JP2663349B2 - Silver halide photographic materials containing antifoggants - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material containing an antifoggant, and more particularly, to fog generated during storage with time at high temperature and high humidity. The present invention relates to a silver halide photographic material containing a fog inhibitor which can be suppressed.

BACKGROUND OF THE INVENTION A silver halide photographic light-sensitive material containing a light-sensitive silver halide emulsion (or simply referred to as a light-sensitive material), particularly a chemically sensitized one, has a nucleus that can be developed without exposure. It is well known that fog tends to occur due to its presence, and this fog tends to occur when developed at high temperatures or for a long time, or during storage of photosensitive materials, particularly during storage over time at high temperature and high humidity. Have been.

An increase in fog causes a decrease in sensitivity and a deterioration in gradation, and significantly impairs image reproducibility. For many years, attempts have been made to add many substances to silver halide emulsions for the purpose of preventing fog.

As a representative example, for example, Research Disclosure, 176, December 1978, 1
7643 (VI). Particularly effective antifoggants include the Theory of the Photographic Process by TH James.
f the Photographic Process), 4th edition, published by Macmillan (1977), pp. 393-399, and also describes the mechanism of action. However, it is difficult for these many fogging suppression techniques to sufficiently cope with recent high sensitivity, high activation, and high speed processing of photosensitive materials. In particular, they are left at high temperatures (about 45 ° C. or higher), In fact, it lacks fog suppression and photographic property stability under severe conditions such as storage under high temperature and high humidity (about 50-60 ° C., relative humidity about 50-90%). That is, when an effective concentration for adapting the above-mentioned many known compounds to the above-mentioned conditions is used, the sensitivity (gradation) in which the decrease in sensitivity and the degradation in gradation are remarkable and are essential elements of the fog inhibitor: fog Can not maintain the balance.

Therefore, there is a strong demand for development of a fog suppression technique that does not deteriorate photographic characteristics such as loss of sensitivity due to fog and deterioration of gradation even under severe conditions.

[Object of the Invention] The present invention has been made in view of the above situation, and a first object of the present invention is to provide stable photographic characteristics even when a photographic material is stored for a long time at high temperature or high temperature and high humidity. Maintain,
An object of the present invention is to provide a silver halide photographic light-sensitive material capable of preventing generation of fog.

A second object of the present invention is to provide a silver halide photographic light-sensitive material containing a fogging inhibitor which does not cause a decrease in sensitivity or deterioration in gradation due to suppression of development.

A third object of the present invention is to provide a silver halide photographic light-sensitive material containing a fogging inhibitor capable of remarkably reducing the occurrence of fog at the time of rapid processing at a high temperature, particularly at a temperature of 30 ° C. or higher.

[Constitution of the Invention] The object of the present invention is to provide a light-sensitive material having at least one silver halide emulsion layer, wherein at least one of the silver halide emulsion layer and a hydrophilic colloid layer adjacent to the silver halide emulsion layer is contained. And at least one selected from 4-thiadiazolidine compounds is achieved by a silver halide photographic material.

In the present invention, the above object can be achieved as long as it has a 1,2,4-thiadiazolidine skeleton. However, it is particularly preferable that the 2,4-diazine represented by the following general formula [I] be used. Substitution-3,5-
Silver halide photographic materials containing at least one selected from disubstituted imino-1,2,4-thiadiazolidine compounds are preferred.

General formula [I] [Wherein, R ¹ , R ² , R ³ and R ⁴ represent an aliphatic group or an aromatic group which may be the same or different. Next, the compound represented by the general formula [I] will be described in detail.

Examples of the aliphatic group for R ¹ , R ² , R ^3, and R ⁴ include an alkyl group, an alkenyl group, and a cycloalkyl group each of which may have a substituent.

The alkyl group is preferably a linear or branched alkyl group having 1 to 8 (preferably 1 to 6) carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. And the like.

The alkenyl group preferably has 3 to 5 carbon atoms, such as an allyl group, a propenyl group and a butenyl group.

The cycloalkyl group preferably includes a 5- to 6-membered cycloalkyl group, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

The aromatic groups represented by R ¹ , R ² , R ³ and R ⁴ may also have a substituent, and examples of the aryl group include a phenyl group and a naphthyl group.

R ¹ , R ² , substituents that the aliphatic group and the aromatic group represented by R ³ and R ⁴ may have, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group Group, aryloxy group, acyl group, acyloxy group, amino group, acylamino group, alkylamino group,
Examples include an arylamino group, a sulfo group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, a cyano group, and a nitro group.

In the present invention, a particularly preferred aliphatic group is a lower alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, and a butyl group. Groups.

Next, specific representative examples of the compound represented by the general formula [I] (hereinafter, referred to as the compound of the present invention) used in the present invention will be shown, but the present invention is not limited thereto.

The method for synthesizing the above compound can be easily obtained by the reaction of a thiourea derivative with benzoyl peroxide, and is described in detail in Takeshi Kinoshita et al. Bulletin of Th.
e Chemical Society of Japan Vol.49, No.8 P2236 ~ 224
4 (1976) or a method analogous thereto can be easily synthesized.

In the present invention, the above compound can be used as a fogging inhibitor, and the silver halide emulsion layer and the adjacent hydrophilic colloid layer (intermediate layer, filter layer,
Antihalation layer, protective layer, undercoat layer). A particularly preferred layer is a silver halide emulsion layer.

The addition amount of the compound of the present invention is not uniform depending on the type of the light-sensitive material and the compound, but the compound represented by the general formula [I] is used in the range of 0.01 mg to 1,000 mg per mol of silver halide. Preferably, more preferably 0.05mg ~ 500m
g. The amount added to the hydrophilic colloid layer is preferably in the range of 0.1 mg to 2,000 mg, more preferably 10 mg to 1,000 mg per 1 m ² of the coating.

These compounds are dissolved in water or a hydrophilic organic solvent (eg, methanol, dimethylformamide, etc.) and added to the necessary constituent layers.

In the case of a silver halide emulsion, the addition time is during chemical ripening, after completion of chemical ripening, and / or immediately before coating of the emulsion, more preferably at the end of chemical ripening of the silver halide emulsion.

The light-sensitive material of the present invention can be applied to various types of light-sensitive materials as described below.

For example, photosensitive materials for general black and white, X-ray recording, plate making, color positive, color negative, color paper, reverse color, direct positive, heat development, etc., or surface latent image type silver halide particles U.S. Pat.Nos. 2,996,382 and 3,17 using silver halide grains having internal fog nuclei
It can be used for a light-sensitive material according to the method described in Japanese Patent No. 8,282, but is particularly advantageous for application to a multi-layered color light-sensitive material.

The silver halide emulsion used in the present invention may be any silver halide emulsion such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Can be used.

The silver halide grains used in the silver halide emulsion are:
The grains may have a uniform silver halide composition distribution within the grains, or may be core / shell grains having different silver halide compositions between the inside of the grains and the surface layer.

The silver halide grains may be grains whose latent image is mainly formed on the surface, or grains whose latent image is mainly formed inside the grain.

The silver halide emulsion having any grain size distribution may be used. Emulsions having a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions having a narrow grain size distribution (referred to as monodisperse emulsions) may be used alone or as a mixture of several kinds. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions formed separately.

The emulsion can be chemically sensitized by a conventional method,
By using a sensitizing dye, it can be optically sensitized to a desired wavelength range.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as a binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened, and can contain a plasticizer and a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer.

A coupler is used in the emulsion layer of the color light-sensitive material. In addition, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, by coupling with a competitive coupler having a color correction effect and an oxidized form of the developing agent.
Compounds that release photographically useful fragments such as hardeners, foggants, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

As the yellow dye-forming coupler, known acylacetanilide-based couplers can be preferably used. Of these, benzoylacetanilide and pivaloylacetoanilide compounds are advantageous.

As the magenta dye-forming coupler, a 5-pyrazolone coupler, a pyrazoloazole coupler, a pyrazolobenzimidazole coupler, an open-chain acylacetonitrile coupler, an indazolone coupler and the like can be used.

As the cyan dye-forming coupler, a phenol or naphthol coupler is generally used.

Photosensitive materials include filter layers, antihalation layers,
An auxiliary layer such as an irradiation prevention layer can be provided. In these layers and / or the emulsion layers, dyes which are discharged from the light-sensitive material or bleached during the development processing may be contained.

Matting agents, lubricants, image stabilizers, formalin scavengers, ultraviolet absorbers, fluorescent brighteners, surfactants, development accelerators, development retarders and bleaching accelerators can be added to the photosensitive material.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

A known method is used for developing the light-sensitive material of the present invention. The processing temperature is between 18 ° C and 50 ° C,
Depending on the purpose, any of black-and-white photographic processing, lithographic development processing, and color photographic processing for forming a dye image can be applied. Further, the photosensitive material for thermal development is processed at a temperature of 100 ° C. or higher.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but this is an example for describing the present invention, and the present invention is not limited to these.

Example 1 A high-sensitivity negative-working silver iodobromide emulsion containing 3.0 mol% of silver iodide was chemically ripened to the highest sensitivity by a gold and sulfur sensitization method, and then 4-hydroxy-6-methyl per mole of silver halide. The ripening was stopped by adding 1.0 g of -1,3,3a, 7-tetrazaindene.

The resulting emulsion was divided into 13 parts, one part of which was used as a blank sample as it was, and the compound according to the present invention and a comparative compound as shown in Table 1 below were added and allowed to adsorb sufficiently, and then saponin was used as a coating aid. An emulsion for coating was prepared by adding an appropriate amount and an appropriate amount of formalin as a hardener.

The coating emulsion was uniformly coated on a subbed polyester base so that the silver amount was 3 g / m ² , and dried to prepare 13 kinds of samples (Nos. 1 to 13).

The photographic material prepared as described above was left as a fresh sample at room temperature for 3 days, and a forced deterioration time-lapse sample was left at 55 ° C for 3 days and at 50 ° C and 80% relative humidity for 3 days. did. Thereafter, exposure was carried out using a usual wedge for sensitometry, followed by development and fixing at 35 ° C. for 30 seconds with the following processing solution [A], followed by washing with water and drying to measure the sensitivity.

Processing solution [A] (Developer for black-and-white photographic materials) 1-phenyl-3-pyrazolidone 1.5 g Hydroquinone 30 g 5-Nitroindazole 0.25 g Potassium bromide 5 g Sodium sulfite anhydride 55 g Potassium hydroxide 30 g Boric acid 10 g Glutaraldehyde (25%) 5 g Add water to bring the total volume to 1.

 Table 1 shows the obtained results.

However, the fog value indicates a value obtained by subtracting the base density,
From the sensitivity at the position of the fog value +0.5, the sensitivity of the blank sample (No. 1) of the emulsion of the present invention obtained on standing for 3 days was 100
The gamma is represented by the slope of the linear portion on the characteristic curve.

As is evident from Table 1 above, all the samples according to the present invention have reduced fog generation and improved stability under film storage, despite severe storage conditions. I understand.

Example 2 According to the method of Example 1, a high-sensitivity negative-working silver iodobromide emulsion was chemically ripened to the maximum sensitivity with a gold and sulfur sensitizer.

Then, as a green-sensitive sensitizing dye, anhydro-5,5 '
A suitable amount of sodium salt of -diphenyl-9-ethyl-3,3'-di-γ-sulfopropyloxacarbocyanine hydroxide was added to prepare a green-sensitive silver halide emulsion.

Then, 1- (2,4,6-trichlorophenyl) -3-magenta coupler was used per mole of silver halide.
80 g of [3- (2,4-di-t-amylphenoxyacetamide) benzamide] -5-pyrazolone and 1- (2,4,6-trichlorophenyl) -4- (1-naphthylazo as a colored magenta coupler ) -3- (2-Chloro-5-octadecenylsuccinimidoanilino) -5
-2.5 g of pyrazolone was weighed, 120 g of tricresyl phosphate and 240 mg of ethyl acetate were mixed and dissolved by heating, and then a coupler emulsified and dispersed in a solution of 5 g of sodium triisopropylnaphthalenesulfonate and 550 ml of a 7.5% aqueous gelatin solution. The solution was added to the above emulsion.

The emulsion was divided and one part was used as a blank sample as it was. As shown in Table 2 below, a comparative compound and a compound according to the present invention were added, respectively, and allowed to sufficiently adsorb. An appropriate amount of sodium 2-hydroxy-4,6-dichlorotriazine was uniformly added to obtain a coated emulsion.

The coated emulsion was uniformly coated and dried on a triacetate film which had been subbed so as to have a silver content of 3.0 g / m ² to obtain samples (Nos. 14 to 24).

The obtained film sample was subjected to a forced deterioration test by the method according to Example 1, then exposed to wedges by a usual method, and developed in color according to the following color processing steps.

The results of color sensitometry obtained from the obtained pieces are shown in Table 2 below.

In addition, the fog in the table is a value obtained by subtracting the base density.
Sensitivity of blank sample left for 2 days (Sample No.1
This is the relative sensitivity when 4) is expressed as 100. Gamma was indicated by the slope of the linear portion on the characteristic curve.

Processing process [Processing temperature 38 ° C] Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Processing used in each processing step The liquid composition is as follows.

[Color developing solution] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate 4.75 g Sodium sulfite anhydrous 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Potassium carbonate anhydrous 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 and adjust the pH to 1 using sodium hydroxide.
Adjust to 0.6.

[Bleaching solution] Iron ammonium salt of ethylenediaminetetraacetic acid 100.0 g Diammonium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water is added to adjust the pH to 1, and the pH is adjusted to 6.0 using aqueous ammonia.

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Water is added to 1 and the pH is adjusted to 6.0 using acetic acid.

[Stabilizing solution] Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Add water to make 1.

From the results in Table 2, it can be seen that the compound of the general formula [I] used in the present invention is compared with a conventionally known compound,
It can be seen that fog suppression without a decrease in sensitivity is obtained in a forced deterioration test under high temperature or high humidity.

Example 3 A multilayer color photosensitive material sample was prepared by sequentially providing each layer having the following composition on a cellulose triacetate film support. However, the third layer, the fourth layer, the sixth layer, the seventh layer,
The amounts of silver halide emulsions in the ninth and tenth layers were silver iodobromide emulsions having the following silver iodide contents.

First layer: Antihalation layer Gelatin layer containing black colloidal silver Second layer: Intermediate layer Gelatin layer Third layer: Red-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver coating amount: 1.79 g / m ² Sensitizing dye I 6 × 10 ⁻⁵ mol per mol of silver Sensitizing dye II 3 × 10 ⁻⁵ mol per mol of silver Coupler A: 0.06 mol per mol of silver Coupler C: per mol of silver 0.003 mole coupler D ... Ag 0.003 mol tricresyl phosphate coating amount relative to the molar 0.3 cc / m ² layer 4: red-sensitive sensitive emulsion layer silver iodobromide emulsion silver laydown ... 1.4 g / m ² sensitizing Dye I: 3 × 10 ⁻⁵ mol per mol of silver Sensitizing Dye II: 1.2 × 10 ⁻⁵ mol per mol of silver Coupler F: 0.0125 mol per mol of silver Coupler C: 1 mol of silver 0.0016 mol tricresyl phosphate coating amount 0.2 cc / m ² 5th layer: intermediate layer Same as 2nd layer 6th layer: green-sensitive low-sensitivity emulsion layer Silver halide emulsion Silver coating amount: 1.0 g / m ² Sensitizing dye III: 3 × 10 ^-5 mol per mol of silver Sensitizing dye IV: 1 × 10 ^-5 mol per mol of silver Coupler B: Silver 0.08 mol per 1 mol Coupler M: 0.008 mol per 1 mol of silver Coupler D: 0.0015 mol per 1 mol of silver Tricresyl phosphate coating amount 1.4 cc / m ² 7th layer: green-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver coating amount: 1.6 g / m ² Sensitizing dye III: 2.5 × 10 ^-5 mol per mol of silver Sensitizing dye IV: 0.8 × 10 ^-5 mol per mol of silver Coupler B ... silver 0.003 mol tricresyl phosphate coating weight relative to 0.02 mole coupler M ... silver mole relative to mole 0.8 cc / m ² eighth layer: gelatin layer containing yellow colloidal silver in the yellow filter layer gelatin solution.

Ninth layer: Blue-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver coating amount: 0.5 g / m ² Coupler Y: 0.125 mol based on 1 mol of silver Tricresyl phosphate coating amount 0.3 cc / m ² 10th layer: Blue-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver coating amount: 0.6 g / m ² Coupler Y: 0.04 mol based on 1 mol of silver Tricresyl phosphate coating amount 0.1 cc / m ² 11th layer: protective layer polymethyl A gelatin layer containing methacrylate particles (1.5 μm in diameter) is applied.

The coupler in each layer was prepared by adding the coupler to a solution of tricresyl phosphate and ethyl acetate, adding sodium p-dodecylbenzenesulfonate as an emulsifier, heating and dissolving, mixing with a heated 10% gelatin solution, and emulsifying with a colloid mill. One used.

A gelatin hardener and a surfactant were added to each layer in addition to the above composition.

The sample prepared as described above was used as a blank sample (No. 2
5)

Compound used to make the sample Sensitizing dye I: anhydro-5,5'-dichloro-3,3'-di-
(Γ-sulfopropyl) -9-ethyl-thiacarbocyanine hydroxide / pyridium salt Sensitizing dye II: anhydro-9-ethyl-3,3′-di (γ-
Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide triethylamine salt Sensitizing dye III: anhydro-9-ethyl-5,5'-dichloro-3,3'-di- (γ -Sulfopropyl) oxacarbocyanine hydroxide sodium salt Sensitizing dye IV: anhydro-5,6,5 ', 6'-tetrachloro-
1,1'-diethyl-3,3'-di- (γ-sulfopropyl)
Benzimidazole carbocyanine hydroxide sodium salt The emulsion layer of the blank sample of the present invention may be prepared by adding the above-mentioned sensitizing dye to the emulsion layer, and then adding a known 4-term ripening inhibitor.
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1 g per mol of silver halide, and the resulting emulsion was used as a blank emulsion. After each addition as shown in Table 3, after sufficient adsorption, a coupler, tricresyl phosphate and the like were added as described above, and then an appropriate amount of sodium 2-hydroxy-4,6-dichlorotriazine was used as a hardening agent. , And seven kinds of samples were coated in layers. (Nos. 26 to 32) The obtained multilayer color photosensitive material was subjected to the same forced deterioration test as in Example-2, and then subjected to normal wedge exposure, and then subjected to the same color processing as in Example-2. Was.

The color sensitometry results obtained are shown in Table 3 below.

The fog in the table indicates the value obtained by subtracting the base density,
The sensitivity value was 10 times for each of the red-sensitive layer, green-sensitive layer and blue-sensitive layer of the blank sample (No.
The relative sensitivity when expressed as 0 is shown.

From the results shown in Table 3, it can be seen that the sample according to the present invention has good balance of each photosensitive layer even under severe storage conditions and high-temperature development conditions of 30 ° C. or higher even in a multilayer color photosensitive material, and has no fogging suppression without a decrease in sensitivity. It is clear that the property is obtained.

[Effect of the present invention] A silver halide emulsion comprising at least one fogging inhibitor having a 1,2,4-thiadiazolidine skeleton used in the present invention, particularly at least one selected from compounds represented by the general formula [I] By adding it to the layer or the adjacent hydrophilic colloid layer, the generation of fog is suppressed even when stored under high temperature or high temperature and high humidity during storage over time, and the sensitivity is reduced and the gradation is softened. An excellent light-sensitive material with little fear of damaging is obtained.

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Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material comprising at least one compound represented by the general formula [I]. General formula [I] [Wherein, R ¹ , R ² , R ³ and R ⁴ represent an aliphatic group or an aromatic group which may be the same or different. ]