JPS63259653A - Silver halide photographic sensitizer - Google Patents

Abstract

PURPOSE:To prevent the generation of fogging of a silver halide photographic material by using a cyclic compd. which binds a group contd. in a constituting component of said compd. and sulfur atoms by a hydrocarbon chain with each other, as the specified ring constituting component. CONSTITUTION:The titled sensitizer contains the cyclic compd. which comprises at least one of a group selected from formula I, at least 3 members of the sulfur atoms and at least one of the hydrocarbon chain, and binds said group and the sulfur atoms with each other by the hydrocarbon chains. In formula I, R is alkyl group such as methyl, or ethyl group, etc., said hydrocarbon chain is an alkylene chain such as methylene or ethylene, or a cycloalkylene chain such as cyclohexylene, or cyclopentylene, etc., said hydrocarbon chain may be substd. with a halogen atom (such as fluorine or bromine atom) or hydroxyl group, etc., a part of said alkylene chain may be a cyclic chain. Thus, the sensitivity of said material is improved, and the generation of the fogging is prevented even in the case of preserving said material under a severe condition.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a sensitizer for silver halide photography.

[Background of the invention]

-CONH- in British Patent No. 942865.

A silver halide photographic sensitizer is disclosed which is a cyclic compound having 1 to 2 sulfur atoms and an alkylene chain as ring constituents.

However, the degree of sensitization of silver halide photographic materials by these sensitizers is still insufficient, and furthermore, silver halide photographic materials using these sensitizers do not have sufficient storage stability against heat and humidity. However, there are drawbacks such as increased fog.

[Purpose of the invention]

The object of the invention is to overcome the above-mentioned drawbacks.

(Structure of the Invention) As a result of intensive research, we have discovered that at least one group selected from -NR- (R is a hydrogen atom or alkyl) and -N I CON II-, at least three sulfur atoms, and at least a hydrocarbon chain. The above object can be achieved by a silver halide photographic sensitizer which has as a ring component and is a cyclic compound in which a radical and the sulfur atom are bonded to each other by the hydrocarbon chain. I found out.

Examples of the alkyl group represented by R include a methyl group, an ethyl group, and a propyl group.

Examples of the hydrocarbon chain that connects groups and atoms include alkylene chains such as methylene, ethylene, propylene, and tetramethylene, cycloalkylene chains such as cyclohexylene and cyclopentylene, and arylene chains such as phenylene. The hydrocarbon chain includes those having substituents such as halogen atoms (e.g. fluorine, bromine) and hydroxyl groups, and alkylene chains include those having a cyclic structure (e.g. alkylene-arylene-alkylene). , alkylene-arylene, alkylene-cycloalkylene-alkylene).

Further, the cyclic compound of the present invention may contain an oxygen atom or the like as a ring component in addition to the above-mentioned ring components.

In addition, when a hydrocarbon chain bonds sulfur atoms, the number of carbon atoms in the chain portion of the hydrocarbon chain is an even number (for example, ethylene, propylene, tetramethylene, 0-phenylene).
It is preferable that 12
Preferably more than one member.

The cyclic compound of the present invention is disclosed in British Patent No. 942.865,
European Patent No. 216,973, J, Chem, So
c., CheIIl.

Com5un, (Journal of Chemical Society Chemical Communication) 1970, 1
055゜＾ngew, CI+em, 1ntern, E
d, (Angevante Hemi International
Edition in English) 13,149
(1974), J.Org.Chem.
Ji.

- Naru of Organic Chemistry), hindrance.

254 (1971), Chem, Rev., (Chemical Review), 77°513 (1977), etc.

Next, synthetic schemes and synthetic examples will be shown for some exemplary compounds.

Exemplified Compound 6゜'・ro / \-1 Exemplified Compound 12゜Exemplified Compound 17゜Exemplified Compound 20゜Exemplified Compound 21゜Exemplified Compound 23゜Exemplified Compound 25゜Exemplified Compound 26゜Exemplified Compound 1 Ethane-1,2-dithiol 2 27.6° of sodium salt and 46.29° of di(2-bromoethyl)amine in 3
1 of ethanol and heated under reflux for 12 hours under nitrogen atmosphere. After the reaction was completed, the solvent was distilled off under reduced pressure, water was added to the oily residue, and the mixture was extracted with ethyl acetate. The extract layer was dehydrated with anhydrous magnesium sulfate, concentrated under reduced pressure, ethanol was added to the residue, and recrystallized to obtain 6.8 g of the target product. Temperature: 123-125°C (white crystals).

The structure was confirmed by NMR and mass spectrometry.

The exacerbating agent 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:
Preference is given to lXl0-' to lX10-2 mol, particularly lXl0-' to 7x10-comole per mole of silver.

The addition time may be during the silver halide emulsion manufacturing process or before coating, but preferably during chemical ripening, at the beginning, at the end, and before coating.

In addition, when added to a non-photosensitive layer, per 100 cm
I x 10-' to 5 x 10-''my are preferred.

The silver halide photographic light-sensitive material using the sensitizer of the present invention may be of any type and purpose, such as black and white, color, negative, reversal, etc., and the silver halide used at this time may be For example, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc.

Examples include particles.

The tabular grains preferably have an aspect ratio (diameter/thickness ratio) of 3 or more, more preferably 5 or more, particularly preferably 8-20. The diameter here is the diameter of the circumscribed circle of the particle, preferably 0.5 to 10
μ ring, more preferably 1.0 to 6.0 μ ring. 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
It can also be produced using the method described in No. 13928, No. 58-113927, etc., or with reference to this.

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-1 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 gamma deterioration even when stored under severe conditions.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples. You are not limited to this.

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 3.5 mol % of sodium thiosulfate per mol of silver halide. (After adding hag, 0.6 mg of chloroauric acid, and Rodan Ansen 1001, it was 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-tetrazaindene per mole of silver halide to the resulting emulsion as a stabilizer, the emulsion was divided into 17 equal parts. A cyclic compound of the present invention or a comparative compound was added as shown in Table 1 below.

Subsequently, after adding 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt as a hardening agent and an appropriate amount of saponin as a coating aid, the amount of coated silver was coated on the subbed triacetate film. A sample was obtained by coating and drying to a concentration of 3 g/m''.

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 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 and dried, and the sensitivity was measured.

Processing liquid [A] [Developer for black and white photographic materials] 1-phenyl-3-pyrazolidone 1.5 g Hydroquinone 30 g 5-Nitroindazole 0.251? potassium bromide
5FI anhydrous sodium sulfite
55g potassium hydroxide
30g boric acid 1
Add 0fI glutaraldehyde (25% solution) and 5FI water to bring the total volume to 1r.

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, Sample No. 1 according to the present invention
, 6 to 17 show that, despite severe storage conditions, sensitization with little capri generation and gamma deterioration is maintained even during film storage, and stable sensitization can be obtained.

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. Aging completed 0U4-hydroxy-6-methyl-1,3,3a
, 7-tetrazaindene per mole of silver halide.
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-dolichlorophe(nyl)) was added as a magenta coupler.
-3-[3-(2,4-di-t-amylphenol)
-xyacetamido)penzamide]-5-pyrazolone as 80y, colored magenta coupler, 1-(2
, 4,6-6-)dichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone after weighing 2.5 g each. Tricresyl phosphate 120g
, 240 ml 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 solution of 7.5% gelatin aqueous solution 550IT1 was added to the above emulsion.

This emulsion was divided into 17 parts, 1 of the compound of the present invention or a comparative compound was added to each as shown in Table 2 below, and after sufficient adsorption, 2 of the compounds were added as a gelatin hardener.
, 4-dichloro-6-hydroxy-1,3,5-sodium triazine was added to one wheel to prepare a silver halide emulsion.

This emulsion was coated uniformly on a subbed triacetate film to a silver thickness of 2.027 m'' 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 fog is for the blank sample left for 2 days (sample No. 1).
8) is expressed as 100. or,
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 1
Drying for minutes 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 nitrate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 nitrate 2.0g Anhydrous potassium carbonate 37.51? Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5y Potassium hydroxide 1.0g Add water to make 11.

Bleach solution Coethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150. hglacial acetic acid
Add LO, 0ml water to make 1p, and adjust to pH 6.0 using aqueous ammonia.

[Fixer] Ammonium thiosulfate t75.01F
Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3° Add water to make 11, and adjust to pH 6.0 using acetic acid.

[Stabilizing liquid j Formalin (37% aqueous solution) 1.5
mj! Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5m
& Add water to make 11.

As is clear from Table 2 above, the samples according to the present invention exhibited superior sensitization in color emulsions compared to the conventionally known comparative compounds, and the sensitization properties of the samples during raw film storage were This shows that there is little deterioration in photographic characteristics.

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 Horn reversal 2 minutes 38℃ color development 6 minutes Horn adjustment
2 minutes horn drifting
white 6 minutes
Horn fixation 4 minutes
Horn water washing 4 minutes
Horn stability 1 minute
The following composition is used for the normal humidity drying treatment solution.

111 Wednesday
700ml Sodium Tetrapolyphosphate 2Fl
Sodium sulfite 20g Hydroquinone monosulfonate 30° Sodium carbonate (monohydrate) 30g 1-phenyl-4methyl-4-hydroxymethyl-3-pyrazolidone g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0,1
% solution) 2 ml Add water to 1,000 rings 1 (pH 1
0,1) [11 Water
700+++I2 dil.rhoN-N-N-trimethyleneoschinic acid 6Na salt 3g stannous chloride (dihydrate) 1g p-aminephenol 0.1° sodium hydroxide 8g glacial acetic acid
Add 15 liters of water 1
0100O Rue”L Encounter Water
700ml sodium tetrapolyphosphate 2g
Sodium sulfite 7g Sodium phosphate (12 hydrate) 36FI potassium bromide
1゜Iodide h liu l-(0.1%
Melt? li) 90@sodium monohydroxide 3g citradinic acid
1.52N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 11g ethylenediamine 3g Add water
1000Ilffi water
700s+ & Sodium Sulfite 12g Ethylenediamine Tetra#
Sodium acid (dihydrate) By thioglycerin 0.4 ml - Add 3 ml of glacial 8' acid water
10,100 O drifting' [Water water]
800゜Sodium ethylenediaminetetraacetate (dihydrate) 2.0gEthylenediaminetetraacetate iron(III) ammonium (dihydrate) 120.0f
Potassium bromide 100.0° Add water 10100O 1L water
800 l sodium thiosulfate
SO, O.

Sodium sulfite 5.0f Sodium bisulfite 5.0g Add water
10100O'eh Ll

Claims (1)

[Claims] -NR- (R is a hydrogen atom or alkyl), -CONH-
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas, ▼, (R is hydrogen or alkyl) and at least one group selected from -NHCONH-, at least three sulfur atoms, and a hydrocarbon chain as ring constituents, and the group and the A sensitizer for silver halide photography, characterized in that it is a cyclic compound in which sulfur atoms are bonded to each other via the hydrocarbon chain.