JPH0528816B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide photographic material,
More specifically, the present invention relates to a silver halide photographic material sensitized with a new sensitizing dye and having improved photographic properties. (Prior Art) It is generally known that when a sensitizing dye is added to a photosensitive silver halide emulsion, the sensitive wavelength range of the silver halide emulsion is expanded and the emulsion is optically sensitized. A large number of compounds have been known as optical sensitizing dyes used for such purposes, such as those described in ``The Theory of the Photographic Process'' by T.H. (2013, Macmillan Publishing, NY) pp. 194-234
Cyanine dyes, merocyanine dyes, xanthene dyes, etc. described on page 1 are known. When these sensitizing dyes are normally applied to silver halide emulsions, they must not only simply expand the sensitive wavelength range of the silver halide emulsions, but must also satisfy the following conditions. (1) The spectral sensitization range by dye sensitization is appropriate. (2) It must have good sensitization efficiency and be able to obtain sufficiently high sensitivity. (3) There is no adverse interaction with other types of additives, such as stabilizers, antifoggants, coating aids, color formers, etc. (4) No fogging should occur. (5) Sensitivity should not decrease over time. The conditions (1) to (5) above have an important meaning in preparing a silver halide emulsion. That is, for example, cyanine dyes have traditionally been considered as sensitizing dyes used in visible wavelength-sensitive silver halide emulsions, but many of the cyanine dyes do not necessarily have sufficient sensitization efficiency, and the desired sensitivity cannot be obtained. However, in many cases, fogging is caused, and sensitivity decreases over time, so no satisfactory solution has been found. (Objective of the Invention) The object of the present invention is, firstly, to provide a silver halide photographic material that is highly sensitive and does not cause fogging, and secondly, to provide a silver halide photographic material that does not cause a decrease in sensitivity over time. The third object is to provide a silver halide photographic material which is sensitized with a novel sensitizing dye and has improved photographic properties. (Structure and operation of the invention) As a result of various studies, the present inventors have found that the above object is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support. It has been found that this can be achieved by using a silver halide photographic light-sensitive material in which the silver halide grains contained in the emulsion layer are color sensitized with a compound represented by the following general formula (). General formula () However, Y ₁ and Y ₂ represent a group of nonmetallic atoms necessary to form a 5- or 6-membered nitrogen-containing multiple ring. The 5- or 6-membered nitrogen-containing multiple rings represented by Y ₁ and Y ₂ include fused rings, and specifically include oxazole (e.g., 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, etc.) , oxazolidine (e.g. 4,4-dimethyloxazolidine etc.), thiazole (e.g. thiazole, 4,5-diphenylthiazole, 4-methylthiazole etc.), thiazolidine (e.g. thiazolidine etc.), thiadiazole (e.g. 2-methylthio-1,3 , 4-thiadiazole, 2-phenyl-1,3,4-thiadiazole, etc.), selenazole (e.g. 4,5-dimethylselenazole, 4-thiadiazole, etc.)
-phenyl selenazole, etc.), benzoxazole (e.g. 5-phenylbenzoxazole, 5
-chlorobenzoxazole, etc.), benzothiazole (e.g. 5-chlorobenzothiazole, 6-
phenylbenzothiazole, 5,6-dimethylbenzothiazole, etc.), benzoselenazole (e.g. 5-methoxybenzoselenazole, 5-methylbenzoselenazole, etc.), benzotellazole (e.g. 5,6-dimethoxybenzotellazole,
5-methylbenzotellurazole, etc.), benzimidazole (e.g. 5,6-dichlorobenzimidazole, 5-cyanobenzimidazole, etc.), naphthoxazole (e.g. naphtho[1,2-d]
oxazole, naphtho[2,3-d]oxazole, etc.), naphthothiazole (e.g. naphtho[1,
2-d]thiazole, naphtho[2,3-d]thiazole, etc.), naphthoselenazole (e.g. naphtho[1,2-d]selenazole, naphtho[2,3-
d] selenazole, etc.), naphthotelazoles (e.g. naphtho[1,2-d]tellazole, naphtho[2,1-d]tellazole, etc.), pyridine, quinoline (e.g. 6-methoxyquinoline, 6-fluoroquinoline, etc.), Examples include cyclic groups such as thieno[1,2-d]thiazole and thiazolo[4,5-b]pyridine. In addition, R ₇ , R ₈ , R ₉ are hydrogen atoms, halogen atoms,
It represents a lower alkyl group, an aryl group, a lower alkoxy group, or a heterocycle, and R ₇ and R ₉ may be connected to form a carbon ring. R ₆ represents an alkyl group, an aralkyl group, or an alkenyl group. X ^- represents an anion, and i, j, k, l, and m each represent an integer of 0 or 1. Further, p of the N-position substituent is 0 or 1, and q
is an integer from 1 to 10, and n represents an integer from 1 to 10. R ₅ represents a hydrogen atom, a lower alkyl group or a fluorine atom. More preferably, among the dyes represented by the general formula (), a sensitizing dye represented by the following general formula () is selected. General formula () However, in the general formula (), R ₁ , R ₂ , R ₃ , R ₄ , R′ ₁ ,
R′ ₂ , R′ ₃ , and R′ ₄ are hydrogen atoms, lower alkyl groups, lower alkoxy groups, aryl groups, carboxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, halogen atoms, nitro groups, hydroxy groups, and cyano groups, respectively. group, amino group, acylamino group, sulfonylamino group, acyloxy group, carbamoyl group, sulfamoyl group, sulfonyl group,
represents an acyl group or a heterocyclic group, R ₁ and R ₂ ,
R ₂ and R ₃ , R ₃ and R ₄ , R′ ₁ and R′ ₂ , R′ ₂ and R′ ₃ or R′ ₃
and R′ ₄ may be linked to each other to form a ring. Z ₁ and Z ₂ are oxygen atoms, sulfur atoms, selenium atoms, nitrogen atoms, tellurium atoms,

[Formula] or Indore hmm

[Embodiments of the invention]

The present invention will be explained in more detail below using Examples. However, it goes without saying that the present invention is not limited to the examples. Example 1 A silver iodobromide polydisperse twin emulsion with an average grain size of 1.0 μm (grain size distribution S/=0.34, silver iodide content 7 mol%, silver iodide uniformly dispersed in the grains) was prepared. , prepared by the double jet method. The emulsion prepared in this way was divided into 15 equal parts, each part was subjected to optimal chemical sensitization using gold salt and a sulfur sensitizer, and 0.06% of the exemplified compound -1, -5 or -12 belonging to the general formula () was added to the emulsion. Samples No. 7 to No. 15 in Table 1 were obtained by adding in a range of ~0.24 mmol/molAgX. or,
For comparison, the comparative dye A or B shown below was used.
Add in the range of 0.06 to 0.24 mmol/molAgX,
Samples No. 1 to No. 6 in Table 1 were obtained. Next, 4-hydroxy-
Appropriate amounts of 6-methyl-1,3,3a,7-tetrazaindene, 1-phenyl-5-mercapto-tetrazole, saponin as a coating aid, and 1,2-bis(vinylsulfonyl)ethane as a hardening agent. and 3 g of polyvinylpyrrolidone were added, and further a dispersion of a mixture of magenta coupler, dodecyl gallate, tricresyl phosphate, ethyl acetate, sodium triisopropylnaphthalene sulfonate and gelatin was added. The emulsion thus prepared was coated on a cellulose triacetate base support and dried to prepare a sample. Next, each sample was subjected to a 1/50 second wedge exposure through a green light filter, and then
Color negative development processing was performed as follows. <Development conditions> Processing process (38℃) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Each process The composition of the treatment liquid used in the process is as follows. Color developer composition:

[Table] Bleach solution composition: Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to 1, and adjust pH using aqueous ammonia.
Adjust to 6.0. Fixer composition: Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to 1 and adjust to PH6.0 using acetic acid. Stabilizing liquid composition: Formalin (37% aqueous solution) 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5ml Add water to make 1. The density of each obtained dye image is measured through a green filter, and the green light sensitivity Sg
and fog were sought. Sensitivity is "fog +0.1"
It was determined from the amount of exposure necessary to give an optical density of . The sensitometry results are shown in Table 2 below. Note that the sensitivity is expressed relative to the sensitivity of sample No. 1 as 100. Table 1 shows the relative sensitivity and fog measurement results immediately after sample preparation, and Table 2 shows the relative sensitivity and fog measurement results after being left at 60° C. and 70% RH for one day. It was found that the relative sensitivity of the product according to the present invention was superior to the conventional product even after moisture absorption. Furthermore, it was found that the fogging of the product according to the present invention showed less deterioration after moisture absorption than the conventional product and had a high sensitivity.

【table】

【table】

[Table] Example 2 Iodobromide grains consisting of silver halide grains of dodecahedral crystals with an average grain size of 0.56μ were prepared according to a method similar to that described in JP-A-57-154232. Silver emulsion (silver iodide content 8 mol%, particle size distribution S/=
A core/shell type emulsion was prepared in which the silver iodide was covered by a silver bromide shell having a thickness of 0.02 microns. The emulsion thus prepared was divided into 15 equal parts, each was chemically sensitized by adding sodium thiosulfate, chloroauric acid, and ammonium thiocyanate, and exemplified compounds -1, -2, or - 8 was added in a range of 0.06 to 0.24 mmol/molAgX to obtain samples No. 22 to No. 30 in Table 3. In addition, for comparison, the following comparative dyes C and D were used at 0.06
〜0.24mmol/molAgX
Samples No. 16 to No. 21 were obtained. After that, the same amounts of the same stabilizer, coating aid, hardener, cyan coupler, etc. as in Example 1 were added, and the samples were prepared by coating and drying on the same cellulose triacetate base support. After exposure, a color negative development process was performed. The density of each of the obtained dye images was measured through a red filter, and the red light sensitivity (Sr) and fog were determined. Sensitivity is "Fog+"
It was determined from the exposure amount required to give an optical density of 0.1''. Table 3 shows the relative humidity and fog measurement results immediately after sample preparation, and Table 4 shows the relative sensitivity and fog measurement results after being left at 60° C. and 70% RH for one day. It was found that the relative sensitivity of the product according to the present invention was excellent after moisture absorption. Furthermore, it was found that the fogging of the product according to the present invention was highly sensitive with little decrease after moisture absorption.

【table】

【table】

[Table] Example 3 Combination of comparative dye E and comparative dye F as sensitizing dyes, comparative dye E and exemplary compounds according to the present invention -
1 in combination, comparative dye E and exemplary compound-12 according to the present invention in combination, comparative dye C in combination with comparative dye D, comparative dye D in combination with exemplary compound-1 according to the present invention Samples No. 31 to No. 36 in Table 5 were prepared in the same manner as in Example 2, except that a combination of Comparative Dye D and Exemplary Compound-7 according to the present invention was used. The sample was processed in the same manner as in Example 1, and the relative sensitivity and fog were measured in the same manner as in Example 1, and color staining was measured in the conventional manner. Table 5 shows the relative sensitivity and fog measurement results immediately after sample preparation, and Table 6 shows the relative sensitivity and fog measurement results after being left at 60° C. and 70% RH for one day. Samples No. 32 and No. 3 using exemplified compounds according to the present invention
It was found that the relative sensitivity and fog of No. 33, No. 35, and No. 36 after being left at 60°C and 70% RH for one day showed little decrease in sensitivity even after moisture absorption.

【table】

【table】

〔Effect of the invention〕

As described above, according to the present invention, it is possible to obtain a silver halide photographic material that is highly sensitive, does not cause fogging, and exhibits little decrease in sensitivity over time.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide grains contained in at least one of the silver halide emulsion layers are A silver halide photographic material characterized by being color sensitized with a compound represented by the following general formula (). General formula () However, Y ₁ and Y ₂ represent a group of nonmetallic atoms necessary to form a 5- or 6-membered nitrogen-containing heterocycle. In addition, R ₇ , R ₈ , R ₉ are hydrogen atoms, halogen atoms,
It represents a lower alkyl group, an aryl group, a lower alkoxy group, or a heterocycle, and R ₇ and R ₉ may be connected to form a carbon ring. R ₆ represents an alkyl group, an aralkyl group, or an alkenyl group. X ^- represents an anion; i, j, k, l, and m each represent an integer of 0 or 1; Further, p of the N-position substituent is 0 or 1, and q
is an integer from 1 to 10, and n represents an integer from 1 to 10. R ₅ represents a hydrogen atom, a lower alkyl group or a fluorine atom.