JPH0252251B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic light-sensitive material, and more particularly, the present invention relates to a silver halide photographic emulsion layer sensitized with a specific cyanine dye, which improves the change over time of a latent image formed after exposure without impairing sensitivity. The present invention also relates to a photographic material that has excellent color reproducibility when used in color applications. Silver halide photographic emulsions sensitized with dyes are used in black-and-white panchromatic photographic materials and color photographic materials. In particular, cyanine dyes are widely and commonly used as sensitizing dyes, and they increase the spectral sensitivity of photographic emulsions. is known to change. Silver halide photographic emulsions spectrally sensitized by the addition of dyes are particularly important in multilayer color photographic materials having emulsion layers having a multilayer structure. However, in silver halide photographic emulsions sensitized with specific cyanine dyes, the latent or sublatent images formed by imagewise exposure change over time, and in many cases,
The latent image or sub-latent image is strengthened over time. This is true, for example, for photographic science and engineering.
Science and Engineering), Vol. 13, No. 3 (1964), p. 134 onwards. In particular, according to research conducted by the present inventors, the more the cyanine dye has a substituted alkyl group having a carboxyl group or sulfo group as a substituent at the N-position, the more easily the latent image or sublatent image is strengthened over time. I understand. Such latent image intensification effect is undesirable for photographic materials. In other words, since photographic materials are often left for a long period of time after exposure before being developed, the length of time between image exposure and development affects the degree of latent image intensification, and the difference between images. In particular, in multilayer silver halide color photographic materials, different types of sensitizing dyes are used for each multisensitivity layer. Because different dyes behave differently in latent image intensification, the best color reproduction, which can only be obtained when the dye images in each individual layer are properly balanced, is not achieved. Therefore, it is important that the latent image or sublatent image of each layer after exposure does not change over time before development, or that even if it changes over time, it changes in a well-balanced manner. As a technique to prevent such latent image intensification, Japanese Patent Publication No. 51-9609 proposes a combination of a specific cyanine dye and a hardening agent that releases acid in the emulsion layer to lower the pH. A technique for preventing latent image intensification by balancing intensification and latent image fading has been disclosed. Further, JP-A-48-6725 discloses a technique for preventing latent image intensification during flash exposure by adding a rhodium compound and an iridium compound during emulsification of silver halide. In addition, Tokukai Akira
No. 54-134621 also discloses an antioxidant that is effective against latent image fluctuations. Also, Tokukai Akira
Japanese Patent No. 53-22409 discloses a technique for preventing changes in latent images over time by adding a water-soluble iron compound to a silver halide emulsion before chemical ripening and after chemical ripening. However, these conventional technologies
There are disadvantages such as having to select a sensitizing dye and an acid-releasing hardener for each color-sensitive layer, difficulty in obtaining a high-speed emulsion, problems with stability, and problems with normal exposure. It has various drawbacks such as low effectiveness and sluggishness. Therefore, the first object of the present invention is to impair the sensitivity of a silver halide photographic emulsion spectrally sensitized with a specific cyanine dye having a substituted alkyl group having a carboxyl group or a sulfo group as a substituent at the N-position. First, it is an object of the present invention to provide a silver halide photographic material in which the change over time of a latent image formed after exposure is improved. A second object of the present invention is to provide a multilayer silver halide color photographic material in which color reproducibility is improved by a long period of time between image exposure and development. The above object of the present invention is a cyanine dye represented by the following general formula [] (hereinafter referred to as the dye of the present invention).
and at least one compound represented by the following general formula [], [] or [] (hereinafter referred to as the compound of the present invention), and at least one compound represented by the following general formula [], [] or []. This can be achieved by a silver halide photographic material containing at least one type of antioxidant (hereinafter referred to as the antioxidant of the present invention). General formula [] In the above formula, Z ₁ and Z ₂ represent a group of atoms necessary to form a heterocycle. R ₁ and R ₂ each represent an alkyl group, a substituted alkyl group, or an allyl group having 1 to 5 carbon atoms. However, at least one of R ₁ and R ₂ is a substituted alkyl group having a carboxyl group or a sulfo group. L ₁ and L ₂ each represent a methine group or a substituted methine group. m ₁ represents 1, 2 or 3; X ₁ represents an acid anion. and,
n ₁ represents 1 or 2, and n ₁ is 1 when a petaine structure is adopted. General formula [] Z-SO ₂ S-M General formula [] General formula [] In each of the above formulas, N represents an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heterocyclic group. Y represents an atomic group necessary to form an aromatic ring or heterocycle having 6 to 18 carbon atoms.
M represents a metal atom or an organic cation. and n ₂
represents an integer from 2 to 10. General formula [] In the general formula [], R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group, an alkenyl group or an acyl group, and R ₄ represents a halogen atom, an alkyl group, an alkenyl group, a cyano group, a cycloalkyl group, - _{SO2R5 _}
or -COR ₅ , and R ₅ represents a hydrogen atom, an alkyl group, a hydroxy group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, or an amino group. General formula [] General formula [] In the general formulas [] and [], R ₆ and R ₇ represent a hydrogen atom or an alkyl group, and R ₈ and R ₉ represent a hydrogen atom or an alkyl group. However, R ₈ and R ₉
are never hydrogen atoms at the same time. First, the dye of the present invention will be explained in detail. In the above general formula [], Z ₁ and Z ₂ are heterocyclic nuclei commonly used in cyanine dyes, especially thiazole nucleus, thiazoline nucleus, benzothiazole nucleus, naphthothiazole nucleus, oxazole nucleus, oxazoline nucleus, benzoxazole nucleus, naphthoxazole Necessary to complete the nucleus, tetrazole nucleus, pyridine nucleus, quinoline nucleus, imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, or indolenine nucleus, etc. represents a group of atoms. These nuclei include lower alkyl groups such as methyl groups, halogen atoms, phenyl groups, hydroxyl groups, alkoxy groups having 1 to 4 carbon atoms, carboxyl groups, alkoxycarbonyl groups, alkylsulfamoyl groups, alkylcarbamoyl groups, and acetyl groups. , acetoxy group, cyano group, trichloromethyl group, trifluoromethyl group, nitro group, etc. L ₁ and L ₂ each represent a methine group or a substituted methine group. Examples of the substituted methine group include methine groups substituted with lower alkyl groups such as methyl group and ethyl group, phenyl group, substituted phenyl group, methoxy group, and ethoxy group. R ₁ and R ₂ are each an alkyl group having 1 to 5 carbon atoms, a substituted alkyl group having a hydroxy group; a substituted alkyl group having a carboxyl group; γ-sulfopropyl group, δ-sulfobutyl group, 2-(3- Substituted alkyl groups with a sulfo group such as sulfopropoxy)ethyl group, 2-[2-(3-sulfopropoxy)ethoxy]ethyl group, 2-hydroxy sulfopropyl group, and other commonly used N-substituents of cyanine dyes. represents a substituted alkyl group. However, at least one of R ₁ and R ₂ is a substituted alkyl group having a carboxyl group or a sulfo group.
m ₁ represents 1, 2 or 3; X ₁ represents an acid anion group commonly used in cyanine dyes, such as iodide ion, bromide ion, p-toluenesulfonate ion, and perchlorate ion. n ₁ is 1 or 2
, and n ₁ is 1 when it has a betaine structure. Next, specific examples of the dye of the present invention will be shown. [Example dye] The dye of the invention is preferably used in an amount of 1.times.10.sup. ^-6 to 1.times.10.sup. ^-3 mol per mol of silver halide, which can be varied depending on the type of emulsion and the properties of the dye of the invention. The dye of the present invention is dissolved in water, methanol, ethanol, pyridine, methyl cellosolve, acetone, etc. and added by a method commonly used for sensitizing dyes. Other methods such as Special Publication No. 44-23389, No. 44-27555
No. 44-22948, U.S. Patent No. 3485634
The methods described in the specifications of No., No. 3342605, No. 2912343, West German Patent Publication No. 1947935, etc. are used. The dye of the present invention may be added at the time of producing the silver halide emulsion, before chemical ripening, during chemical ripening, or after chemical ripening. Further, depending on the purpose, the dyes of the present invention may be used alone or in combination of two or more. Furthermore, sensitizing dyes other than the dyes of the present invention may be used in combination without impairing the effects of the present invention. The silver halide photographic emulsion used in the present invention is
It is produced by containing at least one compound (thiosulfonic acid compound) of the present invention represented by the general formula [], [] or []. These will be explained in detail below. In the general formula [], [] or [], the alkyl group, aryl group, heterocyclic group, aromatic ring and heterocycle represented by Z and Y may be substituted. Examples of substituents include lower alkyl groups such as methyl groups and ethyl groups, aryl groups such as phenyl groups, alkoxyl groups having 1 to 8 carbon atoms, halogen atoms such as chlorine, nitro groups, amino groups, carboxyl groups, etc. I can list them. Examples of the heterocycle represented by Z and Y include thiazole, benzthiazole, imidazole, benzimidazole, and oxazole rings. The metal atom represented by M is preferably an alkali metal atom such as a sodium ion or potassium ion, and the organic cation is preferably an ammonium ion or a guanidine group. Specific examples of the compounds of the present invention represented by the general formula [], [] or [] include the following. [Exemplary compounds] The compound of the present invention represented by the general formula [], [] or [] can be synthesized by a generally well-known method. For example, it can be synthesized by reacting a corresponding sulfonyl fluoride with sodium sulfide, or by reacting a corresponding sodium sulfinate with sulfur. The timing of addition of the compound of the present invention is (1) between the precipitation formation and physical ripening of silver halide grains, and (2) during the desalting process (usually when excess salt is removed from the emulsion with water). ), (3) It may be added at any time selected between chemical ripening and before coating, and at that time, one or more compounds of the present invention may be added in combination. The amount of the compound of the present invention to be added may be 0.001 to 3 g, particularly preferably 0.005 to 0.5 g, per mole of silver halide. Specific examples of the antioxidant of the present invention include the following compounds, but are not limited thereto. [Example antioxidant]

【formula】

【formula】

【formula】

【formula】

【formula】

[21] Sodium sulfite [22] Sodium bisulfite [23] Ascorbic acid

【formula】

【formula】

【formula】

【formula】

【formula】 [Dispersion (M-1)]

1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-
tert-amylphenoxyacetamide)-benzamide]-5-pyrazolone was used in an amount of 8 x 10 ^-2 mol per mol of silver halide, and this was added as a high-boiling organic solvent in an amount of 1 times the weight of the coupler. The mixture was mixed with cresyl phosphate, and ethyl acetate was added to the mixture and heated to 60°C to completely dissolve. Add this solution to a 10% aqueous solution of Alkanol B (alkylnaphthalene sulfonate manufactured by DuPont)
ml and 700 ml of a 10% gelatin aqueous solution and dispersed using a colloid mill. Next, three test strips were cut and collected from each sample, and one strip was subjected to light wedge exposure through a yellow filter and subjected to the following color development process to determine the sensitivity (same-day sensitivity). .
The other strip is KS-I based on JIS method.
Using a type sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.), light wedge exposure was applied through a yellow filter so that the green density was 1.5.
℃ and 10% relative humidity for 7 days. The other strip was left at -20°C for 7 days, exposed to the same light as the strip, and subjected to the following color development process at the same time as the strip to obtain a magenta color image, and the density was measured using an optical densitometer. .
The density difference between and is considered to be a change in the latent image. These results are shown in Table 1 below. In addition, the first
The sensitivity in the table is expressed as a relative value with the sensitivity of sample No. 1 as 100. [Processing process] (37.8℃) Processing time 1 Color development 3 minutes 15 seconds 2 Bleaching 6 minutes 30 seconds 3 Washing with water 3 minutes 15 seconds 4 Fixing 6 minutes 30 seconds 5 Washing with water 3 minutes 15 seconds 6 Stabilization 1 minute Dry for 30 seconds 7 [Color developer] 4-Amino-3-methyl-Nethyl-N-(β
-Hydroxyethyl)-aniline sulfate 4.8g Anhydrous sodium sulfite 0.14g Hydroxyamine 1/2 sulfate 1.98g Sulfuric acid 0.74g Anhydrous potassium carbonate 28.85g Anhydrous potassium bicarbonate 3.46g Anhydrous potassium sulfite 5.10g Potassium bromide 1.16g Sodium chloride 0.14g Nitrilotriacetic acid trisodium salt (monohydrate)
1.20g Potassium hydroxide 1.48g Add water to make 1. [Bleach solution] 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 adjust to 1 and use ammonia water to pH
Adjust to 6.0. [Fixer] 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] Formalin 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1.

[Comparative sensitizing dye]

Each of these emulsions contains 4-hydroxy-6-methyl-
After adding 20 c.c. each of a 1% aqueous solution of 1,3,3a,7-tetrazaindene, 1200 ml of the following dispersion (C-1) was added per mole of silver halide, and the mixture was further added as shown in Table 2 below. As shown above, 3 g of the antioxidant of the present invention/
1 kg of emulsion was added, saponin and 1,2-bisvinylsulfonylethane were added, and the mixture was coated on a cellulose triacetate support and dried to obtain each sample (No. 7 to 33). [Dispersion (C-1)] As a cyan coupler, 1-hydroxy-N-
240 g of {γ-(2,4-di-tert-amylphenoxypropyl)}-2-naphthamide was mixed with tricresyl phosphate, and ethyl acetate was added to the mixture and heated to 62°C to completely dissolve. dissolved in. Add this solution to a 10% aqueous solution of alkanol B
ml and 700 ml of a 10% gelatin aqueous solution and dispersed using a colloid mill. Next, as in Example 1, one strip was subjected to light wedge exposure through a yellow filter, and the same-day sensitivity was determined by carrying out the color development treatment shown in Example 1 for 2 minutes. One strip of the other
Using a KS-1 type sensitometer based on the JIS method, light wedge exposure was applied through a yellow filter so that the red density was 1.0, a forced deterioration test and color development were performed in the same manner as in Example 1, and cyan A color image was obtained. These results are shown in Table 2 below. In addition, the sensitivity in Table 2 is the sensitivity of sample No. 12.
Expressed as relative sensitivity with a value of 100.

[Table] As is clear from Table 2, a combination sample of the compound of the present invention, a pigment, and an antioxidant (sample
Nos. 17, 18, 20, 21, 26, 27, 29, and 30 are comparative samples that do not contain thiosulfonic acid compounds (Nos. 7 to 12) and comparative samples that do not contain antioxidants (Nos. 16, 19, 25 and 28), it can be seen that the same-day sensitivity is not impaired and the change over time of the latent image is greatly improved. Furthermore, it can be seen that when a cyanine dye other than the one according to the present invention is used, the change over time of the latent image is hardly improved even if the compound according to the present invention and an antioxidant are added. Example 3 The following layers were provided on a subbed triacetic acid support from the support side. 1st layer Antihalation layer containing black colloidal silver (dry film thickness 1μ) 2nd layer 1-hydroxy-N-{γ-(2,4-di-tert) as a cyan coupler per mol of silver halide
-amylphenoxy)-butyl}-2-naphthamide 6.8×10 ^-2 mol, 1 as colored coupler
-Hydroxy-N-{δ-(2,4-di-tert-
amylphenoxy)-butyl}-4-(2-ethoxycarbonylphenylazo)-2-naphthamide 1.7×10 ^-2 mol, 2-(1-phenyl-5-tetrazolylthio)- as a development inhibitor-releasing substance.
4-(2,4-di-tert-amylphenoxyacetamide)-1-intanone 4 x 10 ^-3 mol, 3 x 10 ^-4 dyes shown in Table 3 below as cyanine dyes per 1 kg of silver halide emulsion. A red-sensitive silver iodobromide emulsion layer containing a mol/methanol solution (the comparative emulsion described in Example 1 [ ] was used, and the compound-added emulsion of the present invention described in Example 2 [ ] was used. Dry film thickness 6μ) Third layer 1-(2,4,6-trichloro)phenyl-3 as magenta coupler per mole of silver halide
-{3-(2,4-di-tert-amylphenoxy)acetamide}benzamide-5-pyrazolone 5.8×10 ^-2 mol, 1 as a colored coupler
(2,4,6-trichlorophenyl)-3-[3
-octadecenylsarcinimide)-2-chloro]anilide-4-(γ-naphthylazo)-5-
1.7 x 10 ^-2 mol of pyrazolone and 7 x 2-(1-phenyl-5-tetrazolylthio)-4-(2,4-di-tert-amylphenoxyacetamide)-1-indanone as a development inhibitor-releasing substance.
A green-sensitive, ^low -sensitivity silver iodobromide emulsion layer (the emulsion ^of the present invention [] The emulsion was prepared in the same manner as the above emulsion [] except that the amount of silver iodide was changed to 8 mol %.
Comparative emulsion [] was prepared in the same manner as emulsion [] except that the amount of silver iodide was 8 mol %. Dry film thickness
35μ. ) Fourth layer The same compounds as the magenta coupler, colored coupler, and development inhibitor-releasing substance in the third layer were added at 1.1×10 ^-2 mol and 5 mol per mol of silver halide, respectively.
×10 ^-3 mol, 2 × 10 ^-2 mol green-sensitive silver iodobromide emulsion layer (comparative emulsion described in Example 1)
and the emulsion of the present invention [] was used. Dry film thickness
2.5μ) 5th layer Gelatin layer containing yellow colloidal silver and 2,5-di-tert-octylhydroquinone (dry film thickness
1μ) 6th layer Contains 350g of gelatin per mole of silver halide, and uses α-pivaloyl-α-(1-benzyl-2-phenyl-3,5-) as a yellow coupler.
dioxo-triazolidin-4-yl)-5'-
[α-(2,4-di-tert-amylphenoxy)
Butyramide]-2-chloroacetanilide 3×
10 ^-1 mol, 3 x 10 ^-4 mol of the dyes shown in Table 3 below as cyanine dyes per 1 kg of silver halide emulsion.
A blue-sensitive silver iodobromide emulsion layer containing a methanol solution and 1,2-bis(vinylsulfonyl)ethane as a hardening agent (the emulsion of the present invention [] is the same as that of Example except that the amount of silver iodide is 7 mol %) Emulsion 1 was prepared in the same manner as emulsion [].Comparative emulsion [] was prepared in the same manner as emulsion [] except that the amount of silver iodide was changed to 8 mol%.Dry film thickness 6μ) 7th layer As a matting agent Silica with an average particle size of 5μ,
An aqueous gelatin solution containing silica was applied at a rate of 0.02 g/m ² of silica (dry film thickness 0.5 μm). The antioxidants shown in Table 3 were added after the second ripening of the silver iodobromide emulsions in the second, third, fourth and sixth layers. Each sample (No. 34 to 37) obtained in this way has a Blue concentration of 2.0 and a Green concentration of 2.0.
After applying decomposition exposure through a light wedge so that the density was 1.5 and the red density was 1.0, a forced deterioration test (7 days) and color development were performed in the same manner as in Example 1, and a cyan image, magenta image and The density of each yellow image was measured using an optical densitometer (the measurement wavelength was 434 nm,
547nm, 651nm). The results are shown in Table 3. Note that the same-day sensitivity in Table 3 is expressed as a relative sensitivity, with the sensitivity of the magenta image of sample No. 36 being 100.

[Table] As is clear from Table 3, even in the multilayer system of color negative film, the combination sample of the compound of the present invention, dye, and antioxidant (Sample No.
It can be seen that Sample No. 37) is more stable than the comparative samples (Nos. 34 to 36), without impairing the same-day sensitivity and with extremely small changes in density due to changes in the latent image over time.

Claims (1)

[Claims] 1. At least one cyanine dye represented by the following general formula [], at least one compound represented by the following general formula [], [], or [], and the following general formula [], A silver halide photographic material containing at least one antioxidant represented by [] or []. General formula [] [In the formula, Z ₁ and Z ₂ represent the atomic group necessary to form a heterocycle, and R ₁ and R ₂ each have 1 carbon atom.]
-5 represents an alkyl group, substituted alkyl group or allyl group. However, at least one of R ₁ and R ₂ is a substituted alkyl group having a carboxyl group or a sulfo group. In addition, L ₁ and L ₂ each represent a methine group or a substituted methine group, m ₁ represents 1, 2 or 3, X ₁ represents an acid anion, n ₁ represents 1 or 2, and when it has a betaine structure is n ₁ is 1
It is. ] General formula [] Z−SO ₂ S−M General formula [] General formula [] [In the formula, Z represents an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heterocyclic group, and Y represents an aromatic ring or a heterocyclic group having 6 to 18 carbon atoms. It represents a necessary atomic group, M represents a metal atom or an organic cation, and _n2 represents an integer of 2 to 10. ] General formula [ ] In the general formula [], R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group, an alkenyl group or an acyl group, and R ₄ represents a halogen atom, an alkyl group, an alkenyl group, a cyano group, a cycloalkyl group, - _{SO2R5 _}
or -COR ₅ , and R ₅ represents a hydrogen atom, an alkyl group, a hydroxy group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, or an amino group. General formula [] General formula [] In the general formulas [] and [], R ₆ and R ₇ represent a hydrogen atom or an alkyl group, and R ₈ and R ₉ represent a hydrogen atom or an alkyl group. However, R ₈ and R ₉
are never hydrogen atoms at the same time.