JPH0476537A - Fogging inhibitor for silver halide photography - Google Patents

Abstract

PURPOSE:To maintain stable photographic characteristics in spite of long-time preservation at and under a high temp. and high humidity by incorporating a specific compd. into silver halide emulsion layers and the hydrophilic colloidal layers adjacent thereto. CONSTITUTION:The compd. expressed by formula is used. In the formula, R1 and R2 may be the same or different and respectively denote an alkyl group; R1 and R2 may form a hetero ring by making ring condensation together with a nitrogen atom; R3 denotes a hydrogen atom, halogen atom, alkoxy group, hydroxy group or dialkyl amino group. Then, the fogging is inhibited without generating the degradation in photographic characteristics, such as loss of sensitivity by the generation of the fogging and deterioration of gradation even under severe conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a fog suppressant for silver halide photography, and more specifically to a fog suppressant for use in silver halide photography to prevent the occurrence of fog. Regarding drugs.

[Background of the Invention] Chemically sensitized silver halide photographic materials (hereinafter referred to as photosensitive materials) containing light-sensitive silver halide emulsions are characterized by the presence of nuclei that can be developed without exposure to light. It is well known that this fog tends to occur when developing at high temperatures or for long periods of time, or during storage of photosensitive materials, especially during storage over time under high temperature and high humidity. ing.

Increased fogging leads to decreased sensitivity and deterioration of gradation, and significantly impairs image reproducibility. Therefore, attempts have been made over the years to add many substances to silver halide emulsions for the purpose of preventing fogging.

Typical examples include, for example, Research Disclosure;
Volume 176.

December 1978, 17643 (Vl) Detailed description. A particularly effective fog suppressant is The Theory on the Book by T. H. James.
Photographic Process (The Theory)
of the Photographic Process
ss) 4th edition, published by Macmillan (1977), pages 393-399, and the mechanism of action is also explained.

However, it is difficult for these many fog suppression technologies to adequately respond to the recent advances in sensitivity, activation, and rapid processing of photosensitive materials, especially at high temperatures (approximately 45°C or higher).
The reality is that they lack fog control and photographic property stability under harsh conditions, such as being left in the cold or being stored at high temperatures and high humidity (approximately 50 to 80 degrees Celsius, relative humidity approximately 50 to 90%). be. That is, when many of the above-mentioned known compounds are used at effective concentrations to adapt to the above conditions, there is a significant decrease in sensitivity and deterioration of gradation, which is an essential element of a fog suppressant. Unable to maintain fog balance.

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

[Object of the Invention] The present invention has been made in view of the above-mentioned circumstances, and its first purpose is to provide stable photographic properties even when a photosensitive material is stored at high temperatures or at high temperatures and high humidity over time. It is an object of the present invention to provide a fog suppressant for silver halide photography that maintains the image quality and prevents the occurrence of fog.

A second object of the present invention is to provide a fog inhibitor for silver halide photography that does not cause a decrease in sensitivity or deterioration of gradation due to development inhibition.

A third object is to provide a fog inhibitor for silver halide photography that significantly reduces the occurrence of fog during high-temperature rapid processing, particularly during development at 30° C. or higher.

[Structure 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, in which at least one of the silver halide emulsion layer and the woody colloid layer adjacent thereto is
This is achieved by using a photographic fog suppressor containing at least one compound represented by the general formula [I] in the layer.

[In the formula, R and R2 may be the same or different,
Each represents an alkyl group, and R1 and R2 may be condensed together with a nitrogen atom to form a heterocycle.

Moreover, R5 is a hydrogen atom, a halogen atom, an alkoxy group,
represents a hydroxy group or a dialkylamino group] Hereinafter, the present invention will be explained in more detail.

In the compound represented by general formula [I] according to the present invention,
The alkyl group represented by R1 and R2 has 1 carbon number
-10 alkyl groups (preferably alkyl groups having 1 to 5 carbon atoms), such as methyl, ethyl, propyl, butyl, etc., and these alkyl groups may have a branch.

In addition, examples of heterocycles formed by condensing R1 and R7 with a nitrogen atom include a pyrrolidine ring, a piperidine ring,
Examples include morpholine ring.

Examples of the halogen atom represented by R3 include a fluorine atom, a chlorine atom, and a bromine atom, and the alkoxy group includes:
Examples of the dialkylamino group include a methoxy group and an ethoxy group, and examples of the dialkylamino group include a dimethylamino group and a diethylamino group.

Further, the substituent for R3 may be any of the 2-position, 3-position, and 4-position of the phenyl group.

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.

U! O) U The compound represented by the above general formula [1] is
No. 68480, No. 61-68481, European Patent No. 4711, French Patent No. 2215219, Bulletin of the Chemical Society on Japan (Bulletin of the Chemical Society on Japan)
Chemical 5ociety of Japan
n), Volume 59, Pages 201-342018 (19
It can be easily synthesized by the method described in (1986) et al.

In the present invention, the above compound can be used as a fog suppressant, and can be used in silver halide emulsion layers and adjacent hydrophilic colloid layers (intermediate layers, filter layers, antihalation layers, protective layers, undercoat layers, etc.) of photosensitive materials. contained in at least one layer of. A particularly preferred layer is a silver halide emulsion layer.

The amount of the compound of the present invention added varies depending on the photosensitive material and the type of compound, but the compound represented by the general formula [I] is 0.01 mg to 1.0 mg per mole of silver halide.
It is preferably used in a range of 0.00 mg, more preferably 0.05 mg to 500 mg. The amount added to the wood-philic colloid layer is O, 1 mg to 2.0 per 11112 coatings.
It is preferably used in a range of 00 mg, more preferably 10 mg to 1,000 mg.

These compounds are dissolved in water or a wood-philic organic solvent (for example, methanol, dimethylformamide, etc.) and added to the desired constituent layer.

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

The photosensitive material of the present invention can be used as various types of photosensitive materials as follows.

For example, photosensitive materials for general-purpose black and white, Xta recording, plate making, color positive, color negative, color paper, reversal color, direct positive, heat development, etc., or surface latent image type silver halide grains and internal U.S. Pat. No. 2,996.382 using silver halide grains having fog nuclei;
Although it can be used in photosensitive materials produced by the method described in the specification of No. 3,178,282, it is particularly advantageous to apply it to color photosensitive materials having a multilayer structure.

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 a latent image is mainly formed on the surface, or may be such that a latent image is formed mainly inside the grain.

Silver halide emulsions may have any grain size distribution. Emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (monodisperse emulsions) may be used. ) 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.

The emulsion can be chemically sensitized by conventional methods, or optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as 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 sparingly soluble synthetic polymer.

Couplers are used in the emulsion layer of color light-sensitive materials.

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 acylacetanilide 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.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layers may contain dyes that are leached from the light-sensitive material or bleached during the development process.

A matting agent, a lubricant, an image stabilizer, a formalin scavenger-1 ultraviolet absorber, a fluorescent whitening agent, a surfactant, a development accelerator, a development retardant, and a bleach accelerator can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

A known method can be used to develop the photosensitive material of the present invention. The processing temperature used is between 18°C and 50°C, and depending on the purpose, any of black and white photographic processing, lithographic development processing, or color photographic processing to form a dye image can be applied. Furthermore, photosensitive materials for thermal development are processed at temperatures of 100° C. or higher.

[Effects of the present invention] A fog suppressor consisting of a compound represented by the general formula [I] of the present invention, particularly at least one compound selected from the compounds represented by the general formula [1], is added to a silver halide emulsion layer or By adding it to the adjacent hydrophilic colloid layer, the generation of capri is suppressed even when stored at high temperatures over time or at high temperatures and high humidity, and there is a risk of lowering sensitivity and softening of gradation. An excellent photographic material with a small amount of material can be obtained.

[Example] The present invention will be explained in more detail with reference to Examples below.
This is an example for explaining the present invention, and the present invention is not limited thereto.

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-tetrazaindene was added to stop the ripening.

The obtained emulsion was divided into 13 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/n'', and then dried.
Three types of samples were created (No. 1 to 13).

The photographic materials prepared as described above were left as fresh samples at room temperature for 3 days, and forced aging samples were left at a temperature of 55°C for 3 days and at a temperature of 50°C and relative humidity of 80% for 3 days. Created.

Thereafter, exposure was carried out using a conventional sensitometric wedge, and then development was carried out at 35° C. for 30 seconds using the following processing solution [A] to fix the film, followed by washing with water and drying to measure sensitivity.

Processing liquid [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
5g anhydrous sodium sulfite
55 g potassium hydroxide
30g boric acid
10 g glutaraldehyde (2
5%) Add 5g of water to make the total amount IJ2.

The results obtained are shown in Table 1.

However, the fog value indicates 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 by the slope of the straight line on the characteristic curve.

As is clear from Table 1 above, the samples according to the present invention are:
It can be seen that in all cases, the occurrence of fog was suppressed despite the harsh storage conditions, and the stability of the film during storage was 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 highest sensitivity.

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

Then, per mole of silver halide, 1-(2,4,6-1-lichlorophenyl)- is used as a magenta coupler.
80 g of 3-[3-(2,4-di-t-amylphenoxyacetamide)benzamitoc-5-pyrazolone as a 5-colored magenta coupler, 1-(2,4,6-
Triclophenyl)-4-(1-naphthylazo)-3-
Weighed 2.5 g of (2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone, 120 g of tricresyl phosphate, and 2.5 g of ethyl acetate.
40 mg were mixed and dissolved by heating, and then a coupler solution, which was emulsified and dispersed in a solution of 5 g of sodium triisopropylnaphthalene sulfonate and 550 ml of a 7.5% aqueous gelatin solution, was added to the above emulsion.

The emulsion was divided and one part was used as a blank sample, and a comparative compound and a compound according to the present invention were added thereto as shown in Table 2 below, and after sufficient adsorption,
An appropriate amount of sodium 2-hydroxy4,6-cyclotriazine was uniformly added as a gelatin hardener to prepare a coating emulsion.

This coated emulsion was uniformly coated and dried on a subbed triacetate film so that the silver content was 3.0 g/m', and samples were prepared (Nos. 14 to 24).

The obtained film sample was subjected to the same forced deterioration test as in Example 1, then wedge exposed in the usual manner, and color developed according to the following color processing steps.

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

The fog in the table is the value after subtracting the base concentration, and the sensitivity is for the blank sample left for 2 days (sample No. 1).
4) is the relative sensitivity expressed as 100. Furthermore, gamma is shown by the slope of the straight line on the characteristic curve.

Processing process [Processing temperature 38℃] IA physical time color development
Bleach for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
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-(β-hydroxyethyl)-aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine 1/2 sulfate 2.0g anhydrous carbonate potassium
37.5 g sodium bromide
1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add wood to bring the volume to 1, and adjust the pH to 1o and 6 using sodium hydroxide.

[Bleach solution] 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 IIL, and the pH was adjusted to 6 using ammonia water. , adjust to 0.

[Fixer] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite Add sodium metasulfite water to prepare IJZ.

[Stabilizing liquid] Formalin (37% aqueous solution) Konidax (manufactured by Konica Corporation) ! Add water to make IA.

Adjust the pH to 8.6g 2.3g 6.0 using acetic acid 1.5 7.5 (blank below) From the results in Table 2, the general formula [1
] compared to conventionally known compounds. It can be seen that anti-fogging properties can be obtained with no decrease in sensitivity in forced deterioration tests under high temperature or high humidity conditions.

Example 3 A multilayer color photosensitive material sample was prepared by sequentially providing each layer having the composition shown below on a cellulose triacetate film support. However, silver iodobromide emulsions with silver iodide contents as shown below are used in the silver halide emulsion layers of the third layer, Table 4, sixth layer, seventh layer, ninth layer and tenth layer. used.

1st layer: antihalation layer black gelatin layer containing colloidal silver 2nd layer: intermediate layer gelatin layer 3rd layer: red-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver coating amount... Sensitizing dye I... Sensitizing dye II for 1 mole of silver...Coupler A for 1 mole of silver...Coupler C for 1 mole of silver...Coupler D for 1 mole of silver... On the other hand, tricresyl phosphate coating amount 4th layer: Red-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver coating amount... Sensitizing dye I... 1 mole of silver Sensitizing dye II... silver Coupler F for 1 mole Coupler C... Tricresyl phosphate coating amount for 1 mole of silver 1.79 g/m2 6 x IQ-5 mole 3 x 10-5 mole 0.06 mole 0.003 mole 0.003 mole 0.3 cc/m2 1.4 g/rn2 3 Layer: Intermediate layer Same as 2nd layer 6th layer: Green-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver coating amount: 1.0 g/ln2 Sensitizing dye III: 3 X per mole of silver 10-
5 mol sensitizing dye ■... lXl0- per 1 mol of silver
5 mole coupler B...0.08 per mole of silver
Molar coupler M...0.008 per mole of silver
Molar coupler D...0.0015 per mole of silver
Moltricresyl phosphate coating amount 1.4cc/m
2 7th layer: Green-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver coating amount: 1.6 g/m2 Sensitizing dye - 2.5X 10-' mol sensitizing dye per 1 mol of silver ■...0.8X 10" for 1 mole of silver
Molar coupler B: 0.02 mol per mol of silver Coupler M: 0.003 mol per mol of silver Coating amount 0.8 cc/m2 8th layer: Yellow filter layer in gelatin aqueous solution gelatin layer containing yellow colloidal silver.

9th layer: Blue-sensitive, low-sensitivity emulsion layer Silver iodobromide emulsion Silver coating amount: 0.5 g/m2 Coupler Y: 0.125 mol per mole of silver Tricresyl phosphate coating amount: 0.3 cc /m2 10th layer: Blue-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver coating amount...0.6 g/m'Coupler Y...0.04 mol tricresyl phosphate coating amount per 1 mole of silver 0.1cc/m2 11th layer:
Protective layer Apply a gelatin layer containing polymethyl methacrylate particles (diameter 1.5 uμm).

The couplers in each layer are prepared by adding the couplers to a solution of tricresyl phosphate and ethyl acetate, adding sodium p-dodecylbenzenesulfonate as an emulsifier and dissolving them by heating.
The mixture was mixed with a heated 10% gelatin solution and emulsified using a colloid mill.

In addition to the above composition, a gelatin hardener and a surfactant were added to each layer.

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

Compound Sensitizing Dye I used to prepare the sample: Anhydro-5,5”-dichloro-3,3
''-di(γ-sulfopropyl)-9-dityruthiacarbocyanine hydroxyto pyridium salt sensitizing dye I■ = 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 ■: anhydro-5,6,5", 6"-tetrachloro-1,1''-diethyl 3.3”-di(
β-[β-(γ-sulfopropoxy)ethoxycoethylimidazolocarbocyanine hydroxyto sodium salt coupler A coupler C H Shi! In each of the emulsion layers of the blank samples of the present invention, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, known as an aging stopper, was added to the halogen sensitizing dye. 1 g was added per mole of silveride, and this was used as a blank emulsion.

Next, the antifoggants of the present invention and the comparative antifoggants were added as shown in Table 3, and after sufficient adsorption,
After adding the coupler tricresyl phosphate and the like as described above, an appropriate amount of sodium 2-hydroxy-4,6-dichlorotriazine was added as a hardening agent, and seven types of samples were coated in layers. (No. 28 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. Ta.

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

In addition, the fog in the table indicates the value after subtracting the base density, and the sensitivity value is based on the sensitivity of the red-sensitive layer, edge-sensitive layer, and blue-sensitive layer of the blank sample (No. 25) after being left in nature for 2 days as 100. It is shown in terms of relative sensitivity when expressed.

From the results in Table 3 below, it can be seen that the samples according to the present invention have a good balance of each photosensitive layer and no decrease in sensitivity even in multilayer color photosensitive materials despite severe storage and high-temperature development conditions of 30°C or higher. It is clear that antifogging properties are obtained.

Claims (1)

[Scope of Claims] A fog suppressant for silver halide photography, characterized by being a compound represented by the following general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. may be formed. Moreover, R_3 represents a hydrogen atom, a halogen atom, an alkoxy group, a hydroxy group, or a dialkylamino group. ]