JPH03141345A - Silver halide photographic sensitive material spectrally sensitized in red color region - Google Patents

Abstract

PURPOSE:To enhance sensitivity and to improve storage stability of a raw sample and to reduce dye stains by incorporating a specified sensitizing dye in at least one silver halide emulsion layers. CONSTITUTION:At least one of the silver halide emulsion layers contains the sensitizing dye represented by formula I in which each of Z1 and Z2 is 0, S, Se, or Te; each or V1 - V8 is methine; each of L1 - L5 is H, halogen, alkyl, alkoxy, acyl, aryloxy, aryl, or the like; and one of R1 and R2 is a substituent represented by formula II; (n) is 1 or 2; and when both of R1 and R2 are not the group of formula II at the same time, one of them is optionally substituted alkyl, thus permitting the obtained silver halide photographic sensitive material to be reduced in stains due to residual dyes and superior in raw storage stabil ity.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, which is particularly sensitive to red light and has excellent resistance to performance fluctuations due to storage of the light-sensitive material (hereinafter referred to as raw material). The present invention relates to a silver halide photosensitive material that has excellent sample storage stability (referred to as sample storage stability) and reduced residual color staining after processing.

[Prior Art] In recent years, there has been a demand for photosensitive materials with increasingly higher sensitivity from various viewpoints, and research on sensitization techniques is being conducted from various angles.

Research on sensitization technology related to silver halide grains includes, for example, research that theoretically calculates the quantum efficiency of silver halide and considers the influence of particle size distribution, which is related to the progress of photography.
Proceedings of the 1980 Tokyo Symposium “Interactions Pitoqueen.”

Light and Materials for Photographic Applications, page 91. According to this research, creating a monodisperse emulsion is effective in improving quantum efficiency, which means it is possible to increase sensitivity. This suggests that

On the other hand, as part of research into sensitization technology, studies have also been made to apply optimal chemical sensitization to these silver halide emulsions. As sensitizers used for chemical sensitization, sulfur sensitizers, selenium sensitizers, reduction sensitizers, noble metal sensitizers, etc. are well known. These chemical sensitizers may be used alone or in combination of two or more.

Furthermore, it is a well-known technique to add a sensitizing dye to a silver halide emulsion to expand the sensitive wavelength range specific to the silver halide emulsion and to spectrally sensitize it. It is also known that selecting a sensitizing dye with high spectral sensitization efficiency as the sensitizing dye used at this time can significantly contribute to increasing the sensitivity of the light-sensitive material.

The sensitizing dye used for the above purpose should have an appropriate spectral sensitizing wavelength range and should not diffuse into other photosensitive layers or interact with additives other than the sensitizing dye. Those with desirable properties are selected.

Further, more preferable conditions include that when the photosensitive material containing the sensitizing dye is stored, there is little reduction in sensitivity, occurrence of fogging, or occurrence of dye staining after sensitization processing. required. In particular, when sensitizing dyes are used in multilayer color photographic materials,
It is necessary to have higher sensitivity, excellent brown color reproducibility, and to maintain these photographic characteristics stably even when stored for a long period of time. It is known that certain pentamethine dyes are very effective as spectral sensitizing dyes used in red-sensitive emulsions, but these sensitizing dyes have the following drawbacks depending on the conditions of use. was.

1) Since residual color contamination after processing is large, the amount of sensitizing dye used must be reduced even at the expense of spectral sensitivity.

2) High sensitivity can be obtained immediately after manufacture, but as time passes, the initial sensitivity decreases and fog occurs.

What is required of recent photosensitive materials is high sensitivity and high image quality as photographic properties, as well as rapid processing. However, with conventional dyes, if the amount of dye added increases, residual color stains will occur in the finished photograph, degrading the product image, so there are limits to the addition of sensitizing dyes. For this reason, there has been a demand for sensitizing dyes with higher color sensitization efficiency or with less residual color staining.

Furthermore, the various properties of photosensitive materials need to be stable at all times, and when photosensitive materials are stored in various atmospheres, changes in sensitivity and fog may occur depending on the storage conditions, which can degrade image quality. This results in the loss of commercial value as a photosensitive material.

As a technology to improve the preservation of such raw samples, JP-A No. 6
No. 0-202436 and No. 63-264743 propose a technique of using a pentamethine dye in combination with a certain compound, but further improvements have been desired.

As a result of various studies aimed at improving the disadvantages of the pentamethine dyes, such as residual color staining and storage stability of raw samples, the inventors discovered the above-mentioned characteristics of a photosensitive material obtained by using a pentamethine dye with a specific structure. was found to be significantly improved.

[Problems to be Solved by the Invention] The purpose of the present invention is to provide a photosensitive material containing a pentamethine dye that sensitizes in the red region, which has high sensitivity, improved raw sample storage stability, and less dye staining. It is to provide.

Means for Solving Problem L] The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which at least one layer of the silver halide emulsion is This is achieved by a silver halide photographic material containing a sensitizing dye represented by General 2N].

General Formula [I] In this formula, Zl and Z2 each represent an oxygen, sulfur, selenium or tellurium atom.

L1% L2. L3. L4 and shi represent a methine group. This methine group may be substituted or may form a ring with another methine group.

Examples of substituents for the methine group include alkyl groups such as methyl, ethyl, propyl, and butyl, aralkyl groups such as benzyl and phenethyl, and aryl groups such as phenyl and p-tolyl. In addition, when forming a ring with multiple methine groups, the L2 and L4 substituents are linked to form a 5-membered ring such as a 2-cyclopentene ring, a 5.5-dimethyl-2-cyclohexene ring, a 4, Examples include those forming a 6-membered ring such as 4,6.6-tetramethyl-2-cyclohexene ring.

Vl, ■2i V3, V4, VS% V6, V7 and ■8 each represent a hydrogen atom or a substituent, and examples of substituents include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), alkyl groups (e.g. methyl group, ethyl group, etc.), alkoxyl group (e.g. methoxy group, ethoxy group, etc.), acyl group (e.g. acetyl group, benzoyl group, etc.),
Acyloxy group (e.g., acetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (e.g., ethoxycarbonyl group, etc.), carbamoyl group (e.g., carbamoyl group, N-methylcarbamoyl group, N,N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,N-3-oxapentamethyleneaminosulfonyl group, etc.), cyan group, carboxy group, amino group (e.g. amino group, N,N-dimethylamino group, etc.)
, acylamino group (e.g. acetylamino group etc.), hydroxy group, alkylthio group (e.g. methylthio group etc.),
Alkylsulfonyl group (e.g. ethylsulfonyl group, etc.)
, a sulfonic acid group, an aryloxy group (eg, phenoxy group, p-tolyloxy group, etc.), and an aryl group (eg, phenyl group, etc.). Furthermore, two of (1) to (v6) bonded to adjacent carbon atoms may form a condensed ring with each other.

At least one of R1 and R2 is a substituent represented by the general formula [II], and in the general formula [If] and the general formula [Summer ■], n represents 1 or 2.

R,,R2 are at the same time general formula [Summer! ] When not a substituent represented by %RI%R2 represents a substituted or unsubstituted alkyl group.

(X) represents a charge-balanced counterion, and m represents an integer necessary to neutralize charges of 0 or more.

Specifically, when X is an anion, examples include halogen ion (e.g., chloro ion, bromide ion, iodide ion, etc.), p-trienesulfonate ion, perchlorate ion, boron tetrafluoride ion, etc., and when X is a cation, , alkali metal ions (for example, 1-lium ion, potassium ion, etc.), pyridinium ions, ammonium ions (for example, triethylammonium ion, etc.), and the like.

Specific examples of the sensitizing dye represented by the general formula [I] are shown below, but the sensitizing dye used in the present invention is not limited to these compounds.

■-21 ■-22 ■-27 ■-28 ■-29 ■-24 -25 -30 ■-31 ■-32 ■-33 ■-34 -36 Next, the present invention represented by the general formula (1) An example of synthesis of a typical sensitizing dye is shown below.

Synthesis Example 1 (Synthesis of Sensitizing Dye 1-5) 1-1 Synthesis of Compound ■ α-Hydroxy-〇-)luenesulfonic acid γ-sultone 8
．． A mixture of 5 g and 4.2 g of 2-mercapto-benzthiazole was reacted for 1 hour at an external melting temperature of 215°C, and the mixture was left to cool to obtain Compound (1).

1-2 Absorption maximum during synthesis of sensitizing dye 1-5 660n, m) Synthetic compound of synthesis example 2 (sensitizing dye 1-12) ■ Compound I synthesized in 1-1 [[I0,2g, known Compound TV8.3g synthesized by the synthesis method and acetonitrile 1
00 ml of the mixture is stirred at room temperature and 8.1 g of triethylamine are added thereto. This was stirred and reacted at room temperature for 4 hours, and the precipitated blue crystals were collected by filtration and washed with acetonitrile to obtain 52.5 g of sensitizing dye I-52. The obtained compound was purified by recrystallization twice from a chloroform/methanol mixture. (Yield N 2.3 g, methanol solution compound ■ Compound m synthesized in 1-1 10.2 g, compound V8.Og synthesized by a known synthesis method and acetonitrile 70
The mixture of m1 was stirred at room temperature, and 12 g of triethylamine was added thereto. This was stirred and reacted at room temperature for 5 hours,
The precipitated blue crystals were collected by filtration, washed with acetonitrile,
1 g of sensitizing dye I-123 was obtained. The obtained compound was purified by recrystallization twice from a fluoroalcohol/chloroform/methanol mixture. (Yield 2.5g,
The optimum concentration of the sensitizing dye of formula [I] above (absorption maximum at 659 nm in methanol solution) can be determined by methods known to those skilled in the art. Examples include a method of determining by containing sensitizing dyes of different concentrations and measuring the performance of each.

The amount of the sensitizing dye added in the present invention is not particularly limited, but is from 2X10-' mol to tx per mol of silver halide.
Preferably, to-” moles are used, and even 5×10-” moles are used.
Preferably, between 1'molar and 5×10’moles are used.

Methods well known in the art can be used to add the sensitizing dye to the emulsion. For example, these sensitizing dyes can be directly dispersed in emulsions, or dissolved in water-soluble solvents such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, or mixtures thereof, or diluted with water. , or dissolved in water and added to the emulsion in the form of these solutions. Ultrasonic vibrations can also be used during the dissolution process. In addition, the dye can be prepared by dissolving the dye in a volatile organic solvent, as described in U.S. Pat. No. 3,469,987.
A method of dispersing this solution in a hydrophilic colloid and adding this dispersion to an emulsion, as described in Japanese Patent Publication No. 46-24185, etc., disperses the water-insoluble dye in a water-soluble solvent without dissolving it. A method of adding this dispersion to an emulsion is also used. Further, the dye can be added to the emulsion in the form of a dispersion by an acid dissolution/dispersion method. Other additions to emulsions include the specifications of U.S. Patent No. 2,912.345, U.S. Pat. The methods described can be used.

The sensitizing dye represented by formula [I] used in the present invention may be added to the emulsion at any time during the manufacturing process from the time of silver halide grain formation to just before coating on the support. Can be added.

Specifically, before the formation of silver halide grains, during the formation of silver halide grains, after the completion of silver halide grain formation until the start of chemical sensitization, at the start of chemical sensitization, during chemical sensitization, and during chemical sensitization. Any time selected from the end of chemical sensitization and the time of application may be used. It may also be added in multiple portions. -The sensitizing dye represented by the formula [I] is
It can also be used in combination with other sensitizing dyes as a so-called supersensitizing combination. In this case, the respective sensitizing dyes may be dissolved in the same or different solvents, and these solutions may be mixed or separately added to the emulsion prior to addition to the emulsion. If added separately, the order;
The time interval can be arbitrarily determined depending on the purpose.

Higher spectral sensitivity can be obtained by using the sensitizing dye used in the present invention in combination with a compound that provides supersensitizing action. Examples of compounds having such a supersensitizing effect include U.S. Pat. Nos. 2,933,390 and 3,41.
No. 6,927, No. 3.511,664, No. 3,615
, No. 613, No. 3,615,632, No. 3,835.
Compounds having a pyrimidylamino group or triazinylamino group described in specifications such as No. 721, British Patent Nos. 1 and 1
Aromatic organic formaldehyde condensates described in No. 37,580, halogenated benzotriazole derivatives described in U.S. Pat.
42541, bispyridinium compounds described in JP-A No. 59-188641, aromatic heterocyclic quaternary salt compounds described in JP-A-59-191032, JP-A-60-79348
Electron-donating compound described in US Pat. No. 4.307,
Polymers containing aminoallylidene malononitrile units described in No. 183, hydroxytetrazaindene conductors described in JP-A-55-149937, U.S. Patent No. 3
．． Examples thereof include 1,3-oxadiazole derivatives described in US Pat. No. 615,633 and amino-1,2,3,4-thiatriazole conductors described in US Pat. No. 4,780,404. There is no particular restriction on the timing of addition of these supersensitizers, and they can be added at any time according to the timing of addition of the sensitizing dyes. The amount added is selected within the range of 1X10-' to IXIQ-1 mole per mole of silver halide, and the sensitizing dye is 1/1 mole.
It is used in an addition molar ratio of 1o to 1o/1.

The silver halide grains contained in the silver halide emulsion according to the present invention may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver chloroiodobromide. It may be a mixture of Among these, emulsions containing at least silver chloride are more preferred.

The composition of the silver halide grains used in the present invention may be uniform from the inside to the outside of the grain, or the composition between the inside and outside of the grain may be different, or the composition between the inside and outside of the grain may be different. If they are different, the composition may change continuously or discontinuously.

There is no particular restriction on the particle size of the silver halide grains used in the present invention, but considering sensitivity and other photographic performance, etc.
Preferably 0.2 to 1.6 μm1, more preferably 0.2 to 1.6 μm1.
It is in the range of 25 to 1.2 μm.

The particle diameter can be measured by various methods commonly used in the technical field. Typical methods include Loveland's "Analysis of Particle Size J A, S, T, M, Symposium on Light Microcopy 1955, pp. 94-122" or "Theory of Photographic Processes" by Mies and James. Co-author,
3rd edition, published by Macmillan (1966), No. 2:t.

The particle size can be measured using the projected area of the particle or a direct approximation.

If the particles are of substantially uniform shape, the particle distribution can be expressed fairly accurately as diameter or projected area.

The grain size distribution of the silver halide grains according to the present invention may be polydisperse or monodisperse, but a monodisperse emulsion is preferable. More preferably, the coefficient of variation in the particle size distribution of silver halide grains is 0.22 or less, more preferably 0.15 or less, particularly preferably 0.10.
The following monodisperse silver halide grains are shown below.

Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution,
It is defined by the following equation.

S - standard deviation of particle size distribution Here, the particle size of each r+ particle and ni represent the number thereof.

In the case of spherical silver halide grains, the grain size here means:
In the case of a particle having a shape other than a cube or a sphere, it represents the diameter when its projected image is converted into a circular image of the same area.

The silver halide grains used in the emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown temporarily, or may be grown after seed particles are created.

The method of creating and growing the seed particles may be the same or different.

The method of reacting the soluble silver salt with the soluble halogen salt may be any method such as the overt method, the back mixing method, the simultaneous mixing method, or a combination thereof, but it is preferable to use the method obtained by the simultaneous mixing method. As a form of mixed method,
It is also possible to use the pAg-chondrold-double jet method described in No. 4-48521 and the like.

Furthermore, if necessary, a silver halide solvent such as thioether may be used.

Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound, or a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation.

Any shape of the silver halide grains according to the present invention may be used.

One preferred example is a cube having a (100) plane as a crystal surface. Also, U.S. Patent No. 4,183.756
No. 4,225,666, JP-A-55-2658
9, Special Publication No. 55-42737, and Journal of Photography 4'/Rescience (J
, Photogr, 5ci) 21.39, (1973
) Particles having shapes such as octahedrons, tetradecahedrons, dodecahedrons, etc. can be prepared and used.

Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

The silver halide grains used in the emulsion according to the present invention may contain cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, in the process of grain formation and/or grain growth. Iron salts or complex salts thereof can be used to add metal ions to the interior of the particles and/or to the surface of the particles, and by placing them in a suitable reducing atmosphere, metal ions can be incorporated into the interior of the particles and/or on the surface of the particles.
Alternatively, reduction sensitization can be imparted to the particle surface.

In the emulsion according to the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained.

When removing the salts, it can be carried out as described in Research Disclosure No. 17643.

The silver halide grains used in the emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains. Preferably, the particles are particles on which latent images are mainly formed.

In the present invention, chemical sensitizers such as chalcogen sensitizers can be used. Chalcogen sensitizers are a general term for sulfur sensitizers, selenium sensitizers, and tellurium sensitizers.
For photography, sulfur sensitizers and selenium sensitizers are preferred, and known sulfur sensitizers can be used. Examples include thiosulfate, allylthiocarbazide, thiourea, allylisothiocyanate, cystine, P-toluenethiosulfonate, and rhodanine.

Others: U.S. Patent No. 1,574,944, U.S. Patent No. 2.410
, No. 689, No. 2,278,947, No. 2,728,
No. 668, No. 3,501,313, No. 3,656,9
Sulfur sensitizers described in OLS No. 55, OLS No. 1,422,869, JP-A-56-24937, JP-A No. 55-45016, etc. can also be used.

The amount of sulfur sensitizer added varies over a considerable range depending on various conditions such as pH, temperature, and size of silver halide grains, but as a guide, 10 sulfur sensitizers are added per mole of silver halide.
It is preferably about -7 mol to 10-1 mol.

Selenium sensitizers can be used instead of sulfur sensitizers, but examples of selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenamides, and selenium sensitizers. Carboxylic acid salts and esters, selenophosphates, diethylselenide, selenides such as diethylselenide can be used, and specific examples thereof are given in U.S. Patent No. 1.
No. 574,944, No. 1,602,592, No. 1,6
It is described in the specification of No. 23,499, etc. Furthermore, reduction sensitization can also be used together.

The reducing agent is not particularly limited, but includes known stannous chloride, thiourea dioxide, hydrazine, polyamine, and the like. Also, noble metal compounds such as platinum compounds, palladium compounds, etc. can be used.

As the gold sensitizer, the oxidation number of gold may be +1 or +3, and other types of gold compounds may also be used. Typical examples include chloraurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric azide, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, and gold selenide. Can be mentioned.

The amount of gold sensitizer added varies depending on various conditions, but as a guide, it is from 10-6 mol to io-' mol, preferably from 10-7 mol to 10-2 mol, per mol of silver halide. . These compounds may be added at the time of grain formation of silver halide, during physical ripening, during chemical ripening, or at any time after the completion of chemical ripening.

When a gold compound is used in the present invention, it is possible to obtain a photosensitive material having better raw sample preservation properties.

The emulsion may be contaminated during the manufacturing process or storage of the photosensitive material, or
For the purpose of preventing fog during photographic processing and/or keeping photographic performance stable, during and/or at the end of chemical sensitization, and/or after the end of chemical sensitization,
Compounds known in the photographic industry as anti-capri agents or stabilizers can be added prior to coating the silver halide emulsion.

Examples of stabilizers that can be used in the present invention include tetrazaindene compounds such as 7-hydroxy-5-methyl-1°3.4,7a-tetrazaindene.

In the present invention, the inhibitor effectively used has a solubility product (Ksp) with silver ions of 1X10-'' or less, preferably Ksp of txio-'' or less.

A compound having a solubility product exceeding this, that is, a compound having a smaller ability to form a salt with silver ions, cannot be expected to have the desired effect. For the measurement and calculation of the solubility product, reference may be made to "New Experimental Chemistry Course Volume 1" (published by Maruzen), pages 233 to 250.

The above inhibitor may be, for example, Chemical and Pharmaceutical Piurethane.
Pharmaceutical Bulletin)
(Tokyo) Volume 26.

314 (1978), Japanese Patent Publication No. 55-79436, Berishte der Deutschen Chemischen Goeselsdraft
schen Chemischen Ge5ellsd
Raft) 82, 121 (194B), U.S. Patent No. 2,843,491, U.S. Pat.
No. 39, Journal of the American Chemical Society, 44.1502-1510
- (Beilsteins) Iandbuch
dar Organischen (t+en+ie
) Dan, 41, 43, 58. etc., including the compounds described in
The synthesis method can also be carried out in accordance with the methods described in these documents.

When the present invention is applied to color light-sensitive materials, various dye-forming substances are used, and a typical example is a dye-forming coupler.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. A specific example of a yellow coupler that can be used is British Patent No. 1,077.874.
No., Special Publication No. 45-40757, Japanese Patent Publication No. 47-1031
No. 47-26133, No. 48-94432, No. 50-87650, No. 51-3631, No. 52-1
No. 15219, No. 54-99433, No. 54-133
No. 329, No. 56-30127, U.S. Patent No. 2,87
No. 5,057, No. 3,253,924, Same: ], 26
No. 5,506, No. 3,408.194, No. 3,551
゜No. 155, No. 3,551,156, No. 3,664,
No. 841, No. 3゜725.072, No. 3,730,7
No. 22, No. 31,891.445, No. 3,900,4
No. 83, No. 3,929,484, No. 3,933.50
No. 0, No. 3,973,968, No. 3,990,896
No. 4. O22゜259, 4,022,620, 4,029,508, 4゜057.432,
4,106.942, 4.133,958, 4.269.936, 4,286,053, 4
, No. 304,845, No. 4,314,023, No. 4.
3341.327, 4,356゜258, 4,
No. 386,155, No. 4,401,752, etc.

The diffusion-resistant yellow coupler used in the light-sensitive material of the present invention is preferably represented by the following formula [Y].

In the formula, R1 represents a halogen atom or an alkoxy group.

R2 represents a hydrogen atom, a halogen atom, or an alkoxy group which may have a substituent.

R5 is an acylamino group, an alkoxycarbonyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an arylsulfonamide group, an alkylureido group, an arylureido group, a succinimide group, an alkoxy group, which may have a substituent, or Represents an aryloxy group.

zl represents a vine group that is released upon coupling with an oxidized color developing agent.

In the present invention, couplers represented by the following formulas [al and [al] can be preferably used as magenta dye image-forming couplers.

In the general formula [al c formula, ^' represents an aryl group, Rat represents a hydrogen atom or a substituent, and 2 represents a substituent. W represents a substituent that can be removed, and W is -NH--NHCO- (N atom is bonded to the carbon atom of the pyrazolone nucleus) or -NHCONH
-, and m is an integer of 1 or 2. ] Preferred examples of the compound represented by the general formula [al are as follows.

General formula [al] In this formula, C represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and 2. The ring formed by may have a substituent. X represents a hydrogen atom or a substituent which is eliminated by reaction with an oxidized product of a color developing agent.

Moreover, R1 represents a hydrogen atom or a substituent.

Examples of the substituent represented by R1 include a halogen atom,
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group,
Spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, alkoxy group, carbamoyloxy group, amino group,
Acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, peterocyclic thio group Can be mentioned.

These include, for example, U.S. Patent Nos. 2,600,788, 3,061,432, 3,062,653,
Same No. 3,127゜269, Same No. 3,311,476, Same No. 3,152,896, Same No. 3,419,391
No. 3,519,429, No. 3.555.31
No. 8, No. 3,684,514, No. 3,888.6
No. 80, No. 3,907,571, No. 3,928,
No. 044, No. 3.930,861, No. 3,930
, No. 866, No. 3,933,500, etc.,
JP-A-49-29639, JP-A No. 49-111631,
No. 49-129538, No. 50-13041, No. 5
No. 2-58922, No. 53-62454, No. 55-1
No. 111034, No. 55-38043, No. 57-35
No. 858, δ (publications No. 1-23855, British Patent No. 1,247,493, Belly Patent No. 5769,11)
No. 6, No. 792,525, West German Patent No. 2,156,1
Specifications of No. 11, Japanese Patent Publication No. 46-60479, Japanese Patent Publication No. 59-125,732, Japanese Patent Publication No. 59-228,252,
Publications No. 59-162,548, No. 59-171.956, No. 60-33,552, No. 60-43,659, West German Patent No. 1,070,030, and U.S. Patent No. 3
, No. 725°067.

Cyan dye image-forming couplers include phenolic,
Naphthol type 4-equivalent or 2-equivalent type cyan dye image-forming couplers are typical, and U.S. Patent No. 2,306,4
No. 10, No. 2,356,475, No. 2.362,59
No. 8, No. 2,367.531, No. 2,389.929
No. 2,423,730, No. 2,474,293, No. 2,476゜008, No. 2,498,466,
No. 2,545,687, No. 2,728,660, No. 2,772,162, No. 2,895,828, No. 2
, No. 976.146, No. 3,002,836, No. 3,
419°390, 3,446,622, 3.4
76.563, 3゜737.316, 3,75
No. 8,308, No. 3,839,044, British Patent No. 4
No. 78,991, No. 945.542, No. 1,084°480, No. 1,377.233, No. 1,388,0
24 and 1.543,040, as well as JP-A Nos. 47-37425, 50-10135, 50-25228, 50-112038, and 50
-117422, 50-130441, 51-
No. 6551, No. 51-37647, No. 51-5282
No. 8, No. 51-108841, No. 53-109630
No. 54-48237, No. 54-66129, No. 54-131931, No. 55-32071, No. 59
-146050, 59-31953 and 60-
No. 117249.

As a cyan image forming coupler, the following formula [E],
A coupler represented by [F] can be preferably used.

General Formula [E] Song E [In the formula, RE+ represents an alkyl group having 1 to 6 carbon atoms. Ro represents a ballast group. Zo represents a hydrogen atom or an atom or group that can be separated by reaction with an oxidized product of a color developing agent. ] The alkyl group represented by REI may be linear or branched, and includes those having a substituent.

A ballast group, represented by RE2, is an organic group having a bulk and shape that imparts sufficient bulk to the coupler molecule to substantially prevent the coupler from diffusing from the layer to which it is applied to other layers. .

Preferred ballast groups are those represented by the following formula.

-C)I -0-8r E3 Rε3 represents an alkyl group having 1 to 12 carbon atoms, and A
r represents an aryl group such as a phenyl group, and this aryl group includes those having a substituent.

Next, specific examples of the coupler represented by the general formula [E] will be shown, but the coupler is not limited thereto.

The cyan dye-forming coupler of the present invention represented by formula [E] is usually 1xio-3 mol to 1 mol, preferably 1Xl0-" mol to 3XlO" mol per mol of silver halide.
' Can be used in the molar range.

General formula [F] 9 [In the formula, R'' represents an alkyl group or an aryl group.

RI'2 represents an argyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R'' represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.
may form a ring in cooperation with R'', Z represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. In the cyan coupler represented by F], the alkyl group represented by R'' has 1 to 3 carbon atoms.
2 are preferred, and these may be linear or branched,
It also includes those with substituents.

The aryl group represented by RFX is preferably a phenyl group, including those having substituents.

The alkyl group represented by RP2 has 1 to 32 carbon atoms.
These alkyl groups may be linear or branched, and include those having substituents.

The cycloalkyl group represented by RF2 has 3 carbon atoms.
-12 are preferred, and these cycloalkyl groups also include those having substituents.

The aryl group represented by Rr2 is preferably a phenyl group, including those having substituents.

The heterocyclic group represented by Rr2 is preferably a 5- to 7-membered heterocyclic group, may have a substituent, and may be fused.

Rr3 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and the alkyl group and the alkoxy group include those having a substituent, but RF'3 is preferably a hydrogen atom.

Furthermore, the ring formed jointly by RrI and Rr3 is 5
~6-membered rings are preferred, examples of which include.

In formula [F], the groups that can be separated by reaction with the oxidized product of the color developing agent represented by zr include halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups, sulfonyloxy groups, acylamino groups, sulfonylamino groups, Examples include an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, and an imide group (including those each having a substituent), but preferably a halogen atom, an aryloxy group, and an alkoxy group.

Among the above-mentioned cyan couplers, those represented by the following formula [FA] are particularly preferred.

General formula [FA 114 8 FA In the formula, R and A represent a phenyl group substituted with at least one halogen atom, and these phenyl groups include those having a substituent other than a halogen atom.

RFA□ has the same meaning as RFI in formula [F] above.

XPA represents a halogen atom, an aryloxy group or an alkoxy group, and includes those having a substituent.

Typical specific examples of the cyan coupler represented by the general formula [F] are shown below.

The cyan dye-forming coupler of the present invention represented by formula [E] is usually 1X10-' mol to 1 mol, preferably 1X10-'' mol to axio-
' Can be used in the molar range.

General formula [F] H [wherein RFI represents an alkyl group or an aryl group. RF2 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Rr3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Also R
FI may form a ring together with R'', and Z2 represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. In the cyan coupler represented by F], the alkyl group represented by RFI has 1 to 1 carbon atoms.
32 are preferable, and these may be linear or branched, and include those having substituents.

The aryl group represented by RFl is preferably a phenyl group, including those having substituents.

The alkyl group represented by RF2 has 1 to 32 carbon atoms.
These alkyl groups may be linear or branched, and include those having substituents.

The cycloalkyl group represented by RFI has 3 carbon atoms.
-12 are preferred, and these cycloalkyl groups also include those having substituents.

The aryl group represented by RF2 is preferably a phenyl group, including those having substituents.

The heterocyclic group represented by R'2 is preferably 5- to 7-membered, may have a substituent, and may be fused.

RFI represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and the alkyl group and the alkoxy group include those having a substituent, and R'3 is preferably a hydrogen atom.

Furthermore, the number of rings formed by RFI and RFI is 5.
~6-membered rings are preferred, examples of which include.

In the general formula [F], the groups that can be separated by reaction with the oxidized product of the color developing agent represented by 21 include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an acylamino group, and a sulfonylamino group. , an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, and an imide group (including those each having a substituent), but preferably a halogen atom, an aryloxy group, and an alkoxy group.

Among the above-mentioned cyan couplers, those represented by the following formula [F-Al] are particularly preferred.

General formula [FA3 Kokuhachi r^ In the formula, R and A represent a phenyl group substituted with at least one halogen atom, and these phenyl groups include those having a substituent other than a halogen atom.

RrA2 has the same meaning as RFI in formula [F] above.

xrA represents a halogen atom, an aryloxy group or an alkoxy group, including those having a substituent.

Typical specific examples of the cyan coupler represented by the general formula [F] are shown below.

Specific examples of the above-mentioned cyan couplers include Japanese Patent Application No. 61-21853, pages 26 to 35;
0-225155 Publication, page 7, bottom left column - page 10, bottom right column, JP-A-60-222853, page 6, top left column -
Bottom right column on page 8 and JP-A-59-185335 No. 6
It includes the 2,5-diacylamino cyan couplers described in the lower left column of page 9 to the upper left column of page 9, and can be synthesized according to the methods described in these specifications and publications.

The cyan coupler of the present invention is used in a red-sensitive silver halide emulsion layer, and the amount added is 2X per mole of silver halide.
The range is preferably from 10-' to 8x10-' mol, particularly preferably from 1x10-2 to 5x10 i mol.

Although it is advantageous to use gelatin as the hydrophilic colloid for dispersing the silver halide of the present invention, other lignophilic colloids can also be used.

Examples of preferable wood-philic colloids include gelatin such as alkali-treated gelatin or acid-treated gelatin, which is most commonly used, but a portion of this gelatin may be substituted with derivative gelatin such as phthalated gelatin, phenylcarbamoyl gelatin, albumin, or agar. , gum arabic, alginic acid, partially hydrolyzed cellulose derivative, partially hydrolyzed polyvinyl acetate,
Mention may be made of polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone and copolymers of these vinyl compounds.

The silver halide photographic material of the present invention may contain various known photographic additives. Examples of such agents include ultraviolet absorbers (such as benzophenone compounds and benzotriazole compounds), dye image stabilizers (such as phenolic compounds, bisphenol compounds, hydroxychroman compounds, bispirochroman compounds, and hydantoin compounds). compounds, dialkoxybenzene compounds, etc.), stain inhibitors (e.g., hydroquinone derivatives, etc.), surfactants (e.g., sodium alkylnaphthalene sulfonate, sodium alkylbenzene sulfonate, sodium alkyl succinate sulfonate, polyalkylene glycol, etc.) , water-soluble anti-irradiation dyes (e.g. azo compounds, styryl compounds, triphenylmethane compounds, oxonol compounds, anthraquinone compounds, etc.), hardeners (e.g. halogen S-triazine compounds, vinyl sulfone compounds) , acryloyl compounds, ethyleneimino compounds, N-methylol compounds, epoxy compounds, water-soluble aluminum salts, etc.), film property improvers (e.g. glycerin, aliphatic polyhydric alcohols, polymer dispersions (latex), solids) (or liquid paraffin, colloidal silica, etc.), optical brighteners (for example, diaminostilbene compounds), and various oil-soluble paints.

In addition to each emulsion layer, the photographic layers constituting the silver halide photographic material of the present invention include a subbing layer, an intermediate layer, a yellow filter layer, an ultraviolet absorbing layer, a protective layer, an antihalation layer, etc. It can be provided as appropriate.

The support for the silver halide photographic material of the present invention includes:
Supports such as paper, glass, cellulose acetate, cellulose nitrate, polyester, polyamide, polystyrene, etc., or laminates of two or more substrates, such as a laminate of paper and polyolefin (such as polyethylene and polypropylene), etc. , can be used as appropriate depending on the purpose.

This support is generally subjected to various surface treatments in order to improve its adhesion to the silver halide emulsion layer.
For example, it is possible to use a material whose surface has been roughened mechanically or with a suitable organic solvent, which has been subjected to surface treatment such as electron impact treatment or flame treatment, or which has been subjected to a subbing treatment to provide a subbing layer.

An image can be formed on the silver halide photographic material of the present invention by subjecting it to a development process known in the art.

The black and white developing agent used in the present invention includes T,
The Theory of Photographic Process by H. James
graphicProcess) 4th edition pages 291-32
You can use the one listed on page 6.

The color developing agent used in the color developing solution in the present invention includes known color developing agents that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds are generally used at a concentration of about 0.1 g to about 30 g per color developer 11, preferably about 1 g to about 15 g per color developer I°C.

Examples of aminophenol-based developers include O-aminophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1,4-dimethylbenzene and the like.

Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-phinidine diamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-diethyl-p-phenylenediamine hydrochloride,
, N'-dimethyl-p-phenylenediamine hydrochloride,
2-amino-5-(N-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N
-ethyl-N-β-hydroxyethylaminoaniline,
Examples include 4-amino-3-methyl-N,N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate, and the like.

In addition to the above-mentioned developer, known developer component compounds can be added to the developer applied to the processing of the silver halide photographic material of the present invention. For example, alkaline agents such as sodium hydroxide and potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softening agents and thickening agents are optionally included. You can also do that.

The temperature of the developer is 15℃ or higher, - numerically 20℃ to 50℃
For rapid processing, it is preferred to carry out at 30°C. The developer solution usually has a pi value of 7 or higher, most commonly around 10.
13 to about 13.

In carrying out the present invention, when using a silver halide photographic material containing a high silver chloride emulsion as a silver halide emulsion, it is preferable to use a developer that does not substantially contain bromide ions.

That is, the presence of bromine ions significantly impairs rapid developability. A developer containing substantially no bromide ions is one in which the bromide ions are IX 10-3M.
This refers to a processing liquid that contains only the following:

The high chloride silver halide may partially contain silver bromide and silver iodide in addition to silver chloride. Therefore, when silver bromide is contained, a small amount of bromide ions are eluted into the developer during development. This eluted bromine ion partially substitutes with the chlorine ion in the high chloride silver halide which is not developed even in the developer solution and the solubility of silver in areas other than the image area, which is several orders of magnitude. It is also conceivable that the photosensitive material is retained in the photographic material and taken out to the next process.

However, as mentioned above, as long as a small amount of bromide ions are eluted into the developer by developing high chloride silver halide, it is impossible to maintain the bromide ion concentration in the developer at completely zero. There is no paddy. In the present invention, "substantially no bromide ions are contained" means that no bromide ions are contained other than unavoidably mixed bromide ions such as those eluted during development, and 1xlO-
'M indicates the upper limit of the concentration of unavoidably mixed bromine ions.

The silver halide photographic material according to the present invention may contain these color developing agents in the wood-philic colloid layer, either as the color developing agent itself or as its precursor, and may be processed in an alkaline activation bath. Color developing agent precursors are compounds that generate color developing agents under alkaline conditions, including Schiff base type precursors with aromatic aldehyde conductors, polyvalent metal ion complex precursors, phthalic acid imide precursors, and phosphoric acid amide precursors. Sugar amine reactant precursors include urethane type precursors. Precursors for these aromatic primary amine color developing agents are, for example, U.S. Pat.
No. 7,114, No. 2,695.234, No. 3,719
, 492, the specifications of British Patent No. 803.784,
It is described in JP-A-53-185628 and JP-A-54-79035, and Research Disclosure magazine No. 15159, JP-A No. 12148, and JP-A No. 13924.

These aromatic primary amine color developing agents or their precursors need to be added in such an amount that sufficient color development can be obtained upon activation treatment. The amount varies depending on the type of light-sensitive material, but is generally between 0.1 and 5 moles, preferably between 0.5 and 3 moles, per mole of silver halide. These color developing agents or their precursors can be used alone or in combination. In order to incorporate it into a photosensitive material, it can be added by dissolving it in an appropriate solvent such as water, methanol, ethanol, acetone, etc., or it can be emulsified and dispersed using a high boiling point organic solvent such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. It can be added as a liquid or by impregnation into a latex polymer as described in Research Disclosure No. 14850.

After color development, the silver halide photographic material of the present invention is subjected to bleaching and fixing. Bleaching treatment may be performed simultaneously with fixing treatment. Many compounds are used as bleaching agents, among them iron (Ill), cobalt (111),
polyvalent metal compounds such as copper(II), especially complex salts of these polyvalent metal cations with organic acids, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid,
Metal complex salts such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, ferricyanates, dichromic acid, etc. may be used alone or in appropriate combinations.

As the fixing agent, a soluble complexing agent that dissolves silver halide as a complex salt is used. This soluble complexing agent is
For example, sodium thiosulfate, ammonium thiosulfate,
Examples include potassium thiocyanate, thiourea, and thioether.

After the fixing process, a washing process is usually performed.

Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination. The stabilizing liquid used in the stabilization treatment can contain a p)l adjuster, a chelating agent, an anti-spill agent, and the like. For these specific conditions, reference may be made to JP-A-58-134,836 and the like.

Silver halide photographic materials to which the present invention is applied include black-and-white or color photographic materials, but preferred are photographic materials for direct viewing that are viewed as final images, such as black-and-white photographic paper and color photographs. Paper, color reversal film, color reversal paper, etc.

(Margins below) [Example] The present invention will be explained in more detail with reference to Examples, which are just one embodiment of the present invention, and the present invention is not limited thereto.

Example 1 [Preparation of silver halide emulsion (Em-A=D)] The amounts of additives used in the following emulsion preparation are per mole of silver halide unless otherwise specified.

A solution containing a silver nitrate solution, potassium bromide, and sodium chloride was added to an inert gelatin aqueous solution using the double jet method in Table 1.
It was added under the conditions described in .

Next, desalting and washing with water are carried out by a conventional method to obtain silver chlorobromide emulsion E.
A-A-Em-D was prepared.

Using the above emulsion and sensitizing it to red sensitivity as shown below, a multilayer silver halide photographic light-sensitive material was prepared as described below, and the sensitivity, residual color staining, and storage stability of raw samples were evaluated.

[Preparation of silver halide photographic light-sensitive material samples Multilayer silver halide photographic light-sensitive material samples Nos. 101 to 124 were prepared by sequentially coating the following seven layers on copolyethylene resin-coated paper. Note that the amounts added below are per 1 m2 unless otherwise specified.

1st layer: 1.2 g of gelatin, 0.35 g (metallic silver equivalent, the same applies hereinafter) of blue-sensitive silver chlorobromide emulsion (average grain size 0.8 μm, silver bromide content 90 mol%), 0 .9 g of yellow coupler YC-1 and 0.015 g of 2,5-di-t-octylhydroquinone (hereinafter referred to as HQ-1)
Dioctyl phthalate (hereinafter referred to as DOP) dissolved in
A layer containing.

2nd layer...0.7g gelatin and 0.06gHQ
A layer containing DOP in which -1 is dissolved.

3rd layer: 1.25g gelatin, 0.35g green-sensitive silver chlorobromide emulsion (average grain size o, 45μ, silver bromide content 7
0 mol %), 0.53 g of magenta coupler M-3 and 0.12 g (7) [A -1] and 0.2 g of [A
-2] A layer containing DOP in which 0.015 g of HQ-1 was dissolved.

4th layer...1.3g gelatin, 0.083 HQ-
1 and 0.5g of ultraviolet absorber (UV-1) dissolved in D
Layer containing op.

Fifth layer: 1.4g gelatin, 0.3g red-sensitive silver chlorobromide emulsion* and 0.3g cyan coupler CC-1
A layer containing DOP in which 0.28 CC-2 and 0.023 HQ-1 were dissolved.

6th layer: Bow, Og gelatin, 0.032g HQ-
1 and 0.2g<7) 0,14 in which UV-1 was dissolved
g (7) D OP-containing layer.

7th layer: silicon dioxide 0.003g, gelatin 0.
A layer containing 5g.

As a hardening agent, [5 mg of H-1,1 per 1 g of gelatin;
10 mg of [H-2] was added per 1 g of gelatin.

*Red-sensitive silver chlorobromide emulsion The emulsion shown in Table 2 was optimally sensitized at 60°C using sodium thiosulfate and chloroauric acid, and 4 was added as the sensitizing dye and stabilizer shown in Table 2. -Hydroxy-6-methyl-
A red-sensitive silver chlorobromide emulsion was prepared by adding 1,3,3a-7-chitrazaindene.

('A-1) (A-2) Below margin (YC-1) (CC-1) (CC-2) (UV (H-23 Comparative sensitizing dye (S-1) Comparative sensitizing dye ( S-2) The following evaluations were performed on the obtained samples Nos. 101 to 118.

(1) Evaluation of relative sensitivity Each sample was measured using a photosensitive needle KS-7 type (manufactured by Konica).
After exposure to red light using a primary color separation filter, the film was processed according to the following development process. After finishing lA, P
Sensitometric measurements were performed using a DA-65 type densitometer (manufactured by Konica). The results are shown in Table 2 for sample No. 101.
It is expressed as a relative sensitivity when the sensitivity of is set as 100.

(2) Evaluation of residual color contamination Each sample was treated unexposed according to the processing steps shown below, and the reflection density from 640 nm to 700 nm was measured using a Hitachi spectrophotometer model 320, and the cyan fog density was measured. It was calculated from the difference between

(3) Evaluation of raw sample storage stability Raw sample storage stability is evaluated by the sensitivity change before storage and after being left at 25°C and 60% (relative humidity) for one month, and is expressed as the sensitivity change rate expressed by the following formula. Ta. The sensitivity was determined by performing the same exposure as above, then performing the development process shown below, and measuring the cyan density.

[Color development process] Color development, bleaching, fixing, washing, drying [Processing solution composition] (Color development solution) Benzyl alcohol ethylene glycol Potassium sulfite Potassium bromide Sodium chloride Potassium carbonate Hydroxylamine sulfate Polyphosphoric acid (TPPS) 38°C 38°C 25℃~30℃ 75℃~80℃ 3 minutes 30 seconds 1 minute 30 seconds 3 minutes 2 minutes 15 ml 15 m (2.0g 0.7g 0.2g 30.0g 3.0g 2.5g 3-methyl-4 -Amino-N-ethyl-N-(β-methanesulfonamidoethyl) Aniline sulfate 5.5g Optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g Potassium hydroxide
Add 2.0g water to bring the total volume to IIL, p
Adjust to H10,20.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% solution) 100 + 1 l Ammonium sulfite (40% solution) 27.5 mj + Adjust to pH 7.1 with potassium carbonate or glacial acetic acid and add water to bring the total volume to 1f.
Let it be t.

As is clear from Margin Table 2 below, the samples using the sensitizing dyes of the present invention were found to be excellent in sensitivity, residual color contamination, and preservation of raw samples, which are the effects of the present invention. The effects of the present invention can also be observed when used as a supersensitizer.

[Example 2] The blue-sensitive silver chlorobromide emulsions contained in the first layer of samples Nos. 112 to 118 prepared in Example 1 were prepared with a silver bromide content of 0,
The green-sensitive emulsion contained in the third layer has a silver bromide content of 1 mol% and an average grain size of 0.75 μm.
Samples No. 2 and 2 were prepared in the same manner except that the diameter was 45 μm.
01 to 209 were produced. Further, sensitivity, residual color contamination, raw sample storage stability, and infrared sensor fog were evaluated in the same manner as in Example 1, except that the following processing steps were performed, and the results shown in Table 3 were obtained. In addition, the sensitivity is sample No. 20
The sensitivity of j is set to 100, and the relative sensitivity is shown as in Example 1.

[Processing process] (Temperature) (Time) Color development
30±0.3℃ 15.30 seconds bleach fixing
30±0.5℃ Stabilization 30-34℃ Drying 60-80℃ [Color developer] Pure water Triethanolamine N,N-diethylhydroxylamine Potassium chloride Potassium carbonate Potassium sulfite 1-hydroxyethylidene-1,1 - Diphosphonic acid 45 seconds 90 seconds 60 seconds Ethylenediaminetetraacetic acid Catechol-3,5-disulfonic acid disodium salt N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate Fluorescent brightener ( 4,4'-diaminostilbenesulfonic acid conductor) 300 mA' 10 rni! 10 mi+ 2.0g 0.3g 0.2g 1.0g 1.0g 1.0g 4.5g 1.0g Add water to make up the total volume.

°C and adjust to pl=10.1 [Bleach-fix solution] Ethylenediaminetetraacetic acid iron(II) Ammonium dihydrate Ethylenediaminetetraacetic acid Ammonium thiosulfate (70% aqueous solution) Ammonium sulfite (40% aqueous solution) pH 8 with potassium carbonate or glacial acetic acid , 2 Add water to bring the total volume to IIl.

[Stabilizing liquid] 5-chloro-2-methyl-4-isothiazolin-3-one ethylene glycol 1-hydroxyethylidene-1,1-phosphonate ethylenediaminetetraacetic acid Ammonium hydroxide (20% solution) Ammonium sulfite 0 g g 100 mf ! Adjust to 27.5g, 1.0g 1.0g 2.0g 1.0g 3.0g 3.0g Fluorescent brightener (4,4'-diaminostilbenesulfonic acid rust conductor) Add water to make 1λ, add sulfuric acid Or use 1.5g of potassium hydroxide and adjust to p) 17.0.

As is clear from Table 3, the samples using the sensitizing dyes of the present invention were found to be excellent in sensitivity, residual color staining, and raw storage stability, which are the effects of the present invention. Further, the sensitizing dye of the present invention can provide the effects of the present invention regardless of the processing steps.

[Effects of the Invention] The present invention provides a silver halide photographic material with little residual color staining and excellent raw storage stability by using a specific sensitizing dye represented by formula [I].

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one silver halide emulsion layer on a support, in which at least one layer of the silver halide emulsion is a sensitizing dye represented by the general formula [I]. A silver halide photographic material characterized by containing. General Formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Z_1 and Z_2 represent oxygen, sulfur, selenium, or tellurium atoms, respectively. L_1, L_2, L_3, L_4 and L_5 represent methine groups. This methine group may be substituted or may form a ring with another methine group. V_1, V_2, V_3, V_4, V_5, V_6, V
_7 and V_8 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, an acyl group, an acyloxy group,
It represents an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, a carboxy group, an amino group, an acylamino group, a hydroxy group, an alkylthio group, an alkylsulfonyl group, a sulfonic acid group, an aryloxy group, and an aryl group in V_1 to V_8. and two atoms bonded to adjacent carbon atoms may form a fused ring with each other. At least one of R_1 and R_2 is a substituent represented by the general formula [II]. General formula [II] ▲ Numerical formula, chemical formula, table, etc. are available▼ In the general formula [II], n represents 1 or 2. When R_1 and R_2 are not both substituents represented by the general formula [II], either R_1 or R_2 represents a substituted or unsubstituted alkyl group. (X)_m represents a charge-balancing counterion, and m represents an integer necessary to neutralize charges of 0 or more. ]