sulfite 17g Sodium acetate ・ trihydrate 6.5g Boric acid 6g Sulfuric acid 2.4g Aluminum sulfate 2.2g Finish with water to 1l Adjust pH to 5.8 with acetic acid (Evaluation) Development unevenness: blackening density A solid-exposed sample was prepared by adjusting the exposure amount to 1.5. The one with the most unevenness was ranked as rank 1, and the one that was finished evenly and uniformly was ranked as rank 5.

Scratch resistance: The needle was scanned while a load was applied to the film surface, and the scratched load was evaluated. The larger the load, the better the scratch resistance.

Development speed: Expressed as relative sensitivity at a development time of 10 seconds. Minus means delay.

Fixing speed: The time (seconds) when the film was soaked in a fixing solution and silver was eluted from the film to become transparent was measured.

Dryability: Touch the film developed from the automatic processor with your hand to remove the terribly sticky one.
And the completely dried state was 5.

Development stain: 30 m ² of film was processed by a roller-conveying type automatic developing machine having a developing tank capacity of 5 liters. Treatment is 0.1m ² each with 12ml developer and 16m
It was carried out while replenishing the fixing solution (1). 50 at the end of processing
A cm × 61 cm unexposed film was processed and the film was visually evaluated for stains. The film with severe dirt was ranked 1 and the clean film without dirt was ranked 5.

The results obtained are shown in Table 1 below.

[0043]

[Table 1]

As is clear from the above results, the sample to which the compound of the present invention is added has improved development unevenness and excellent scratch resistance. Further, it can be seen that there is no decrease in the developing, fixing and drying speeds, good photographic performance is obtained, and there is no development stain on the film when processed in large quantities.

[0045]

According to the present invention, a silver halide photographic light-sensitive material having no development unevenness and good scratch resistance, developability, fixability and drying property can be obtained. Further, according to the present invention, it is possible to provide a silver halide photographic light-sensitive material in which the development stain of the film which occurs when a large amount of processing is performed is improved.

Claims (1)

[Claims] 1. A compound having a component containing glucose, mannose, glucuronic acid and derivatives thereof as a unit,
A silver halide photographic light-sensitive material comprising at least one.