JPH02153346A - Silver halide photographic sensitive material which is suppressed in generation of fogging - Google Patents

Abstract

PURPOSE:To stabilize photographic performance and to prevent the generation of fogging even if the photosensitive material is preserved at and under a high temp. and high humidity by incorporating a specific compd. into silver halide emulsion layers or the hydrophilic colloidal layers adjacent thereto. CONSTITUTION:The compd. expressed by the formula is incorporated as an antifogging agent into the silver halide emulsion layers and/or the hydrophilic colloidal layers adjacent to the emulsion layers. In the formula, R<1> denotes alkyl, aryl, etc.; R<2> denotes H, halogen; the more specific example of the compd. expressed by the formula includes the compd. in which R<1> is -C3F7 and R<2> is -F. This compd. can be added into the emulsion after the end of the chemical maturation of the emulsion at the time of incorporating this compd. into the emulsion layers.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material in which fogging is prevented.

[Background of the invention]

Photosensitive materials containing photosensitive silver salts, particularly photographic materials containing chemically sensitized silver halide grains (hereinafter referred to as photosensitive materials), suffer from fog due to the presence of nuclei that can be developed without being exposed to light. is well known to occur.

This phenomenon tends to occur when photosensitive materials are stored for long periods of time (particularly when stored under conditions of high temperature and high humidity), and tends to increase over time. The occurrence of fog also brings about undesirable results such as a decrease in sensitivity and deterioration of gradation.

It has been known for a long time to add so-called antifoggants or stabilizers to the constituent elements of photosensitive materials for the purpose of reducing fog. A large number of technologies have been published, including azoles and azaindenes.

In addition, in recent years, antifoggants have been proposed in which hydrophilic substituents such as carboxy groups, sulfo groups, hydroxy groups, amine groups, acylamino groups, or sulfonamide groups are introduced into these heterocyclic compounds to reduce desensitization. For example, US Patent No. 3,330,658,
Examples include Belgian Patent No. 737.809, Belgian Patent No. 739,709, Japanese Patent Publication No. 58-9939, and Japanese Patent Publication No. 51102639.

However, it is difficult for many of these conventional techniques to sufficiently respond to the recent high sensitivity and high activation of photosensitive materials, especially those that are left at high temperatures (approximately 45°C or higher) or exposed to high temperatures and high humidity. (Approximately 50-80℃, relative humidity approximately 60
The actual situation is that they lack antifogging properties and stability of photographic properties under severe conditions such as storage at temperatures of up to 90%.

Therefore, there is a strong demand for fog suppression technology that exhibits sufficient antifogging performance under both high temperature and high humidity conditions and does not adversely affect photographic characteristics (sensitivity, gradation, etc.). .

[Purpose of the invention]

The present invention was made in view of the above-mentioned circumstances, and its first purpose is to maintain stable photographic properties even when a photosensitive material is stored at high temperatures or at high temperatures and high humidity over time, and to prevent fogging. The object of the present invention is to provide a photosensitive material that prevents this from occurring.

A second object of the present invention is to provide a photosensitive material that does not cause a decrease in sensitivity or deterioration of gradation due to suppression of development.

A third object of the present invention is to provide a photosensitive material in which the occurrence of fog is significantly reduced during high-temperature rapid processing, particularly when developing at 30° C. or higher.

[Structure of the invention]

The above object of the present invention is achieved by a light-sensitive material containing at least one compound represented by the following format [I] in the silver halide emulsion layer and/or the adjacent hydrophilic colloid layer.

-Format (1) [In the formula, R+ represents an alkyl group, an aryl group, or an alkyl group.
R) and R4 each represent a hydrogen atom, an alkyl group, or an aryl group, and R2 represents a hydrogen atom or a halogen atom. ] Hereinafter, the present invention will be explained in more detail.

The antifoggant represented by the above-mentioned form (I) used in the present invention is an m-nitrophenol derivative.

Examples of the alkyl group, aryl group, alkoxy group, and aryloxy group represented by R1 include groups having 1 to 25 carbon atoms (preferably 1 to 18 carbon atoms), and these groups include those having substituents, Preferred substituents -C include a halogen atom, an aryloxy group, a nitro group, and the like.

Further, the halogen atom represented by R2 includes a fluoro group,
Examples include chlorine, bromine, and iodine.

The alkyl group represented by R3 and R' has a carbon number of 1
~8 (preferably 1 to 4) argyl groups, examples of aryl groups include phenyl groups, naphthyl groups,
These alkyl groups and aryl groups include those having substituents, and preferred substituents include halogen atoms, cyano groups, and alkylsulfonyl groups.

Typical specific examples of the compound represented by one type [I] (hereinafter referred to as the compound of the present invention) used in the present invention are shown below, but the compounds are not limited thereto.

Compound I-7 Compound C,F.

-N) lc, H,, (n) Compound 10 - (CFyo) 4H - (CFri 4H - (CFx)*)l ■-14 -CsH+x(n) Ca KanaeCH,CH,OhC,H9( n) H ■-19 -OC,Fl H ■-20 -OC,H, ACQ These compounds are described in JP-A-57-204545 and JP-A-57-204545, JP-A-59-
31953, the method described in Publication No. 61-72245,
Alternatively, it can be synthesized by a similar method.

The compound of the present invention is contained in at least one of the silver halide emulsion layer and/or the adjacent hydrophilic colloid layer (intermediate layer, filter layer, antihalation layer, protective layer, undercoat layer, etc.) of the light-sensitive material.

A particularly preferred layer is a silver halide emulsion layer.

In the case of a silver halide emulsion layer, the amount of the compound of the present invention added is preferably in the range of In+g to 2g, more preferably 10mg-1g, per mole of silver halide. When it is added to a non-photosensitive layer, it is used in the same manner as when it is added to an emulsion layer.

Further, in the case of a silver halide emulsion, it is added during chemical ripening, after chemical ripening, and/or immediately before coating the emulsion, but it is more preferably added at the end of chemical ripening of the silver halide emulsion.

The silver halide emulsion used in the present invention includes any silver halide used in conventional 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 silver halide emulsions may have a uniform silver halide composition distribution within the grain, or they may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain. good.

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

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

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

Known photographic additives can be used in the silver halide photographic emulsion of the present invention.

Examples of known photographic additives include Research Disclosure's RD-176438 and RD- shown in the table below.
Examples include compounds described in 18716.

Additive RD-17643RD-
18716 pages Classification Page Classification Chemical sensitizers 23 III 648-Upper right sensitizing dye 23 IV 648 Right-Upper right development accelerator
29 1n 648-Right upper blade anti-blur agent 24
Vl 649-Lower right stabilizer
// 11 Color anti-staining agent 25 ■ 650 Left-right image stabilizer 25 ■ Ultraviolet absorber 25-26 ■ 649 Right-6
50 left filter dye //〃 brightening agent 24 V hard
Curing agent 26 X
651 Right coating aid 26-27ri650 Right surfactant 26-27XI650 Right plasticizer 27 n
tt super agent
〃Static prevention agent 27 XI [tt Matting agent 28 1VI
650 right binder 26 XI
651 Right When applying the present invention to color photosensitive materials,
A coupler is used. Furthermore, by coupling with a competing coupler having a color correction effect and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, Compounds that release photographically useful fragments such as antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

As the yellow dye-forming coupler, known anruacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta dye-forming coupler, 5-pyrazolone couplers, pyrazoloazole couplers, pyrazolopenzimidazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, etc. can be used.

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers.

Examples of the support that can be used in the photosensitive material of the present invention include the above-mentioned RD-17643, page 28, and RD-
18716, page 647, left column. Suitable supports include polymer films, paper, etc., which may be treated to enhance adhesiveness, antistatic properties, etc.

The photosensitive material according to the present invention is the above-mentioned RD-17643-2.
Pages 8 to 29, and page 651 left column of RD-18716 ~
Development processing can be carried out by the usual methods described in the right column.

This photographic processing method may be a black and white photographic processing to obtain a silver image or a color photographic processing to obtain a color image. The processing temperature applied to photogeography is usually 18°C ~
Although the temperature is 50°C, the treatment can be performed at a temperature lower than 18°C or higher than 50°C.

Photographic materials to which the photographic emulsion of the present invention can be applied include:
Mention may be made of various color and black-and-white photosensitive materials.

For example, color negative film for photography (general use, movie use, etc.)
, color reversal film (for slides, movies, or with or without couplers), color photographic paper, color positive film (for movies, etc.), color reversal photographic paper, color photosensitive materials for heat development, plate making photographic materials (lithographic film, scanner film, etc.), X-ray photographic materials (direct/indirect medical use, industrial use), black and white negative film for photography, black and white photographic paper, microphotosensitive materials (00
M, micro film, etc.) color diffusion transfer photosensitive materials (
Examples include DTR), silver salt diffusion transfer photosensitive materials, and printout photosensitive materials.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

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

The obtained emulsion was divided into 15 parts, one part was used as a blank sample, and the compounds according to the present invention and comparative compounds as shown in Table 1 below were added to the emulsion, and after sufficient adsorption, saponin was added as a coating aid. An emulsion for coating was prepared by adding an appropriate amount of formalin and a suitable amount of formalin as a hardening agent.

The coating emulsion was uniformly coated on the undercoated polyester base to a silver content of 3 g/m'' and then dried for 15 minutes.
Seed samples were prepared (No. l”15).

The photographic materials prepared as described above were used as fresh samples, and were left at room temperature for 3 days, and at 65°C for 3 days.
One sample was prepared for one day, and the other sample was subjected to forced deterioration after being left at a temperature of 50° C. and a relative humidity of 80% for three days.

After this, exposure was performed using a regular sensitometric wedge, and then the following treatment solution [A] was used for 30 minutes at 35°C.
After developing for a few seconds and fixing, the film was washed with water and dried, and the sensitivity was measured.

Processing liquid [A] (Developer for black and white photographic materials) l-phenyl-3-pyrazolidone 1.5g Hydroquinone 30g 5-nitroindazole 0.25g Potassium bromide
5g anhydrous sodium sulfite
55g potassium hydroxide
30g boric acid
], Ogglutaraldehyde
(25%) Add 5g water and reduce the total amount to 1(
Set it to 2.

The results obtained are shown in Table 1 below.

However, the fog value shows the value after subtracting the base density, and the sensitivity value is calculated from the sensitivity at the fog value + 0.5 position, with the blank sample (No. 1) of the emulsion of the present invention left for 3 days as 100. Gamma is expressed as the slope of the straight line on the characteristic curve.As is clear from Table 1 above, all the samples of the present invention showed no fog despite being stored under severe storage conditions. It can be seen that the occurrence is suppressed and the stability of the film during storage is improved.

Example 2 A multilayer color photosensitive material sample (comparison) was prepared by sequentially providing each layer having the composition shown below on a cellulose triacetate film support.

1st layer, antihalation agent black gelatin layer containing colloidal silver 2nd layer; intermediate gelatin layer 3rd layer: red-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 5 mol% Average grain size 0.5 μm Silver coating amount: 1.79 g/m" Sensitizing dye I: 6 x 10 per mole of silver
-'molar sensitizing dye ■...3 x 10 per mole of silver
-'Molar coupler A: 0.06 mol per mol of silver Coupler B: 0.003 mol per mol of silver Coupler D: 0 per mol of silver .003 Moltri-cresyl phosphate coating amount 0.3 mff/m2 4th layer: red-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide = 4 mol% Average grain size 0.7 μm Silver coating amount...・1.4g/m2 Sensitizing dye I...3 x 10 per mole of silver
-'molar sensitizing dye■...1.2X 1 per mole of silver
0-' mole coupler F...0.0125 mole per mole of silver Coupler C...0.0016 per mole of silver
Coating amount of mol tricresyl phosphate 0.2 m4/m" 5th layer: Intermediate layer Same as 2nd layer 6th layer: Green sensitive low sensitivity emulsion layer Silver iodobromide emulsion Silver iodide = 44 mol% Average diameter 0. 5 μm Silver coating amount: 1.0 g/m” Sensitizing dye ■: 3 x 10 per mole of silver
-'molar sensitizing dye ■...I x 10 per mole of silver
-5 mole coupler B: 0.08 mole per mole of silver Coupler M: o, ooa mole per mole of silver Coupler D: per mole of silver 0.0015
Moltricresyl phosphate coating amount: 1.4 mQ/m'' 7th layer: Green-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 5 mol% Average grain size: 0.75 μm Silver coating amount... 1.6g/m" Sensitizing dye■...2.5X 1 per mole of silver
0-'Mole sensitizing dye■...0.8X per mole of silver 1
0-' mole coupler B...0.02 moles per mole of silver Coupler M...0.003 moles per mole of silver Tricresyl phosphate coating amount 0.8 m (2/ a+2 8th layer: Yellow filter layer A gelatin layer containing yellow colloidal silver in an aqueous gelatin solution.

9th layer: Blue-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 6 mol% Average grain size 0.7 μm Silver coating amount: 0.5 g/m" Coupler Y...・0.125 mole tricresyl phosphate coating amount per 1 mole of silver 0.3n+12/m2 1st theta layer: Blue sensitive high sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 6 mol% Average grain size 0.8 μm Coating amount of silver: 0.6 g/m" Coupler Y: 0.04 mol of tricresyl phosphate per mole of silver 0.1 v2/m" 11th layer: Protection Apply a layer of gelatin containing tolumethyl methacrylate particles (1.5 μm in diameter).

The couplers for each layer were prepared by adding the coupler to a solution of tricresyl phosphate and ethyl acetate, adding p-dodecylbenzenesulfone as an emulsifier, dissolving it by heating, mixing it with a heated 10% gelatin solution, and emulsifying it in a colloid mill. In addition to the above composition, a gelatin hardener and a surfactant were added to each layer.

Compounds used to prepare samples> Sensitizing dye I: Anhydro 5,5'-dichloro-3.3
'-di(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridium salt sensitizing dye ■: anhydro-9-ethyl-3.3'-di(
T-sulfopropyl)-4.5.4',5'-dianzothiatric lupocyanine hydroxide triethylamine salt sensitizing dye ) Oxacarbocyanine hydroxide/sodium salt sensitizing dye■
:anhydro-5.6.5',6'-tetrachloro1,1'-diethyl-3.3'-di(β-[β-(γ
-sulfopropoxy)ethoxy]ethylimidazolocarbocyanine hydroxide sodium salt coupler A coupler B coupler F CH.

Coupler C and α Coupler Y L; μ Blue in the red-sensitive layers of the third and fourth layers, the green-sensitive layers of the sixth and seventh layers, the ninth layer and the M2O layer, which are the silver halide emulsion layers. In each case, a sensitizing dye was added to the sensitive layer, and then a comparative compound and a compound of the present invention were added as shown in Table 2, and the layers were adjusted and coated in a multilayer manner. (Sample 16
~36) The obtained multilayer color photosensitive material was subjected to high temperature and high humidity treatment for storage test in the same manner as in Example-1, and then
After normal wedge exposure, the following color processing was performed.

Treatment process [Processing temperature 38°C] Processing time Color development phenomenon
Bleach for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
6 minutes 30 seconds water
Washing: Stabilization for 3 minutes and 15 seconds; Drying for 1 minute and 30 seconds. The composition of the treatment liquid used in each treatment step is as follows.

[Color developer]

4-Amino-3-methyl-N-ethyl-N-oxyethyl)aniline sulfate Anhydrous sodium sulfite Hydroxyamine l/2 sulfate Anhydrous potassium carbonate I-lium nitrilotriacetic acid 3-s(β-hydride 4.75 g 4.25g 2.0g 37.5g 1.3g Thorium salt (I hydrate) 2.5g 1.0g Using sodium hydroxide, add potassium hydroxide water to make IQ, and adjust to pH 10.6.

[Bleach solution]

IQ
and adjust the pH to 6.0 using aqueous ammonia.

[Fixer]

Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make up to 1Q, and adjust to pH 6.0 using acetic acid.

[Stabilizing liquid]

Holimarin (37% aqueous solution) 1.5+a (
2 Konidax (manufactured by Konica Corporation) 7.5011
2 Add water to make 1Q.

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

Note that the capri in the table is the value after subtracting the pace concentration, and the sensitivity is the relative sensitivity when each color-sensitive layer of comparative sample 16 left for 3 days is expressed as 100.

From the results in Table 2, it is clear that the samples according to the present invention have a good balance of each photosensitive layer even in multilayer color photosensitive materials, despite severe storage conditions and high-temperature development conditions of 30°C or higher, and fog without deterioration in sensitivity. It is clear that suppressive properties are obtained.

〔Effect of the invention〕

The silver halide photographic light-sensitive material of the present invention contains at least one compound selected from the compounds represented by the general formula (1) of the present invention in a silver halide emulsion layer or an adjacent hydrophilic colloid layer. The occurrence of fog is suppressed even when stored at high temperatures or under high temperature and high humidity, and
It is a highly sensitive photographic material that is less likely to cause a decrease in sensitivity or softening of gradations.

Claims (1)

[Scope of Claims] A silver halide photograph characterized in that a silver halide emulsion layer and/or an adjacent hydrophilic colloid layer contains at least one compound represented by the following general formula [I] photosensitive material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 represents an alkyl group, aryl group, alkoxy group, aryloxy group, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R^3 and R^4 represent a hydrogen atom, an alkyl group, and an aryl group, respectively, and R^2 is a hydrogen atom,
Represents a halogen atom. ]