JPS63261252A - Sensitizer for silver halide photography - Google Patents

Abstract

PURPOSE:To improve the preservation of a photosensitive material, and to reduce the generation of fog by using a specified sensitizer for the titled sensitizer. CONSTITUTION:The titled sensitizer is composed of a condensed-ring compd. A which bonds >=3 sulfur atoms. and >=1 oxygen atoms. with carbon bonds. The single ring constituting the compd. A may be either a heterocyclic ring or a carbon ring, or either an aromatic ring or a nonaromatic ring. Said sulfur and oxygen atoms. may be contained in any one of the single rings constituting the condensed ring, or distributed into the plural single rings. The concrete example of the compd. A is exemplified by the compd. shown by the formula. The preservation of the photosensitive material against heat and humidity is improved, and the generation of the fog is reduced by incorporating the compd. A in said material.

Description

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

The present invention relates to a sensitizer for silver halide photography.

[Background of the invention]

European Patent Publication No. 216973 discloses a cyclic thioether compound in which at least three sulfur atoms and at least one oxygen atom are bonded via a polymethylene chain as a sensitizer for silver halide photography. Although these compounds have a sensitizing effect, silver halide photographic materials using these sensitizers have drawbacks such as insufficient storage stability against heat and humidity and increased fog.

[Purpose of the invention]

An object of the present invention is to solve the above-mentioned deficiencies and α.

[Structure of the invention]

As a result of extensive research, we have achieved the above objective with a silver halide photographic sensitizer characterized by being a fused cyclic compound in which at least three sulfur atoms and at least one oxygen atom are bonded through carbon chains. I found scales. The monocyclic ring constituting the above-mentioned condensed cyclic compound may be a heterocyclic ring, a carbocyclic ring, or an aromatic ring or a non-aromatic ring. or,
The sulfur atom and the oxygen atom may all be contained in any one of the monocycles constituting the condensed ring, or may be dispersed and present in a plurality of monocycles. In the above-mentioned condensed cyclic compound, the carbon chain connecting each sulfur atom and oxygen atom is an alkylene chain such as methylene, ethylene, propylene, tetramethylene, 1,3
- In addition to alkanediyl ylidene chains such as propanesilyl-2-ylidene, cycloalkylene chains such as cyclohexylene and cyclopentylene, alkantriyl chains such as fropanetriyl, and 717-lene chains such as phenylene,
Examples include carbon chains in which two or more of the above groups are bonded, such as an alkylene arylene chain and an alkylene cycloalkylene alkylene chain. When the carbon chain has a cyclic portion such as a 7-arylene chain, a cycloalkylene chain, or an alkylene arylene chain, this cyclic portion constitutes one single ring in the condensed ring. The fused cyclic compounds of the present invention include those having substituents such as halogen atoms (eg, fluorine and bromine) and hydroxyl groups. Further, when a carbon chain bonds sulfur atoms to each other, it is preferable that the number of carbon atoms in the chain portion of the carbon chain is an even number (for example, ethylene, flopylene, tetramethylene, O-7enylene). Further, as the condensed cyclic compound, one having 12 or more shells is preferable. Next, the specific compound side of the fused cyclic compound of the present invention The fused cyclic compound of the present invention is described in J. Org, Chell, (Journal of Organic Chemistry). 36.254 (1971), ^ngew, Chew, I
nt, Ed, Engl.
s, (Chemical Levi, -) t 77, 513° (1
977) and others. A synthetic scheme and a synthetic example are illustrated below. Exemplified Compound (3) Exemplified Compound (5) Exemplified Compound (1) Exemplified Compound (2) trans-1,2-cyclohexanedithiol 57.
41? (0.37 mol), sodium hydroxide 14.8 g
<0.365 mol) tf)” 1 ozl aqueous solution, 5001
26.1 g of bis(2-chloroethyl) ether (0,182
After dropping 70yl 1-butyl/-ol solution of
The mixture was further refluxed for 30 minutes. After cooling the mixture to 95°C,
Add 14.6 g of 2011 aqueous solution (26% bis(2-chloroethyl)ether). Ig 7
0xl 1-butanol solution was added dropwise. The mixture was filtered and concentrated, the residue was dissolved in 20 (hl) of dichloromethane and 200 y of 5% aqueous sodium hydroxide solution was added.
It was washed with f and concentrated. Brown oil 31.5. was purified through an alumina column using benzene. The first 200 ml of effluent contained 8.9 g of the target product. Exemplified compound (8) Toluene-3,4-dithiol 48.8g (0,313
mole), 85% potassium hydroxide 20.7y (0,313
mol), 500a+β of 1-butyl-7-ol in
50i11 of 22.5 g (0,157 mol) of bis(2-chloroethyl)ether while heating to 6°C and refluxing.
The -butyl/-al solution was added dropwise over a period of 2 hours. Lower the temperature of the mixture to 75°C and add 20.7 g of 85% potassium hydroxide.
was added, and while heating and refluxing, a solution of 22.5 g of bis(2-chloroethyl)ether in 50IIIN1-butyl7-al was added dropwise over 1 hour. Refluxing was continued for an additional 4 hours. After acidification with concentrated hydrochloric acid 3111, 1-butyl 7-l was distilled off and water was added to keep the volume of the mixture constant. The paste separated from the aqueous layer was washed with chloroform 600x.
It was dissolved in N and extracted with 400 iyf of a 5% aqueous sodium hydroxide solution. The chloroform solution was dried with calcium chloride and concentrated. 67.2 g of the paste-like residue was extracted with 0-heptane and further extracted with acetone. 4.2 g of white crystals of the target product were obtained from these extracts. The sensitizer of the present invention is preferably used in a silver halide photographic light-sensitive material, and its addition locations include silver halide emulsion layers as well as non-photosensitive layers such as intermediate layers and protective layers. . The amount to be added to the silver halide emulsion layer is as follows:
It is preferably added in an amount of lXl0-5 to Ixl0-2 mol per mol of silver, particularly preferably lXl0-' to 7 However, during chemical ripening, ~ at the beginning,
Preferably at the end and before application. In addition, when adding it to a non-photosensitive layer, 1. OOcm
The silver halide photographic light-sensitive material using the sensitizer of the present invention can be used regardless of its type or purpose, such as black and white, color, negative, or reversal. Examples of the silver halide used at this time include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide.Silver halide A preferred example of the grains is tabular grains. The tabular grains preferably have an aspect ratio (diameter/thickness ratio) of 3 or more, more preferably 5 or more, and particularly preferably 8 to 20. Here, the diameter is the diameter of the circumscribed circle of the particle, preferably 0.5 to 10
μm, more preferably 1.0 to 6.0 μm. Thickness is the distance between two parallel faces in a tabular crystal. An emulsion containing tabular silver halide grains is disclosed in Japanese Patent Application Laid-Open No.
-153428, 58-55426, 58-1
1:'1928, No. 58-11:'1927, etc., or by referring to these methods. The silver halide photographic material according to the present invention may contain a coupler in order to form a multicolor image. The silver halide photographic material of the present invention includes a color antifoggant, an image stabilizer, an ultraviolet absorber, a hardening agent, a plasticizer, a polymer latex, a formalin scavenger, a mordant,
Development accelerators, development retarders, optical brighteners, matting agents, solvents, antistatic agents, surfactants, and the like can be optionally used. In the present invention, any treatment used in the art can be carried out, such as black and white development, color development, bleaching, fixing, bleach-fixing, stabilization, washing with water, and stopping. The cyclic compound of the present invention improves the sensitivity of silver halide photographic materials, and does not cause fogging or deterioration of gamma even when stored under severe conditions.

【Example】

Next, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto. Example-1 A silver iodobromide gelatin emulsion containing 2.5 mol% of silver iodide (average size of silver halide grains 0.8 μm) was mixed with 3.0 mfI of sodium thiosulfate and chloroauric acid per mol of silver halide. 0.6n+g and Rodin Ansen 100m1? was added and then heated at 60° C. for 50 minutes to perform chemical ripening. After adding 1.0 g of 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene per mole of silver halide to the resulting emulsion as a stabilizer, the emulsion was divided into 16 equal parts. A cyclic compound of the present invention or a comparative compound was added as shown in Table 1 below. Subsequently, 2,4-dichloro-6-hydroxy-1,3,5-) riazine sodium salt as a hardening agent and an appropriate amount of saponin as a coating aid are added, and then silver is coated on the subbed triacetate film. A sample was obtained by coating and drying so that the amount was 3 g/m2. The photographic materials prepared as described above were left at a temperature of 55°C for 2 days as a forced deterioration test, and the photographic materials were left at a temperature of 50°C.
Sample 3 that was left for 2 days at 80% humidity, and sample 3 that was left for 2 days at room temperature (20°C) as a control sample.
Seeds were produced. After exposing these samples to light using a sensitometer, the following processing solution [A] was used as a developer for 30 minutes at 35°C.
After developing for a few seconds and fixing, the film was washed with water, dried, and measured once. Processing liquid [A] [Developing solution for black and white photographic materials] 1-phenyl-3-pyrazolidone 1.5 g Hydroquinone 3095-nitroindazole 0.251? potassium bromide
51? anhydrous sodium sulfite
55g potassium hydroxide
30g boric acid 10g
Add 5 g of glutaraldehyde (25% solution) and water to bring the total volume to 11. The results obtained are shown in Table 1. However, the sensitivity is the reciprocal of the exposure amount required to obtain a density of fog+0.2, and is expressed as a relative value when that of comparative sample No. 1 (blank sample) is taken as 100. Also, gamma is expressed by the slope of the straight line on the characteristic curve,
The fog value is the value obtained by subtracting the base density. As is clear from Table 1 above, although the comparative compounds showed an increase in sensitivity, there was a noticeable increase in fog in the film forced deterioration test, whereas the samples containing the compounds of the present invention (Nos. 5 to 16) It can be seen that the increase in fog is small. Example 2 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. After completion of ripening, 4-hydroxy-6-methyl-1,3,3a,
7-chitrazaindene per mole of silver halide) 1
．． Chemical ripening was stopped by adding 0 g. Next, anhydro-5゜5'- was used as a green-sensitive sensitizing dye.
An appropriate amount of diphenyl-9-ethyl-3,3'-di-γ-sulfopropyloxacarbocyanine sodium salt was added to prepare a green-sensitive silver halide emulsion. Then, per mole of silver halide, 1-(2,4,6-)lichlorophenyl)-3 was added as magenta coupler.
-[3-(2,4-di-t-7mil7e7-y-kidiacetamide)penzamide]-5-pyrazolone, 80 g, as a colored magenta coupler, 112.4
．． After weighing 2.5 g of each of 6-6-dolichlorophenyl)-4-(1-na7tylazo)-3-(2-chloro-5-octadecenylsuccinimideanili/)-5-pyrazolone, Tricresylphos 7A) 120g
, 240 mN of ethyl acetate was mixed and dissolved by heating, and then 5 g of sodium triisopropylnaphthalene sulfonate was added.
A coupler solution emulsified and dispersed in a 7.5% aqueous gelatin solution was added to the above emulsion. After dividing this emulsion into 17 parts and adding the compound of the present invention or comparative compound as shown in Table 2 below,
After sufficient adsorption, use 2. as a gelatin hardener.
An appropriate amount of 4-dichloro-6-hydroxyl(1.3.5-) ryanone sodium was uniformly added to prepare a silver halide emulsion. This emulsion was coated uniformly on a subbed triacetate film so that the silver content was 2.0 g/m 2 and dried to prepare a sample. 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 based on the blank sample left for 2 days (sample No. 17).
) is expressed as 100. Also, gamma is expressed 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
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Stabilized 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 1 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline nitrate 4.75g Anhydrous sodium sulfite 4.25fI
Hydroxylamine 1/2 nitrate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 11. [Bleach solution 1 ethylenediaminetetraacetic acid iron ammonium salt 100.0° ethylenecyaminetetraacetic acid 2 ammonium salt to,og ammonium bromide 150.0g glacial acetic acid
Add 10.0 ml of water to bring the total volume to 11, and adjust the pH to 6.0 using aqueous ammonia. [Fixer 1 Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Add water to make 11, and adjust to pH 6.0 using acetic acid. [Stabilizing liquid 1 Formalin (37% aqueous solution) 1,
5ml Konigux (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5+
Add nf water to make 1f. Below is the margin ゛1 As is clear from Table 2 above, although the comparative compound showed an increase in sensitivity, the fog increased significantly in the film forced deterioration test, whereas the sample containing the compound of the present invention (No. Nos. 24 to 32) show little increase in fog and exhibit excellent sensitizing effects even on color emulsions. Example-3 Instead of the silver halide grains of the sample in Example-2, grains with an aspect ratio of 5.0 or more accounted for 50% of the projected area of all grains. Silver iodide content was 2.5 mol. A sample was prepared in the same manner except that the colored magenta coupler was used and the colored magenta coupler was removed. After performing the same forced deterioration test as in Example-1, wedge exposure was performed in the usual manner, and color development was performed according to the color reversal process described below, and the effects of the present invention were observed as in Example-2. Treatment process Step Time Temperature first phenomenon 6 minutes 38℃ water washing
2 minutes 〃Reversal
2 minutes 〃Coloring phenomenon
6 minutes Adjustment 2 minutes
Bleach 6 minutes 〃
Fixing 4 minutes Washing 4 minutes Stable 1 minute Constant
The composition of the wet-drying solution used is as follows. Nissui Sosui
700mf Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 0g Sodium carbonate (monohydrate) 3091-phenyl-4methyl-4-hydroxymethyl-3-pyrazolidone a Potassium bromide 2.5g Potassium thiocyanate 1.2g Iodide Potassium (0,1
% solution) 2+Il water added
1000II11 (pH10,1> [1 Sosui 7
00ml nitro-N,N,N-)limethyleneoschinic acid ・6Na salt 3g 1st chloride
Tin (dihydrate) 19 p-7mi/7ヱ7-l O,t. Sodium hydroxide 8g glacial acetic acid
Add 15+n4 water
1000I111 shot 11 (wei) L water
700ml Sodium tetrapolyphosphate 2g Sodium sulfite 7g Sodium tertiary phosphate (decahydrate) 36g Potassium bromide
1fI potassium iodide (0.1% solution)
90n+/sodium hydroxide 3
g Citrazine @ 1.5gpJ-
Engineering f-N-(β-methanesulfonamidoethyl)-3
-Methyl-4- Aminoaniline sulfate 11g Ethylenediamine 3g Add water
1000II1111 Sosui 7
00ml Sodium sulfite 12g Ethylenecyamine Sodium tetraacetate (dihydrate) 8g Thioglycerin 0.41111 Glacial acetic acid
31111 Add water
10100O float” 1-Wed 8
oOg Sodium ethylenecyaminetetraacetate (dihydrate) 2,0g-23= Iron(II) ammonium ethylenediaminetetraacetate (dihydrate) 120.01+
Potassium bromide 100.0g Add water to 1000ml [Reed water 800ml Sodium thiosulfate SO,O. Sodium sulfite S, Og Sodium bisulfite 5.09 Add water
1000m1r Akiso

Claims (1)

[Claims] A sensitizer for silver halide photography, which is a fused cyclic compound in which at least three sulfur atoms and at least one oxygen atom are bonded through a carbon chain.