JP2617755B2 - Silver halide photographic materials containing a novel hardener - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material containing a novel hardener, and more particularly, to an improved degree of hardening of a hydrophilic colloid layer, and The present invention relates to a silver halide photographic material having excellent photographic characteristics.

[Related Art] In recent years, systems for developing silver halide photographic materials in a short time by high-temperature rapid processing by an automatic transport system have been widely used based on the spread of automatic developing apparatuses. The development for rapid processing, the high temperature of the fixing processing solution, and the shortening of the transport time degrade the film physical properties of a hydrophilic colloid substance constituting the silver halide photographic material, particularly gelatin and / or a gelatin derivative, As a result, a large amount of silver halide, a storage stabilizer, a high contrasting agent, and other auxiliaries constituting the silver halide photographic light-sensitive material may be eluted in the processing solution in a large amount. In addition, a photographic material for rapid processing often has a high silver chloride content as a silver halide composition from the viewpoint of its suitability for rapid processing, and a preservative used for improving the stability of a processing solution ( Since it is necessary to increase the concentration of sulfites, for example, silver halide is easily eluted into the developer, and if the physical properties of the hydrophilic colloid layer deteriorate, the above tendency is further promoted, which is preferable. Not that.

When gelatin elutes from the hydrophilic colloid layer of the photographic material or silver halide elutes from the constituent layers, gelatin scum and silver sludge are easily generated, and as a result, the processed silver halide photographic material has Black matter such as gelatin deposits or silver deposits on the film surface, thereby deteriorating the finished quality of the photograph.

Therefore, in order to maintain the physical properties of the hydrophilic colloid layer, it is necessary to add and contain various additives such as a gelatin hardener in the hydrophilic colloid layer.

Conventionally, the above-mentioned gelatin hardeners which are contained in a gelatin colloid layer of a light-sensitive material and used for curing the same include, for example, aldehyde compounds, polyfunctional epoxy compounds, active halides, ethyleneimine compounds, active vinyl Compounds and the like have been proposed.

[Problems to be Solved by the Invention] However, even if these gelatin hardeners are used, a sufficient effect cannot be obtained with respect to the elution of the gelatin and the silver halide and the improvement of the generation of stains due to these. Many of these further increase the viscosity of the photographic emulsion to make the coating of the emulsion layer difficult, or require a long aging period after coating the emulsion layer due to the slow curing speed,
If an attempt is made to accelerate the curing by heating, there are disadvantages such as unevenness in the degree of hardening due to uneven temperature and loss of photographic characteristics.

Furthermore, if a large amount of hardener is used in order to reach the required curing level in a short time after coating, photographic properties will be adversely affected, and curing will gradually progress later, eventually causing the hardening to go too far This causes a phenomenon of so-called post-hardening, which remarkably impairs the developability and is not preferred.

The present invention is intended to eliminate various problems caused when using the conventional hardener as described above, to improve the finish quality and physical properties of photographs, and to further improve the desired saturated hardening level. Use the minimum amount of hardener needed to reach it,
And by reaching the saturated dura level in a short time,
An object of the present invention is to provide a hardener having a stable hardening level with less post-hardening phenomenon and a silver halide photographic light-sensitive material containing such a hardener.

[Means for Solving the Problems] As a result of repeated studies to solve the above problems, the present inventors have found that a hydrophilic colloid layer comprising at least one photosensitive silver halide emulsion layer on a support is provided. Wherein the gelatin in the hydrophilic colloid layer is at least one selected from N, N'-dissuccinimide oxalate compounds represented by the general formula [I]. It has been found that the above object can be achieved by a silver halide photographic light-sensitive material characterized by being cured.

Hereinafter, the present invention will be described in more detail. The present invention relates to a hardening agent for gelatin in a hydrophilic colloid layer of a silver halide photographic material (hereinafter simply referred to as a photographic material).
It is characterized by using N, N'-disuccinimide oxalate compounds and derivatives thereof, and these compounds can be represented by the following general formula [I].

General formula [I] (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group,
Represents an acyl group, an aromatic group or a heterocyclic group, including those having a substituent. In the general formula [I], the halogen atom represented by each of R ₁ , R ₂ , R ₃ and R ₄ includes, for example, a chlorine atom,
Examples thereof include a bromine atom and an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, a butyl group, and a hydroxyalkyl group. Further, examples of the alkoxy group include a methoxy group and an ethoxy group, and examples of the acyl group include an acetyl group. Examples of the aromatic group include a phenyl group and a naphthyl group, and examples of the heterocyclic group include a pyridyl group, a thiophene group, and a furan group.

Hereinafter, typical specific examples of the compound represented by the general formula [I] will be shown.

The hardening agent of the above exemplified compound can be easily synthesized with reference to Tetrahedron letters, vol. 24, p. 4451, 1983.

The addition amount of the hardener according to the present invention varies depending on the type of the hardener used and the type of the emulsion, but is effective at about 0.2 to 2 mmol per 1 g of dry gelatin. The addition may be made at any stage of preparing a coating solution for forming a gelatin film, but when it is added to a silver halide emulsion, it is generally added after the second ripening of the silver halide emulsion. Good.

When the hardener is added to the emulsion, water, methanol, ethanol, acetone, ethyl acetate or the like is usually used as a solvent, but the effect of the present invention is impaired even when the hardener is dispersed in the emulsion. It will not be.

Examples of the silver halide emulsion include silver halide emulsions such as silver bromide, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. It may be sensitized by a chemical sensitizer such as a sensitizer, a sulfur sensitizer or a reduction sensitizer, a sensitizing dye and a polyalkylene oxide-based compound, and various other commonly used photographic additives. Can be added.

The silver halide incorporated in the silver halide emulsion layer according to the present invention has, but is not limited to, an average grain size of 0.05 to 1.5 microns, preferably 0.1 to 0.5 microns, and at least 75% of the total number of grains. Preferably 80% or more is 0.5 to 1.5 times the average particle size, preferably 0.6
It is desirable to include silver halide having a grain size of .about.1.4 times.

According to one most preferred embodiment of the present invention, the silver halide used in the present invention has an average grain size of 0.10 to 0.8μ and 80% or more of all grains have a mean grain size of 0.
It is silver chloroiodobromide or silver chlorobromide having a grain size of 6 to 1.4 times.

Further, the silver halide is iridium in the crystal grains,
Metal atoms such as rhodium, osmium, bismuth, cobalt, nickel, palladium, ruthenium, iron, copper, zinc, lead and cadmium may be contained. When these metal atoms are contained, 10 to 10 moles per mole of silver halide
^-8 to 10 ^-2 moles, preferably 10 ^-6 to
It is preferred to contain 10 ^-4 mol. Further, it may be a surface latent image type or an internal latent image type. Silver halides prepared by various different methods may be mixed.

The crystal form is not limited to any of cubic, octahedral and spherical forms.

The hydrophilic colloid used particularly advantageously in the present invention is gelatin. Examples of hydrophilic colloids other than gelatin include colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, and polyvinyl alcohol. , Hydrolyzed polyvinyl acetate, gelatin derivatives,
For example, U.S. Pat. And styrene acrylates, acrylates, methacrylic acid, and methacrylic acid esters as described in paragraphs. Colloids can also be applied to layers containing no silver halide, such as antihalation layers, protective layers, intermediate layers, and the like.

The silver halide photographic light-sensitive material of the present invention is obtained by coating a hydrophilic colloid layer including the above-mentioned silver halide emulsion layer on a suitable photographic support. Examples of the support used in the present invention include: Baryta paper, polyethylene coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, for example, a polyester film such as polyethylene terephthalate, a polyamide film, a polypropylene film, a polycarbonate film, a polystyrene film and the like are included as typical examples. These supports are appropriately selected depending on the purpose of use of the silver halide photographic light-sensitive material.

The silver halide photographic light-sensitive material of the present invention is obtained by coating a support with at least one hydrophilic colloid layer containing the silver halide according to the present invention. The material has a protective layer having an appropriate thickness, that is, preferably 0.1 to 10μ, particularly preferably 0.7.
It is desirable to apply a gelatin protective layer of ~ 2μ.

The hydrophilic colloid used in the present invention may optionally contain various photographic additives such as a gelatin plasticizer, a hardener, a surfactant, an image stabilizer, an ultraviolet absorber, an antistain agent, and a pH adjuster. , An antioxidant, an antistatic agent, a thickener, a graininess improver, a dye, a mordant, a whitening agent, a developing speed regulator, a matting agent, etc., within a range that does not impair the effects of the present invention. it can.

Among the various additives described above, those which can be particularly preferably used in the present invention include, for example, U.S. Pat.No. 2,960,404 as a thickener or a plasticizer, Japanese Patent Publication No. 43-4939,
West German Application Publication No. 1,904,604, JP-A-48-63715
No., JP-B-45-15462, Belgian Patent No. 762,833
No. 3,767,410; Belgian Patent No. 558,143
The substances described in each of the specifications, for example styrene-
Hardening agents that can be used in combination with the hardening agent of the present invention, such as sodium maleate copolymer and dextran sulfate, include aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinylsulfone-based, isocyanate-based, and sulfonic acid. Ester type, carbodiimide type, mucochloric acid type, various hardening agents such as acyloyl type, as ultraviolet absorbers, for example, U.S. Pat.No. 3,253,921, compounds described in each specification of UK Patent No. 1,309,349, especially 2- (2'-
(Hydroxy-5-tertbutylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tertbutylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tertbutyl-5' -Butylphenyl)-
Examples thereof include 5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tertbutylphenyl) -5-chlorobenzotriazole, and examples of the dye include U.S. Pat. No. 2,072,908. German Patent 107,990
, US Pat. No. 3,048,487, US Pat. No. 515,998, etc., and these compounds may be contained in a protective layer, an emulsion layer or an intermediate layer. Further, as coating aids, emulsifiers, improvers of permeability to processing solutions, etc., foaming agents or surfactants used for controlling various physical properties of photosensitive materials, UK Patent Nos. 548,532 and Nos. 1,216,389, U.S. Pat.Nos. 3,026,202, 3,514,293
44-26580, 43-17922, 43-17926, 43-1
Nos. 3166 and 48-20785, French Patent No. 202,588
No., each specification of Belgian Patent No. 773,459, JP-A-48
Anionic, cationic, nonionic or amphoteric compounds described in JP-A-101118 can be used. Also, as an antistatic agent, JP-B-46-24159
Nos., JP-A-48-89979, U.S. Pat.No. 2,882,157
No. 2,972,535, JP-A-48-20785,
No. 48-43130, No. 48-90391, JP-B-46-24159,
JP-A-46-39312, JP-A-48-43809, compounds described in JP-A-47-33627 and the like.As matting agents, for example, British Patent No. 1,221,980, U.S. Pat.
No. 2,101, No. 2,956,884, each specification of French Patent No. 1,395,544, compounds described in JP-B-43-43125, etc., particularly silica gel having a particle size of 0.5 to 20 μm,
Examples thereof include a polymer of polymethyl methacrylate having a particle size of 20 μm.

The silver halide photographic light-sensitive material of the present invention is subjected to development processing after exposure. Examples of the developer to be contained in a developer used in the processing include the following.

For example, as a dihydroxy type developer, catechol, pyrogallol and its derivatives and ascorbic acid are typical, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2,3-dibromohydroquinone, 2,5-dihydroxyacetophenone, 2,5-diethylhydroquinone, 2,5-di-p-phenethylhydroquinone, 2,5
-Dibenzoylaminohydroquinone, catechol, 4
-Chlorocatechol, 3-phenylcatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-
There are acetyl-pyrogallol, 4- (2'-hydroxybenzoyl) pyrogallol, sodium ascorbate and the like. As an aminohydroxy type developer, ortho- and para-aminophenol or aminopyrazolone are typical, and 4-amino Phenol, 2-amino-6
-Phenylphenol, 2-amino-4-chloro-6-
Phenylphenol, 4-amino-2-phenylphenol, 3,4-diaminophenol, 3-methyl-4,5-diaminophenol, 2,4-diaminoresorcinol, 2,
Examples thereof include 4,6-triaminophenol, N-methyl-p-aminophenol, N-β-hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid, and 2-aminonaphthol. Further, as the diamine type developer, for example, 4-amino-2-methyl-N, N-diethylaniline, 2,4-diamino-N, N-diethylaniline, N- (4-amino-3-methylphenyl) ) -Morpholine, p-phenylenediamine, 4-amino-N, N-dimethyl-3-hydroxyaniline-N, N,
N ', N'-tetramethylparaphenylenediamine, 4-
Amino-N-ethyl-N- (β-hydroxyethyl)-
Aniline, 4-amino-3-methyl-N-ethyl-N-
(Β-hydroxyethyl) -aniline, 4-amino-N
-Ethyl- (β-methoxyethyl) -3-methyl-aniline, 4-amino-3-ethyl-N-ethyl-N- (β
-Methylsulfonamidoethyl) -aniline, 4-amino-N-butyl-N-γ-sulfobutylaniline, 1-
(4-aminophenyl) -pyrrolidine, 6-amino-1
-Ethyl, 1,2,3,4-tetrahydroquinoline, 9-aminoeurolidein and the like. Further, examples of the heterocyclic developer include 1-phenyl-3-pyrazolidone (phenidone), 1-phenyl-4-amino-5-pyrazolone, 1- (p-aminophenyl) -3-amino-2-pyrazoline, 1-phenyl-3-methyl-4-amino-5
-Pyrazolone, 4,4'-dimethyl-1-phenyl-pyrazolidone (dimedone), 5-aminouracil, 5-amino-2,4,6-trihydroxyphyrimidene and the like.

In addition, The James of the Theory of the James
Photographic Process 4th Edition (The Theory of th
e Photographic Process, Fourth Edition) 291-334
Terms and Journal of the American Chemical
Society (Journal of the American Chemical Socie
ty) Developers described in Vol. 73, Item 3100 (1951) can be effectively used in the present invention.

These developers may be used alone or in combination of two or more, but it is preferable to use two or more in combination. Examples of preferred combinations include a combination of hydroquinone and phenidone or hydroquinone and dimedone, and the amount used at this time is 5 g to 50 g of hydroquinone.
, Phenidone or dimedone in the range of 0.05 g / 5 g /.

Further, the effect of the present invention is not impaired even if a sulfite such as sodium sulfite, potassium sulfite, or ammonium sulfite is used as a preservative in the developer used in the present invention. Can be mentioned. The sulphite concentration used is suitably between 0.06 and 1 gram ion /. Also, hydroxyamine and hydrazide compounds may be used as preservatives.

Others such as those used in common black-and-white developers, caustic alkalis, alkali carbonates or amines to adjust the pH and have a buffer function, and inorganic development inhibitors such as bromocali, metal ion scavengers such as ethylenediaminetetraacetic acid, methanol, Ethanol, benzyl alcohol, development accelerators such as polyalkylene oxide, sodium alkylaryl sulfonate, natural saponins, surfactants such as saccharides or alkyl esters of the above compounds, glutaraldehyde, formalin, hardening agents such as glyoxal, It is optional to add an ionic strength adjusting agent such as sodium sulfate.

The pH can be arbitrarily set in the range of 9 to 12, but the pH is preferably in the range of 10 to 11 in view of the effect of the preservative and the photographic performance.

Examples of the organic solvent that can be contained in the developer of the present invention include alkanolamine and glycol.

Alkanolamines useful in the present invention include monoethanolamine, diethanolamine, triethanolamine and the like, with ethanolamine being preferred. The amount used is 20 to 500 g, preferably 60 to 300 g, per developer. Further, glycols useful in the present invention include, for example, ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol and the like, with diethylene glycol being particularly preferred. The amount used is 20 to 500 g, preferably 60 to 300 g, per developer.

The above alkanolamines and glycols are used alone or in combination of two or more.

Development inhibitors useful in the present invention include 5-nitroindazole, 6-nitroindazole, 5-methylbenzotriazole, 6-methylbenzotriazole,
Preferred are 5-nitrobenzimidazole, 5-nitrobenzimidazole, 1-phenyl-5-mercaptotetrazole and the like. The amount of these used is 10 ^-1 per developer.
1010 ^-5 mol, preferably 10 ^{-2 -10 -4} mol. Preferably, the development inhibitor is dissolved in alkanolamine and glycol and added to the developer.

The photographic light-sensitive material of the present invention can be processed under various conditions. For example, the processing temperature is preferably 50 ° C. or less, particularly preferably about 30 ° C., and the developing time is 3 hours.
It is common to finish in less than a minute, but particularly preferably less than 2 minutes often provides good results. Processing steps other than development, such as washing, stopping, stabilizing, fixing and, if necessary, steps such as pre-hardening and neutralization are optional, and these steps can be omitted as appropriate. Furthermore, these processes may be so-called hand development processes such as dish development and frame development, or may be mechanical developments such as roller development and hanger development.

The silver halide photographic light-sensitive material of the present invention includes black-and-white photographic light-sensitive materials for general use, various X-ray photographic light-sensitive materials, photographic light-sensitive materials for printing (including those for printing plates), and photographic light-sensitive materials for various colors.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1 A silver chlorobromide gelatin emulsion having a composition of 5 mol% of silver bromide and 95 mol% of silver chloride and having an average grain size of 0.20 μm was prepared by a neutral single jet method.

After physical ripening, desalting was performed by washing with water, gelatin was added, and then sodium thiosulfate and chloroauric acid were added to perform chemical sensitization, followed by 2,3,5-triphenyl-2H-tetrazolium as a contrast agent. 0.3 g / mol Ag chloride,
An emulsion was completed by adding 1 g / mol Ag of 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene as a stabilizer and sodium dodecylbenzenesulfonate as a surfactant. The resulting gelatin silver halide emulsion was divided into 5 parts. As shown in Table 1 below, an aqueous solution of the exemplified compound of the above hardener was added to each of the divided parts in an amount of 0.2 mmol per 1 g of gelatin to prepare an emulsion coating solution.

The five types of emulsion coating solutions obtained above were coated on a photographic paper base coated with a double-sided polyethylene layer at 3.0 g / silver.
m ² and gelatin at 3 g / m ² and dried. The obtained sample was heated at 40 ° C. for 4 days. The sample thus prepared was developed using a developing solution having the following composition at 40 ° C. for 15 seconds, fixed with the following fixing solution at 35 ° C. for 10 seconds, treated with 3 m ² per 1 minute, and allowed to stand for 2 days. The amount of eluted silver and the amount of eluted gelatin were measured. The results are shown in Table 1 below.

(Developer composition) Water 750 ml Potassium sulfite 50 g Potassium carbonate 35 g Hydroquinone 20 g Phenidone 0.25 g N-methyl-p-aminophenol 0.10 g 1-Phenyl-5-mercaptotetrazole 30 mg 5-Methylbenzotriazole 60 mg 5 -Nitroindazole 100 mg 2-Benzimidazole 2-mercapto-5-sulfonate 20
mg Diethylene glycol 100 mg Potassium bromide 6 g Add water to make 1000 ml.

(Composition A) (Composition A) Ammonium thiosulfate (72.5 w / v aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate 2 g Acetic acid (90% w / v) (W aqueous solution) 13.6 ml (Composition B) Pure water (ion exchange water) 17 ml Sulfuric acid (50% w / w aqueous solution) 4.7 g Aluminum sulfate (Al ₂ O ₃ equivalent, content of 8.1% w / w aqueous solution) 26.5 g At the time of use of the fixer, the composition A and the composition B were dissolved in 500 ml of water in this order in order, and finished to 1 before use. The pH of the fixing solution was about 4.3.

As is clear from the results in Table 1, it was found that the hardener according to the present invention had more excellent results with respect to the eluting gelatin and the eluting silver than the conventional hardener.

Further, the obtained degree of hardening was practically sufficient, and there was almost no post-hardening.

Example 2 A silver chlorobromide gelatin emulsion having a composition of 90 mol% of silver bromide and 10 mol% of silver chloride and an average grain size of 0.20 μm was prepared by a neutral single jet method.

After physical ripening, desalting was performed by washing with water, gelatin was added, and then sodium thiosulfate was added to perform chemical sensitization, followed by 5-methylbenzotriazole 20 mg / mol Ag,
An emulsion was completed by adding 1 g / mol Ag of polyethylene glycol, a stabilizer, 1 g / mol Ag of the compound of the following structural formula (a), 2 g / mol Ag of the compound of the following structural formula (b), and a surfactant.

Structural formula (a) Structural formula (b) The resulting gelatin silver halide emulsion was divided into 5 parts. As shown in Table 2 below, an aqueous solution of the exemplified compound of the hardener was added to each of the divided parts in an amount of 0.2 g / g of gelatin.
By adding mmol, an emulsion coating solution was obtained.

The five types of emulsion coating solutions obtained above were coated on a photographic paper base coated with a double-sided polyethylene layer at 3.0 g / silver.
m ² and gelatin at 3 g / m ² and dried. The obtained sample was heated at 40 ° C. for 4 days. The sample thus prepared was developed with a developer having the following composition at 40 ° C. for 20 seconds, treated with 3 m ² per one, and allowed to stand for 2 days, and the amounts of eluted silver and eluted gelatin in the developer were measured. . The results are shown in Table 2 below.
It was shown to.

(Developer composition) Water 750 ml Potassium sulfite 50 g Potassium bromide 3 g Potassium carbonate 35 g Sodium phosphate 20 g Hydroquinone 20 g Polyethylene glycol (molecular weight 1540) 1 g Phenidone 0.25 g N-methyl-p-aminophenol 1 Phenyl-5-
Mercaptotetrazole 30 mg 5-Methylbenzotriazole 20 mg 5-Nitroindazole 100 mg 1-Methyl-2-mercapto-5-benzimidazole sulfonate 20 mg Diethylene glycol 100 mg Butylaminodiethanolamine 15 g Make up to 1000 ml with water.

 pH was adjusted to 11.5.

As is clear from the results in Table 2, it was found that the hardener according to the present invention had better results with respect to the eluted gelatin and the eluted silver than the conventional hardener.

Further, the obtained degree of hardening was practically sufficient, and there was almost no post-hardening.

[Effects of the Invention] By using the hardener according to the present invention, a silver halide photographic light-sensitive material is provided, in which gelatin and silver halide are less eluted into a processing solution and a stain on a developer and a film surface is less. did it.

As a result, a silver halide photographic light-sensitive material having improved photographic finish quality and physical properties was obtained.

Further, a hardening agent and a silver halide photographic light-sensitive material which provide a stable hardening level with little post-hardening development by using a minimum amount of a hardening agent to reach a target saturated hardening level in a short time. Could be provided.

Claims (1)

(57) [Claims] 1. A silver halide photographic material comprising a support and a hydrophilic colloid layer comprising at least one photosensitive silver halide emulsion layer, wherein the gelatin in the hydrophilic colloid layer is as follows: A silver halide photographic light-sensitive material cured by at least one selected from N, N, -disuccinimide oxalate compounds represented by the formula [I]. General formula [I] (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group,
Represents an acyl group, an aromatic group or a heterocyclic group, including those having a substituent. )