JP2678610B2 - Silver halide photographic fog suppressant - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a fogging inhibitor for silver halide photographic, and more particularly to a photographic fogging inhibitor used for a silver halide photographic light-sensitive material to prevent the occurrence of fog. Agent.

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

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 respond to recent high sensitivity, high activation, and high speed processing of photosensitive materials, particularly at high temperatures (about 45 ° C. or higher).
In reality, it lacks the fog suppression property and photographic property stability under severe conditions such as being left unattended or stored under high temperature and high humidity (about 50-80 ° C, equivalent humidity about 50-90%). is there. That is, in order to adapt the above-mentioned many known compounds to the above-mentioned conditions and when an effective concentration is used, the sensitivity and gradation deteriorate remarkably, and the sensitivity (gradation) which is an essential element of the fog inhibitor is: The balance of fog cannot be maintained.

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 fogging inhibitor for silver-deficient photographic which prevents fogging.

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

A third object of the present invention is to provide a silver halide photographic fogging inhibitor which remarkably reduces fogging upon rapid processing at a high temperature, particularly when developed at 30 ° C. or higher.

[Constitution of the Invention] The above object of the present invention is to provide a light-sensitive material having at least one silver halide emulsion layer, wherein a heteroaromatic cation is provided in at least one of the silver halide emulsion layer and a hydrophilic colloid layer adjacent thereto. This is achieved by a photographic fog inhibitor used by incorporating at least one selected from 1,4,2-dithiazolium salt compounds having a ring structure.

The cation ring structure of the 1,4,2-dithiazolium salt according to the present invention can achieve the object as a photographic fog inhibitor, but is preferably 3,5 represented by the following general formula [I]. The di-substituted form is most preferred.

General formula [Wherein R ¹ and R ² are lower alkyl groups which may be the same or different, or aryl groups, and R ¹ and R ² are bonded to each other to form a 5- or 6-membered heterocycle. May be.
R ³ represents a substituted or unsubstituted phenyl group, naphthyl group or heterocycle, and X represents an anion. Next, the compound represented by the general formula [I] will be described in detail.

The lower alkyl group in R ¹ and R ² has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group,
Examples include sec-butyl group and tert-butyl group.

Examples of the aryl group include a phenyl group and a naphthyl group.

R ¹ and R ² may be bonded together with a nitrogen atom to form a 5- or 6-membered heterocycle, for example, a pyrrolidine ring,
You may form a pyrazole ring, a pyridine ring, a piperidine ring, a piperazine ring, a morpholine ring etc.

The above-mentioned alkyl group, aryl group and heterocycle may have a substitutable substituent.

R ³ represents a substituted or unsubstituted phenyl group, naphthyl group or heterocyclic group, and the substituent is a lower alkyl group, preferably a C 1 to C 4 group such as a methyl group, an ethyl group, a propyl group and a butyl group. A lower alkoxy group, preferably a C1 to C4 group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group, and a halogen atom such as a chlorine atom or a bromine atom. Examples of the heterocycle of R ³ include a thienyl group and a furyl group. R ³ may also substitute two 1,4,2-dithiazolium salts via a divalent linking group.

X represents an anion, and examples thereof include ClO ₄ ⁻ and BF ₄ ⁻ .

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 is a novel compound which allows N-aroyl-S-disubstituted thiocarbamoylsulfenamide to be easily synthesized by a dehydration cyclization reaction in the presence of a strong inorganic acid.

Specifically, it can be easily synthesized according to the methods described in JP-A Nos. 61-68480 and 61-68481, and an example of the synthesis will be given.

Synthetic example (Exemplified compound NO.2) 2.68 g (0.01 mol) of N-benzoyl-S-diethylthiocarbamoylsulfenamide is dissolved in a solution of 15 ml of acetic anhydride and 1 ml of 70% perchloric acid, and the mixture is heated on an aqueous solution for 2 hours. After cooling, the reaction solution was cooled to room temperature, and 20 ml of dry ether was added to the reaction solution.

The precipitated white plate crystals were filtered and recrystallized from acetonitrile. White plate crystals with a melting point of 141 ° C 3-phenyl-5
2.79 g of -diethylamino-1,4,2-dithiazolium perchloric acid (exemplified compound NO.2) was obtained.

(Yield 80%) Elemental analysis (C ₁₂ H ₁₅ N ₂ S ₂ ClO ₄ calculated value (%) C: 41.08 H: 4.31 N: 7.98 Measured value (%) C: 41.02 H: 4.30 N: 8.07 Infrared It was confirmed by absorption spectrum that the compound was the above compound.

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 required 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 after coating of the emulsion, and 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, general-purpose black and white, X-ray recording, plate making, color blur, color negative, color paper, reversal color, direct positive, heat development, etc., or surface latent image type silver halide grains. 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 of silver halide emulsions used in common silver halide emulsions 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, and
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 type coupler, a pyrazoloazole type coupler, a pyrazolobenzimidazole type coupler, an open chain acylacetonitrile type coupler, an interazolone type 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.

[Effect of the present invention] 1,4,2- having the heteroaromatic cation ring structure of the present invention
A fog inhibitor comprising a dithiazolium salt compound, particularly at least one selected from the compounds represented by the general formula [I]
Addition to the silver halide emulsion layer or the adjacent hydrophilic colloid layer suppresses fog generation even when stored at high temperature or under high temperature and high humidity during storage over time, and also reduces sensitivity. It is possible to obtain an excellent photographic light-sensitive material that is less likely to cause gradation and softening of gradation.

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 emulsion for coating was uniformly coated on the undercoated polyester ester base so that the amount of silver was 3 g / m ³ , and dried to prepare 13 kinds of samples (No. 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.

After that, exposure was carried out using an ordinary wedge for sensitometry, development was then carried out at 35 ° C. for 35 seconds with the following processing solution [A] to fix, and then washed with water and dried 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 as a colored magenta coupler, 1- (2,4,6-triclophenyl) -4- (1-naphthylazo ) -3- (2-Chloro-5-octadecenylsuccinimidoanilino) -5
After weighing 2.5 g of each pyrazolone, 120 g of tricresyl phosphate and 240 mg of ethyl acetate were mixed and dissolved by heating, and then a coupler solution emulsified and dispersed in a solution of 5 g of sodium triisopropylnaphthalenesulfonate and 550 ml of a 7.5% aqueous gelatin solution. Was added to the above emulsion.

The emulsion was divided into 1 part and used as a blank sample as it was, and then, as shown in Table 2 below, a comparative compound and a compound according to the present invention were respectively added, and after sufficient adsorption, a gelatin hardener was prepared. An appropriate amount of sodium 2-hydroxy-4,6-dichlorotriazine was uniformly added to prepare a coating 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 the same forced deterioration test as in Example 1, then exposed to wedges by a usual method, and color-developed 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 ℃] Processing time Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying each The composition of the processing liquid used in the processing step 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 diaminetetraacetate 100.0 g Diammonium ethylenediaminetetraacetate 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 Add water to make 1 and adjust to pH 6.0 with acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5 ml Conidax (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 table, the sixth layer, the seventh layer,
For the ninth and tenth silver halide emulsion layers, silver bromobromide emulsions having the following silver iodide contents were used.

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.

9th layer: Blue-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver coating amount ... 0.5 g / m ² Coupler Y ... 0.125 mol per 1 mol of silver Torqueryl 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 per mol silver Silver tricresyl phosphate coating amount 0.1 cc / m ² 11th layer: protective layer Polymethyl Apply a gelatin layer containing methacrylate particles (1.5 μm diameter).

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 (β- [β- (γ-sulfopropoxy) ethoxy] ethylimidazolocarbocyanine 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.
A blank emulsion was prepared by adding 1 g of hydroxy-6-methyl-1,3,3a, 7-tetrazaindene per mole of silver halide.

Then, the present invention and the antifoggant for comparison were added as shown in Table 3, respectively, and then sufficiently adsorbed. Then, as described above, a coupler, tricresyl phosphate and the like were added, and then a hardening agent was added. Seven kinds of samples were coated in layers by adding and adjusting an appropriate amount of sodium 2-hydroxy-4,6-dichlorotriazine. (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.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Isao Shibuya 1-1, Higashi, Tsukuba, Ibaraki Prefectural Institute of Industrial Science and Technology (72) Inventor, Eiichi Sakamoto 1 Hino, Tokyo Konica Stock Company (72) Inventor Yutaka Kaneko 1 Sakura-cho, Hino-shi, Tokyo Konica Stock Company Examiner Toshiyasu Kimura (56) Reference JP 62-262041 (JP, A) JP 61-179433 (JP, A) JP-A-60-178445 (JP, A)

Claims (1)

(57) [Claims] 1. A 1,4,2 having a heteroaromatic cation ring structure.
An antifoggant for silver halide photography, which is a dithiazolium salt compound.