JP2000275778A - Silver halide photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material having high sensitivity and high contrast and less liable to desensitization, fog and the change in photographic performance even after a long-term preservation by adding specified compounds to a silver halide photographic emulsion layer and/or another hydrophilic colloidal layer. SOLUTION: The silver halide photographic sensitive material has at least one silver halide photographic emulsion layer on the substrate and at least one of compounds of formulae I and II and at least one of compounds of formula III, etc., have been added to the silver halide photographic emulsion layer and/or another hydrophilic colloidal layer. In the formulae I-III, each of M1-M5 is a cation, each of R1-R3 is a substitutable group, R2 and R3 may be, mutually the same or different, each of (1), (m) and (n) is an integer of 0-4 and Z is an alkyl, aryl or a heterocyclic group.

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, and more particularly to a silver halide photographic light-sensitive material having little change in photographic performance even after long-term storage.

[0002]

2. Description of the Related Art In recent years, silver halide photographic light-sensitive materials have been required to have higher quality and handleability with the progress of use and versatility. In order to satisfy these demands, various improvements have been devised and put into practical use, from the production of silver halide crystals and the development of various additives to processing techniques.

[0003] Monocarboxy-substituted phenylbenzoic acid and its oxidized disulfide compound are known as useful compounds for improving the quality of silver halide photographic materials. For example, according to JP-B-46-21989,
When silver halide crystals are precipitated (physical ripening) in the presence of a monocarboxy-substituted phenylmercaptan, the compound acts as a physical ripening inhibitor to give a very fine silver halide emulsion and good latent image stability. It is described that the emulsion becomes an excellent emulsion. Japanese Patent Application Laid-Open No. 61-198147 discloses that
It is described that by including a hydrazine derivative and a disulfide compound in a light-sensitive material, a super-high contrast negative image can be rapidly processed with a stable processing solution. In addition, JP-A-63-50833 and JP-A-3-280039 disclose that a disulfide compound introduced into a light-sensitive material is useful for improving halftone dot reproducibility, preventing fog, and improving stability over time after preparation. JP-A-7-56284 reports that a disulfide compound added to a light-sensitive material and to a developer is useful as a sludge inhibitor. In addition, Shoko 60
-25774 and JP-A-10-301225 show that the stability of a latent image is improved by a monocarboxy-substituted benzoic acid or a disulfide compound.

[0004] By introducing the compound, effects such as improvement of contrast, reduction of fog, improvement of stability of latent image, etc. could be enjoyed. Unfortunately, however, these prior arts have the problem of desensitizing over time and increasing fog.

In order to prevent fogging during the production process, storage or photographic processing of the photographic material, or to stabilize photographic performance, various compounds are contained.
Well-known are heterocyclic compounds containing different elements, namely azoles such as benzothiazoliums, nitroindazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, amino There are triazoles, benzothiazoles, nitrobenzotriazoles, mercaptopyrimidines, azaindenes and the like. In order to achieve the object of the present invention, many compounds conventionally known as these antifoggants or stabilizers were studied.Each of these compounds reduced fog and at the same time caused a serious decrease in sensitivity. I couldn't find a possible level.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material having high sensitivity, high contrast, less desensitization even after long-term storage, less fogging and less fluctuation in photographic performance. To provide.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to provide a photographic material having at least one silver halide photographic emulsion layer on a support, wherein the silver halide photographic emulsion layer and / or other hydrophilic materials are used. In the colloid layer, at least one of the compounds represented by the general formulas (I) and (II) and at least one of the compounds represented by the general formulas (III), (IV) and (V) are added. The problem is solved by the addition of a silver halide photographic light-sensitive material.

Next, the compounds represented by formulas (I) and (II) will be described in more detail. In formulas I and II, M ₁ to
M ₄ is a cation such as hydrogen or an alkali metal or a quaternary ammonium, and is preferably hydrogen, sodium, or potassium. R ₁ , R ₂ and R ₃ are a hydroxyl group, a substituted or unsubstituted alkyl group, an alkoxy group, a carboxyl group, an acyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted nitro group, a substituted or unsubstituted amide group, chlorine, It is a halogen atom such as bromine. Preferred (I),
Examples of the compound represented by (II) are listed below, but the invention is not limited thereto.

[0009]

Embedded image

[0010]

Embedded image

[0011]

Embedded image

[0012]

Embedded image

[0013]

Embedded image

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

These compounds are available from The Journal of
Organic Chemistry, Vol. 8, p. 1380, The Journal of Indian Chemical Society, Vol. 4, p. 295, or by oxidizing monomers produced by the method. it can.

These compounds may be added at any stage of the preparation of the silver halide photographic emulsion, at the end of the chemical sensitization or after the completion of the sensitization. These compounds exhibit an effect when used in the range of 1 × 10 ^-7 to 1 × 10 ^-1 mol per mol of silver halide, and 1 × 10 ^-6.
１1 × 10 ⁻² mol is more preferable, and 1 × 10 ^-5 −1 × 1
0 ^-3 mol and most preferred.

Next, the compounds represented by formulas (III), (IV) and (V) will be described in detail. M ₅ is hydrogen or a cation such as an alkali metal or a quaternary ammonium,
Preferably, it is hydrogen, sodium, or potassium. The alkyl group, aryl group, heterocyclic group, aromatic ring and hetero ring represented by Z and Y _{1 to} Y ₄ may be substituted. Examples of the substituent include an alkyl group such as a methyl group and an ethyl group, an aryl group such as a phenyl group, an alkoxy group, a halogen atom such as chlorine and bromine, a carboxyl group, an amino group, a nitro group, and an amide group. it can.
Examples of the hetero ring represented by Z and Y _{1 to} Y ₄ include thiazole, benzthiazole, imidazole, benzimidazole, oxazole ring and the like. Preferred examples of the compounds represented by (III), (IV) and (V) are listed below, but the present invention is not limited thereto.

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

These compounds may be added at any stage during grain growth, chemical sensitization, or coating before preparing a silver halide photographic emulsion. These compounds are used in an amount of 1 × 10 ^-6 to 1 × 10 ^-2 per mol of silver halide.
It is used in the range of 1 mol, and particularly preferably in the range of 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol.

In the present invention, general formulas (I), (II),
When the compounds represented by (III) to (V) are contained in a photographic light-sensitive material, it is preferable that all of them are contained in a silver halide emulsion layer, but other non-light-sensitive hydrophilic colloid layers (For example, a protective layer, an intermediate layer, a filter layer, an undercoat layer, an antihalation layer, etc.).

The above-mentioned effects are remarkable when the silver halide emulsion used in the present invention is produced by any of an acidic method, a neutral method, and an ammonia method.

The present invention relates to the properties of a silver halide photographic emulsion,
For example, it can be carried out irrespective of the composition of silver halide (for example, silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide) and the crystal form, crystal habit and size of silver halide.

Various additives can be contained in the emulsion according to the present invention. For example, a gold compound can be used for chemical sensitization. Examples of the gold compound used in the present invention include chloroauric acid, potassium chloroaurate, potassium gold thiocyanate, and ammonium gold thiocyanate. The amount of addition is 0.1 mg to 200 mg, preferably 1 mg to 5 mol per 1 mol of silver halide in terms of the weight of the gold compound.
0mg is good. Other chemical sensitizers (for example, sulfur sensitizers such as thiourea and hypo, noble metal sensitizers other than gold, and reduction sensitizers) can be used, and these can be chemically sensitized with gold compounds. Can be used in combination.
Also, spectral sensitizers, supersensitizers, stabilizers, antifoggants,
Surfactants, developers, development accelerators, hardeners, hardeners, couplers, desilvering accelerators, dye removal improvers, brighteners,
It may contain a thickener, a matting agent and the like.

The protective colloid of the silver halide emulsion used in the present invention includes modified gelatin such as gelatin and phthalated gelatin, denatured gelatin, natural products such as albumin, agar, acacia, alginic acid, polyvinyl alcohol, polyvinyl pyrrolidone, and the like. Water-soluble synthetic resins such as copolymers of acrylamide, acrylic acid and vinylimidazole are exemplified.

The emulsions of the present invention are coated on a suitable support, such as glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta coated paper, polyolefin (eg, polyethylene, polypropylene, etc.) coated paper. . These supports may be subjected to a corona treatment by a known method, or may be subjected to a subbing process by a known method as necessary.

Exposure of the silver halide photographic light-sensitive material of the present invention is not limited to light, and the effect of the present invention is remarkable even when the material is exposed to X-rays, γ-rays, electron beams or the like.

The silver halide photographic emulsion according to the present invention is coated, if necessary, with a protective layer, an intermediate layer, an ultraviolet absorbing layer, an undercoat layer or another silver halide emulsion.

The type and use of the silver halide photographic light-sensitive material to which the present invention can be applied are not particularly limited, such as black-and-white photographic materials, color photographic materials, general use, printing, X-ray films, and electron microscope films. . The features of the present invention are:
The point is that a silver halide photographic light-sensitive material having high sensitivity, high contrast, little desensitization even after long-term storage, less fogging and less fluctuation in photographic performance can be obtained.

[0053]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but it should be understood that the present invention is by no means restricted to such specific Examples. An emulsion was prepared according to the following formulation. A silver nitrate aqueous solution and a water-soluble iridium salt (3.25 × 10 ⁻⁶ mol per mol of silver) were prepared by an aqueous solution containing 5 g of sodium chloride and 40 g of gelatin in 600 ml of water by a double jet method at 40 ° C. and a pAg of 8.6. And a silver halide solution containing a water-soluble rhodium salt (1.8.times.10.sup.- ⁷ mol per mol of silver), and a silver chlorobromide (30 mol% silver bromide) emulsion having an average particle size of 0.25 .mu.m. Was added, and an aqueous solution of potassium iodide was added so as to be 0.4 mol% with respect to 1 mol of silver, and the precipitate was washed with water and redissolved. The pAg of the thus obtained emulsion was adjusted to 7.5, and the compounds of the general formulas (III) to (V) shown in Table 1 or the comparative compound were added at 1 × 10 ^-4 mol per mol of silver halide. , 20 mg sodium thiosulfate per mole silver halide and 15 mg chloroauric acid per mole silver halide were added.
Chemical ripening was performed at 60 ° C. for 60 minutes. After ripening, 4-hydroxy-6-methyl-1,3,3 per mole of silver halide
a, 7-Tetrazaindene was added in an amount of 5 × 10 ⁻³ mol.

[0054]

Embedded image

This emulsion was treated with the general formula (I) shown in Table 1
Compound (II) was added in an amount of 5 × 10 ^-4 per mol of silver halide.
Molar additions of hardener and surfactant were added.

These emulsions were overcoated with a protective layer on a polyethylene terephthalate film provided with an undercoat layer and dried to prepare samples. The silver amount was 4.5 g / m ² .

The sample thus prepared was cut into a suitable size, exposed through a wedge having a density difference of 0.15 for 10 ^-5 seconds, and then developed with a developing solution having the following composition at 20 ° C. for 2 minutes. Water (about 30 ° C.) 500 ml Methol 3.1 g Hydroquinone 12 g Anhydrous sodium sulfite 45 g Anhydrous sodium carbonate 67.5 g Potassium bromide 1.9 g Add water 3000 ml

Thereafter, after stopping, fixing, washing with water and drying, characteristics were determined. Table 1 shows the results. The sensitivity was shown as a relative sensitivity, where the sensitivity at a transmission density of Sample 1 of 3.0 was taken as 100. Gamma is the tan of the linear part with an optical density of 0.5 to 3.5.
It was represented by θ.

In the test of storage stability, a part of the sample was left under the conditions of 50 ° C. and a relative humidity of 80% for 5 days, and then subjected to the same exposure and development processing as described above.

[0060]

[Table 1]

As is clear from the results shown in Table 1, Samples 10 to 27 of the present invention have a small decrease in sensitivity and a small decrease in gamma and a rise in fog in the aging test. On the other hand, the comparative sample has a remarkable increase in fog or a remarkable decrease in sensitivity and gamma, and does not reach the scope of the present invention.

[0062]

As will be understood from the examples, according to the present invention, a silver halide photographic light-sensitive material having high sensitivity, high contrast, little desensitization and increase in fog due to storage, and little fluctuation in photographic performance can be obtained. Can be.

Claims (1)

[Claims] 1. A photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, wherein the silver halide photographic emulsion layer and / or other hydrophilic colloid layers have the following general formula (I): A silver halide photographic material comprising at least one compound represented by the formula (II) and at least one compound represented by the following formulas (III), (IV) and (V). Embedded image [Wherein M ₁ and M ₂ represent cations, R ₁ represents a substitutable group, and 1 represents an integer of 0 to 4. [Chemical formula 2] [In the formula, M ₃ and M ₄ each represent a cation, and R ₂ and R ₃ each represent a substitutable group, which may be the same or different.
m and n represent the integer of 0-4. [Chemical formula 3] Wherein Z is an alkyl group, an aryl group, or a heterocyclic group,
M ₅ represents a cation. [Formula 4] [Wherein Y ₁ and Y ₂ represent atoms necessary for forming an aromatic ring or a hetero ring. [Chemical formula 5] [In the formula, Y ₃ and Y ₄ represent atoms necessary for forming an aromatic ring or a hetero ring, and p represents an integer of 2 to 10. ]