JPS63106652A - Silver halide color photographic sensitive material reducing fogging - Google Patents

Abstract

PURPOSE:To reduce fogging during the storage of a sensitive material by color- developing the sensitive material at >=30 deg.C in the presence of a specified compd. CONSTITUTION:A color photographic sensitive material is color-developed at >=30 deg.C in the presence of a compd. represented by formula I (where Q is a group represented by formula II, each of R<1> and R<2> is hydrogen atom, carboxyl, alkoxycarbonyl, alkyl, aryl or a heterocyclic group and R<1> and R<2> may bond to each other to form a benzene ring). An anti-fogging agent represented by the formula I is a 1,2-dithiole-3-thione or 1,3-dithiole-2-thione deriv. During the storage of the sensitive material, the deterioration of the photographic characteristics is prevented and fogging can be especially inhibited.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material in which generation of capri is reduced during storage of the light-sensitive material over time or during color development.

[Background of the invention]

Silver halide photographic light-sensitive materials (hereinafter referred to as light-sensitive materials) tend to produce capri due to the presence of nuclei that can be developed even without exposure to light. Alternatively, it may cause deterioration of gradation (very often). Since it is desirable to minimize such undesirable phenomena, it is conventional to add anti-capri agents or stabilizers to silver halide emulsions. For example, U.S. Pat. No. 2.403.927;
804,633, Japanese Patent Publication No. 39-2825, etc., 1-phenyl-5-flucaptotetrazoles, 4-hydroxy-6-methyl-1°3.3at7-tetrazaindene, etc. are capri inhibitors. It has been used as. However, these compounds do not necessarily have a sufficient capri-suppressing effect during storage over time, and have drawbacks such as decreased sensitivity and softening of gradations, and have not yet reached a satisfactory level. In addition, in the case of color light-sensitive materials, capri inhibitors used with the intention of improving storage stability over time may adsorb to the silver halide emulsion more strongly than necessary, thereby inhibiting spectral sensitization, or This has had many disadvantages such as delaying desilvering properties during the development process.

[Purpose of the invention]

Therefore, the present invention has been made in view of the above-mentioned circumstances, and its first object is to prevent the deterioration of photographic performance of a color photosensitive material during storage over time, and in particular to provide a color photosensitive material that suppresses the occurrence of capri. Our goal is to provide the following. A second object of the present invention is to provide a color photosensitive material containing a capri inhibitor that is less likely to cause a decrease in sensitivity or softening of gradation due to development inhibition. A third object is to provide a color photosensitive material in which the generation of capri is significantly suppressed when color development is performed at a high temperature, particularly at 30° C. or higher.

[Structure of the invention]

The above object is achieved by a color photosensitive material which is color-developed at 30° C. or higher in the presence of a compound represented by the following general formula CI). General formula (1), R1 and R2 each represent a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group, an aryl group, or a heterocyclic group, and %R' and R2 combine with each other to form a benzene ring. The present invention will be described in more detail below. The anti-capri agent represented by the above general formula (r) used in the present invention is 1.2-dithiol-3-thione or 1.2-dithiol-3-thione.
It is a 3-diothyl-2-thione derivative and is represented by the following general formula (n) or (II). General formula (n) General formula (1) General formula (II) and R1 and R2 in (1)
have the same meaning as R1 and R2 in general formula (1), respectively. The alkoxycarbonyl group represented by R1 and R2 is preferably an alkoxycarbonyl group having 2 to 11 carbon atoms, specifically groups such as 7-toxycarbonyl, ethoxycarbonyl, butoxycarbonyl, hexyloxycarbonyl, dodecyloxycarbonyl, etc. can be mentioned. The furkyl group represented by R1 and R2 is preferably a furkyl group having 1 to 20 carbon atoms, which may be linear or branched, and specifically includes methyl, ethyl, isopropyl,
Examples include groups such as butyl, t-butyl, 5ec-pentyl, octyl, dodecyl, pentadecyl, octadecyl, eicosyl, and the like. The aryl group represented by R1 and R2 is a 7-enyl group,
A naphthyl group is preferred and may be substituted. The heterocyclic group represented by R' and R2 is preferably a 5- or 6-shell heterocyclic group, specifically 2-thionyl, 2
-Imidazolyl, 2-pyridyl, 4-pyridyl and other groups can be mentioned. Further, R + R2 may be combined with each other to form a benzene ring, but this benzene ring may further have a substituent, and specifically, a halogen atom (for example, chlorine, bromine atom, etc.), an alkyl groups (e.g. methyl, ethyl, butyl, 2
-ethylhexyl, tesyl group, etc.), aryl group (e.g. phenyl group), flukoxy group (e.g. methoxy, ethoxy, butoxy, octyloxy group, etc.), hydroxyl group, cyano group, nitro group, carboxyl group, and salts thereof. Can be done. The compound showing the best capri-inhibiting effect when used in the present invention is the compound represented by the above general formula (If), and among these, in particular, a 1°2-pendinothiol-3thione derivative in which R1 and R2 form a benzene ring. is preferred. Next, specific representative examples of the compound represented by the general formula (1) used in the present invention (hereinafter referred to as the compound of the present invention) will be shown, but the present invention is not limited thereto. These compounds are described by David S. Preslow, David S.
ow. 5ULFU
RAND 0XYGEN FIVE-8AND 5IX-
HEHBERED HETEROCYCLES), Pa.
'rt 1. Interscience Publishers (
INTERSCIENCE-PUBLISHERS (1966) I: It can be synthesized according to the sale-deyl synthesis method described. Layers of a color photosensitive material to which the compound of the present invention can be added include a silver halide emulsion layer, a protective layer, an intermediate layer, a filter layer, a halide prevention layer, an undercoat layer, etc. that are provided in ordinary photosensitive materials. The most preferred layer, which may be any of the constituent layers, is a silver halide emulsion layer and a hydrophilic colloid layer adjacent to the emulsion layer. Examples of the processing solution to which the compound of the present invention can be added include a color developer or a step prior to the color developer (eg, a pre-hardening solution, a first developer, a neutralization tower, etc.). The amount of the compound of the present invention to be added varies depending on the photosensitive material and the type of compound, but when used in a silver halide emulsion, it is preferably lX10-s to 10-1 mol per mol of silver halide, more preferably is 1×io, −'~IX
It is 10-2 mol. For the hydrophilic colloid layer adjacent to the emulsion layer, the amount used is preferably 10 to 1000 mg per 1.2, more preferably 100 to 70011F. When added to the treatment liquid, O,lay~1 per 11 of the treatment liquid.
The amount is preferably 0, more preferably 5 mg to 1 g. The compound of the present invention can be added to a light-sensitive material by dissolving it in a suitable water-miscible organic solvent (for example, methanol, ethanol, ethylene glycol, trimethyl sulfoxide, nomethylfomulamide, etc.). In addition, known capri inhibitors can also be used in combination within a range that does not impede the effects of the present invention. Also, when adding to silver halide emulsion, the timing of addition is as follows:
Preferably, during chemical ripening, after chemical ripening, and/or after chemical ripening and before emulsion coating, and more preferably at the end of chemical ripening of the silver halide emulsion. The color photosensitive material of the present invention can be, for example, color black and white film, color photographic paper, etc., but the effect of the method of the present invention is particularly effective when using color negative film, which is susceptible to fog. be done. The color photosensitive materials of the present invention, including this color film, may be monochromatic or multicolor. In the case of multicolor silver halide photographic materials, magenta, magenta, and It has a structure in which a silver halide emulsion layer containing yellow and cyan couplers and a non-light-sensitive layer are laminated on a support in an appropriate number and order of layers, but the number and order of layers are It may be changed as appropriate depending on the important performance and purpose of use. The silver halide emulsion used in the color light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any used can be used. The silver halide emulsion is chemically sensitized by conventional methods. Furthermore, it can be optically sensitized to a desired wavelength range. The color light-sensitive material of the present invention includes a color capri-preventing agent, a dye image stabilizer, an ultraviolet inhibitor, which are commonly used in light-sensitive materials,
Antistatic agents, matting agents, surfactants, etc. can be used. These silver halide emulsions. Regarding the production of , various additives and addition methods, etc., please refer to Research Discology + - (R
esearch Disclosure), Volume 176 (
(1978). The technique described in Section 17643 can be applied. An image can be formed on the color photographic material of the present invention by subjecting it to a color development process known in the art. The color photographic material according to the present invention may contain a color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor, and may be processed in an alkaline activation bath. After color development, the color photographic material of the present invention is subjected to bleaching and fixing. Bleaching treatment may be performed simultaneously with fixing treatment. After the fixing process, a washing process is usually performed. Further, a stabilization treatment may be performed as an alternative to the water washing treatment, or both may be used in combination. [Example] The present invention will be explained in more detail with reference to Examples below. Example 1 A silver iodobromide emulsion containing 7 mol % of silver iodide and having an average grain size of 1.2 μm was chemically ripened with gold and sulfur sensitizers to the highest sensitivity. Next, an appropriate amount of 5,5'-diphenyl-9-ethyl-3,3'-no-gamma-sulfobyl aviroxacarbocyanine sodium salt was added as a green-sensitive sensitizing dye to prepare a green-sensitive silver halide emulsion. . Then, per mole of silver halide, 1-(2,4,6-)lichloro7-enyl)-3- was used as a magenta coupler.
80 g of [3-(2,4-not-7-milphenoxyacetamide)benzamide]-5-pyrazolone as a colored magenta coupler, 1-(2,4,6-)chlorophenyl)-4-(1-st 7tylazo)-3-(2
Weigh out 2.5 g of -chloro-5-octadecenylsuccinimideanilino)-5-pyrazolone, then 120 g of tricresylphos 7-ether), and 240 g of ethyl acetate.
+sQ was mixed and dissolved by heating, and then a coupler solution emulsified and dispersed in a solution of 5 g of sodium triisopropylnaphthalene sulfonate and 550 mQ of a 7.5% aqueous gelatin solution was added to the above emulsion. This emulsion was divided into 13 parts and the compounds according to the present invention or comparative compounds were added thereto as shown in Table 1 below.
After sufficient adsorption, 2-
An appropriate amount of sodium hydroxy-4,6-chloroa-trianon was uniformly added to prepare a silver halide emulsion. This emulsion was coated uniformly on a subbed triacetate film to give a silver content of 3.0 g/m 2 and dried to prepare a sample (No. 1 to 13). The monochromatic color photographic material prepared as described above was prepared as a sample and left at room temperature for 3 days and at a temperature of 65°C.
Forced aging samples were prepared by leaving them for 3 days at a relative humidity of 7% and a temperature of 50° C. and a relative humidity of 80%. Thereafter, wedge exposure was performed in a conventional manner, and color development was performed according to the following color processing steps. The color sensitometry results obtained from the obtained pieces are shown in the following tJS1 table. The fog in the table is the value after subtracting the base concentration, and the sensitivity is based on the blank sample left for 3 days (sample No. 1).
This is the relative sensitivity when expressed as 100. Also, the comma is indicated by the slope of the straight line. Processing process [Processing temperature 38℃] Processing time Color development
Bleach for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
3 minutes 15 fixed arrival
Wash with water for 6 minutes and 30 seconds 3
Stabilization for 1 minute 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 potassium carbonate 37.5° Sodium bromide 1.3g Nitrilotriacetic acid 3
Sodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make one solution, and adjust the pH to 10.6. 4 Adjust. [? Whitening agent] Ethylene-7minetetraacetic acid iron ammonium salt 100.0g Ethylenenoaminetetraacetic acid fi2 ammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0m Add standing wood to make IQ, and use ammonium water to adjust pH to 6 , adjust to 0. [Fixer] Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to adjust to IQ, and adjust to pH 6.0 using acetic acid. [Stabilizing liquid] Formalin (37% aqueous solution) 1.5 So Q Conidax (
(manufactured by Roku Konishi Photo Industry Co., Ltd.) 7.5-q 'T-゛・'W Table 1 above shows that the shelf life of color photosensitive materials at high temperatures is improved by the combined use of the fog inhibitor according to the present invention. This shows that the heat resistance (capri suppression property), especially at high temperatures, is improved during the treatment. 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: halide prevention layer black gelatin layer containing colloidal silver 2nd layer: intermediate gelatin layer 3rd layer: red-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Iodide @: S mol% (average grain size 0. 5μ Tsuru) Silver coating amount...1.79g/m2 Sensitizing dye I...6X10-' per mole of silver
Molar sensitizing dye■...2X10-' per mole of silver
Molar coupler A: 0.06 mole per mole of silver Coupler C: o, ooa per mole of silver Molar coupler D: o, per mole of silver ooa
Moltricresylphos 7A)! Cloth 1i 0.3mQ/So2 4th layer: Red-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 4 mol% Average grain size 0.7μ Silver coating amount...1.41H/ So2 sensitizing dye■...
...3X10-' mole sensitizing dye for 1 mole of silver■...1.2X for 1 mole of fi
10-'Molar coupler F...f! 0.01 per 11 moles
25 mole coupler C... o, oote per mole of silver
Moltricresyl phosphate coating amount 0.2 d/m" 5th layer: Intermediate layer Same as 2nd layer 6th layer: Green sensitive low sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 4 mol% Average grain size 0 .5
μ theory Silver coating amount: 1.0 g/m” Sensitizing dye: 3X per mole of silver 10-
'Molar sensitizing dye ■... IX 10- per mole of silver
'Molar coupler B: 0.08 mole per mole of silver Coupler M: o, oos per mole of silver Molar coupler: 0:0 per mole of silver .0015
Moltricresyl phosphate coating amount 1.4 candy Q/+a'' 7th layer: green sensitive high sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 5 mol% Average grain size 0.7
5μ Exim silver coating amount...1.6g/m2 Sensitizing dye ■...2.5X per mole of silver 1
0-'Mole sensitizing dye■...0.8X per mole of silver 1
0-' mole coupler B...0.0Z mole per mole of silver Coupler M...0.003 mole per mole of silver Tricresyl phosphate coating amount 0.8IIIQ/112 8th layer: Yellow filter single layer 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 μ theory Silver coating amount: 0.5 g/+2 Coupler Y: 0.125 mol tricresyl phosphate coating amount per 1 mole of silver: 0.3 mQ/m2 10th layer: Blue Highly sensitive emulsion layer Silver iodobromide emulsion Silver iodide: 6 mol% Average grain size 0.8
μ silver coating amount...Q, 6g/111" coupler Y.
...0.04 mole tricresyl phosphate coating amount per mole of silver 0.1 theory Q/m" 11th layer: Protective layer Gelatin layer containing polymethyl methacrylate particles (diameter 1.5μ theory) For the couplers in each layer, add the couplers to a solution of tricresyl phosphate and ethyl acetate, add sodium p-dodecylbenzenesulfonate as an emulsifier, and dissolve 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 hardening agent and a surfactant were added to each layer. The sample prepared as described above was designated as sample 14. Compound used to make the sample. Sensitizing dye f: anhydride H-5,5'-νri a a -3
, 3'-No(γ-sulfopropyl)-9-ethyl-thiacarposi7ine hydroxide pyridium salt sensitizing dye ■: Anhydro-9-ethyl-3,3'-di(
γ-sulfopropyl)-4,5,4',5'-dibenzothiacarbocyanine hydroxide triethylamine salt sensitizing dye -sulfopropyl) oxacarpodi7ine hydroxide sodium salt sensitizing dye
-(γ-Sulfopropoxy)ethoxy]ethylimigzolocarbocyanine hydroxide sodium salt and below -Brown white 1 ν1 Coupler D Coupler F Coupler Y Furthermore, the red of the third and fourth layers which are the silver halide emulsions mentioned above Green sensitive layer, 6th layer and 7th layer, 9th layer and 10th layer
In each case, a sensitizing dye was added to the blue-sensitive layer of the layer, and then the compound of the present invention or a comparative compound was added as shown in Table 2 below.
Five types of samples were created (No. 14 to 28). The resulting multilayer color light-sensitive material sample was subjected to seven retrench and forced deterioration treatments under the same conditions as in Example-1, followed by ordinary wedge exposure, and then subjected to color processing in the same manner as in Example-1. Color sensitometry results from the pieces obtained are shown in Table 2. The sensitivities in the table are based on the comparative samples of the blue, green and red sensitive layers left for 3 days (sample No. 14) at 10
Table 2 shows the relative sensitivity when expressed as 0. From the results of the forced deterioration aging test on each layer in Table 2,
It can be seen that by adding the compound of the present invention, the occurrence of fogging under high temperature and high humidity conditions is suppressed, and fluctuations in photographic properties are also small. Example 3 Compounds (9), (13), (15) and (26) of the present invention were added to the color development 81 (blank) of Example 1 as shown in Table 3 to obtain four types of compounds. Li the developer!
! ! did. Multilayer color photosensitive material sample 14 (without the addition of the compound of the present invention) coated for comparison in Example 2 was exposed with a wedge, and then color development was performed using each color developer, and the resulting pieces were processed. Capri, sensitivity, and gamma were measured in the same manner as in Example-1. The results are shown in Table 3. Note that the sensitivity in the table is based on the sensitivity of the piece processed at 25°C using the color developer (comparison) of Example-1 as 100. From Table 3, the comparative developer (blank) has a high temperature rapid processing. However, with the developing solution containing the compound of the present invention, capri can be sufficiently suppressed even in high-temperature and rapid processing, and the color balance can be lost. It can be seen that a clear color image can be obtained without losing balance.

Claims (1)

[Claims] At 30°C in the presence of a compound represented by the following general formula [I]
A silver halide color photographic material characterized by being color-developed using the above methods. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Q represents ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ group or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ group, R^1
and R^2 each represent a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group, an aryl group, or a heterocyclic group, and R^1 and R^2 may be combined with each other to form a benzene ring. good. ]