JPS6024929B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material comprising a silver halide emulsion containing a specific pentamethine sensitizing dye. It is.

As is well known, when a sensitizing dye is added to a silver halide emulsion, the sensitivity wavelength range of the silver halide emulsion is expanded and the emulsion is optically sensitized. Many sensitizing dyes used for this purpose are known. For example, C. E. K. Mies and T
．． Day. “The Theory of the Photographic Process” (3rd edition), co-authored by James, 196 Yooh Macmillan,
Co. ,N. Examples include cyanine dyes, merocyanine dyes, xanthene dyes, etc. described on pages 198 to 228 of Y. When these sensitizing dyes are applied to an alkyl group, they must satisfy not only the expansion of the sensitive wavelength range but also the following requirements.
That is, (1) the spectral sensitization is appropriate;

■ Other photographic additives, such as stabilizers, anti-capri agents,
No adverse interaction with coating aids, color couplers, etc. (Sensitivity should not decrease during storage of the 3' silver halide emulsion, especially at high temperatures.

'4) Do not cause capri to occur. '5- The sensitizing dye should not diffuse into other photosensitive layers and cause color turbidity (color mixing) after development.

These matters are particularly important for red-sensitive silver halide emulsions for color photographic materials. For example, as sensitizing dyes that give red sensitivity, rhodacyanine dyes,
Pentamethine dyes are known, but silver halide emulsions spectrally sensitized with rhodacyanine dyes exhibit a significant decrease in sensitivity during storage at high temperatures; While the sensitized silver halide emulsion does not suffer from a decrease in sensitivity during storage under high temperature conditions, bentamethine dyes generally have poor sensitization efficiency, and therefore, it is necessary to use the dye to obtain the desired sensitivity. As a result, the content of silver halide must be increased, resulting in the formation of capri in the silver halide emulsion. Furthermore, pentamethine dyes are generally diffusive, and therefore, in multilayer color photographic materials, pentamethine dyes also spectral sensitize other light-sensitive layers, resulting in the oxidation of unnecessary color couplers and color developing agents after development. It has the fatal drawback of producing a warm color due to the coupling reaction with substances. An object of the present invention is to provide a silver halide photographic material that has high sensitivity, has little capri, and prevents warm colors.

Another object of the present invention is to provide a silver halide emulsion that exhibits less loss in sensitivity during storage, particularly under conditions of high temperature and high humidity.

Furthermore, another object of the present invention is to provide a red-sensitive silver halide emulsion with high spectral sensitivity and low capri.

Another object of the present invention is to provide a red-sensitive silver halide emulsion which is effective for color photographic materials and prevents warm colors.

Furthermore, another object of the present invention is to provide specific pentamethine dyes useful in red-sensitive silver halide emulsions.

The object of the present invention is to prepare a silver halide emulsion with the following general formula [
This is achieved by incorporating the sensitizing dye shown in 1).

In the formula, R,,R2 represents a sulfoalkyl group (e.g., 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfoptyl group, etc.), a carpoxyalkyl group (e.g., carboxymethyl group, 2-carboxyethyl group) , 3-carboxypropyl group, 4-carboxybutyl group, etc.), aralkyl group (e.g., benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, tolylethyl group, p-toxyphenylethyl group, etc.) It may have.

However, a group that is not substituted with a sulfo group or a carboxyl group), an aryloxyalkyl group (for example, a 2-phenoxy group, a 3-phenoxypropyl group, etc.) may have a substituent.However, a sulfo group or a group that is not substituted with a carboxyl group (a group that is not substituted with a group). However, one of R and R2 is a sulfoalkyl group or a carboxyalkyl group. R3 represents a hydrogen atom or an alkyl group (eg, methyl group, ethyl group, propyl group, etc.).

X represents an anion (eg, chloride ion, bromide ion, iodide ion, perchlorate ion, paratoluenesulfonate ion, ethylsulfate ion, etc.).

n represents 1 or 2, and when n is 1, an inner salt is formed. Next, typical examples of the sensitizing dye represented by the above general formula [1] will be listed, but the present invention is of course not limited to these.

[Dye-1] [Dye-2] [Dye-3] [Dye-4] [Dye-5] [Dye-6] [Dye-7] [Dye-8] [Dye-9] [Dye-10] [Dye-11] These sensitizing dyes can be easily synthesized based on known methods, for example, the methods described in British Patent No. 595784 and British Patent No. 77471y.

The sensitizing dye used in the present invention is about 1 x 10-5 mol to 2 x 10 mol per mol of silver halide in the silver halide emulsion.
-13 molar concentrations are advantageously used.

Furthermore, when adding such a sensitizing dye to a silver halide emulsion, a method may be used in which the sensitizing dye is directly dispersed into the silver halide emulsion, or a suitable solvent such as methyl alcohol, ethyl alcohol, or the like may be used. It is also possible to dissolve it in a mixed solvent such as and then add it to the silver halide emulsion.
Methods generally used in the field can be applied. It is convenient to add these sensitizing dyes to the silver halide emulsion before coating the support. The silver halide emulsion used in the present invention may be in the form of coarse or fine particles such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver chloroiodobromide, or the like. Mixed particulate silver halide crystals are dispersed in a binder such as gelatin, acid-treated gelatin, acylated gelatin, gelatin derivatives such as phthalated gelatin, albumin, gum arabic, polyvinyl alcohol, polyvinylpyrrolidone, etc. Such silver halide emulsions are produced by a single jet method or a double jet method.

These methods are described in ``PHOTOGRAPHI''.
"CCHEMISTRY" written by Piene ClaMes,
Fountain Press, Indon (1958)
Pages 327 to 330: “NUCLATION
IN SILVER BROMm EPRECIPI
TATION” C. R. Beny and P'C. S
Killman, J. Ph. Chem, No. 6, pp. 1138-1143 (1964): “THET
HEORYOFTHEPHOTOGRAPHIC PRO
CESS” 3rd edition, C. E. K. Mees and T. Day. James (1966), page 34. The silver halide emulsion used in the present invention is preferably an ordinary surface latent image type emulsion, and a silver halide emulsion obtained by the so-called "compersion method" as described in U.S. Pat. No. 3,622,318 is chemically A surface latent image type milk obtained by sensitization can also be used.

These silver halide emulsions can be prepared using commonly used chemical sensitization methods, such as U.S. Pat.
No. 9y, chemical sensitization method using natural active gelatin or sulfur compound described in US Pat. No. 241,068y, ruthenium as described in US Pat. No. 244,806,
Chemical sensitization method using noble metals such as rhodium, palladium, iridium and platinum, gold salts (potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate) described in U.S. Patent Nos. 2,399,083 and 2,642,361. , auric trichloride and 2-oresulfobenzothiazolemethochloride), stannic chloride as described in U.S. Pat. No. 2,487,85; Chemical sensitization method using reducing agents such as polyamines, or US Patent No. 162349y, US Patent No. 160259
Chemical sensitization can be carried out by the chemical sensitization method using destabilized selenium as described in each specification of No. 2. 7
- Photographic additives such as tetrazaintene, hardening agents, coating aids, and anti-irradiation dyes can be included. The silver halide photographic light-sensitive material according to the present invention can be used as a suitable support, for example, cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, glass, paper,
Papers coated with metals, polyolefins such as polyethylene, polypropylene, etc. can be used.

The silver halide photographic material of the present invention containing the sensitizing dye represented by the general formula [1] can impart suitable red sensitivity to a halide emulsion, and has excellent properties as shown in the Examples below. It has the following.

Therefore, it exhibits excellent properties as a sensitizing dye for high-sensitivity red-sensitive silver halide light-sensitive materials depending on the purpose of use, especially red-sensitive silver halide emulsions for color photographic light-sensitive materials. In addition, it can be applied not only to ordinary black-and-white photosensitive materials, but also to various photosensitive materials of plate making and copying type, and furthermore, to color photosensitive materials containing colored dyes based on the silver bleaching method. In particular, in multilayer color photographic materials, the emulsion containing the sensitizing dye represented by the general formula [1] is a Q naphthol emulsion, which is a red-sensitive silver halide emulsion that prevents the diffusion of the sensitizing dye applied to the layer. Or a phenolic cyan coupler is particularly suitable.

Typical examples of cyan couplers are shown below, but the present invention is of course not limited to these. Particularly suitable examples include cyan couplers represented by the following general formula [0].

(In the formula, R4, R5 and R6 are hydrogen atoms, halogen atoms, alkyl groups, aryl groups or alkoxy groups, R7
and R8 represents a hydrogen atom, an alkyl group or an alkoxy group, R9 represents a hydrogen atom or an alkyl group, and Y represents an atom or group to be separated upon coupling.

) For example, other representative examples of the above [C-4], [C-5], [C-6] and [C-7] include, etc. In addition to these oil-protected couplers, sulfonated Fissey type couplers containing a hydrophilic group such as a group in the structural formula can also be applied.

Furthermore, during the coupling reaction, a so-called "DIR coupler" capable of releasing a development inhibitor can be used. The green-sensitive silver halide emulsion is sensitized with a suitable sensitizing dye to a suitable wavelength, and the emulsion contains a suitable magenta coupler. The sound-sensitive silver halide emulsion may also be sensitized with a suitable sensitizing dye, and the emulsion contains a suitable yellow coupler. This color photographic light-sensitive material can be processed, for example, by the so-called "three-bath processing" described in US Pat. No. 3,582,322. Hereinafter, embodiments of the present invention will be described according to examples.

Example 1 A sonic silver chlorobromide emulsion containing a yellow coupler of the following structural formula [Y-1] (bromine 95 mol%, chlorine 5
Mol%) layer [21 Gelatin intermediate layer '3} Green-sensitive silver chlorobromide emulsion containing a magenta coupler of the following structural formula [M-1] (bromine 70 mol%, chlorine 30
mol%) layer {41 Gelatin intermediate layer {5- Red-sensitive silver chlorobromide emulsion containing the cyan coupler of [C-6] (bromine 60 mol%, chlorine 40 mol%)
'6) A gelatin protective layer was applied to produce a multilayer color photographic material.

Each color coupler was dissolved in tricresyl phosphate, and then the coupler solution was finely dispersed in a gelatin binder. The red-sensitive silver chlorobromide emulsion has Table 1
A sample was prepared containing the sensitizing dye shown below. This multilayer color photographic light-sensitive material sample was divided into three parts, one of which was exposed to light through a red filter (base .92 Wratten filter) immediately after sample preparation, and then color developed according to the following recipe to determine the relative sensitivity. and capri were measured.

The results are shown in Table 1. Processing process Temperature Time Color development 31.5℃ 3 minutes 30 seconds Bleach fixing
Wash with water for 1 minute and 30 seconds 〃'' Stability Dry for 1 minute The processing solution used is as follows.

Color developer penzyl alcohol 12.0 [
Sodium sulfite 2.7# Sodium hydroxide 0.6# Sodium carbonate
20.0 Potassium bromide
0.4 ta sodium chloride
1.0 Hydroxylamine sulfate 2
．． 5 Tatri Sodium polyphosphate 1.0 TaC
D-m* Add 4.0 tsp of water to make a total of 1 dm [CD 1 m*: 4
1 (N-ethyl-N-B-methanesulfonamidoethyl)amino-2-methylaniline] Bleach-fix solution Ethylenediaminetetraacetic acid iron (m) sodium salt 50% 70% ammonium thiosulfate aqueous solution 110 [Sodium sulfite 15 terethylenediaminetetraacetate iron 2] Sodium salt 5-taphosphate monoammonium salt
Add 7 tsp of water and reduce the total volume to 1. Stable sodium citrate 7
Takari alum ban 20 minutes Sodium carbonate 3 hours Add water
In addition, one of the other samples was stored for 7 hours at a temperature of 6030℃ and a relative humidity of 80% as a forced deterioration test, and then subjected to the same exposure and color development treatment as above, and then the sensitivity was measured. did.

The sensitivity was determined from the density value of -fog + 0.6'' using an optical densitometer through a red filter (M.92, Wratten filter). Note that the sensitivity display in Table 1 indicates the relative sensitivity when the red sensitivity of sample 1 immediately after sample preparation is set to "100". Additionally, another sample was used to measure the diffusivity of the applied sensitizing dye.

The sample was exposed to light through a red filter (No. 92, Wratten filter), and the diffusivity was measured based on the yellow sensitivity of the color image sample obtained by the same color development process as described above. Note that the diffusivity in Table 1 is obtained by measuring a yellow dye image using a blue filter (No. 94 Ratten Filter) of an optical densitometer, and the higher the value, the greater the diffusivity of the applied sensitizing dye. It shows. The above measurement results are shown in Table 1.

Table 1 Glue side pigment astringent evening dirt demand thin cloud (Nadamasu Yume Yume Hiroshi Tsuma U plan Sagisame Jitsudo (weaving) 1 Comparison Ax, 2 1
00 0.09 79 102
Comparison Bx2 2 76 0.
09 71 183 Comparison○×3
2 68 0.08
66 254 Dye-1
2 96 0.07 91
05 Dye-4 2
93 0.07 89 0(
In the table, the sensitivity display indicates the red sensitivity of sample 1 immediately after sample preparation.
The relative sensitivity is shown when it is set to 0.

)*, Comparison A (for comparison) *2 Comparison B (for comparison) *3 Aoi C (for comparison) As is clear from Table 1, comparison A (rhodacyanine dye) has a relatively high sensitizing effect. However, the degree of decrease over time is large, and Comparison B and Comparison C (Meso-position/methyl-substituted pentamethine dyes) have a small degree of decrease over time but have poor sensitization efficiency.

In addition, Comparatives A, B, and C had remarkable diffusivity, and therefore the color mixture of the obtained color images was remarkable. On the other hand,
Dye-1 and Dye-4 according to the present invention were extremely excellent, eliminating the drawbacks of the comparative dyes. Example 2 A red-sensitive emulsion was prepared by containing the sensitizing dyes shown in Table 2 in a silver chlorobromide emulsion (bromine 70 mol%, chlorine 30 mol%), and the cyan coupler [C-7] was added to this emulsion in dibutyl. A finely dispersed dispersion of a coupler solution dissolved in tephthalate in a gelatin solution was added, and this was coated on photographic base paper laminated on both sides with polyethylene, and then a gelatin protective layer was coated on top of this to prepare the sample. Created.

After dividing each sample into two, one was exposed and color developed in the same manner as in Example 1, and the red sensitivity and capri were measured.
After being forced to change in quality at 0% for 7 cycles, it was subjected to exposure and color development in the same manner as in Example 1, and used to measure red sensitivity and capri. The results are shown in Table 2. Note that the sensitivity display in the table indicates relative sensitivity when the red sensitivity of sample 10 immediately after sample preparation is set to 100. Table 2 10 mol/sample preparation Immediately after forced alteration loom dye entanglement rich solution Sensitivity (Pine Solo emulsion) Fog sensitivity Capri 6 Comparison B 2 80 0.09 87
0.097 Comparison B 8 138 0.
13 135 0.128 Comparison C
74 0.08 73 0.089 Comparison C
8 110 0.14 105 0.141
0 Dye-1 2 100 0.07 9
7 0-0711 dye-1 8 185 0
．． 10 1800.1012 Dye-2 2
101 0.07 98 0.0713 Dye-2
8 187 0.10 183 0.101
4 Dye-3 2 96 0-07 9
2 0-0715 dye-3 8 174
0.10 170 0.0916 dye-6 2
98 0.07 95 0.0717 Dye-6
8 174 0.10 171 0.10
18 dye-7 95 0.07 93
0.0719 Dye-7 8 180 0.
10175 0.10 As is clear from Table 2, the sensitizing dye according to the present invention has a higher sensitizing effect than the comparative sample, and
Capri occurrence and desensitization over time are significantly less.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material containing a sensitizing dye represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R
_2 represents a sulfoalkyl group, a carboxyalkyl group, an aralkyl group, or an aryloxyalkyl group (however, the aralkyl group and the aryloxyalkyl group exclude those substituted with a sulfo group or a carboxyl group). However, any one of R_1 and R_2 is a sulfoalkyl group or a carboxyalkyl group. R_3 represents a hydrogen atom or an alkyl group. X represents an anion. n
represents 1 or 2. ]