JPH0527359A - Anti-foggant for silver halide photography - Google Patents

Abstract

PURPOSE:To prevent fogging and to suppress fogging at the time of rapid processing at high temp. by using a specified compd. as an anti-foggant. CONSTITUTION:A compd. represented by formula I is used as an anti-foggant for silver halide photography. In the formula I, each of R1 and R2 is alkyl, R1 and R2 may be different from each other and R3 is alkoxy or dialkylamino. At least one kind of anti-foggant made of the compd. represented by the formula I is incorporated into a silver halide emulsion layer or an adjacent hydrophilic colloidal layer. This anti-foggant inhibits fogging during storage even at high temp. or high temp. and humidity and does not cause the lowering of sensitivity and the softening of gradation.

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 fog inhibitor, and more particularly to a photographic fog inhibitor used in a silver halide photographic light-sensitive material to prevent fog formation.

[0002]

BACKGROUND OF THE INVENTION A halogenated photographic light-sensitive material containing a light-sensitive silver halide emulsion (hereinafter referred to as a light-sensitive material), which is chemically sensitized, has a nucleus which can be developed without being exposed to light. It is well known that this fog tends to occur, and that this fog is likely to occur when developed at high temperature or for a long time, or during storage of the light-sensitive material, particularly during storage at high temperature and high humidity. There is.

Since an increase in fog causes a decrease in sensitivity and deterioration in gradation, and remarkably impairs image reproducibility, attempts have been made to add many substances to a silver halide emulsion for many years for the purpose of preventing fog. Came.

A typical example is research
Disclosure (Research Disclo
sur), 176, December 1978, 17643.
It is described in detail in (VI). Further, as a particularly effective fog inhibitor, T. H. James The Theory of the Photographic Process (The
Theory of the Photograph
ic Process) 4th edition, published by Macmillan (1977), pages 393-399, and the mechanism of action is also described.

However, it is difficult for many of these fog control techniques to sufficiently cope with the recent trend toward high sensitivity, high activation and high speed processing of photosensitive materials, especially at high temperatures (about 4
It is left at 5 ℃ or higher, or under high temperature and high humidity (about 50-8).
In reality, the fog-inhibiting property and the photographic property stability are poor under severe conditions such as storage at 0 ° C. and relative humidity of about 50 to 90%). That is, when an effective concentration for adapting the above-mentioned many known compounds to the above-mentioned conditions is used, the sensitivity is lowered and the gradation is remarkably deteriorated, 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 the development of a fog suppressing technique that does not deteriorate the photographic characteristics such as the loss of sensitivity and the deterioration of gradation due to fog under severe conditions.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. A first object of the present invention is to provide stable photographic characteristics even when the light-sensitive material is stored at high temperature or under high temperature and high humidity over time. It is an object of the present invention to provide a fog inhibitor for silver halide photography, which maintains and prevents the occurrence of fog.

A second object of the present invention is to provide a fog inhibitor for silver halide photography which is free from the risk of deterioration of sensitivity and deterioration of gradation due to development inhibition. A third object of the present invention is to provide a fog inhibitor for photographic silver halide which can remarkably reduce fog generation when developed at high temperature and rapid processing, especially at 30 ° C. or higher.

[0008]

The above object of the present invention is achieved by a silver halide photographic fog inhibitor which is a compound represented by the following formula 1.

[0009]

[Formula 1]

[In the formula, R ₁ and R ₂ may be the same or different and each represents an alkyl group, and R ₃ represents an alkoxy group or a dialkylamino group. The present invention will be described in more detail below.

In the compound represented by formula 1 according to the present invention, the alkyl group represented by R ₁ and R ₂ is an alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 5 carbon atoms). , For example, methyl group, ethyl group, propyl group,
Examples thereof include a butyl group, and these alkyl groups may have a branch.

Examples of the alkoxy group represented by R ₃ include a methoxy group and an ethoxy group, and examples of the dialkylamino group include a dimethylamino group and a diethylamino group. Next, specific representative examples of the compound represented by Formula 1 used in the present invention (hereinafter, referred to as the compound according to the present invention) are shown, but the present invention is not limited thereto.

[0013]

[Chemical 1]

[0014]

[Chemical 2]

[0015]

[Chemical 3]

The compound represented by the above formula 1 is disclosed in Japanese Patent Application No.
It can be easily synthesized by the method described in the specification of No. -32214 and the specification of No. 2-118457. In the present invention, the compound is a silver halide emulsion layer of a light-sensitive material and an adjacent hydrophilic colloid layer (intermediate layer,
Filter layer, antihalation layer, protective layer, undercoat layer, etc.). A particularly preferred layer is a silver halide emulsion layer.

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

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 silver halide emulsions, they are added during chemical ripening, after chemical ripening, and / or immediately after emulsion coating, and more preferably at the end of chemical ripening of silver halide emulsions.

The fog inhibitor of the present invention can be applied to various types of photosensitive materials as follows. For example, a light-sensitive material for general-purpose black and white, X-ray recording, plate making, color positive, color negative, color paper, reversal color, direct positive, heat development, or surface latent image type silver halide grains. US Pat. Nos. 2,996,382 and 3,178,2 using silver halide grains having an internal fog nucleus.
It can be used for a light-sensitive material according to the method described in Japanese Patent No. 82, but the application to a color light-sensitive material having a multilayer structure is particularly advantageous.

The silver halide emulsion used in the present invention is an optional silver halide emulsion such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, which are used in ordinary silver halide emulsions. Can be used. The silver halide grains used in the silver halide emulsion may be those having a uniform silver halide composition distribution within the grain or core / shell grains having a different silver halide composition between the inside and the surface layer of the grain. Good.

The silver halide grain may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain. The halogenated emulsion may have any grain size distribution. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination of several kinds. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used. As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be mixed and used.

The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye. Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as the binder of 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 sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of the color light-sensitive material. Furthermore, by coupling with a competing coupler having an effect of color correction and an oxidized product of a developing agent, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener, a fogging agent, Antifoggant, chemical sensitizer,
Compounds that release photographically useful fragments such as spectral sensitizers and desensitizers can be used.

As the yellow dye-forming coupler, a known acylacetanilide type coupler can be preferably used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. As the magenta dye-forming coupler, a 5-pyrazolone-based coupler, a pyrazoloazole-based coupler, a pyrazolobenzimidazole-based coupler, an open-chain acylacetonitrile-based coupler, an indazolone-based coupler and the like can be used. As the cyan dye forming coupler, a phenol or naphthol coupler is generally used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. In these layers and / or in the emulsion layers, dyes which may be bleached or bleached from the light-sensitive material during the development processing may be contained. Matting agents, lubricants, image stabilizers, formalin scavengers, ultraviolet absorbers, fluorescent whitening agents, surfactants, development accelerators, development retarders and bleaching accelerators can be added to the light-sensitive material.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film,
Baryta paper, cellulose triacetate and the like can be used. A known method is used for developing the light-sensitive material containing the fog inhibitor of the present invention. Processing temperature is 18
It is used at a temperature between 50 ° C. and 50 ° C., and depending on the purpose, either black-and-white photographic processing, lithographic development processing, or color photographic processing for forming a dye image can be applied. Further, the photosensitive material for heat development is processed at a temperature of 100 ° C. or higher.

[0027]

The present invention will be described in more detail with reference to the following examples, which are merely examples for explaining the present invention and the present invention is not limited thereto. Example 1 A silver iodobromide emulsion for high-sensitivity negatives containing 3.0 mol% of silver iodide was chemically ripened to the maximum sensitivity by a gold and sulfur sensitization method, and then 4-hydroxy-6-per mol of silver halide. 1.0 g of methyl-1,3,3a, 7-tetrazaindene
Addition stopped aging.

The obtained emulsion was divided into 13 parts, and 1 part was used as it was as a blank sample. In addition, the compounds according to the present invention and comparative compounds were added as shown in Table 1 below, and after sufficient adsorption, they were used as coating aids. Prepared an emulsion for coating by adding an appropriate amount of saponin and an appropriate amount of formalin as a hardening agent.

The coating emulsion was uniformly coated on an undercoated polyester base so that the amount of silver was 3 g / m ² , and dried to prepare 13 kinds of samples (Nos. 1 to 13).
The photographic material produced as described above was left as a fresh sample at room temperature for 3 days, and a sample was subjected to forced deterioration after being left for 3 days at a temperature of 60 ° C. and at a temperature of 55 ° C. and a relative humidity of 80% for 3 days. .. After that, exposure was carried out using an ordinary wedge for sensitometry, followed by development with the following processing solution [A] at 35 ° C. for 30 seconds to fix, followed by washing with water and drying to measure the sensitivity.

Processing Solution [A] (Developer for Black and White Photosensitive Material) 1-Phenyl-3-pyrazolidone 1.5 g Hydroquinone 30 g 5-Nitroindazole 0.25 g Potassium bromide 5 g Anhydrous sodium sulfite 55 g Hydroxide Potassium 30 g Boric acid 10 g Glutaraldehyde (25%) 5 g Water is added to bring the total volume to 1 liter.

The results obtained are shown in Tables 1 and 2. However, the fog value shows a value obtained by subtracting the base density, and the sensitivity value is 100 at the sensitivity of the fog value +0.5 for the blank sample (No. 1) of the emulsion used in the present invention for 3 days. Is expressed by relative sensitivity, and gamma indicates the slope of the straight line portion on the characteristic curve.

[0032]

[Table 1]

[0033]

[Table 2]

As is clear from Tables 1 and 2, the samples containing the antifoggant of the present invention all had suppressed fog even under severe storage conditions, and thus were not stored in a film. It can be seen that the stability is improved. Example 2 According to the method of Example 1, a high-sensitivity negative silver iodobromide emulsion was chemically ripened with gold and sulfur sensitizers to the maximum sensitivity.

Then, as a green-sensitizing sensitizing dye, anhydro-5,5'-diphenyl-9-ethyl-3,3 "-di-
An appropriate amount of γ-sulfopropyloxacarbocyanine hydroxide sodium salt was added to prepare a green-sensitive silver halide emulsion. Then, 1- (2,4,6, -trichlorophenyl) -3- [3- (2,4-di-t-amylphenoxyacetamide) benzamide] -5 was used as a magenta coupler per mol of silver halide. -80 g of pyrazolone as a colored magenta coupler, 1-
(2,4,6-Trichlorophenyl) -4- (1-naphthyl

2.5 g of each of ruazo) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone was weighed, and then 120 g of tricresyl phosphate and 240 g of ethyl acetate were mixed. A coating solution was prepared by dissolving under heating and then adding the coupler solution emulsified and dispersed in a solution of 5 g of sodium triisopropylnaphthalenesulfonate and 550 ml of a 7.5% aqueous gelatin solution to the above emulsion.

The above coating solution was divided into 11 parts, and 1 part was used as a blank sample as it was. Then, as shown in Table 3 below, a comparative compound and a compound according to the present invention were respectively added, and after sufficient adsorption, A suitable amount of 2-hydroxy-4,6-dichlorotriazine sodium was uniformly added as a gelatin hardener to give a coated emulsion. This coating emulsion was uniformly coated and dried on a triacetate film which had been undercoated so that the amount of silver was 3.0 g / m ² (No. 14).
~ 24).

The obtained film sample was subjected to the same forced deterioration test as in Example 1 and then subjected to wedge exposure by a usual method, followed by color development according to the following color processing steps. The color sensitometry results obtained from the obtained pieces are shown in Tables 3 and 4 below. The fog in the table is a value obtained by subtracting the base density, and the sensitivity is a relative sensitivity when the blank sample after 3 days of natural standing (Sample No. 14) is 100. Further, gamma is shown by the slope of the straight line portion on the characteristic curve.

Treatment step [treatment temperature 38 ° C.] Treatment time Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dryness

The composition of the processing liquid used in each processing step is as follows. [Color developer] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g

Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water was added to make 1 liter and hydroxylated. Adjust to pH 10.2 with sodium.

[Bleach] Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter, and aqueous ammonia was added. PH using
Adjust to 6.0.

[Fixer] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Water was added to make 1 liter, and pH was adjusted to 6.0 with acetic acid.

[Stabilizing Solution] Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter.

[0045]

[Table 3]

[0046]

[Table 4]

From the results shown in Tables 3 and 4, the compound of formula 1 of the present invention is better than the conventionally known compound in the forced deterioration test under high temperature or high humidity without lowering the sensitivity. It can be seen that the antifogging property is exhibited.

Example 3 A multilayer color light-sensitive material sample was prepared by sequentially providing each layer having the following composition on a cellulose triacetate film support. However, the silver halide emulsion layers of the third, fourth, sixth, seventh, ninth and tenth layers contain iodobromide having a silver iodide content as shown in Table 5 below. A silver emulsion was used.

[0049]

[Table 5]

First layer: Antihalation agent 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 1 mol of silver Sensitizing dye II: 3 × 10 ⁻⁵ mol per 1 mol of silver Coupler A: 1 mol per silver 0.06 mol Coupler C ... 0.003 mol per 1 mol of silver Coupler D ... 0.003 mol per 1 mol of silver Tricresyl phosphate coating amount 0.3 cc / m ²

Fourth layer: red sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver coating amount: 1.4 g / m ² Sensitizing dye I: 3 × 10 ^-5 mol increase per 1 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: 0.0016 mol per mol of silver Tricresyl phosphate coating amount 0.2 cc / m ² 5th layer: intermediate layer Same as 2nd layer

Layer 6: Green-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver coating amount: 1.0 g / m ² Sensitizing dye III: 3 × 10 ^-5 mol sensitized per 1 mol of silver Dye IV: 1 × 10 ⁻⁵ mol per mol of silver Coupler B: 0.08 mol per mol of silver Coupler M: 0.008 mol of coupler D per mol of silver · 0.0015 mol tricresyl per mol of silver phosphate coating amount 1.4 cc / m ²

Seventh 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 1 mol of silver Sensitizing dye IV: 0.8 × 10 ⁻⁵ mol per mol of silver Coupler B: 0.02 mol per mol of silver Coupler C: 0.003 per mol of silver Molar tricresyl phosphate coating amount 0.8 cc / m ²

Eighth layer: Yellow filter layer A gelatin layer containing yellow colloidal silver in an aqueous 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 tricresyl phosphate coating amount per mol of silver 0.1. 3 cc / m ²

Layer 10: Blue-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver coating amount ... 0.6 g / m ² coupler Y ... 0.04 mol tricresyl phosphate coating per mol of silver Quantity 0.1 cc / m ² 11th layer: protective layer A gelatin layer containing polymethylmethacrylate particles (diameter 1.5 μm) was applied.

The coupler of 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, and then mixing with a heated 10% gelatin solution to prepare a colloid mill. What was emulsified in was used. In addition to the above composition, a gelatin hardening agent and a surfactant were added to each layer.
The sample prepared as described above was a blank sample (No. 25)
And

[Compound used for preparing sample] Sensitizing dye I: anhydro-5,5 "-dichloro-3,
3 ″ -di- (γ-sulfopropyl) -9-ethyl-thiacarbocyanine hydroxide / pyridinium 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

[0059]

[Chemical 4]

[0060]

[Chemical 5]

In each of the emulsion layers of the blank samples of the present invention, 4-hydroxy-6-methyl-1,3,3a, 7, which is known as a aging stopper after the addition of the sensitizing dye, is used.
-Tetrazaindene was added to 1 g per mol of silver halide to prepare a blank emulsion.

Next, the antifoggants of the present invention and the comparative antifoggant were added respectively as shown in Table 6, and after sufficiently adsorbing, couplers, tricresyl phosphate, etc. were added as described above, and then the hard film was formed. 2-hydroxy-4 as an agent
An appropriate amount of sodium 6-dichlorotriazine was added and adjusted, and 7 types of samples were coated in layers. (Nos. 26 to 32) The obtained multilayer color light-sensitive material was subjected to the same forced deterioration test as in Example 2, then subjected to ordinary wedge exposure, and subjected to the same color processing as in Example 2.

The color sensitometry results obtained are shown in Tables 6, 7 and 8 below. The fog in Table 6 shows a value obtained by subtracting the base density, and the sensitivity value is 100 for the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer of the blank sample (No. 25) after 3 days of natural standing. The relative sensitivity is shown.

[0064]

[Table 6]

[0065]

[Table 7]

[0066]

[Table 8]

From the results shown in Tables 6, 7, and 8, the compound of Formula 1 of the present invention is balanced in each photosensitive layer even in a multilayer color light-sensitive material despite severe storage and high-temperature development conditions of 30 ° C. or higher. It is clear that it exhibits good fog-inhibiting property without deterioration of sensitivity.

[0068]

EFFECT OF THE INVENTION At least one fog inhibitor consisting of the compound represented by the formula 1 of the present invention is added to the silver halide emulsion layer or the adjacent hydrophilic colloid layer to contain it at a high temperature during aging storage. It is possible to obtain an excellent photographic light-sensitive material in which generation of fog is suppressed even when stored under high temperature or high humidity, and there is little risk of deterioration of sensitivity and softening of gradation.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Isao Shibuya 1-1, East Higashi, Tsukuba, Ibaraki Institute of Industrial Science and Technology (72) Inventor Shigeto Hirabayashi 1, Sakuracho, Hino, Tokyo Konica Stock Company ( 72) Inventor Yutaka Kaneko 1 Sakura-cho, Hino City, Tokyo Konica Stock Company

Claims (1)

Claims: 1. A fog inhibitor for photographic silver halide, which is a compound represented by formula 1. [Formula 1] [In the formula, R ₁ and R ₂ may be the same or different,
Each represents an alkyl group, and R ₃ represents an alkoxy group or a dialkylamino group. ]