JP2689195B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material.
For more details on dyes, sensitize with specific cyanine dyes
Silver halide photographic emulsion layer
The latent image formed after exposure is improved over time, and
-For photographic light-sensitive materials with excellent color reproducibility
You. [0002] BACKGROUND OF THE INVENTION Dye-sensitized silver halide photographic emulsions.
Black and white panchromatic photographic light-sensitive materials and color photographs
It is used as a sensitizing material, especially as a sensitizing dye.
Nin dyes are widely and commonly used, and the spectral sensitivity of photographic emulsions
It is known to change degrees. And by adding dye
The spectrally sensitized silver halide photographic emulsion is a multi-layered milk.
Especially in multi-layer color photographic light-sensitive materials having a developer layer
It is important. However, it was sensitized with a specific cyanine dye.
Silver halide photographic emulsion formed by imagewise exposure
The latent or sub-latent image changes over time, often with latent or
The sub-latent image is intensified over time. This means, for example,
Graphic Science End Engineering
(Photo graphic Science an
d Engineering, Vol. 13, No. 3, (19)
(64) 134 pages and later. Especially the inventor
According to researches such as, as a substituent at the N-position of cyanine dye
Having a substituted alkyl group having a carboxyl group or a sulfo group
The more the cyanine dye is, the more latent or sub-latent image is enhanced over time.
I found it easy. Such a latent image intensifying action is unique to a photographic light-sensitive material.
Is not desirable. That is, the photographic light-sensitive material is
It is often left unattended for a long time before image processing.
Therefore, the length of the period from the image exposure to the development process depends on the latent image compensation.
It affects the strength of the image and does not cause variations in the finish between images.
Undesired drawbacks such as
There are different types of silver halide color photographic light-sensitive materials for each color-sensitive layer.
Different sensitizing dyes are used.
If this happens, the behavior of latent image intensification also differs, so the dye image of each individual layer
The best color reproduction possible only when the
Because it is not achieved. Therefore, the latent image of each layer after exposure
Or the sub-latent image does not change with time before development, or
Even if it changes over time, it is important that it changes in a well-balanced manner.
is there. As a technique for preventing such latent image assisting force,
Japanese Patent Publication No. 51-9609 discloses a specific cyanine.
Hardeners that release acids in dyes and emulsion layers to lower pH
To combine latent image intensification and latent image fading.
Discloses a technique for preventing latent image intensification.
Further, in JP-A-48-6725, silver halide is disclosed.
Add rhodium and iridium compounds during emulsification
Discloses technology to prevent latent image intensification by flash exposure
Have been. Further, in Japanese Patent Laid-Open No. 54-134621.
Also discloses an antioxidant effective against latent image fluctuation.
ing. Further, in Japanese Patent Laid-Open No. 53-22409, water is added.
Soluble iron compound in silver halide emulsion before chemical ripening, chemical
Addition of latent image by adding during aging or after chemical aging
A technique for preventing a change over time is disclosed. [0006] However, these prior arts use the respective color-sensitive layers.
Sensitizing dye and acid-releasing hardener must be selected for each
There was a disadvantage that it was difficult to obtain a high-sensitivity emulsion
, Stability problems, or little effect on normal exposure
It has various drawbacks such as scratching. [0007] Therefore, the first object of the present invention.
Is a carboxyl group or a sulfo group as the N-position substituent.
Depending on the specific cyanine dye having a substituted alkyl group
The sensitivity of spectrally sensitized silver halide photographic emulsions
And the latent image formed after exposure was improved with time.
The object is to provide a silver halide photographic light-sensitive material. A second object of the present invention is to perform a development process after image exposure.
The color reproducibility has been
To provide a multi-layer type silver halide color photographic light-sensitive material.
And [0009] The above object of the present invention is as follows.
The cyanine dye represented by the general formula [I] (hereinafter referred to as the present invention
Called the dye. ) And at least one of the following general formula [I
A compound represented by I], [III] or [IV] (hereinafter
Hereinafter referred to as the compound of the present invention. ) At least one of
When added to the silver halide emulsion layer, one silver halide is used.
0.01 to 100 g per vine, hydrophilic colloid
Hydrophilic colloid when added to the non-photosensitive layer
Contains 0.01 to 50 g of ascorbic acid per gram
With a silver halide photographic light-sensitive material characterized by
Achieved. [0010] Embedded image In the above formula, Z₁ And Z_Two Forms a heterocycle
Represents the atomic group necessary for R₁ And R_Two Are carbon atoms
1-5 alkyl group, substituted alkyl group or allyl group
Represents Where R₁ And R_Two At least one of the
It is a substituted alkyl group having a xyl group or a sulfo group. L
₁ And L_Two Each represent a methine group or a substituted methine group. m
₁ Represents 1, 2 or 3. [0012] [Outside 2] Represents an acid anion. And n₁ Represents 1 or 2,
N for a betaine structure₁ Is 1. [0013] Embedded imageIn each of the above formulas, Z is an atom having 1 to 18 carbon atoms.
Rukyl group, aryl group having 6 to 18 carbon atoms or hetero
Represents a ring group. Y is an aromatic ring having 6 to 18 carbon atoms or het
B represents an atomic group necessary for forming a ring. M is a metal atom,
Represents an organic cation. And n_Two Represents an integer from 2 to 10
You. First, the dye of the present invention will be described in detail. Up
Z in the general formula [I]₁ And Z_Two Is usually a cyanine dye
Heterocycle nuclei used, especially thiazole nuclei, thiazolines
Nucleus, benzothiazole nucleus, naphthothiazole nucleus, oxa
Zole nucleus, oxazoline nucleus, benzoxazole nucleus, na
Futoxazole nucleus, tetrazole nucleus, pyridine nucleus, key
Norrin nucleus, imidazoline nucleus, imidazole nucleus, benzoi
Midazole nucleus, naphthoimidazole nucleus, selenazoline
Nucleus, selenazole nucleus, benzoselenazole nucleus, naphthose
Required to complete lenazole nucleus or indolenine nucleus
Atomic group. These nuclei consist of lower groups such as methyl groups.
Alkyl group, halogen atom, phenyl group, hydroxyl
Group, alkoxy group having 1 to 4 carbon atoms, carboxyl
Group, alkoxycarbonyl group, alkylsulfamoyl
Group, alkylcarbamoyl group, acetyl group, acetoxy
Group, cyano group, trichloromethyl group, trifluoromethyl
It may be substituted with a benzyl group, a nitro group or the like. L₁ And L_Two Is a methine group or a substituted methine group, respectively.
Represents a group. Substituted methine groups are methyl and ethyl groups
Lower alkyl group, phenyl group, substituted phenyl group,
A methine group substituted with a toxy group, an ethoxy group, etc.
No. R₁ And R_Two Each has 1 to 5 carbon atoms
Alkyl group, substituted alkyl group having hydroxy group;
Substituted alkyl group having a voxyl group; γ-sulfopropyl
Group, δ-sulfobutyl group, 2- (3-sulfopropoxy group
Si) ethyl group, 2- [2- (3-sulfopropoxy) eth
Toxy] ethyl group, 2-hydroxysulfopropyl group
Substituted alkyl groups with sulfo groups such as
Substituted alkyl group used for N-substituent of nin dye
Represents Where R₁ And R_Two At least one of the
It is a substituted alkyl group having a xyl group or a sulfo group. m
₁ Represents 1, 2 or 3. [0018] [Outside 3] Is iodine ion, bromine ion, p-toluenesulfonic acid
It is usually used for cyanine dyes such as on and perchlorate ions.
Represents an acid anion group. n₁ Represents 1 or 2 and is solid
N when taking in structure₁ Is 1. Next, specific examples of the dye of the present invention are shown. [0020] Embedded image[0021] Embedded image[0022] Embedded image[0023] Embedded image[0024] Embedded image[0025] Embedded image[0026] Embedded image[0027] Embedded image[0028] Embedded image[0029] Embedded image[0030] Embedded imageThe dye of the present invention is preferably a silver halide.
1 x 10 per mole^-6~ 1 × 10^-3Mole used, emulsion
Can be varied depending on the type and properties of the dye of the present invention.
it can. The dye of the present invention is not usually used for sensitizing dyes.
Depending on the method used, for example, water, methanol, ethanol
Solvent, pyridine, methyl cellosolve, acetone, etc.
It is added as a solution. Other methods, for example, Japanese Patent Publication No. 44-2
No. 3389, No. 44-27555, No. 44-2294
No. 8, US Pat. Nos. 3,485,634 and
Nos. 3,342,605 and 2,912,343
Specification and West German Patent Publication No. 1,947,935
The method described in, etc. is used. The addition timing of the dye of the present invention is silver halide milk.
During agent production, before chemical aging, during chemical aging, or after chemical aging
Is fine. In addition, the dye of the present invention may be used alone or according to the purpose.
You may use together 2 or more types. Further effects of the present invention
In combination with a sensitizing dye other than the dye of the present invention within a range that does not impair
May be. Silver halide photographic emulsion used in the present invention
Is represented by the above general formula [II], [III] or [IV].
A small amount of the compound of the present invention (thiosulfonic acid compound)
It is manufactured by containing at least one. Hereinafter, these will be described in detail. one
In the general formula [II], [III] or [IV], Z and
And an alkyl group represented by Y, an aryl group, a heterocyclic group,
The aromatic ring and the hetero ring may be substituted. Substituent and
Is, for example, a lower alkyl such as a methyl group or an ethyl group.
Groups, aryl groups such as phenyl groups, and C1-C8 aryl groups.
Rukoxyl group, halogen atom such as chlorine, nitro group, amine
And a carboxyl group. The heterocycle represented by Z and Y is
Azole, benzthiazole, imidazole, benzii
Examples thereof include imidazole and oxazole rings. As the metal atom represented by M, Natriu
Alkali metal atoms such as mu ions and potassium ions
As organic cations, ammonium ion, guanidinium
Groups are preferred. General formula [II], [III] or [IV]
Specific examples of the compound of the present invention represented by
Can be mentioned. [0038] Embedded image General formula [II], [III] or [IV]
The compound of the present invention represented by
Can be synthesized. For example, the corresponding sulfonyl
React fluoride with sodium sulfide, or
Synthesized by a method of reacting sodium inoate with sulfur
be able to. The timing of addition of the compound of the present invention is (1) halo
(2) between the time of precipitation formation of silver genide grains and the time of physical ripening.
During the desalting process (usually water removes excess salt from the emulsion)
I do. ), (3) selected between during chemical aging and before application
The compound of the present invention can be added at any time.
One or more substances may be used in combination and added. The amount of the compound of the present invention added is silver halide.
The amount may be 0.001 to 3 g per mol, and particularly 0.005 to
0.5 g is preferred. The ascorbic acid used in the present invention is originally
Direct addition to the silver halide emulsion layer of the photographic light-sensitive material
Most preferably, the intermediate layer is added.
Protective layer, yellow filter layer, anti-halation layer, etc.
Containing the dyes and compounds of the invention on a support
The silver halide emulsion layer (hereinafter, referred to as the photosensitive emulsion of the present invention)
It is called a drug layer. ) Side hydrophilic colloid as a binder
It may be added to the non-photosensitive layer. Further, with the photosensitive emulsion layer of the present invention
It is also effective if added to both of the above non-photosensitive layers. Of the present invention
Ascorbic acid is added in the photosensitive emulsion layer of the present invention.
When added to, it may be any time until the coating process,
The period from chemical aging to coating is more preferable,
More preferably, it may be added after the completion of chemical ripening. Also, non-photosensitive
It may be added to the layer and diffused during coating. The ascorbic acid of the present invention comprises water or a phase that is compatible with water.
Soluble lower alcohols, esters or ketones
Add it after dissolving it in a solvent or a mixed solvent of these.
No. Alternatively, it may be dispersed in a solvent having a high boiling point and then added. Addition
The amount is in the range of 0.01 to 100 g per mol of silver halide.
In particular, the range of 0.05 to 50 g is particularly preferable, but the addition amount
May be appropriately selected depending on the type of silver halide.
When incorporated in the non-photosensitive layer, 1 g of hydrophilic colloid
In the range of 0.01 to 50 g, more preferably 0.
Including the ascorbic acid of the present invention in the range of 05 to 10 g
Good results can be obtained by applying an aqueous solution of hydrophilic colloid.
Fruit can be obtained. Used in the emulsion layer of the photographic light-sensitive material according to the present invention
The silver halide used is generally halogenated in a hydrophilic colloid.
Silver halide grains dispersed as silver halide.
Is silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, chloroiodide
There are silver bromides, etc., and these silver halides are ammonia.
Law, Neutral Method, Acid Method, British Patent No. 635,841
No. 3,622,318.
Various methods such as so-called conversion method and simultaneous mixing method
Made by law. Included Dyes and Compounds of the Invention
Noble metal sensitizers, sulfur sensitizers,
Advantageous application of chemical sensitization using sensitizers and reduction sensitizers
can do. This photographic emulsion also contains a light-sensitive material manufacturer.
However, during storage or during processing, sensitivity may decrease and fog may occur.
Various compounds can be added to prevent. That
Examples of such compounds include 4-hydroxy-6-methyl
-1,3,3a, 7-tetrazaindene, 3-methyl ester
Nzothiazole, 1-phenyl-5-mercaptotetra
Many heterocyclic compounds including sol, mercury-containing compounds,
Very many known compounds such as mercapto compounds and metal salts
Compounds. When the present invention is applied to a color photographic light-sensitive material
In the case of
It is preferable to use a silver halide emulsion containing
Therefore, each of these layers should have a coupler as described below.
Can be used. As the yellow coupler, there are known ring-opening compounds.
Tomethylene compounds can be used. For example in general
Widely used benzoylacetanilide type yellow
-Coupler, pivaloyl acetanilide type yellow cap
Can be used, and the carbon source at the coupling position can be used.
Substituents that can be removed during the coupling reaction
2-equivalent yellow coupler substituted with
It has been. Examples of these are US Pat. No. 2,875,0
No. 57, No. 3,265,506, No. 3,664.
841, No. 3,408, 194, No. 3,44
No. 7,928, No. 3,277,155, No. 3,4
Each specification of No. 15,652, Japanese Patent Publication No. 49-13576
Nos. 48-29432 and 48-66834.
No. 49-10736, No. 49-122335,
50-28834 and 50-132926
Information. As the magenta coupler, pyrazolone
Series, pyrazolotriazole series, pyrazolinobenzimida
Examples thereof include sol-based and indazolone-based compounds.
As a pyrazolone magenta coupler, US Patent No.
No. 2,600,788, No. 3,062,653, No.
No. 3,127,269, No. 3,311,476,
No. 3,419,391, No. 3,519,429
No. 3,558,318, No. 3,684,51
4 and 3,888,680, JP-A-4
9-29639, 49-111631, 49-
No. 129538, No. 50-13041, JP-A-51-
No. 105820, Japanese Patent Application Nos. 50-134470 and 50
-156327 compounds; pyrazolot
As a reazole-based magenta coupler, British patent No.
1,247,493, Belgian Patent 792,525
Compounds described in 1 .; Pyrazolino benzimidazo
US Pat. No. 3,061, as a red magenta coupler,
No. 432, West German Patent No. 2,156,111, Japanese Patent Publication No. 4
Compounds described in 6-60479;
Belgian Patent No. 76 as a zolone magenta coupler
Compounds described in 9,116 are advantageous for the present invention
Can be used. As the cyan coupler, phenol or
Examples include naphthol derivatives. Even if those examples
For example, U.S. Pat. Nos. 2,423,730 and 2,47.
No. 4,293, No. 2,801,171, No. 2,8
No. 95,826, No. 3,476,563, No. 3,
No. 737,316, No. 3,758,308, No. 3
3,839,044, JP-A-47-3742, and JP-A-47-3742.
0-10135, 50-25228, 50-1
No. 12038, No. 50-117422, No. 50-13
No. 0441 and the like. In addition to the above couplers, colored magenta
Also, tap couplers and colored cyan couplers can be used to advantage.
Can be. In the present invention, the silver halide emulsion layer is
Any DIR compound may be included. Further, the present invention
In the silver halide emulsion layer, dye anti-fading agent, stay
It may contain any photographic additive such as
No. Hardening treatment of the silver halide emulsion of the present invention is usually performed.
It may be performed according to the law. As a hardener used
Conventional photographic hardeners such as formaldehyde and green
Aldehydes such as oxal and glutaraldehyde
Compound and their acetal or sodium bisulfite addition
Derivative compound, such as methane sulfonate
Compounds; mucochloric acid or mucohalogen acid compounds
Compounds; epoxy compounds; aziridine compounds; active halo
Gen compounds; Maleimide compounds; Active vinyl
-Based compounds; carbodiimide-based compounds; isoxazole
Compounds; N-methylol compounds; isocyanate compounds
Compounds: Inorganic hard films such as chrome alum and zirconium sulfate
Agents can be given. The silver halide emulsion of the present invention contains a surfactant.
You may add individually or in mixture. Also, sliding friction
To reduce scratches and prevent scratches on photographic materials
Lubricants can be used on the back of the body, the top layer of the emulsion layer, etc.
Wear. The silver halide photographic light-sensitive material according to the present invention is
Besides silver halide emulsion layer, protective layer, intermediate layer, filter
Layer, antihalation layer, back layer, etc.
Can be opened. Silver halide photographic light-sensitive material according to the present invention
In its constituent layers (for example, protective layer, intermediate layer, emulsion layer,
UV layer) may be contained in the coating layer). Especially
Tinubin PS manufactured by Ciba Geigy Co., 320 and 32
6, 327, 328, etc. can be used individually or in combination.
Is preferred. The support used in the present invention is a halogen.
Films and papers usually used in silver halide photographic materials
Etc., which generally strengthen the adhesion with the photographic emulsion layer.
In order to do this, subbing is applied. The cost used for undercoating
Vinyl chloride or vinylidene chloride as a substantive agent
Copolymers of vinyl alcohol and copolymers of vinyl alcohol esters
Products, copolymers containing unsaturated carboxylic acids, butadiene, etc.
Diene copolymers, acetal copolymers, anhydrous
A copolymer of an unsaturated carboxylic acid anhydride such as maleic acid,
Especially vinyl alcohol ester such as vinyl acetate, if
Copolymer with styrene or its water, alkali,
Ring-opened products with rucols or amines, and
Celluloses such as trocellulose and diacetyl cellulose
Derivatives, compounds containing epoxy groups, gelatin or zera
Examples include tin modified products and polyolefin copolymers. In the case of actually undercoating the support,
The subbing agents can be used alone or in combination. or
These undercoating processes form a single-layer or multiple-layer undercoating layer.
It may be squeezed, or of course, the lower layer of the lower layer and the lower layer of the lower layer are mixed together.
The layer to be used may have a multilayer structure in which an intermediate layer is provided. Support other than the above-mentioned subbing by the subbing agent
Corona discharge, glow discharge, other electron impacts on the body surface,
Flame treatment, UV irradiation, oxidation treatment, saponification treatment, roughening
And the like, and then contact the support with the photographic layers such as the emulsion layer.
You can wear it. These treatments can be used alone or in combination.
Can be used as a
Sufficient undercoating is performed by using it together with the used processing.
You can also. The silver halide emulsion layer of the present invention and other
The coating method of the photographic constituent layers of the silver halide photographic light-sensitive material is
For example, dip coating, double roll coating
Gu, air knife coating, extrusion co
Choose from coating and curtain coating
Can be. The photographic light-sensitive material of the present invention is generally black and white.
, X-ray, printing, micro, electron beam recording,
For infrared recording, color recording, etc.
Is also good. Next, the present invention will be described in detail with reference to Examples.
However, the embodiment of the present invention is limited thereby.
is not. [0062] 【Example】 Example 1 Contains gelatin, potassium iodide and a small amount of potassium bromide
By the simultaneous mixing method while maintaining at 50 ° C in an aqueous solution
Aqueous potassium bromide and ammoniacal silver nitrate
After the completion of the addition, perform physical aging at 50 ° C for 10 minutes.
Acetic acid was added to adjust the pH to 6.0, and 5 mol%
A silver iodobromide emulsion containing silver iodide was prepared. The resulting emulsion flat
The average particle size was 0.8μ. This emulsion is desalted by the usual method
And remove unnecessary salts to adjust pH and pAg to the specified values.
It was adjusted. This is designated as emulsion [I]. Of this emulsion [I]
In the adjustment, the present invention as shown in Table 1 below during physical ripening
Prepared by adding the compound (Exemplified compound [a])
Was. This is designated as emulsion [II]. Also physical ripening end
After the completion of the desalting process, the compound of the present invention (exemplified compound
It was prepared by adding [a]). This is an emulsion [II
I]. Gold sensitization by heating each of these emulsions to 60 ° C
And chemical ripening were carried out by the sulfur sensitization method. Each emulsion thus obtained is divided into two
However, the dye of the present invention (exemplified compound [D-
12]) 3 × 10^-FourAdded as a molar methanol solution
Was. 4-hydroxy-6-methyl-1,
20% of 1% aqueous solution of 3,3a, 7-tetrazaindene
After adding c each, the following dispersion (M-1) was added to 1200 mm
1 liter of the ascorbic acid of the present invention
Add as shown in the table to add saponin and 1,2-bisbi
Add nylsulfonylethane and add cellulose triacetate.
Each sample (No. 1 to 6) is coated on a substrate and dried.
I got [Dispersion (M-1)] Magenta coupler
Then 1- (2,4,6-trichlorophenyl) -3-
[3- (2,4-di-tert-amylphenoxyacetate
Toamide) -benzamide] -5-pyrazolone
8 × 10 to 1 mol of silver halide^-2Use moles,
As the boiling point organic solvent, the amount of tricle which is 1 times the weight of the coupler is used.
Mix with di-phosphate and add acetic acid to these mixtures.
Ethyl was added and heated to 60 ° C. to completely dissolve it. This solution
Alkanol B (Alkylnaphthalene manufactured by DuPont)
50 ml of a 10% aqueous solution of sulfonate and
Mix with 700 ml of 10% gelatin aqueous solution and
Dispersed using a Lloyd mill. Next, from each sample, three test strips are provided.
Cut and collect, and one strip is yellow
Optical wedge exposure is performed via a laser, and the following color development processing is performed.
We performed and sought the sensitivity (same day sensitivity). Another strip
Is a KS-I type sensitometer based on the JIS method.
-(Konica Corporation) as the Green concentration
Light wedge dew through the yellow filter to have 1.5
7 days at 50 ° C and 10% relative humidity after applying light
I left it. The other strip is -20 ° C for 7 days
After leaving, give the same exposure as the strip and strip.
Color development process at the same time to obtain a magenta color image
The concentration was measured using a scientific densitometer. And the density difference between
It is considered to be a change in latent image. The results are shown in Table 1 below. In addition,
The sensitivity in Table 1 is the sample No. The sensitivity of 1 is 100
It was expressed as a relative value. [0068] [Processing step] (37.8 ° C) Processing time 1. Color development 3 minutes 15 seconds 2. Bleach 6 minutes 30 seconds 3. Rinse 3 minutes 15 seconds 4. Fixation 6 minutes 30 seconds 5. Rinse 3 minutes 15 seconds 6. Stabilization 1 minute 30 seconds 7. Dry [0069] [Color developing solution]   4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -anili Sulphate 4.8g   Anhydrous sodium sulfite 0.14g   Hydroxyamine 1/2 sulfate 1.98g   Sulfuric acid 0.74 g   Anhydrous potassium carbonate 28.85g   Anhydrous potassium hydrogen carbonate 3.46g   Anhydrous potassium sulfite 5.10g   1.16 g of potassium bromide   Sodium chloride 0.14g   Nitrilotriacetic acid ・ 3 sodium salt (monohydrate) 1.20 g   1.48 g of potassium hydroxide   Add water to make 1 liter. [0070] [Bleaching solution]   Ethylenediaminetetraacetic acid iron ammonium salt 100.0g   Ethylenediaminetetraacetic acid diammonium salt 10.0 g   Ammonium bromide 150.0 g   Glacial acetic acid 10.0 ml   Water is added to make 1 liter, and the pH is adjusted to 6.0 with aqueous ammonia. [0071] [Fixer]   Ammonium thiosulfate 175.0 g   Anhydrous sodium sulfite 8.6g   Sodium metasulfite 2.3g   Water is added to make 1 liter, and the pH is adjusted to 6.0 with acetic acid. [0072] [Stabilizing liquid]   Formalin 1.5 ml   Conidax (Konica Corporation) 7.5 ml   Add water to make 1 liter. [0073] [Table 1] As can be seen from Table 1, according to the invention
Cyanine dye, thiosulfonic acid compound, and ascorbine
Same-day sensitivity for combination samples with acid (No. 4 and 6)
And the change over time of the latent image is reduced.
You can see that it is in a state. On the other hand, ascorbic acid
Comparative sample (No. 2) using only thiosulfonic acid
Comparative samples (No. 3 and 5) using salt alone are comparative samples.
The change in latent image over time is slightly smaller than that of the sample (No. 1)
However, the samples of the present invention (Nos. 4 and 6)
It turns out that it is far inferior to. Embodiment 2 5 mol% iodide obtained by the method described in Example 1
A silver iodobromide emulsion containing silver is heated to 60 ° C. to perform gold sensitization and
Chemical ripening was performed by the sulfur sensitization method. At this time, the
The compounds (exemplified compounds [c] and [f]) were added. This
The compound [c] -added emulsion of is the emulsion [IV],
Emulsion added with compound [f] was designated as emulsion [V], and each emulsion was divided into
For each 1 kg of emulsion, the dye of the present invention and the following comparison
3x10 sensitizing dye^-FourAdded as a molar methanol solution
Was. [0076] Embedded image To each of these emulsions was added 4-hydroxy-6-methyl ester.
1% aqueous solution of le-1,3,3a, 7-tetrazaindene
After adding 20 cc each, the following dispersion (C-1) was halo.
Add 1200 ml per mol of silver genide, then
As shown in Table 2, 3 g of ascorbic acid of the present invention
/ Add 1 kg of emulsion and add saponin and 1,2-bisbi
Add nylsulfonylethane and add cellulose triacetate.
Each sample (No. 7 to 3)
3) was obtained. [Dispersion (C-1)] as a cyan coupler
, 1-hydroxy-N- {γ- (2,4-di-ter
t-amylphenoxypropyl)}-2-naphthamide
240 g was mixed with tricresyl phosphate and
Add ethyl acetate to these mixtures and warm to 62 ° C to complete
Was dissolved. This solution is a 10% aqueous solution of alkanol B
150 ml and gelatin 10% aqueous solution 700
Mix with milliliter and disperse using colloid mill
Was. Then, as in the first embodiment, one strip is formed.
Performs optical wedge exposure through a yellow filter, and
Perform the color development process shown in 1 for 2 minutes and obtain the sensitivity on the same day.
Was. The other one is KS based on JIS method.
1. Using an I-type sensitometer as Red concentration, 1.
Optical wedge exposure through a yellow filter to have 0
Then, the same forced deterioration test and color development as in Example 1 were performed.
I got a cyan image. These results are shown in Table 2 below.
did. The sensitivities in Table 2 are those of Sample No. 12 feelings
It was expressed as a relative sensitivity with a degree of 100. [0080] [Table 2] As is clear from Table 2, the compounds of the present invention
Sample of a combination of a dye and a dye and an antioxidant (Sample N
o. 14,16,20,22) is a thiosulfone oxidation compound.
Comparative samples (No. 7-10) and ascorbi containing no material
Comparative samples containing no acid (Nos. 13, 15, 19 and
And 21), the sensitivity on the same day is not impaired and the latent image changes with time.
It can be seen that the conversion is greatly improved. In addition,
When an anine dye is used, the compound of the present invention and Asco
Addition of rubic acid almost improved the latent image change over time.
I understand that it does not. Example 3 Subsequent layers from the support side on the triacetic acid support that has been subjected to undercoating
Provided. First layer Antihalation layer containing black colloidal silver (dry film thickness 1
μ) Second layer 1-Hydride as a cyan coupler per mol of silver halide
Roxy-N- {γ- (2,4-di-tert-amylph
Enoxy) -butyl} -2-naphthamide 6.8 × 10
^-21-Hydroxy-N-as a molar coupler
{Δ- (2,4-di-tert-amylphenoxy)-
Butyl} -4- (2-ethoxycarbonylphenyl)
Z) -2-naphthamide 1.7 × 10^-2Mole, development suppression
2- (1-phenyl-5-tetrazo as an agent-releasing substance
Lilthio) -4- (2,4-di-tert-amylfe
Noxyacetamide) -1-indanone 4 × 10^-3Mo
As a cyanine dye per kg of silver halide emulsion
The dyes shown in Table 3 were added at 3 × 10^-FourMol / methanol solution
A red-sensitive silver iodobromide emulsion layer containing (comparison described in Example 1
Emulsion [I] is used and the invention is described in Example 2.
A compound addition emulsion [IV] was used. Dry film thickness 6μ) Third layer As a magenta coupler per mol of silver halide 1-
(2,4,6-Trichloro) phenyl-3- {3-
(2,4-di-tert-amylphenoxy) acetoa
Mido} benzamide-5-pyrazolone 5.8 × 10^-2Mo
1- (2,4,6-tric as colored coupler
Lorphenyl) -3- [3-octadecenyl sarcin
Imido) -3-chloro] anilide-4- (γ-naphthyl)
Azo) -5-pyrazolone 1.7 × 10^-2Mole and development
2- (1-phenyl-5-teto as an inhibitor-releasing substance
Razolylthio) -4- (2,4-di-tert-amyl
Phenoxyacetamide) -1-indanone 7 × 10^-3
As a cyanine dye per mol of silver halide emulsion
3 × 10 dyes shown in Table 3^-FourMol / methanol solution
Green-sensitive low-sensitivity silver iodobromide emulsion layer containing (emulsion of the present invention [VI
I] is the above emulsion [I] except that the amount of silver iodide is 8 mol%.
V]. Comparative emulsion [VI] is silver iodide
Prepared in the same manner as Emulsion [I] except that the amount was 8 mol%.
did. Dry film thickness 35μ. ) Fourth layer Third layer magenta coupler, colored coupler and current
1 mol of silver halide containing the same compound as the image-suppressing agent release type substance
1.1 x 10 each^-2Mole, 5 × 10^-3Moles, 2
× 10^-2Green-sensitive high-sensitivity silver iodobromide emulsion layer containing moles (implemented
Comparative emulsion [I] described in Example 1 and emulsion of the present invention [I]
V] was used. Dry film thickness 2.5μ) Fifth layer Yellow colloidal silver and 2,5-di-tert-octyl
Gelatin layer containing hydroquinone (dry film thickness 1μ) Sixth layer Contains 350 g of gelatin per mol of silver halide,
As a yellow coupler α-pivaloyl-α- (1-
Benzyl-2-phenyl-3,5-dioxo-triazo
Lysin-4-yl) -5 ′-[α- (2,4-di-te
rt-Amylphenoxy) butyramide] -2-chloro
Acetanilide 3 × 10^-1Mol, silver halide emulsion 1k
Dyes shown in Table 3 below as cyanine dyes per g 3 ×
10^-Four1,2 as mol / methanol solution and hardener
-Blue-sensitive iodine containing bis (vinylsulfonyl) ethane
Silver bromide emulsion layer (emulsion [IX] of the present invention has a silver iodide content of 7 mol.
In the same manner as in Emulsion [IV] of Example 1 except that
Created. The comparative emulsion [VIII] has a silver iodide content of 8 mol%.
Was prepared in the same manner as the emulsion [I]. Dry film
Thickness 6μ) Seventh layer Zera containing silica having an average particle size of 5μ as a matting agent
Chin aqueous solution, silica 0.02g / m^Two Applied at the ratio of
(Dry film thickness 0.5 μ). The second layer, the third layer, the fourth layer and the sixth layer
As shown in Table 3 after the second ripening of the silver iodobromide emulsion of
Ascorbic acid was added. Each obtained in this way
1. Samples (No. 25 to 28) were used as Blue concentration and 2.
0, Green concentration is 1.5, Red concentration is
After giving a resolution exposure through the optical wedge so that it has 1.0,
Forced deterioration test (7 days) and color development process similar to Example 1
Processing is performed and the cyan image and magenta image are processed for each sample.
Each density of yellow and yellow images is measured by an optical densitometer
(Measurement wavelengths are 434 nm, 547 nm, 6 respectively.
51 nm). Table 3 shows the results. In addition, in Table 3
The same day sensitivity in Sample No. Feeling of 27 magenta images
It was expressed as a relative sensitivity with a degree of 100. [0091] [Table 3]As is apparent from Table 3, the color negative
The compounds and dyes of the present invention also in the multilayer system of film.
And a combination sample with ascorbic acid (Sample No. 2
8) is on the same day as the comparative sample (No. 25-27)
The density change due to the change of the latent image with time is extremely high without impairing the sensitivity.
It is very small and stable.

Claims (1)

(57) [Claims] At least one cyanine dye represented by the following general formula [I] and the following general formula [II], [III] or [I]
V] and at least one compound represented by the formula V] and 0.01 to 100 g per mol of silver halide when added to the silver halide emulsion layer). Is a silver halide photographic light-sensitive material containing 0.01 to 50 g of ascorbic acid per 1 g of the hydrophilic colloid. Embedded image [In the formula, Z ₁ and Z ₂ represent an atomic group necessary for forming a heterocycle, and R ₁ and R ₂ each represent an alkyl group having 1 to 5 carbon atoms, a substituted alkyl group or an 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. Also L ₁ and L ₂
Each represents a methine group or a substituted methine group, and m ₁ represents ₁ , 2
Or 3 is shown, and [External 1] Represents an acid anion, n ₁ represents 1 or 2, and n ₁ is 1 when it has a betaine structure. ] [Chemical 2] [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 atomic group necessary for forming an aromatic ring or a heterocyclic ring having 6 to 18 carbon atoms, M represents a metal atom or an organic cation, and n ₂ represents an integer of ₂ to 10. ]