JP3489710B2 - Silver halide photographic emulsion and silver halide photographic light-sensitive material containing the emulsion - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a spectrally sensitized silver halide photographic emulsion, a method for producing the same, and a silver halide photographic light-sensitive material using the emulsion.

[0002]

2. Description of the Related Art The sensitivity of a silver halide photographic light-sensitive material is determined by the light absorption rate of grains, the latent image forming efficiency including the spectral sensitization efficiency, and the minimum latent image size. It is considered that the improvement of the light absorptivity of the grains increases the transmission of light energy to the silver halide and achieves high spectral sensitivity.

There are two possible methods for improving the light absorption of particles. One is a method of increasing the amount of dye adsorbed by increasing the surface area of one particle to improve the light absorption rate. In this respect, some techniques that have been known so far are shown below. US Patent 5,494,789
In the high aspect ratio tabular grain emulsion technology disclosed in Japanese Patent No. 1989, the grain surface area can be increased by adjusting the aspect ratio to a high value. However, there is a limit to the increase in surface area by this method, and in order to improve the light absorption rate of one particle, it is necessary to increase the size of the particle. Increasing the size of tabular grains having a high aspect ratio not only deteriorates the monodispersity of the grain size but also causes problems such as being easily accompanied by pressure overload. In addition, JP-A-58-106532,
The method of making a hole in a part of the particles described in JP-A-60-221320 and the ruffle particles described in US Pat. No. 4,643,966 are also methods for increasing the particle surface area. However, with these methods, the morphology of the particles is unstable and practically difficult.

In order to improve the light absorptivity of one particle while maintaining a stable particle morphology and keeping the particle size small, it is necessary to improve the light absorptivity per unit surface area of the particle. For this reason, a method of increasing the adsorption density of the sensitizing dye can be considered as the second technique for improving the light absorption rate. Ordinary sensitizing dyes adsorb in a nearly monolithic packing in a monolayer and no more. Several methods have been proposed so far as a method for solving this problem and adsorbing a sensitizing dye on the surface of a particle in multiple layers. It is shown below. P. B. Gilman, J.
r. ) Et al. Are Photographic Science and Engine Nearing (Photographic S
Science and Engineering) 2nd
In Vol. 0, No. 3, No. 97 (1976), a cation dye was adsorbed on the first layer, and an anion dye was further adsorbed on the second layer using electrostatic force. Also, GB Bird et al., US Pat. No. 3,622,316.
In the No. issue, a plurality of dyes are adsorbed in multiple layers on silver halide, and Forster type excitation energy-
Sensitized by the contribution of movement. However, even with the methods of these patents and literatures, the improvement of the light absorption rate per unit surface area is insufficient, and the amount of the dye adsorbed on the silver halide grains is unknown. Therefore, grasp the dye adsorption amount,
It was necessary to develop a technology for improving the light absorption rate by increasing the adsorption amount.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a silver halide emulsion having a high amount of spectral sensitizing dye per unit area of the grain surface, and a highly sensitive photographic light-sensitive material using the emulsion. Is to provide.

[0006]

The above objects of the present invention are as follows.
It was achieved by the following (1) to (5). (1) A silver halide photographic emulsion containing at least one spectral sensitizing dye represented by the general formula 1.
General formula 1

[0007]

[Chemical 2]

R in the formula₁₁And R₁₂Is substituted or unsubstituted
Represents an alkyl group of₁₁And R ₁₂Hydrophobic parameters of
The sum of the log (logP) has a value of 10.5 or more. Z
₁₁And Z₁₂May be the same or different and may be 5 or 6 members
Represents a nitrogen-containing heterocyclic nucleus-forming atom group of₁₁, L₁₂,
L₁₃, L₁₄, L₁₅, L₁₆, And L₁₇Represents the methine group
You p₁₁And p₁₂Represents 0 or 1, and n₁₁Is 0,
Represents 1, 2 or 3. X ₁₁Represents a charge-balanced counterion
Then m₁₁Is 0 or more and 8 or more necessary to neutralize the charge of the molecule.
Represents the number below. Spectral sensitization represented by the general formula 1 in (2) and (1)
The total amount of the dye added is 16 times the saturated coverage of the silver halide emulsion.
Halogen according to (1), which is 0% or more.
Silver halide photographic emulsion. In (3) and (2), a halo containing a spectral sensitizing dye.
Solvent polarity (q) in silver genide emulsion is 70 or less
(2) The silver halide photographic emulsion as described in (2) above. Spectral sensitization represented by the general formula 1 in (4) and (2)
R of dye₁₁And R₁₂Is an aryl group and a heteroaromatic ring
That the alkyl group is not substituted with a group containing a group
A silver halide photographic emulsion as described in (2) above. (5), The silver halide described in (1) to (4) on a support.
At least one silver halide emulsion layer containing a photographic emulsion
A silver halide photographic light-sensitive material having a layer. In the preparation of silver halide photographic emulsion, the substituent R₁₁And R
₁₂Total hydrophobic parameter (logP) of 10.5 or more
A small amount of the spectral sensitizing dye represented by the general formula 1 having the above value is used.
Spectral sensitized color containing at least one and represented by the general formula 1.
The total addition amount of the element is 16 times the saturated coating amount of the silver halide emulsion.
Silver halide photographic emulsion characterized by 0% or more
Is preferred.

Hydrophobicity parameter (log P) in the present invention
Was calculated based on the "hydrophobic fragment constant of the molecular constituent factor" described in "Structure-Activity Relationship of Drugs" edited by the Structure-Activity Relationship Forum, page 122 of the special issue of chemistry. Substituent
The log P was calculated by replacing the methylene group on the nitrogen side with a methyl group. For example, in the case of an octadecyl group, octadecane is used, and log P = 10.42. Table 1 collectively shows log P of the spectral sensitizing dyes given as specific examples of the general formula 1. The preferred log P is 10.5 to 100, more preferably 12 to 50, and particularly preferably 15 to 100.
23.

[0010]

[Table 1]

The solvent polarity (q) in the present invention is the product of the dielectric constant (25 ° C.) of water and the dye-added solvent in the emulsion and the volume fraction (volume of water or solvent / total volume of water and solvent). It is the sum. For example, 50 ml of emulsion is mixed with 50 ml of methanol as a solvent.
The solvent polarity (q) when contained is 50 g of the emulsion and 50% of the water.
It was 55.45 by replacing with ml. Preferred q
Is 5 to 70, more preferably 39 to 70,
It is particularly preferably 50 to 70.

The saturated adsorption amount in the present invention is the amount of the sensitizing dye that completely covers the emulsion grain surface when the molecular occupation area of the sensitizing dye is 0.8 nm ² . In the present invention, the total addition amount of the spectral sensitizing dye is preferably 160% or more (preferably 1000% or less) of the saturated coverage of the silver halide emulsion, more preferably 170 to 410%. Yes, and particularly preferably in the range of 180 to 310%.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. In the general formula 1, preferable nitrogen-containing heterocyclic nuclei represented by Z ₁₁ and Z ₁₂ include thiazole, benzothiazole, naphthothiazole, dihydronaphthothiazole, selenazole, benzoselenazole, naphthoselenazole, dihydronaphthoselenazole, oxazole, Benzoxazole, naphthoxazole, benzimidazole, naphthimidazole, pyridine, quinoline, imidazo [4,
5-b] quinoxaline or a nitrogen-containing heterocyclic nucleus such as 3,3-dialkylindolenine. More preferable nitrogen-containing heterocyclic nucleus, benzothiazole, naphthothiazole, dihydronaphthothiazole, benzoselenazole,
This is a case of representing a nitrogen-containing heterocyclic nucleus such as naphthoselenazole, dihydronaphthoselenazole, benzoxazole, naphthoxazole, benzimidazole, and naphthimidazole. The nitrogen-containing heterocyclic nucleus represented by Z ₁₁ and Z ₁₂ may have one or more substituents. The substituent is not particularly limited, but when the nitrogen-containing heterocyclic nucleus represented by Z ₁₁ and Z ₁₂ is other than benzimidazole or naphthimidazole, examples of preferred substituents include a lower alkyl group (even if branched). Further substituents {for example, a hydroxy group,
It may have a halogen atom, an aryl group, an aryloxy group, an arylthio group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, or the like}. More preferably, it is an alkyl group having a total carbon number of 8 or less. For example, methyl group, ethyl group, butyl group, chloroethyl group, 2,2,3,3-tetrafluoropropyl group, hydroxyethyl group, benzyl group, methoxyethyl group, ethylthioethyl group, ethoxycarbonylethyl group, etc., Can be mentioned. ), A lower alkoxy group (which may further have a substituent. Examples of the substituent include the same substituents as those mentioned above as examples of the substituent of the alkyl group. More preferably, the total number of carbon atoms is 8 or less alkoxy groups such as methoxy group, ethoxy group, pentyloxy group, ethoxymethoxy group, methylthioethoxy group, phenoxyethoxy group, hydroxyethoxy group,
A chloropropoxy group etc. are mentioned. ), A hydroxy group, a halogen atom, an aryl group (for example, a phenyl group,
Tolyl group, anisyl group, chlorophenyl group, etc.), heterocyclic group (eg, thienyl group, furyl group, pyridyl group, etc.), aryloxy group (eg, tolyloxy group, anisyloxy group, phenoxy group, chlorophenoxy group), arylthio group ( For example, a tolylthio group, a chlorophenylthio group, a phenylthio group) and a lower alkylthio group (which may be further substituted, examples of the substituent include those mentioned as examples of the substituent of the lower alkyl group). Preferably, it is an alkylthio group having a total carbon number of 8 or less, for example, a methylthio group, an ethylthio group, a hydroxyethylthio group, a chloroethylthio group, a benzylthio group, etc., an acylamino group (more preferably, an acylamino group having a total carbon number of 8 or less, for example, Acetylamino group, benzoylamino group,
Methanesulfonylamino group, benzenesulfonylamino group, etc., carboxy group, lower alkoxycarbonyl group (more preferably alkoxycarbonyl group having a total carbon number of 6 or less, such as ethoxycarbonyl group, butoxycarbonyl group, etc.), perfluoroalkyl group (more Preferably a perfluoroalkyl group having a total carbon number of 5 or less, such as a trifluoromethyl group, a difluoromethyl group, etc., and an acyl group (more preferably, an acyl group having a total carbon number of 8 or less, such as an acetyl group, a propionyl group, a benzoyl group, And a benzenesulfonyl group). In addition, when the nitrogen-containing heterocyclic nucleus represented by Z ₁₁ and Z ₁₂ represents benzimidazole or naphthimidazole, examples of preferable substituents include a halogen atom, a cyano group, a carboxy group and a lower alkoxycarbonyl group (more preferably total An alkoxycarbonyl group having 6 or less carbon atoms, such as an ethoxycarbonyl group, a butoxycarbonyl group), a perfluoroalkyl group (more preferably, a perfluoroalkyl group having a total carbon number of 5 or less, such as a trifluoromethyl group, a difluoromethyl group) And an acyl group (more preferably, an acyl group having a total carbon number of 8 or less, such as an acetyl group, a propionyl group, a benzoyl group, a benzenesulfonyl group, etc.).

Specific examples of the nitrogen-containing heterocyclic nucleus represented by Z ₁₁ and Z ₁₂ include, for example, benzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-ethylbenzothiazole and 5,6-dimethylbenzo. Thiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-butoxybenzothiazole, 5,
6-dimethoxybenzothiazole, 5-methoxy-6-
Methylbenzothiazole, 5-chlorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5-phenylbenzothiazole, 5-acetylaminobenzothiazole, 6-propionylaminobenzothiazole,
5-hydroxybenzothiazole, 5-hydroxy-6
-Methylbenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, naphtho [1,2-d] thiazole, naphtho [2,1-d] thiazole, 5-methylnaphtho [1,2-d] thiazole, 8-methoxynaphtho [1,2-d] thiazole, 8,9-dihydronaphthothiazole, 3,3-diethylindolenin,
3,3-dipropylindolenine, 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, benzoselenazole, 5-methylbenzoselenazole, 6
-Methylbenzoselenazole, 5-methoxybenzoselenazole, 6-methoxybenzoselenazole, 5-chlorobenzoselenazole, 5,6-dimethylbenzoselenazole, 5-hydroxybenzoselenazole, 5-hydroxy-6-methyl Benzoselenazole, 5,6-dimethoxybenzoselenazole, 5-ethoxycarbonylbenzoselenazole, naphtho [1,2-d] selenazole, naphtho [2,1-d] selenazole, 8,9-dihydronaphthoselenazole, Benzoxazole, 5-hydroxybenzoxazole, 5-methoxybenzoxazole, 5-phenylbenzoxazole, 5-phenethylbenzoxazole, 5-phenoxybenzoxazole, 5-chlorobenzoxazole, 5-chloro-6-
Methylbenzoxazole, 5-phenylthiobenzoxazole, 6-ethoxy-5-hydroxybenzoxazole, 6-methoxybenzoxazole, naphtho [1,2-d] oxazole, naphtho [2,1-d] oxazole, naphtho [2 , 1-d] Oxazole, 1-ethyl-5
Cyanobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-6-chloro-5-cyanobenzimidazole, 1-ethyl-6-chloro-5- Trifluoromethylbenzimidazole, 1-ethyl-6
-Fluoro-5-cyanobenzimidazole, 1-propyl-5-butoxycarbonylbenzimidazole, 1
-Benzyl-5-methylsulfonylbenzimidazole, 1-allyl-5-chloro-6-acetylbenzimidazole, 1-ethylnaphtho [1,2-d] imidazole,
1-ethylnaphtho [2,1-d] imidazole, 1-ethyl-6-chloronaphtho [2,1-d] imidazole, 2-quinoline, 4-quinoline, 8-fluoro-4-quinoline, 6
-Methyl-2-quinoline, 6-hydroxy-2-quinoline, 6-methoxy-2-quinoline and the like can be mentioned.

R ₁₁ and R ₁₂ in the general formula 1 may be the same or different substituents, and the sum of the individual hydrophobic parameters (log P) is 10.5 or more. R ₁₁ and R ₁₂ may each contain an oxygen atom, a nitrogen atom or a sulfur atom in the main chain, may contain a double bond or a triple bond, and may be a branched or substituted alkyl group. Represents Furthermore,
Within the range in which the sum of the hydrophobic parameters of R ₁₁ and R ₁₂ satisfies 10.5 or more, either one of the substituents is the substituent described above as the substituent of Z ₁₁ and Z ₁₂ as a preferable substituent. You can also list them. Examples of preferred substituents are higher alkyl groups (substituents even if branched, for example, hydroxy group, halogen atom, aryl group, allyl group, amino group, aryloxy group, arylthio group, alkoxy group, alkylthio group, It may have an alkoxycarbonyl group etc.).

L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ , L in the general formula 1
₁₅ , L ₁₆ and L ₁₇ each independently represent a methine group.
The methine group represented by L _{11 to} L ₁₇ may have a substituent, and examples of the substituent include a substituted or unsubstituted carbon number 1 to 15, preferably carbon number 1 to 10, and more preferably carbon. An alkyl group having 1 to 5 carbon atoms (eg, methyl group, ethyl group, 2-carboxyethyl group), substituted or unsubstituted 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms An aryl group (for example, a phenyl group, an o-carboxyphenyl group),
A substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms, preferably 4 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg, N, N-diethylbarbituric acid group), a halogen atom (eg, chlorine, Bromine, fluorine, iodine), carbon number 1 to 15, preferably carbon number 1 to 1
0, more preferably an alkoxy group having 1 to 5 carbon atoms (eg, methoxy group, ethoxy group), 1 to 1 carbon atoms
5, preferably 1 to 10, more preferably 1 to 5 carbon alkylthio groups (eg, methylthio groups,
An ethylthio group), an aryloxy group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (for example, a phenoxy group), and 6 to 2 carbon atoms.
An arylthio group having 0, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (for example, a phenylthio group), 0 to 15 carbon atoms, preferably 2 to 1 carbon atoms
0, more preferably an amino group having 4 to 10 carbon atoms (for example, N, N-diphenylamino group, N-methyl-N-
Phenylamino group, N-methylpiperazino group) and the like. Moreover, you may form a ring with another methine group.

N ₁₁ represents a number of 0 to 3, preferably 0, 1 or 2, and more preferably 0 or 1. p ₁₁ and p ₁₂ are 0 or 1 and preferably 0. X ₁₁ represents a charge-balancing ion required to neutralize the ionic charge of the dye. Typical cations are hydrogen ion (H ⁺ ), alkali metal ion (eg sodium ion, potassium ion, lithium ion),
Examples thereof include inorganic cations such as alkaline earth metal ions (eg calcium ion) and organic ions such as ammonium ion (eg ammonium ion, tetraalkylammonium ion, pyridinium ion, ethylpyridinium ion). The anion may be an inorganic anion or an organic anion, a halogen anion (eg, fluorine ion, chlorine ion, iodine ion), a substituted aryl sulfonate ion (eg, p-toluene sulfonate ion, p-chloro ion). Benzenesulfonate ion), aryldisulfonate ion (eg 1,3
-Benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkylsulfate ion (for example, methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate Acid ion, picrate ion,
Examples thereof include acetate ion and trifluoromethanesulfonate ion. It is preferably an anion. Further, an ionic polymer or another dye having a charge opposite to that of the dye may be used. m ₁₁ is 0 necessary to neutralize the charge of the molecule.
It is a number of ˜8, preferably 0 to 6, more preferably 0 to 3, and particularly preferably 1 or 2.

Among the spectral sensitizing dyes represented by the general formula 1, more preferable spectral sensitizing dyes are benzothiazole, naphthothiazole, benzoselenazole and naphthoselenazole as preferable nitrogen-containing heterocyclic nuclei represented by Z ₁₁ and Z _12. ,
This is a case where it has benzoxazole, naphthoxazole, and benzimidazole, and R ₁₁ and R ₁₂ represent an alkyl group which is not substituted with a group containing an aryl group and a heteroaromatic ring group. In this case, they may be the same or different, and each main chain may contain an oxygen atom, a nitrogen atom or a sulfur atom, and may also contain a double bond or a triple bond and may be branched. Most preferably, R ₁₁ and / or R ₁₂ represents an unsubstituted higher alkyl group. For example, the total number of carbon atoms in the alkyl chain is preferably 8 to 30, more preferably 10 to 25, and particularly preferably 10 to 18. Specific examples of preferred higher alkyl groups include decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group,
Hexadecyl group, heptadecyl group, octadecyl group and the like, more preferable examples are tridecyl group, tetradecyl group,
A pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group, and particularly preferable examples thereof include a hexadecyl group, a heptadecyl group, an octadecyl group, and the like. Specific examples of dyes are shown below.

[0019]

[Chemical 3]

[0020]

[Chemical 4]

[0021]

[Chemical 5]

[0022]

[Chemical 6]

[0023]

[Chemical 7]

[0024]

[Chemical 8]

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical 12]

In the present invention, in the silver halide emulsion and / or silver halide photographic light-sensitive material of the present invention, in combination with the spectral sensitizing dye represented by the above general formula 1, cyanine dye, merocyanine dye, composite Cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes can be used. A particularly useful dye is a cyanine dye.

For these dyes, any of the nuclei usually used for cyanine dyes as a basic heterocyclic nucleus can be applied. That is, a pyrroline nucleus, a toxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imigzole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzthiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzo Imidazole nucleus,
A quinoline nucleus or the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a virazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and a rhodanine are used. 5-6 membered heterocyclic nuclei such as nuclei, thiobarbituric acid nuclei, 2-thioselenazoline-2,4-dione nuclei can be applied.

For example, Research Disclosure 17
643, page 23, item IV (December 1978) or compounds described in the cited documents can be used. More specifically, the following compounds (pigments) can be used. a: 5,5'-dichloro-3,3'-diethylthiacyanine bromide, b: 5,5'-dichloro-3,3'-di (4-sulfobutyl) -thiacyanine Na salt, c: 5-methoxy- 4,5-benzo-3,3'-di (3
-Sulfopropyl) thiacyanine Na salt, d: 5,5'-dichloro-3,3'-diethylselenacyanine iodide, e: 5,5'-dichloro-9-ethyl-3,3'-di (3- Sulfopropyl) thiacarbocyanine pyridinium salt, f: anhydro-5,5'-dichloro-9-ethyl-3
-(4-sulfobutyl) -3'-ethyl hydroxide, g: 1,1-diethyl-2,2'-cyanine bromide, h: 1,1-dipentyl-2,2'-cyanine perchloric acid, i : 9-methyl-3,3'-di (4-sulfobutyl)-
Thiacarbocyanine pyridinium salt, j: 5,5'-diphenyl-9-ethyl-3,3'-di (2-sulfoethyl) -oxacarbocyanine Na salt, k: 5-chloro-5'-phenyl-9- Ethyl-3-
(3-Sulfopropyl) -3 '-(2-sulfoethyl)
Oxacarbocyanine Na salt, 1: 5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine Na salt, m: 5,5'-dichloro-6,6 ' -Dichloro. -1,
1'-diethyl-3,3'-di (3-sulfopropyl)
Imidacarbocyanine Na salt, n: 5,5'-diphenyl-9-ethyl-3,3'-di (3-sulfopropyl) thiacarbocyanine Na salt.

To incorporate the sensitizing dyes used in the present invention in the silver halide photographic emulsion of the present invention, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, acetone, Methyl cellosolve,
2,2,3,3-tetrafluoropropanol, 2,
2,2-trifluoroethanol, 3-methoxy-1-
It may be added to the emulsion by dissolving it in a single solvent or a mixed solvent of propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, acetonitrile, tetrahydrofuran, N, N-dimethylformamide and the like. Preferably, the effect of the present invention is further exhibited by preparing the dye-adding solvent so that the solvent polarity (q) of the emulsion is 70 or less. Further, as described in US Pat. No. 3,469,987, the dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion. Method, Japanese Examined Patent Publication No. 46-24, 1
No. 85, etc., a method in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and the dispersion is added to an emulsion, JP-B-44-23,389 and JP-B-4.
4-27,555, JP-B-57-22,091, etc., a dye is dissolved in an acid and the solution is added to the emulsion, or an acid or a base is coexistent to prepare an aqueous solution emulsion. Addition method, US Pat. No. 3,822,135
And U.S. Pat. No. 4,006,025, a method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant to an emulsion, JP-A-53-53.
-102,733 and JP-A-58-105,141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion, JP-A-51-
No. 74,624, it is also possible to use a method in which a dye is dissolved using a compound that causes red shift and the solution is added to an emulsion. Also, ultrasonic waves can be used for dissolution.

The sensitizing dye represented by the general formula 1 used in the present invention is, for example, JP-A-52-104,917, JP-B-43-25,652, and JP-B-57-22,368.
No. etc., FM Hamer, The Chemistry of Hetero
cyclic Compounds, Vol.18, The Cyanine Dyes and Rela
ted Compounds, A. Weissberger ed., Interscience, New
York, 1964., DMSturmer. The Chemistry of Hetero
cyclic Compounds, Vol.30, A. Weissberger and ECTay
lor ed., John Willy, New York, p.441.
It can be synthesized by referring to No. 270,164 or the like.

When the dyes are added in portions, the fluorescence yield of the dyes added later in the gelatin dry film is preferably 0.5 or more, and more preferably 0.8 or more. The reduction potential of the dye added later is preferably equal to or less than the reduction potential of the dye added earlier, and more preferably 0.03 V or more and base. Further, the oxidation potential of the dye to be added later is preferably 0.01 V or more and more base than the oxidation potential of the dye to be added first, and more preferably 0.03 V or more. The dye may be added at any time during preparation of the emulsion. The temperature of addition of the dye may be any number, but the emulsion temperature at the time of addition of the dye is preferably 10 ° C. or higher and 75 ° C. or lower, and particularly preferably 30 ° C. or higher and 65 ° C. or lower. The emulsion used in the present invention may be not chemically sensitized, but is preferably chemically sensitized. The total addition amount of the dye may be added before the chemical sensitization or after the chemical sensitization, but it is preferable to carry out the chemical sensitization after adding a part of the added dye, and then the remaining dye. The chemical sensitization can be performed more optimally by adding.

As the chemical sensitization method, a so-called gold compound sensitization method (for example, US Pat. No. 2,448,060) is used.
No. 3,320,069) or a sensitization method using a metal such as iridium, platinum, rhodium, palladium (for example, US Pat. Nos. 2,448,060 and 2,566,2).
45, 2,566,263) or a sulfur sensitizing method using a sulfur-containing compound (for example, US Pat. No. 2,222,222).
No. 264), a selenium sensitization method using a selenium compound, or a reduction sensitization method using tin salts, thiourea dioxide, polyamine, etc. (for example, US Pat. Nos. 2,487,850, 2,518,698, 2,521,925), or a combination of two or more of these. The silver halide photographic emulsion of the present invention is more preferably gold-sensitized or sulfur-sensitized, or a combination thereof. The addition amount of the gold sensitizer and the sulfur sensitizer is preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻² mol, and more preferably 5 × 10 ⁻⁶ to 1 × 10 ⁻³ , per mol of silver. is there. When gold sensitization and sulfur sensitization are used together, the molar ratio of the gold sensitizer and the sulfur sensitizer is preferably 1: 3 to 3: 1 and more preferably 1: 2 to 2.
It is 2: 1. The temperature at which the chemical sensitization of the present invention is performed,
It can be selected from any temperature between 30 ° C and 90 ° C. The pH for chemical sensitization is 4.5 to 9.0, preferably 5.0 to 7.0. The chemical sensitization time cannot be decided unconditionally because it varies depending on the temperature, the type and amount of the chemical sensitizer used, the pH, etc., but it can be arbitrarily selected from several minutes to several hours, usually from 10 minutes. 200
Done in minutes.

In the photographic emulsion controlling the light-sensitive mechanism in the present invention, any of silver bromide, silver iodobromide, silver chlorobromide, silver iodide, silver iodochloride, silver iodobromochloride, and silver chloride is used as a silver halide. Although the halogen composition on the outermost surface of the emulsion may be 0.1 mol% or more, more preferably 1 mol% or more, and particularly preferably 5 mol% or more iodine, a stronger multilayer adsorption structure can be constructed. The particle size distribution may be wide or narrow, but narrower is more preferable. The silver halide grains of a photographic emulsion are those having regular crystal grains such as cubes, octahedra, tetradecahedrons and rhombic dodecahedrons, and irregular grains such as spheres and plates. (Irregular) crystal form,
It may have a higher-order plane ((hkl) plane) or a mixture of grains of these crystal forms, but it is preferably tabular grains, particularly preferably 10 or more, more preferably 20 or more. It is a particle. The aspect ratio mentioned here is a value obtained by dividing the equivalent circle diameter of tabular grains by the thickness.
For particles with higher surface, see the Journal of Imaging Sci
ence magazine, volume 30 (1986), pages 247-254.
You can refer to the page. Further, the silver halide photographic emulsion used in the present invention may contain the above-mentioned silver halide grains alone or in a mixture of plural grains. The silver halide grains may have different phases in the inside and the surface, may have a multi-phase structure having a junction structure, may have a localized phase on the grain surface, or may have a uniform grain as a whole. It may consist of phases. Moreover, they may be mixed. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The photographic emulsion used in the present invention is described in "Graphic Chemistry and Physics" by Graphide (P. Glafkides, Chemie et P.
hysique Photographique, Paul Montel, 1967. ), "Photoemulsion Chemistry" by Duffin (GFDaffin, Photographic E
mulsion Chemistry, Focal Press, 1966.), Zelikman et al., "Manufacturing and coating of photographic emulsions" (VLZelikman et al.,
Making and Coating Photographic Emulsion, Focal Pr
ess, 1964.), FHClaes et al., The Journal of Pho
tographic Science, (21) 39-50, 1973. and FHClae
s et al., The Journal of Photographic Science, (2
1) 85-92, 1973., etc., JP-B-55-42,737
U.S. Pat. No. 4,400,463, U.S. Pat.
801,523, JP-A-62-218,959, 63-213,836, 63-218,938,
It can be prepared by the method described in the specification of Japanese Patent Application No. 62-291,487 and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. . A method of forming grains in the presence of excess silver (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. According to this method, a silver halide photographic emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Further, an emulsion prepared by a so-called conversion method including a process of converting into silver halide which has already been formed by the time the silver halide grain forming process is completed, or after completion of the silver halide grain forming process Emulsions which have undergone similar halogen conversion can also be used.

A silver halide solvent may be used during the production of the silver halide grains of the present invention. As a silver halide solvent often used, for example, a thioether compound (for example, US Pat. Nos. 3,271,157 and 3,57,57) is used.
4,628, 3,704,130, 4,27
6,347), thione compounds and thiourea compounds (for example, JP-A Nos. 53-144,319 and 53-8).
No. 2,408, No. 55-77,737, etc.), amine compounds (for example, JP-A No. 54-100,717, etc.) and the like, and these can be used. Ammonia can also be used within a range that does not have any adverse effect. During the production of the silver halide grains of the present invention, in order to accelerate the grain growth, the addition rate, the addition amount, and the addition concentration of the silver salt solution (for example, silver nitrate aqueous solution) and the halide solution (for example, saline solution) to be added are set to The method of increasing the temperature is preferably used. Regarding these methods, for example, British Patent 1,335,925 and US Pat.
72,900, 3,650,757, 4,24
2,445, JP-A-55-142,329, and 55.
-158,124, 55-113,927, 5
The description in 8-113,928, 58-111,934, 58-111,936 and the like can be referred to.

In the course of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, rhenium salt, ruthenium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or You may make the complex salt etc. coexist. Particularly, rhenium salt, iridium salt, rhodium salt, or iron salt is more preferable. As the addition amount of these, any amount can be added as necessary, and for example, an iridium salt (eg, Na ₃ IrC) can be added.
l ₆ , Na ₂ IrCl ₆ , Na ₃ Ir (CN) ₆ etc.)
Is a rhodium salt (for example, RhCl ₃ , K ₃ R, etc.) in an amount of 1 × 10 ⁻⁸ or more and 1 × 10 ⁻⁵ or less per mol of silver.
h (CN) ₆ etc. is 1 × 10 ⁻⁸ or more per mol of silver, 1
An amount in the range of × 10 ^-6 or less is desirable.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-CG, and N
o. Although described in the patents and the like described in 307105 and VII-C to G, the non-diffusible one having a hydrophobic group called a ballast group or the polymerized one is preferable. The coupler is 4 equivalent or 2 with respect to silver ion.
Either equivalence may be used. Further, a colored coupler having a color correction effect or a coupler releasing a development inhibitor upon development (so-called DIR coupler) may be included. In addition, the product of the coupling reaction is colorless,
Colorless DIR coupling compounds that release development inhibitors may also be included. Examples of couplers preferably used in the present invention include cyan couplers such as naphthol couplers and phenol couplers.
U.S. Patents 2,369.929, 2,772,162, 2,801,171
Issue 2, Issue 2,895,826, Issue 3,446,622, Issue 3,758,308
No., No. 3,772,002, No. 4,052,212, No. 4,126,396
Issue No. 4,146,396 Issue 4,228,233 Issue 4,254,212
No. 4,296,199, 4,296,200, 4,327,173
Issue 4,433,999, Issue 4,334,011, Issue 4,343,011
Issue 4,427,767, Issue 4,451,559, Issue 4,690,889
No. 4,775,616, West German Patent Publication 3,329,729, European Patents 121,365A, 249,453A, JP-A-61-42,658.
More preferably, the couplers described in US Pat. Examples of magenta couplers include imidazo [1,2-b] pyrazoles described in U.S. Pat.No. 4,500,630 and pyrazolo [1,5-b] [1,2,4] triazoles described in U.S. Pat. Particularly preferred. In addition, a pyrazolotriazole coupler in which a branched alkyl group as described in JP-A-61-65,245 is directly bonded to the 2-, 3- or 6-position of a pyrazolotriazole ring, and JP-A-61-65,246 is described. As described above, a pyrazoloazole coupler containing a sulfonamide group in the molecule, a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254, and a European patent (publication) ) It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. 226,849 and No. 294,785, and US Pat.
3,725,067, 4,310,619, 4,351,897, and
4,556,630, European Patent 73,636, JP-A-55-118,034
No., No. 60-35,730, No. 60-43,659, No. 60-185,951
No. 61-72,238, International Publication WO88 / 04795, and Research Disclosure No. 24220, same N
o. The couplers described in the patents described in 24230 are more preferable. Examples of yellow couplers include U.S. Patents 3,933,501, 3,973,968, 4,022,620, and
4,248,961, 4,314,023, 4,326,024,
4,401,752, 4,511,649, European Patent 249,473A
No. 5, Japanese Patent Publication No. 58-10,739, British Patent No. 1,425,020,
The couplers described in 1,476,760 and the like are more preferable, and the use of pivaloylacetanilides is more preferable. The above-mentioned couplers that can be preferably used in the present invention are the same as the couplers described in detail in JP-A-2-248,945 as preferred couplers, and can be preferably used in the present invention. Specific examples of the coupler include the same compounds as the specific examples of the coupler described in JP-A 2-248,945, pages 22 to 29.

Typical examples of polymerized dye-forming couplers include US Pat. Nos. 3,451,820 and 4,080,211;
No. 4,367,282, No. 4,409,320, No. 4,576,910, European Patent 341,188A, British Patent No. 2,102,137 and the like, and their use is more preferable. Examples of couplers in which the color forming dye has an appropriate diffusibility include U.S. Pat.
6,237, European patent 96,570, British patent 2,125,570
And those described in West German Patent Publication No. 3,234,533 are preferable. Colored to correct unwanted absorption of coloring pigments
The coupler is Research Disclosure No. 17
643, section VII-G, ibid. 307105, Patents described in Section VIIG, US Pat. Nos. 4,004,929, 4,138,25
8, 4,163,670, British Patent 1,146,368, Japanese Patent Publication
Those described in 57-39413 are preferable. US patent
A coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling described in 4,774,181 or a dye precursor group capable of reacting with a developing agent described in U.S. Pat.No. 4,777,120 to form a dye as a leaving group It is also preferable to use a coupler.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are described in RD.
No. 17643, section VII-F, ibid. 30710
5, patents described in paragraph VII-F, JP-A-57-151944
Issue 57-154234, Issue 60-184248, Issue 63-37346
No. 63-37350, U.S. Patent Nos. 4,248,962, 4,78
Those described in No. 2,012 are preferable. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include JP-A-59-157638, JP-A-59-170840, and British Patent
Those described in Nos. 2,097,140 and 2,131,188 are preferable. Further, by an oxidation-reduction reaction with an oxidant of the developing agent described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and 1-45687, a desensitizing agent, development acceleration Compounds that release agents, silver halide solvents, etc. are also preferred.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,338,3.
93, 4,310,618, etc., multiequivalent couplers, DIR, JP, 60-185950, 62-24252, etc.
Redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent 17
No. 3,302A, No. 313,308A, and the like, couplers that release dyes that recolor after separation, RD. No. 11449,
Same No. Patents described in 24241 and Japanese Patent Laid-Open No. 61-
Bleach accelerator releasing coupler described in 201247, etc., US patent
Examples thereof include ligand releasing couplers described in US Pat. No. 4,555,477, couplers releasing a leuco dye described in JP-A-63-75747, and couplers releasing a fluorescent dye described in US Pat. No. 4,774,181.

The above-mentioned couplers may be used in combination in two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and the same compound may be added in two or more different layers. Absent. The coupler is usually contained in the silver halide photographic emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 1.0 mol, per mol of silver halide.
Contains 0.5 mol. In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protect method. After being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or a gelatin aqueous solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by the so-called Fisher dispersion method. The low boiling point organic solvent may be removed from the coupler dispersion by a method such as distillation, washing with noodles or ultrafiltration, and then mixed with a photographic emulsion. The dispersion medium for such couplers includes a dielectric constant (25 ° C 2 to 20) and a refractive index (25 ° C 1.5
It is preferable to use a high-boiling point organic solvent of ~ 1.7 and / or a water-insoluble polymer compound. As a preferable high boiling point organic solvent, a solvent as described on page 30 of JP-A-2-248,945 is used, but it is immiscible with water having a melting point of 100 ° C. or lower and a boiling point of 140 ° C. or higher. Any compound can be used as long as it is a good solvent for the coupler. The melting point of the high-boiling organic solvent is preferably 80 ° C or lower, and the boiling point is preferably
The temperature is 160 ° C or higher, more preferably 170 ° C or higher. For details of these high boiling point organic solvents, see JP-A-62-215,27.
See No. 2, page 137, lower right column to page 144, upper right column.
Further, these couplers are impregnated with a loadable latex polymer (for example, US Pat. No. 4,203,716) in the presence or absence of the above high boiling point organic solvent, or dissolved in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a hydrophilic colloid aqueous solution. The homopolymers or copolymers described in International Publication WO 88/00723, pages 12 to 30 are preferably used, and the use of an acrylamide polymer is particularly preferable in terms of color image stabilization and the like.

In addition to the above-mentioned couplers, it is preferable to use the following compounds. That is, a compound that chemically bonds to an aromatic amine-based developing agent remaining after color development to form a chemically inactive and substantially colorless compound and / or an aromatic amine-based color development remaining after color development. It is possible to use, simultaneously or alone, a compound that forms a chemically inactive and substantially colorless compound by combining with an oxidized form of the main agent, for example, residual color development in the film during storage after processing. It is preferable for preventing the occurrence of stains and other side effects due to the formation of a coloring dye by the reaction of the main drug or its oxidant with the coupler. For such compounds and their preferable conditions, see JP-A-2-248,945.
Pp. 32 to 32, and preferred specific examples of the former compound include JP-A Nos. 63-158,545 and 62-283,338.
No. 62 / 158,342, European Patent Publication EP 277,589
No. 298,321 and the like, and preferred specific examples of the latter compound include JP-A-6-
2-143,048, 62-229,145, European published patent EP 25
5,722, Japanese Patent Application 62-158,342, Japanese Patent Application 62-214,681
No. 63 / 136,724, European Patent Publication No. 277,589,
Examples thereof include compounds described in JP-A No. 298,321.
Further, details of the combination of the former compound and the latter compound are described in European Patent Publication No. 277,589.

In the halogenated emulsion layer and / or other hydrophilic colloid layer of the silver halide photographic light-sensitive material containing the emulsion according to the present invention, image sharpness and safelight safety are further enhanced, and color mixing is further improved. A dye may be used for the purpose of prevention. The dye may be a layer containing the emulsion or a layer not containing the emulsion, but it is preferably fixed in a specific layer. For that purpose, the dye is contained in the colloid layer in a diffusion resistant state and used so that it can be decolorized during the development process. The first is to use a fine particle dispersion of a dye that is substantially insoluble in water having a pH of 7 and becomes soluble in water having a pH of 7 or more. Second, the use of acid dyes with polymers or polymer latices that provide cation sites. Dyes represented by formulas (VI) and (VII) described in JP-A-63-197,947 are useful in the first and second methods. In particular, a dye having a carboxy group is useful in the first method.

In the light-sensitive material of the present invention, phenethyl alcohol, JP-A-62-272248, JP-A-63-257747 and JP-A-62-272747 are used.
1,2-benzisothiazoline-3 described in 1-80941
-One, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol,
It is preferable to add various preservatives or antifungal agents such as 2-phenoxyethanol and 2- (4-thiazolyl) benzimidazole.

There are no particular restrictions on the other additives to the photographic light-sensitive material of the present invention. For example, Research Disclosure, Volume 176, Item 17643 (RD17643), and Volume 187, Item 18716.
(RD18716) and Volume 308 Item 308119 (RD30811
The description in 9) can be referred to. The places where various additives are described in RD17643 and RD18716 are listed below.

[0051]     Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer 23 pages 648 pages right column 996 pages 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, supersensitizer 23 to 24 pages 648 right column 996 right column                                             ~ 649 right column ~ 998 right column 4 Whitening agents Page 24 Page 998 Right column 5 Antifoggants, Stabilizers 24 to 25 pages 649 right column page 998 right column                                                           ~ 1000 page right column 6 Light absorbers, filter dyes, pages 25 to 26, page 649, right column, page 1003, left column     UV absorbers ~ page 650 left column ~ page 1003 right column 7 Anti-stain agent Page 25 Right column Page 650 Left column 1002 Right column                                                   ~ Right column 8 Dye image stabilizer Page 25 Page 1002 Right column 9 Hardener 26 pages 651 left column 1004 right column                                                           ~ Page 1005 left column 10 Binder page 26 same as above page 1003 right column                                                           ~ Page 1004 right column 11 Plasticizers and lubricants Page 27 Page 650 Right column Page 1006 Left column                                                           ~ Page 1006 right column 12 Coating aids, surface active agents Pages 26-27 Same as above Page 1005 Left column                                                           ~ Page 1006 left column 13 Antistatic agent Page 27 Same as above Page 1006 Right column                                                           ~ Page 1007 left column 14 Matting agent 1008 Page left column

The photographic light-sensitive material of the present invention is, for example, a black-and-white and color negative film for photography (general use, movie), a color reversal film (slide, movie), black-and-white and color photographic paper, color positive film (movie). , Color reversal printing paper, black and white and color photosensitive materials for heat development, black and white and color photographic photosensitive materials for plate making (lith film, scanner film, etc.), black and white medical and industrial photosensitive materials, black and white and color diffusion transfer photosensitive materials Although it can be applied to (DTR) and the like, it can be particularly preferably used for color paper.

Suitable supports usable in the present invention are described, for example, in RD. No. 17643, page 28, No. 18716, page 647, right column to page 648, left column, and No. 307105, page 879. Has been done.

Photographic processing of a light-sensitive material using the present invention includes
Any known method can be used, and a known processing solution can be used. The treatment temperature is usually selected between 18 ° C and 50 ° C,
Lower temperatures or temperatures above 50 ° C. may be used. Depending on the purpose, either a development process for forming a silver image (black and white photographic process) or a color photographic process including a development process for forming a dye image can be applied. Black and white developers include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3).
-Pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol), and other known developing agents can be used alone or in combination. The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg, 4-amino-N-diethylaniline, 4-amino-3-methyl-N,
N-diethylaniline, 4-amino-N-ethyl-N-
β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline,
4-amino-3-methyl-N-ethyl-N-β-methanesulfonylaminoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline and the like) can be used. In addition, L. F. A. Mason's "Photographic Processing Chemistry", published by Focal Press (1966), 226-
229. , US Pat. Nos. 2,193,015, 2,592,364, and JP-A-48-64,933 may be used. The developer may further contain a pH buffering agent such as an alkali metal sulfite, a carbonate, a borate and a phosphate, a bromide, an iodide, and a development inhibitor or an antifoggant such as an organic antifoggant. it can. If necessary, a water softener, a preservative such as hydroxyamine, an organic solvent such as benzyl alcohol or diethylene glycol, a polyethylene glycol, a quaternary ammonium salt, a development accelerator such as amines, a dye-forming coupler, a competitive coupler. , A covering agent such as sodium boron hydride, 1-phenyl-3-
Auxiliary developing agent such as pyrazolidone, viscosity imparting agent, US patent
The polycarboxylic acid type chelating agent described in 4,083,723 and the antioxidant described in West German publication (OLS) 2,622,950 may be included. When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. The bleaching process is
It may be performed at the same time as the fixing process, or may be performed individually. Examples of the bleaching agent include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV), copper (II), peracids, quinones, nitroso compounds and the like. For example, ferricyanide, dichromate, iron (II
I) or an organic complex salt of cobalt (III), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and 1,3-diamino-2-propanoltetraacetic acid, or organic acids such as citric acid, tartaric acid, and malic acid. Complex salts, persulfates, permanganates, nitrosophenols, etc. can be used. Of these, potassium ferricyanide, sodium ethylenediaminetetraacetic acid iron (III) complex salt and ethylenediaminetetraacetic acid iron (III) ammonium complex salt are particularly useful. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in the independent bleaching solution and in the one-bath bleach-fixing solution. For bleaching or bleach-fix solutions,
U.S. Pat.Nos. 3,042,520, 3,241,966, Japanese Patent Publication No. 45-8,506
No., in addition to the thiol compounds described in JP-B-45-8,836, etc.,
Various additives can also be added. Further, after the bleaching or the bleaching / fixing treatment, washing treatment may be carried out or only stabilizing bath treatment may be carried out.

The present invention can be preferably applied to a silver halide photographic light-sensitive material having a transparent magnetic recording layer. A silver halide photosensitive material carrying a magnetic recording layer used in the present invention is disclosed in Japanese Patent Application Laid-Open No. Hei 6 (1994)
-35118, JP-A-6-17528, and JIII Journal of Technical Disclosure No. 94-6023, in which a pre-heat-treated polyester thin layer support, for example, a polyethylene aromatic dicarboxylate-based polyester support, having a thickness of 50 μm is used.
To 300 μm, preferably 50 μm to 200 μm, more preferably 80 to 115 μm, and particularly preferably 85 to 1
The heat treatment (annealing) of 05 μm at a temperature of 40 ° C. or higher and a glass transition temperature or lower for 1 to 1500 hours is performed.
2603, Japanese Patent Publication No. 43-2604, Japanese Patent Publication No. 45-382
Ultraviolet irradiation described in No. 8, JP-B-48-5043, JP-A-SHO-5
Corona discharge described in 1-131576, etc.
7578, Japanese Patent Publication No. 46-43480, surface treatment such as glow discharge, undercoating described in US Pat. No. 5,326,689, and optionally an undercoating layer described in US Pat. -23505, Japanese Patent Laid-Open No. 4-350
The ferromagnetic particles described in 195726 and JP-A-6-59357 may be applied. The above-mentioned magnetic layer is disclosed in
The stripe shape described in JP-A-124642 and JP-A-4-124645 may be used.

Furthermore, if necessary, Japanese Patent Application Laid-Open No. 4-62543.
The antistatic treatment is applied, and finally a silver halide photographic emulsion is applied. As the silver halide photographic emulsion used here, JP-A-4-16693, JP-A-3-41436, and JP-A-3-41437 are used. It is preferable that the light-sensitive material thus produced is manufactured by the manufacturing control method described in Japanese Patent Publication No. 4-86817, and the manufacturing data is recorded by the method described in Japanese Patent Publication No. 6-87146. After that, or before that, JP-A-4-125
According to the method described in 560, a film narrower than the conventional 135 size is cut, and perforations are perforated with 2 holes per side for the small format screen to match the smaller format screen.

The film thus produced is described in JP-A-4-15.
7459 cartridge package and Japanese Patent Laid-Open No. 5-21020
Two examples of the cartridge shown in FIG. 9 or the film cartridge of US Pat. No. 4,221,479, US Pat. No. 4,834,306, US Pat. No. 4,834,366, US Pat. 846,41
It is used by putting it in the cartridge described in 8. The film cartridge or film cartridge used here is US Pat. No. 4,848,693, US Pat. No. 5,317,355.
From the viewpoint of light shielding properties, a type in which the tongue can be stored is preferable. Further, a cartridge having a lock mechanism as in US Pat. No. 5,296,886, US Pat.
It is preferable to use a cartridge in which the usage state described in 334 is displayed or a cartridge having a double exposure prevention function. Further, as described in JP-A-6-85128, a cartridge in which the film is easily attached by simply inserting the film into the cartridge may be used.

The film cartridge thus produced can be used for the purpose of photographing, developing, and enjoying various photographs by using a camera, a developing machine, and a laboratory device described below.
For example, a simple loading type camera described in JP-A-6-8886 or 6-99908, an automatic roll-up type camera described in JP-A-6-57398 or 6-101135, or a shooting process described in JP-A-6-205690. A camera in which the type of film can be taken out and exchanged with JP-A-5-29313
8. A camera capable of magnetically recording information on photographing, such as panoramic photographing, high-vision photographing, and normal photographing (magnetic recording with selectable print aspect ratio), as described in JP-A-5-283382, and JP-A-6-1011.
If the camera having the double exposure prevention function described in 94 or the camera having the use state display function of the film described in JP-A-5-150577 is used, the function of the film cartridge (patrone) can be sufficiently exhibited.

The film thus photographed is processed by the automatic developing machine described in JP-A-6-222514 and JP-A-6-212545, or before or during the processing or in JP-A-6-95265. The method of utilizing magnetic recording on a film described in JP-A-4-123054 may be used, or the aspect ratio selection function described in JP-A-5-19364 may be used. In the case of cine-type development during development processing, Japanese Patent Application Laid-Open No. Hei 5
Splicing and processing by the method described in 119461.
Also, during or after the development treatment, JP-A-6-14880
The attachment and detachment processing described in 5 is performed. After processing in this way, JP-A-2-184835 and JP-A-4-1863
35, the film information may be converted into a print through back printing and front printing on a color paper by the method described in JP-A-6-79968. Further, it may be returned to the customer together with the index print and return cartridge described in JP-A-5-11353 and JP-A-5-232594.

Evaluation of the amount of the sensitizing dye adsorbed on the emulsion grains is as follows.
A method of determining the amount of adsorbed dye by separating the emulsion adsorbing the dye into emulsion particles and supernatant gelatin aqueous solution by centrifuging, and determining the concentration of unadsorbed dye from the spectral absorption measurement of the supernatant and subtracting it from the amount of added dye , The precipitated emulsion particles are dried, a certain weight of the precipitate is dissolved in a 1: 1 mixture of sodium thiosulfate aqueous solution and methanol, and the amount of the adsorbed dye is determined by measuring the spectral absorption. went. A method for determining the amount of dye adsorbed by quantifying the amount of dye in the supernatant is described in, for example, W. West et al. Journal of Physical.
Chemistry (Journal of Physica)
l Chemistry, Vol. 56, page 1054 (1952), etc. can be referred to. Under conditions where the amount of dye added is large, even unadsorbed dye may settle, and the method of measuring the dye concentration in the supernatant may not always give the correct amount of adsorption. On the other hand, if the method of measuring the amount of dye adsorbed by dissolving the precipitated silver halide grains, the precipitation rate of emulsion particles is predominantly faster, so the particles and the precipitated dye can be easily separated, and the dye adsorbed on the particles can be easily separated. It turns out that only quantity can be measured accurately.

[0061]

The following examples are given to illustrate the present invention in more detail, but the present invention is not limited thereto. <Example 1> Preparation of pure silver bromide tabular grain emulsion and silver iodobromide tabular grain emulsion 6.4 g of potassium bromide in 1.2 liter of water and low molecular weight gelatin having an average molecular weight of 15,000 or less 6. While dissolving 2 g and maintaining the temperature at 30 ° C., 8 ml of a 16.4% silver nitrate aqueous solution and 7.2 ml of a 23.5% potassium bromide aqueous solution were added by a double jet method over 10 seconds. Next, 11.7% gelatin aqueous solution was further added, the temperature was raised to 75 ° C. and aging was performed for 40 minutes, and then 32.2% silver nitrate aqueous solution 370 ml and 2 were added.
A 0% aqueous potassium bromide solution was added over 10 minutes while maintaining the silver potential at -23 mV, and the temperature was lowered to 35 ° C after 1 minute physical ripening. Thus, the average projected area diameter is 2.32 μm, the thickness is 0.07 μm, and the variation coefficient of diameter is 1
A 5.1% monodisperse pure silver bromide tabular emulsion (specific gravity: 1.15) was obtained. After this, soluble salts were removed by the coagulation sedimentation method.
Keeping the temperature at 40 ℃ again, gelatin 45.6g, 1mol
10 ml of an aqueous solution of sodium hydroxide having a concentration of 1 / liter,
Add 167 ml of water and 10 ml of 5% phenol, p
Emulsion A was obtained by adjusting Ag to 6.83 and pH to 6.20. Thereafter, emulsion A was added with potassium thiocyanate, chloroauric acid and sodium thiosulfate so as to obtain optimum sensitivity, and ripened at 55 ° C. for 50 minutes. While maintaining the emulsion obtained as described above at 50 ° C, the dyes shown in Table 2 were added and stirred at 50 ° C for 30 minutes.

[0062]

[Chemical 13]

[0063]

[Table 2]

The amount of dye adsorbed was 200 for the obtained liquid emulsion.
The precipitate was lyophilized by centrifugation at 0 rpm for 20 minutes, and 25 mg of the precipitate was added to a 25% sodium thiosulfate aqueous solution 2
It was suspended in 5 mL, added with methanol to make 50 mL and dissolved, and this solution was subjected to spectroscopic absorption measurement to quantitatively determine the dye concentration.

A gelatin hardener and a coating aid were added to the obtained emulsion, and a gelatin protective layer was formed on the cellulose acetate film support so that the coated silver amount was 3.0 g-Ag / m ^2. And simultaneously applied. The resulting film was exposed to a tungsten bulb (color temperature 2856K) through a continuous wedge color filter for 1 second.
As a color filter, by combining a UVD33S filter and a V40 filter (manufactured by Toshiba Glass Co., Ltd.) for blue exposure for exciting silver halide, a wavelength range of 330 is obtained.
The sample was illuminated with light from nm to 400 nm. Also, as a minus blue exposure that excites the dye side, it can be passed through Fuji Gelatin Filter SC-52 (manufactured by FUJIFILM Corporation) 5
The light of 20 nm or less was blocked and the sample was irradiated. The exposed sample was developed for 10 minutes at 20 ° C. using the surface developer MAA-1 described below.

Surface developer MAA-1 Metol 2.5 g L-ascorbic acid 10 g Nabox (Fuji Film Co., Ltd.) 35 g Potassium bromide 1 g Water added 1 liter pH 9.8 Developed film is Fuji automatic densitometer The optical density is measured with and the fog is the density of the unexposed area, and the sensitivity is +0.2.
The reciprocal of the amount of light required to give the optical density of was shown as a relative value based on Comparative Example 1. The results are shown in Table 3 and Table 4.
Shown in. As shown in Table 3, with the sensitizing dyes other than the present invention, even if added in a large amount, they cannot be adsorbed on the surface of the particles by a saturated adsorption amount (coverage rate 100%) or more. It was possible to dramatically increase the amount of spectral sensitizing dye on the grain surface. Further, as shown in Table 4, the sensitivity of the dye-sensitized region was dramatically increased.

[0067]

[Table 3]

[0068]

[Table 4]

Example 2 In the preparation of emulsion A, an emulsion prepared by using a 20% aqueous solution of potassium bromide at the time of tabular grain growth and a mixed aqueous solution of 17% potassium bromide and 3% potassium iodide was designated as emulsion B. did. Thereafter, Emulsion B was added with potassium thiocyanate, chloroauric acid and sodium thiosulfate so as to obtain optimum sensitivity, and ripened at 55 ° C. for 50 minutes. 0.7 kg of silver iodobromide was contained in 1 kg of this emulsion. 25 g each of Emulsion B was weighed and kept at 50 ° C., 25 ml of a 2.8 × 10 ⁻³ mol / liter S-17 methanol solution was added, and the mixture was stirred at 50 ° C. for 30 minutes. 0.8 × 10 ^-3 mol / liter S-4
An emulsion prepared by adding 25 ml of 1-methanol solution and stirring at 50 ° C. for 30 minutes was designated as emulsion 2B. Samples 201 and 202 were prepared by coating the emulsions 2A and 2B as described below. The amount of coating liquid is 1.25 g / m ^{2 of} silver and 1.9 of gelatin.
It is set to be g / m ² and the amount of gelatin in the upper layer is 1.0 g /
such that m ^2, sodium dodecylbenzene sulfonate 0.22 g / l, p- sulfo sodium styrene homopolymers 0.50 g / l, 2,4-dichloro -
An aqueous solution mainly containing 3.1 g / liter of sodium 6-hydroxy-1,3,5-triazine and 50 g / liter of gelatin was simultaneously applied. Dye adsorption amount measurement, exposure and development were performed in the same manner as in Example 1, and the developed film was measured for optical density with a Fuji automatic densitometer. The fog was the density of the unexposed area and the sensitivity was +0.1 fog. The reciprocal of the amount of light required to give the optical density is shown as a relative value based on the sample 201.

The results are shown in Tables 5 and 6. As shown in Table 5, the spectral sensitizing dye of the present invention can increase the amount of the spectral sensitizing dye on the grain surface because the N-position substituent has no aryl group, and as shown in Table 6, The color sensitization sensitivity increased.

[0071]

[Table 5]

[0072]

[Table 6]

<Example 3> Preparation of silver iodobromide cubic emulsion 1000 ml of water, deionized bone gelatin in a reaction vessel
25g, 50% NH _FourNO₃15 ml of aqueous solution and 25%
NH₃Add 7.5 ml of the aqueous solution and keep it at 50 ° C.
Stir and 750 ml of 1N silver nitrate aqueous solution and 1 mol / l of bromide
Contains potassium and 0.05 mol / liter potassium iodide
Solution is added in 50 minutes to increase the silver potential during the reaction to +50.
kept at mV. The obtained silver iodobromide grains are cubic and have sides.
The length was 0.78 ± 0.06 μm. Temperature of the above emulsion
Lower the amount of isobutene and maleic acid monosodium salt
Copolymer is added as a coagulant, washed with sedimentation water and desalted.
It was Next, 95 g of deionized bone gelatin and water 43
0 ml was added to bring the pH to 6.5 and pAg 8.3 at 50 ° C.
After preparation, add sodium thiosulfate for optimum sensitivity.
The mixture was added and aged at 55 ° C. for 50 minutes. In 1 kg of this emulsion
Contained 0.74 moles of silver iodobromide. This emulsion
This is Emulsion C. Emulsion C 25 g each is weighed and brought to 60 ° C.
3.4x10 while keeping^-3mol / l of S-18
Add 5 ml of Tanol solution and 20 ml of water and add 30 minutes at 60 ℃.
The emulsion stirred for 3 A was changed to 3 A, and 6.9 × 10^-Fourmol / lit
25 ml of S-18 in methanol at 60 ° C
The emulsion stirred for 30 minutes was designated as Emulsion 3B. Emulsion 3A and
Samples coated with 3B are referred to as Sample 301 and Sample 302.
It was The coating conditions were the same as in Example 2. Dye adsorption amount measurement
The same procedure as in Example 1 was performed for the fixing, exposure and development, and the development
The film was measured for optical density with a Fuji automatic densitometer and
Is the density of the unexposed area and the sensitivity is +0.1
The reciprocal of the amount of light required to give the concentration is based on the sample 301
Was shown as a relative value.

The results are shown in Tables 7 and 8. As shown in Table 7, the spectral sensitizing dye of the present invention can increase the amount of the spectral sensitizing dye on the grain surface by adjusting the solvent polarity (q) to 70 or less. As shown in 8, the color sensitization sensitivity was increased.

[0075]

[Table 7]

[0076]

[Table 8]

Example 4 Preparation of Silver Iodobromide Octahedral Emulsion In the preparation of Emulsion C, the silver potential during grain growth was -40 mV.
The emulsion thus prepared was designated as Emulsion D. The obtained silver iodobromide grains were octahedral and had a projected area diameter of 0.86 ± 0.07μ.
It was m. 25 g each of Emulsion D was weighed and kept at 60 ° C., 5 ml of a methanol solution of 4.0 × 10 ⁻³ mol / liter of S-39 and 20 ml of water were added, and the emulsion was stirred at 60 ° C. for 30 minutes. 8.0 × 10 ^-4 mol / l S
An emulsion prepared by adding 25 ml of a -39 methanol solution and stirring at 60 ° C. for 30 minutes was designated as 4B. Samples coated with emulsions 4A and 4B were designated 401 and 402, respectively. The coating conditions were the same as in Example 2. The amount of coating liquid is 1.25 g / m ^{2 of} silver,
The gelatin amount was set to 1.9 g / m ^2, and the upper layer was adjusted to a gelatin amount of 1.0 g / m ² with sodium dodecylbenzenesulfonate 0.22 g / liter and p-sulfostyrene sodium homopolymer 0. .50 g / liter,
An aqueous solution containing 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium 3.1 g / liter and gelatin 50 g / liter as main components was simultaneously applied. Dye adsorption amount measurement, exposure and development are performed in the same manner as in Example 1,
The optical density of the developed film was measured by Fuji automatic densitometer, and the fog was the density of the unexposed area and the sensitivity was +0.1.
The reciprocal of the amount of light required to give the optical density of
Is shown as a relative value based on.

The results are shown in Tables 9 and 10. As shown in Table 9, the spectral sensitizing dye of the present invention has a solvent polarity (q)
The amount of the spectral sensitizing dye on the surface of the grain can be increased by adjusting the amount so that it becomes 70 or less, and as shown in Table 10, the color sensitizing sensitivity is remarkably increased.

[0079]

[Table 9]

[0080]

[Table 10]

Example 5 To 500 g of Emulsion B, 0.5 liter of water was added and maintained at 40 ° C., the first dye shown in Table 10 was added, and the mixture was stirred at 40 ° C. for 10 minutes. Thereafter, the temperature was raised to 55 ° C., and a 0.1 M potassium thiocyanate aqueous solution 7.8c was added.
c, 0.01% of chloroauric acid (3 cc) was added, and further 0.0
1% sodium thiosulfate 6.6 cc and M / 10000
5.3 cc of (diphenyl)-(pentafluorophenyl) -phosphine selenide was added and the mixture was aged at 55 ° C. for 30 minutes. After that, the second dye was added and the mixture was stirred at 55 ° C. for 30 minutes. The dye adsorption amount of the obtained emulsion was determined by the same method as in Example 1. Exposure and development were performed in the same manner as in Example 1. The optical density of the developed film was measured with a Fuji automatic densitometer, and the fog was defined as the density of the unexposed area, and the sensitivity was based on the reciprocal of the light amount required to give an optical density of +0.2 fog based on Comparative Example 1. Indicated.

[0082]

[Chemical 14]

[0083]

[Table 11]

The results are shown in Tables 12 and 13. Table 12
As shown in (3), even if the spectral sensitizing dye of the present invention was divided into two parts and added in large amounts, it was possible to adsorb a dye amount equal to or more than the saturated adsorption amount (coverage rate 100%) on the particle surface. . Further, as shown in Table 13, the particle surface of the first dye is about 80
% By performing chemical sensitization in the coated state, the chemical sensitized nuclei are site-limited, and the intrinsic sensitivity can be sensitized.
It was possible to further increase the sensitivity increase due to the increase in the amount of the spectral sensitizing dye.

[0085]

[Table 12]

[0086]

[Table 13]

<Example 6> Example 5 of JP-A-8-29904
A tabular silver iodobromide emulsion was prepared in the same manner as in Emulsion D. A multilayer color light-sensitive material was similarly prepared according to Sample 101 of Example 5 of JP-A-8-29904. Japanese Patent Laid-Open No. 8-
Fifth layer emulsion D in Sample 101 of Example 5 of 29904
Was replaced with Emulsion 4A, and H × ³ of 0.2 × 10 ⁻³ mol / mol Ag was added instead of ExS-1, 2 and 3, and then H-
601 was added to the sample to which 2.1 × 10 ⁻³ mol / mol Ag was added.
Alternatively, a sample in which H-3 was added at 0.2 × 10 ⁻³ mol / mol Ag and then S-41 was added at 2.1 × 10 ⁻³ mol / mol Ag was 602, and S-37 was 0.2 × 10 3. after addition ^-3 mol / mol Ag was S-41 to 2.1 × 10 ^-3 mol / mol Ag added sample was 603. In order to examine the sensitivity of the sample thus obtained, the light of a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was passed through an optical wedge and a red filter to
After exposure for 100 seconds, color development processing was performed using the same processing steps and processing solutions as in Example 1 of JP-A-8-29904, and cyan density was measured. The sensitivity was expressed as a relative value of fog density + 0.2. The results are shown in Table 14.

[0088]

[Chemical 15]

[0089]

[Table 14]

The spectral sensitizing dye of the present invention is applied to cover about 230%.
It was found that when a considerable amount was added, a dye having a coverage of 185% was adsorbed on the surface of the grain, and the sensitivity was increased even in a negative type multilayer color light-sensitive material.

<Example 7> Example 1 of JP-A-7-92601
In Emulsion 1 of Example 1, H-2 was replaced by 0.5 × 10 ⁻³ mol / mol Ag and H-5 was replaced by 1.9 × 10 ⁻³ mol / mol Ag instead of the spectral sensitizing dyes S-4 and S-5. Add the added emulsion to Emulsions 7A, S
-27 is 0.5 × 10 ^-3 mol / mol Ag and S-31 is 1.9.
The emulsion added with × 10 ^-3 mol / mol Ag was designated as Emulsion 7B. Further, in the emulsion 1 of Example 1 of JP-A-7-92601, the silver potential in the second double jet was changed from +65 mV to +11.
5 mV, spectral sensitizing dyes S-4 and S-
H-2 instead of 5, 0.5 × 10-3 mol / mol Ag and H
Emulsion 7 was prepared by adding -5 to 1.9 × 10 ^-3 mol / mol Ag.
Emulsion 7D was prepared by adding C and S-27 to 0.5 × 10 ⁻³ mol / mol Ag and S-31 to 1.9 × 10 ⁻³ mol / mol Ag. The multilayer color light-sensitive material is described in Example 4 of JP-A-7-92601.
A sample 401 was prepared in the same manner. Samples 701 and 702 were prepared by changing Emulsion 1 of the ninth layer of Sample 401 of Example 4 of JP-A-7-92601 to Emulsion 7A or Emulsion 7B. Similarly, Samples 703 and 704 were prepared by changing Emulsion 1 of the ninth layer in the same Example to Emulsion 7C or Emulsion 7D. The sensitivity of the sample thus obtained was evaluated. 1/5 as in Example 4 of JP-A-7-92601
The magenta density was measured after exposure for 0 seconds and color reversal development processing. The sensitivity was shown as a relative value when the reciprocal of the exposure amount required to give a density of the minimum density + 0.2 obtained by giving sufficient exposure was obtained and the sensitivity of Sample 701 was 100. The results are shown in Table 15.

[0092]

[Chemical 16]

[0093]

[Table 15]

It was found that when the dye of the present invention was added in an amount corresponding to a coverage of about 250%, the dye having a coverage of 190% was adsorbed on the surface of the grain, and the sensitivity was increased even in the inversion multilayer color light-sensitive material.

<Example 8> Example 1 of JP-A-5-313297
In the same manner as in Emulsions 1 and 5 above, an octahedral silver bromide internal latent image type direct positive emulsion and a hexagonal tabular silver bromide internal latent image type direct positive emulsion were prepared and designated as Emulsion 8A and Emulsion 8B. A color diffusion transfer photographic film was similarly prepared according to Sample 101 of Example 1 of JP-A-5-313297. Japanese Patent Laid-Open No. 5-
Emulsion 2 of 16th layer of Sample 101 of Example 1 of 313297
Was replaced with Emulsion 8A, and a sample to which H-6 was added at 1.0 × 10 ⁻³ mol / mol Ag instead of the addition of the sensitizing dye (3) was Sample 801 and S-21 at 1.0 × 10 ^−3. A sample to which mol / mol Ag was added was designated as Sample 802. Similarly, sample 10 of the same example
Emulsion-2 in the 16th layer of No. 1 was replaced with Emulsion 8B, and H-6 was replaced by 1.0 × 10 ⁻³ mol / instead of addition of the sensitizing dye (3).
Sample 803 with mol Ag added, 1.0 × with S-21
A sample to which 10 ⁻³ mol / mol Ag was added was designated as Sample 804. In order to examine the sensitivity of the sample thus obtained, Japanese Patent Laid-Open No. 5-313297
The same exposure, processing steps and processing solutions as in Example 1 of No. 1 were used, and the transfer density was measured with a color densitometer. The sensitivity was expressed as a relative value at a density of 1.0. The results are shown in Table 16.

[0096]

[Chemical 17]

[0097]

[Table 16]

When the dye of the present invention was added in an amount corresponding to a coverage of about 300%, S-21 was adsorbed on the surface of the particle in a dye corresponding to a coverage of 192% in Sample 803 and a coverage of 195% in Sample 806. It has been found that the sensitivity is also increased in the diffusion transfer photographic film.

<Example 9> Example 2 of JP-A-4-142536
In the preparation of Emulsion F, the red sensitizing dye (S-1) was not added before the sulfur sensitization, and in addition to the sulfur sensitization of triethylthiourea, chloroauric acid was also used in combination for optimal gold sulfur sensitization. After sensitizing with gold and sulfur, the emulsion containing 1.7 × 10 ^-3 mol / mol Ag of H-7 was added to emulsions 9A and S-29 at 1.7 × 10 ^-3 mol / mo.
l Emulsion 9B, S-22 was added to the emulsion with Ag added to 1.7 × 10
^The emulsion added with ^-3 mol / mol Ag was designated as Emulsion 9C. A multilayer color photographic printing paper was prepared in the same manner as the sample 20 of Example 1 of JP-A-6-347944. Samples 901, 902 and 903 were prepared by changing the emulsion of the first layer in Sample 20 of Example 1 of JP-A-6-347944 to emulsion 9A, emulsion 9B or emulsion 9C. In order to examine the sensitivity of the sample thus obtained, the light of a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was passed through an optical wedge and a blue filter to
After exposure for 10 seconds, color development processing was performed using the same processing steps and processing solutions as in Example 1 of JP-A-6-347944, and yellow density was measured. The results are shown in Table 17.

[0100]

[Chemical 18]

[0101]

[Table 17]

When the dye of the present invention was added in an amount corresponding to a coverage of about 250%, sample 903 had a coverage of 1 on the particle surface.
It was found that 88% of the dye was adsorbed and the sensitivity was increased even in a multilayer color printing paper.

<Example 10> A tabular silver chloride emulsion was prepared in the same manner as the emulsion A of Example 1 of Japanese Patent Application No. 7-232036, and the sensitizing dye in the chemical sensitization (B) of the same example was prepared. After adding 7.5 × 10 ⁻⁴ mol / mol Ag of H-8 instead of −1 and 2, addition of gold and sulfur selenium was carried out, and H-8 was added to 1.55.
× 10 ^-3 mol / mol Ag and H-2 3.0 × 10 ^-3 mol / mol
Emulsion 10A with Ag added, 7.5 × 10 with S-30
After adding ^-4 mol / mol Ag, it was sensitized with gold-sulfur selenium, and further, S-30 was 1.55 × 10 ^-3 mol / mol Ag and S-27 was 3.0 × 10 ^-3 mol / mol Ag. The added emulsion was designated as Emulsion 10B. The coated sample was prepared by replacing the emulsion of Example 1 of Japanese Patent Application No. 7-232036 with Emulsion 10A or Emulsion 10B, and combining both the emulsion layer and the surface protective layer on the support in the same manner as in the same example to obtain both sides by the simultaneous extrusion method. Was applied to the sample, and this was designated as sample 1001 and sample 1002. 1.75 silver coated on one side
It was set to g / m ² . In order to examine the sensitivity of the sample thus obtained, an X-ray orthoscreen HGM manufactured by Fuji Photo Film Co., Ltd. was used to perform exposure for 0.05 seconds from both sides, and an example of Japanese Patent Application No. 7-232036 was applied. Processing was carried out in the same manner as in No. 1 using an automatic processor and a processing solution. The sensitivity is expressed by the logarithm of the reciprocal of the exposure amount required to give a density of fog + 0.1.
The sensitivity of 1 was defined as 100, and the others were represented by relative values. The results are shown in Table 18.

[0104]

[Chemical 19]

[0105]

[Table 18]

It was found that when the dye of the present invention was added in an amount corresponding to a coverage of about 250%, the dye having a coverage of 195% was adsorbed on the particle surface, and the sensitivity was increased even in the Xray sensitive material. Similar effects were obtained by exposing with HR-4 or HGH instead of the X-ray orthoscreen HGM used at the time of exposure.

<Example 11> A tabular silver chloride emulsion was prepared which was different from the emulsion D of Example 2 of Japanese Patent Application No. 7-146891 only in that sensitizing dyes-2 and 3 were not added. Emulsion 11A was used. The applied sample is Example 3 of Japanese Patent Application No. 7-146891.
A coating sample F was prepared in the same manner. Emulsion F of coating sample F of Example 3 of Japanese Patent Application No. 7-146891 was replaced with Emulsion 11A, and H-8 was replaced with 3.9 × 10 ⁻³ mo instead of Sensitizing Dye-1.
Sample 110 replaced with a sample replaced with emulsion containing l / mol Ag
Sample 1102 was a sample in which S-1 and S-30 were replaced with an emulsion to which 3.9 × 10 ⁻³ mol / mol Ag was added. In order to examine the sensitivity of the sample thus obtained, the light of a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was exposed for 1/100 second through an optical wedge and a blue filter, and Fuji Photo Film CN16 treatment was applied to improve the photographic properties. Compared. The sensitivity was expressed by the logarithm of the reciprocal of the exposure amount required to give a density of fog + 0.2, and the sensitivity of Sample 1101 was set to 100. The results are shown in Table 1.
9 shows.

[0108]

[Table 19]

When the dye of the present invention was added in an amount corresponding to a coverage of about 250%, the dye having a coverage of 180% was adsorbed on the grain surface, and the sensitivity was also high in a silver chloride tabular emulsion having the (111) face as the outer surface. It turned out to rise.

<Example 12> An octahedral silver chloride emulsion was prepared in the same manner as Emulsion F in Example 3 of Japanese Patent Application No. 7-146891, and this was designated as Emulsion 12A. The coating sample was prepared in the same manner as the coating sample F in Example 3 of Japanese Patent Application No. 7-146891. Japanese Patent Application 7-14
The emulsion F of the coating sample F of Example 3 of No. 6891 was replaced with the emulsion 12A, and H-9 was replaced with 2.1 × 1 instead of the sensitizing dye-1.
Sample 1 was replaced with the emulsion added with 0 ^-3 mol / mol Ag
Sample 1202 was a sample in which 201 and S-23 were replaced with an emulsion in which 2.1 × 10 ⁻³ mol / mol Ag was added. In order to examine the sensitivity of the sample thus obtained, the light of a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was exposed for 1/100 second through an optical wedge and a blue filter, and Fuji Photo Film CN16 treatment was applied to improve the photographic properties. Compared. The sensitivity was expressed as the logarithm of the reciprocal of the exposure amount required to give a density of fog + 0.2, and the sensitivity of Sample 1201 was set to 100. The results are shown in Table 20.

[0111]

[Chemical 20]

[0112]

[Table 20]

It was found that when the dye of the present invention was added in an amount corresponding to a coverage of about 250%, the dye having a coverage of 181% was adsorbed on the grain surface, and the sensitivity increased even in an octahedral silver chloride emulsion.

Example 13 European Patent No. 0699950
When a tabular grain emulsion was prepared in the same manner as the emulsion CC of No. 1 and chemically sensitized, H-10 was replaced by 2.
After chemical sensitization by adding 1 × 10 ^-3 mol / mol Ag, H-1
0 to 4.6 × 10 ^-3 mol / mol Ag was added to Emulsion 13
Emulsion 13B was prepared by adding 2.1 × 10 ⁻³ mol / mol Ag of A and S-42 for chemical sensitization and then adding 4.6 × 10 ⁻³ mol / mol Ag of S-42. European Patent No. 0
Samples were prepared in the same manner as the coated sample of the Example of 699950, and the sample using the emulsion 13A was designated as sample 1301 and the sample using the emulsion 13B was designated as sample 1302. Exposure and development were performed in the same manner as in the patent, and the photographic properties were compared. Sensitivity is fog +0.
Expressed by the logarithm of the reciprocal of the exposure required to give a density of 2,
The sensitivity of Sample 1301 was set to 100. The results are shown in Table 21.

[0115]

[Chemical 21]

[0116]

[Table 21]

It was found that when the dye of the present invention was added in an amount corresponding to a coverage of about 250%, the dye having a coverage of 184% was adsorbed on the grain surface, and the sensitivity was increased even in a tabular grain emulsion.

[0118]

According to the present invention, it is possible to obtain an emulsion having a high amount of spectral sensitizing dye on the grain surface and a high-level photographic light-sensitive material using the emulsion.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI // C07D 215/04 C07D 215/04 235/20 235/20 (56) Reference JP-A-4-104138 (JP, A) JP-A-7-306512 (JP, A) JP-A-8-15832 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/14 G03C 1/015

Claims (5)

(57) [Claims] 1. A small amount of the spectral sensitizing dye represented by the general formula 1 is used.
Photographic silver halide containing at least one
emulsion. General formula 1 [Chemical 1] R in the formula₁₁And R₁₂Is a substituted or unsubstituted alkyl group
And R₁₁And R ₁₂Hydrophobic parameter of (log
The sum of P) has a value of 10.5 or more. Z₁₁And Z
₁₂May be the same or different and may be a 5- or 6-membered nitrogen containing
Represents a group of elementary heterocyclic nuclei, L₁₁, L₁₂, L₁₃,
L₁₄, L₁₅, L₁₆, And L₁₇Represents a methine group. p
₁₁And p₁₂Represents 0 or 1, and n₁₁Is 0, 1, 2
Or represents 3. X ₁₁Represents a charge-balancing counterion, m₁₁
Is the number from 0 to 8 required to neutralize the charge of the molecule.
Represent 2. The method according to claim 1, wherein the total addition amount of the spectral sensitizing dye represented by the general formula 1 is 160% or more of the saturated coating amount of the silver halide emulsion. Silver halide photographic emulsion. 3. The silver halide photographic emulsion according to claim 2, wherein the silver halide emulsion containing the spectral sensitizing dye has a solvent polarity (q) of 70 or less. 4. The method according to claim 2, wherein R ₁₁ and R ₁₂ of the spectral sensitizing dye represented by the general formula 1 is an alkyl group which is not substituted with a group containing an aryl group and a heteroaromatic ring group. The silver halide photographic emulsion according to claim 2, which is characterized in that. 5. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing the silver halide photographic emulsion according to claim 1 on a support.