JPH10171058A - Sliver halide photographic emulsion, and silver halide photographic sensitive material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide emulsion having high light absorbance per unit area of each rain surface and a photographic sensitive material containing this emulsion and having high sensitivity by incorporating an anionic dye and a cationic dye either having a specified valence or more and both in a specified proportion of a saturation coating amount or more in total. SOLUTION: The silver halide photographic emulsion contains an anionic dye and a cationic dye and either of the dyes has 2 or more valences, and the total addition amounts of both dyes are >=160% of a saturation coating amount. The silver halide photographic sensitive material is provided with at least one emulsion layer containing such a emulsion. The anionic dye has positive charge and the cationic dye has negative charge.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a spectrally sensitized silver halide photographic emulsion 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 latent image forming efficiency including the light absorptance of grains, spectral sensitization efficiency, and the minimum latent image size. Among them, several techniques that have been known so far regarding the technique for improving the light absorption of particles are shown below. The high aspect ratio tabular grain emulsion technology disclosed in U.S. Pat.
This is a technique capable of increasing the amount of dye adsorbed per particle because the surface area of the particle increases, and consequently improving the light absorption rate. However, there is a limit to the increase in the particle surface area due to an increase in the aspect ratio, and to increase the light absorptance of one particle, it is necessary to increase the size of the particle. Other methods for increasing the particle surface area per particle include those described in JP-A-58-106532 and JP-A-60-1985.
No. 221320, a method of forming a hole in a part of the particles, and a raffle particle described in US Pat. No. 4,643,966. However, in these methods, the morphology of the particles is unstable and extremely difficult in practice. Also, U.S. Pat. No. 5,302,499 discloses that a light-absorbing rate is improved by performing a layer configuration in which spectral sensitization characteristics and grain thickness are optimized. However, the improvement in light absorption by optimizing the particle thickness is at most about 10%. Therefore, it is necessary to improve the light absorptivity per unit surface area of a particle in order to dramatically improve the light absorptivity of one particle while keeping the particle size small in a stable particle form. For this purpose, it is necessary to increase the adsorption density of the sensitizing dye. However, the ordinary spectral sensitizing dye is adsorbed in a monomolecular layer with almost close packing, and is not adsorbed any more.

[0003] The method proposed for multilayer adsorption of a sensitizing dye on the particle surface will be described below. PBGilman, Jr. and colleagues describe Photographic Science and Engine Nearing (Ph
otographic Science and Engineering) Volume 20, Issue 3,
On page 97 (1976), a cationic dye was adsorbed on the first layer, and an anionic dye was adsorbed on the second layer using electrostatic force. Also GB Bird (GBBir
d) et al., in U.S. Pat. No. 3,622,316, multilayer dye adsorption of multiple dyes to silver halide and sensitization by the contribution of Forster type excitation energy transfer. However, even the methods of these patents and literatures are insufficient in terms of the light absorptance per unit surface area of the silver halide grains, and thus require further technical development.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide emulsion having a high light absorption rate per unit area of a grain surface and a high-sensitivity photographic material using the emulsion.

[0005]

The object of the present invention has been attained by the following (1) and (2). (1) It contains an anionic dye and a cationic dye, and the charge of either the anionic dye or the cationic dye is 2
And a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing the silver halide photographic emulsion. (2) A silver halide photographic emulsion characterized in that the total amount of the sensitizing dye added is 160% or more of the saturated coating amount, and at least one silver halide emulsion layer containing the silver halide photographic emulsion. The silver halide photographic material according to (1).

In the present invention, the cationic or anionic dye refers to a dye having a positive charge or a negative charge, respectively. The dye can be multi-layer-adsorbed on the surface of the silver halide grain by the above method, and the light absorption intensity of the sensitizing dye per unit area of the surface of the silver halide grain is 100.
I was able to do more. The “light absorption intensity” refers to the light absorption intensity of the sensitizing dye per unit surface area, and the light absorption intensity of the sensitizing dye per unit surface area refers to the amount of light incident on the unit surface area of the particle as I _0. , The optical density L where I is the amount of light absorbed by the sensitizing dye on the surface
og (I ₀ / (I ₀ −I)) is defined as a value obtained by integrating the wave number (cm ⁻¹ ), and the integration range is from 5000 cm ⁻¹ to 35 cm.
Up to 000 cm ^-1 . In a silver halide photographic emulsion containing silver halide grains having a light absorption intensity of 100 or more, it is preferable that the silver halide grains having a light absorption intensity of 100 or more include 1/2 or more of all silver halide grains. Further, the light absorption intensity is preferably 100 or more and 100,000 or less. Depending on the type of photographic light-sensitive material, it is necessary to have strong absorption in a narrower wave number range. Therefore, 90% or more of the light absorption intensity is from xcm ^-1 to x + 5000 cm ^-1 (where x is the light absorption intensity in the above range). Maximum value, 5000 cm ^-1 <x <3
It is more preferable to select the dye species so as to concentrate on the integration interval of 0000 cm ^-1 ). The saturation coverage of the present invention is a sensitizing dye amount to completely cover the emulsion grain surface when the molecular area of the sensitizing dye and 80 Å ^2.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The cationic dye used in the present invention is preferably represented by the following general formula (I). General formula (I)

[0008]

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In the formula (I), Q ₁ represents a methine group or a polymethine group necessary for forming a methine dye. It is also possible to form any methine dye by Q _1, preferred are cyanine dyes, merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, allopolar dyes, hemicyanine dyes, and styryl dyes. For a detailed description of these dyes, see FM Harmer, Heterocyclic Compounds-Cyanine Dyes and Relative Compounds.
ated Compounds), John Wiley & Sons-New York, London,
Published in 1964, DMSturmer
Written by Heterocyclic Compound Special
Topics in heterocyclic chemistry
(Heterocyclic Compounds-Special topics in heterocy
clic chemistry), Chapter 18, Section 14, pages 482 to 515, and the like. The general formulas of cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in U.S. Pat. No. 5,340,694, p.
Those shown in (XII) and (XIII) are preferred. The cationic dye used in the present invention is more preferably one represented by the following general formula (II). General formula (II)

[0010]

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In the general formulas (I) and (II), Z ₁ and Z ₂
And Z ₃ represent a group of atoms necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring. Preferred nitrogen-containing heterocyclic nuclei represented by Z ₁ , Z ₂ and Z ₃ include thiazole, benzothiazole, naphtho Thiazole, dihydronaphthothiazole, selenazole, benzoselenazole, naphthoselenazole, dihydronaphthoselenazole, oxazole,
Nitrogen-containing heterocyclic nuclei such as benzoxazole, naphthoxazole, benzimidazole, naphthoimidazole, pyridine, quinoline, imidazo [4,5-b] quinoxaline or 3,3-dialkylindolenin. More preferred nitrogen-containing heterocyclic nuclei, nitrogen-containing heterocycles such as benzothiazole, naphthothiazole, dihydronaphthothiazole, benzoselenazole, naphthoselenazole, dihydronaphthoselenazole, benzoxazole, naphthoxazole, benzimidazole, naphthimidazole and the like In this case, it represents a nucleus. The nitrogen-containing heterocyclic nucleus represented by Z ₁ , Z ₂ and Z ₃ may have one or more substituents. There are no particular restrictions on the substituent, but Z ₁ , Z ₂
And when the nitrogen-containing heterocyclic nucleus represented by Z ₃ represents a group other than benzimidazole or naphthoimidazole, and a preferable substituent is V, examples of V include a lower alkyl group (substituents even if branched; Group, a halogen atom, an aryl group, an aryloxy group, an arylthio group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, etc. More preferably, an alkyl group having a total carbon number of 8 or less, for example, a methyl group , Ethyl group,
Butyl, chloroethyl, 2,2,3,3-tetrafluoropropyl, hydroxy, benzyl, methoxyethyl, ethylthioethyl, ethoxycarbonylethyl and the like. ), A lower alkoxy group (which may further have a substituent. Examples of the substituent include the same substituents as those described above as examples of the substituent of the alkyl group. More preferably, the total number of carbon atoms And an alkoxy group of 8 or less, for example, a methoxy group, an ethoxy group, a pentyloxy group, an ethoxymethoxy group, a methylthioethoxy group, a phenoxyethoxy group, a hydroxyethoxy group, a chloropropoxy group, etc.), a hydroxy group, a halogen atom, An aryl group (eg, phenyl group, tolyl group, anisyl group, chlorophenyl group, etc.), a heterocyclic group (eg, thienyl group, furyl group, pyridyl group, etc.), an aryloxy group (eg, tolyloxy group, anisyloxy group, phenoxy group, Chlorophenoxy group), arylthio group (for example, tolylthio group, chlorophenylthio group) Group, phenylthio group) and lower alkylthio group (examples of the substituent which may be further substituted include those mentioned as examples of the substituent of the lower alkyl group, more preferably 8 or less total carbon atoms). Alkylthio groups such as methylthio group, ethylthio group, hydroxyethylthio group, chloroethylthio group, benzylthio group and the like, acylamino group (more preferably acylamino group having a total of 8 or less carbon atoms such as acetylamino group, benzoylamino group , A methanesulfonylamino group, a benzenesulfonylamino group, etc.), a lower alkoxycarbonyl group (more preferably, an alkoxycarbonyl group having a total of 6 or less carbon atoms, such as an ethoxycarbonyl group, a butoxycarbonyl group, etc.), a perfluoroalkyl group (more preferably, Perfluoroal with total carbon number of 5 or less Group, such as trifluoromethyl group, difluoromethyl group) and acyl group (more preferably a total carbon number of 8 or less acyl group such as acetyl group, propionyl group, benzoyl group, benzenesulfonyl group, etc.).
When the nitrogen-containing heterocyclic nucleus represented by Z ₁ , Z ₂ and Z ₃ represents benzimidazole or naphthimidazole, examples of preferred substituents include a halogen atom, a cyano group and a lower alkoxycarbonyl group (more preferably, An alkoxycarbonyl group having a number of 6 or less, for example, an ethoxycarbonyl group, a butoxycarbonyl group, and the like, a perfluoroalkyl group (more preferably, a perfluoroalkyl group having a total carbon number of 5 or less, for example, a trifluoromethyl group, a difluoromethyl group, and the like) and An acyl group (more preferably, an acyl group having a total of 8 or less carbon atoms, such as an acetyl group, a propionyl group, a benzoyl group, and a benzenesulfonyl group) is exemplified.
Z ₂ and Z ₃ may be the same or different.

Specific examples of the nitrogen-containing heterocyclic nucleus represented by Z ₁ , Z ₂ and Z ₃ include, for example, benzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole,
5-ethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-butoxybenzothiazole,
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-diethylindolenine, 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-methylbenzoselenazole, 5,6-dimethoxybenzoselenazole, 5-ethoxycarbonylbenzoselenazole, naphtho [1,2-d] selenazole, naphtho [2,1-d] selenazole, benzoxazole, 5 -Hydroxybenzoxazole, 5-methoxybenzoxazole, 5-phenylbenzoxazole, 5-phenethylbenzoxazole, 5-phenoxybenzoxazole, 5-chlorobenzoxazole, 5-chloro-6-methylbenzoxazole, 5-phenylthio Benzoxazole, 6-ethoxy-5-hydroxybenzoxazole, 6-methoxybenzoxazole, naphtho [1,2-d] oxazole, naphtho [2,1-d] oxazole, naphtho [2,3-
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 [2,3-d] imidazole, 1-ethyl-6-
Chloronaphtho [2,3-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.

R ₁ in the general formulas (I) and (II),
R ₂ and R ₃ represent an alkyl group or an aralkyl group;
Preferably it is an aralkyl group. The alkyl group described herein includes an alkenyl group and an alkynyl group. For example, an unsubstituted alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms (eg, methyl, ethyl, propyl) , Isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), a substituted alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms (as the substituent,
V, etc.). As the alkenyl group, an alkenyl group having 2 to 18, preferably 2 to 7, and particularly preferably 2 to 4 carbon atoms (for example,
Ethenyl, 1-methyl-ethenyl, 1,2-dimethylethenyl, (1-propenyl), (2-butenyl and the like), which may be substituted. Examples of the substituent include those described in the description of V. The alkynyl group is an alkynyl group having 2 to 18, preferably 2 to 7, and particularly preferably 2 to 4 carbon atoms (for example, ethynyl, propynyl, etc.) and may be substituted. Examples of the substituent include those described in the description of V. The aralkyl group is an aralkyl group having 7 to 24, preferably 7 to 16 carbon atoms (for example, a benzyl group, a phenethyl group, a 3-phenyl-propyl group, etc.),
It may be substituted. Examples of the substituent include those described in the description of V.

In the present invention, R ₁ , R ₂ and R ₃ are more preferably an alkyl group or an aralkyl group substituted with an ammonium salt so that the entire dye has a positive charge of 2 or more. An alkyl group or an aralkyl group substituted with an ammonium salt means an alkyl group or an aralkyl group substituted with an ammonium group, respectively. R
₁ may be any alkyl or aralkyl group substituted with an ammonium group, and the term "ammonio group" used herein includes a quaternary salt of a nitrogen-containing heterocyclic ring. Preferred ammonio groups include unsubstituted trialkylammonio groups having 1 to 7 carbon atoms (for example, trimethylammonio group, triethylammonio group, tripropylammonio group, tributylammonio group, dimethylethylammonio group, dibutylammonium group, dibutylammonium group). Ethyl ammonium group),
Examples of the substituted trialkylammonio group having 1 to 7 carbon atoms ｛substituents include those represented by V described above.
For example, a trichloromethylammonio group, a tri (2-methoxy) ethylammonio group, a tri (3,3-dichloropropyl) ammonio group, a dibutyl (2-hydroxyethyl) ammonio group), and a nitrogen-containing nitrogen atom having 1 to 18 carbon atoms Heterocyclic nitrogen quaternary salts (e.g., 1-pyridinio group, 1-methylpyridinio-4-yl group, 1-quinolinio group, 3-thiazolinio group, which are further substituted with the aforementioned substituent V or the like. Is also good). R ₁ is more preferably an unsubstituted trialkylammonio group having 1 to 4 carbon atoms (for example, a trimethylammonio group,
Triethylammonio group, tripropylammonio group,
Tributylammonio group), and a pyridinio group,
Particularly preferred are a trimethylammonio group, a triethylammonio group, and a pyridinio group. In the present invention, R ₁ , R ₂ , and R ₃ may have an anionic substituent (for example, a sulfo group or a carboxyl group), but the number thereof should not exceed the number of ammonium groups in the entire dye. Is preferred.

In formulas (I) and (II), L ₁ , L ₂ ,
L ₃ , L ₄ , L ₅ , L ₆ , L ₇ , L ₈ and L ₉ each independently represent a methine group. The methine group represented by L _{1 to} L ₉ may have a substituent. Examples of the substituent include a substituted or unsubstituted C ₁ to C 15, preferably C ₁ to C 10, more preferably C ₁ to C 10 carbon atom. An alkyl group of the formulas 1 to 5 (for example, a methyl group, an ethyl group, or a 2-carboxylethyl group); An aryl group (for example, a phenyl group or an o-carboxyphenyl group), a substituted or unsubstituted C 3 to C 2
A heterocyclic group having 0, preferably 4 to 15, more preferably 6 to 10 carbon atoms (eg, N, N-diethylbarbituric acid group), a halogen atom (eg, chlorine, bromine,
Fluorine, iodine), an alkoxy group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, a methoxy group or an ethoxy group);
To 15, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methylthio group, ethylthio group), 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 5 to 15 carbon atoms. 6 to 10
Aryloxy group (for example, phenoxy group) having 6 carbon atoms
To 20, preferably 6 to 15 carbon atoms, more preferably an arylthio group having 6 to 10 carbon atoms (eg phenylthio group), 0 to 15 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 10 carbon atoms. Amino group (for example, N, N-diphenylamino group, N-methyl-
N-phenylamino group, N-methylpiperazino group) and the like. Further, a ring may be formed with another methine group.

P ₁ , p ₂ and p ₃ represent 0 or 1.
n ₁ represents 0, 1, 2, or 3. M ₁ and M ₂ are included in the formula to indicate the presence of the anion required to neutralize the ionic charge of the dye. The anion may be either an inorganic anion or an organic anion,
Halogen anions (for example, fluorine ions, chlorine ions,
Iodine ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryldisulfonate ion (for example, 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonic acid ion) , 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (eg, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonic acid Ions. Further, another dye having a charge opposite to that of the ionic polymer or the dye may be used. m ₁ and m ₂ each represent a number from 0 to 8 required to neutralize the charge of the molecule. Specific dyes are shown below.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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The anionic dye used in the present invention is:
It is preferably represented by the following general formula (III). General formula (III)

[0027]

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In the formula (III), Q ₂ represents a methine group or a polymethine group necessary for forming a methine dye. Q
It is also possible to form any methine dye by ₂ but, preferred methine dyes and methine dyes listed in example Q _1. The anionic dye used in the present invention is more preferably represented by the following general formula (IV). General formula (IV)

[0029]

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Z ₄ , Z ₅ and Z ₆ in the general formulas (III) and (IV) may be the same or different.
And a 6- or 6-membered nitrogen-containing heterocyclic nucleus forming atom group, and preferred nitrogen-containing heterocycles include the nitrogen-containing heterocycles mentioned as preferred nitrogen-containing heterocycles formed by Z ₁ , Z ₂ and Z ₃ above. be able to. Further, the nitrogen-containing heterocyclic nucleus represented by Z ₄ , Z ₅ and Z ₆ may have one or more substituents,
Examples of preferred substituents include the aforementioned Z ₁ , Z ₂ and Z
_In addition to the substituents mentioned as preferable substituents which ₃ may have, a sulfo group, a sulfoalkyl group, a carboxyl group and the like can be mentioned. Specific examples of the nitrogen-containing heterocyclic nucleus represented by Z ₄ , Z ₅ and Z ₆ include the aforementioned Z ₁ , Z ₂ and Z ₃
Specific examples of the nitrogen-containing heterocyclic nucleus represented by are exemplified.

R ₄ , R ₅ and R ₆ represent an alkyl group or an aralkyl group having an anionic substituent, preferably an aralkyl group. Examples of the alkyl group or aralkyl group include those described as preferable alkyl groups or aralkyl groups represented by R ₁ , R ₂ and R ₃ . The anionic substituent referred to in the present invention is a substituent having a negative charge, and is an atomic group which is easily dissociated under neutral or weak alkaline conditions, particularly a substituent having a hydrogen atom. For example, a sulfo group (-SO ₃ ^-), sulfate group (-OSO ₃
^-), carboxyl group (-CO ₂ ^-), a phosphate group (-PO ₃ ^-), alkyl sulfonyl carbamoyl group (e.g., methanesulfonyl carbamoylmethyl group), acylcarbamoyl alkyl group (e.g., acetyl carbamoylmethyl group), acyl Examples include a sulfamoylalkyl group (eg, acetylsulfamoylmethyl group) and an alkylsulfonylsulfamoylalkyl group (eg, methanesulfonylsulfamoylmethyl group). In the present invention, R ₄ , R ₅ and R ₆ more preferably have a plurality of the above-mentioned anionic substituents so that the dye as a whole has a negative charge of 2 or more.

P ₄ , p ₅ and p ₆ represent 0 or 1. _{L 10, L 11, L 12} , L 13, L 14, L 15, L 16,
L ₁₇ and L ₁₈ each independently represent a methine group. L ₁₀
The methine group represented by L ₁₈ may have a substituent, and examples of the substituent include the substituents which L _{1 to} L ₉ may have. Further, a ring may be formed with another methine group.

N ₂ represents 0, 1, 2, or 3. M ₃ and M ₄ represent cations necessary for neutralizing the ionic charge of the dye. Typical cations include inorganic cations such as hydrogen ion (H +), alkali metal ion (eg, sodium ion, potassium ion, lithium ion), alkaline earth metal ion (eg, calcium ion), and ammonium ion (eg, ammonium ion). Organic ions such as an ion, a tetraalkylammonium ion, a pyridinium ion and an ethylpyridinium ion. Further, another dye having a charge opposite to that of the ionic polymer or the dye may be used. m ₃ and m ₄ each represent a number from 0 to 8 required to neutralize the charge of the molecule. Examples of specific dyes are shown below.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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In the present invention, general formulas (I) to (IV)
Sensitizing dyes other than the sensitizing dyes represented by may be used in combination, for example, a cyanine dye, a merocyanine dye, a complex cyanine dye, a holopolar cyanine dye, a hemicyanine dye,
A styryl dye and a hemioxonol dye can be used. Particularly useful dyes are cyanine dyes.

As these dyes, any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei 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 imigazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; Nucleus fused with an aromatic hydrocarbon ring, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzo Imidazole nucleus,
A quinoline nucleus or the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye has a ketomethylene structure as a nucleus having a birazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and rhodanine. A 5- to 6-membered heterocyclic nucleus such as a nucleus, a thiobarbituric acid nucleus and a 2-thioselenazoline-2,4-dione nucleus can be applied.

For example, Research Disclosure 17
643, page 23, IV (December 1978) or the compounds described in the cited documents. More specifically, the following compounds (dyes) can be used. a: 5,5'-dichloro-3,3'-diethylthiocyanine bromide, b: 5,5'-dichloro-3,3'-di (4-sulfobutyl) -thiocyanine Na salt, c: 5-methoxy- 4,5-benzo-3,3'-di (3
-Sulfopropyl) thiocyanine Na salt d: 5,5'-dichloro-3,3'-diethyl selenocyanine iodide, e: 5,5'-dichloro-9-ethyl-3,3'-di (3-sulfo Propyl) 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, l: 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 into the silver halide photographic emulsion of the present invention, they may be directly dispersed in the emulsion or may be dispersed in water, methanol, ethanol, propanol, acetone, Methylcellosolve,
2,2,3,3-tetrafluoropropanol, 2,
2,2-trifluoroethanol, 3-methoxy-1-
A solvent such as propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, acetonitrile, tetrahydrofuran, N, N-dimethylformamide or the like may be dissolved alone or in a mixed solvent and added to the emulsion. Further, as described in U.S. Pat. No. 3,469,987, a 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. A method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to an emulsion as described in JP-B-46-24,185; 389, JP-B-44-27,
No. 555, JP-B-57-22091, etc., the dye is dissolved in an acid and the solution is added to the emulsion, or the solution is added to the emulsion as an aqueous solution in the presence of an acid or base. As described in U.S. Pat. No. 3,822,135 and U.S. Pat. No. 4,006,025, a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion, JP-A-53-102,
No. 733, JP-A-58-105,141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion.
As described in (1), a method in which a dye is dissolved using a compound that causes a red shift, and the solution is added to an emulsion can also be used. Also, ultrasonic waves can be used for dissolution.

The general formulas (I) and (I) used in the present invention
The sensitizing dyes represented by I), (III) and (IV) are described, for example, in JP-A-52-104,917,
3-25,652, JP-B-57-22,368, etc .; and FMHamer, The Chemistry of Heterocyclic.
Compounds, Vol. 18, The Cyanine Dyes and Related C
ompounds, A. Weissberger ed., Interscience, New Yor
k, 1964., DMSturmer. The Chemistry of Heterocycl
ic Compounds, Vol. 30, A. Weissberger and ECTaylor
ed., John Willy, New York, p. 441.
It can be synthesized by referring to No. 6966 and the like.

The total amount of the cationic dye and the anionic dye used in the present invention is preferably 100% to 700% of the saturated coating amount, more preferably 16%.
0% or more and 500% or less, particularly preferably 200%
Not less than 400%. The cationic dye and the anionic dye can be used in any ratio, but preferably the ratio of the cationic dye / anionic dye is 0.1 to 0.1.
10, more preferably 0.5 to 2, and particularly preferably 0.8 to 1.25. The dye may be added to the emulsion by mixing several dyes in advance,
It is preferable that the cationic cyanine dye and the anionic cyanine dye are added separately. Further, each dye may be divided and added several times. Either the anionic dye or the cationic dye may be added first, but the dye added first has a saturation coverage of 100%.
% Or more, preferably 150% or more, more preferably 2% or more.
It is preferable to add at least 00%. When the dye is added in portions, the fluorescence yield of the dye to be added later in the gelatin dry film is preferably 0.5 or more, more preferably 0.8 or more. Further, the reduction potential of the dye added later is equal to or lower than the reduction potential of the dye added earlier, and more preferably 0.03 V or more. The oxidation potential added later is 0.01 V or more lower than the oxidation potential of the dye added earlier.
Further, it is more preferable that the base voltage is 0.03 V or more. The dye may be added at any time during the preparation of the emulsion. The temperature at which the dye is added may be any number of times, but the emulsion temperature at the time of adding the dye is preferably from 10 ° C to 75 ° C, particularly preferably from 30 ° C to 65 ° C. The emulsion used in the present invention may be unchemically sensitized, but is preferably chemically sensitized. The total amount of the dye added may be added before the chemical sensitization or may be added after the chemical sensitization, but the chemical sensitization is performed after a part of the added dye is added, and then the remaining dye is added. Is more preferable.

As a chemical sensitization method, a gold sensitization method using a so-called gold compound (for example, US Pat. No. 2,448,060)
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).
No. 45, No. 2,566,263) or a sulfur sensitization method using a sulfur-containing compound (for example, US Pat.
264), a selenium sensitization method using a selenium compound, or a reduction sensitization method using tin salts, thiourea dioxide, polyamine or the like (for example, U.S. Pat. Nos. 2,487,850 and 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. Preferred amounts of the gold sensitizer and sulfur sensitizer to be added are 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 in combination, the preferable ratio of the gold sensitizer to the sulfur sensitizer is 1: 3 to 3: 1 in terms of a molar ratio, and more preferably 1: 2 to 2.
2: 1. As the temperature for performing the chemical sensitization of the present invention,
Any temperature between 30 ° C and 90 ° C can be selected. The pH at the time of chemical sensitization is in the range of 4.5 to 9.0, preferably 5.0 to 7.0. The time of the chemical sensitization varies depending on the temperature, the type and the amount of the chemical sensitizer used, the pH, etc., and therefore cannot be unconditionally determined, but can be arbitrarily selected from several minutes to several hours, and usually from 10 minutes to 10 minutes. 200
Done between minutes.

In the present invention, the photographic emulsion which controls the photosensitive mechanism includes any of silver bromide, silver iodobromide, silver chlorobromide, silver iodide, silver iodochloride, silver iodobromochloride and silver chloride as silver halide. Although a halogen composition on the outermost surface of the emulsion may contain iodine of 0.1 mol% or more, more preferably 1 mol% or more, particularly preferably 5 mol% or more, 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 have regular crystals such as cubic, octahedral, tetradecahedral, and rhombohedral, and irregular grains such as spheres and plates. (Irregular) crystal form,
It may have a higher-order plane ((hkl) plane), or may be a mixture of grains of these crystal forms, but are preferably tabular grains, particularly preferably 10 or more, more preferably 20 or more. Particles. The aspect ratio referred to here is a value obtained by dividing the equivalent circle diameter of the tabular grains by the thickness.
See the Journal of Imaging Sci for particles with higher order surfaces.
ence, Vol. 30 (1986), pages 247 to 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 singly or in combination. The silver halide grains may have different phases between the inside and the surface layer, may have a multiphase structure having a bonding structure, may have a localized phase on the grain surface, or may have a uniform grain as a whole. It may consist of phases. They may be mixed. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside a grain.

The photographic emulsions used in the present invention are described in "Graft Kides, Chemistry and Physics" (P. Glafkides, Chemie et P.).
hysique Photographique, Paul Montel, 1967.), "Emulsion Chemistry" by Daffin (GFDaffin, Photographic E
mulsion Chemistry, Focal Press, 1966.), Zerikman et al., "Production 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) Documents such as 85-92,1973.
No. 4,400,463, U.S. Pat.
Nos. 801 and 523, JP-A-62-218,959, JP-A-63-213,836 and JP-A-63-218,938.
It can be prepared using the method described in the specification such as JP-A-2-32. That is, any of an acidic method, a neutral method, an ammonia method, and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a simultaneous mixing method, a combination thereof, and the like. .
A method of forming grains in the presence of excess silver (so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, 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 nearly uniform grain size can be obtained.

Further, an emulsion prepared by a so-called conversion method including a step of converting silver halide grains into silver halide grains already formed before the silver halide grain formation step is completed, or after the silver halide grain formation step is completed. Emulsions subjected to the same halogen conversion can also be used.

During the production of the silver halide grains of the present invention, a silver halide solvent may be used. Examples of frequently used silver halide solvents include, for example, thioether compounds (for example, U.S. Pat. Nos. 3,271,157 and 3,57
4,628, 3,704,130, 4,27
No. 6,347, etc.), thione compounds and thiourea compounds (for example, JP-A Nos. 53-144,319 and 53-8).
2,408, 55-77,737), amine compounds (for example, JP-A-54-100,717) and the like, and these can be used. Ammonia can also be used in a range that does not cause adverse effects. In the production of the silver halide grains of the present invention, in order to accelerate the grain growth, the addition rate, amount and concentration of the added silver salt solution (for example, aqueous silver nitrate solution) and the halide solution (for example, aqueous sodium chloride solution) are changed. Is preferably used. Regarding these methods, for example, British Patent 1,335,925, US Pat.
Nos. 72,900, 3,650,757, 4,24
2,445, JP-A-55-142,329, and 55
-158,124, 55-113,927, 5
Nos. 8-113,928, 58-111,934 and 58-111,936 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 The complex salt may coexist. Particularly, a rhenium salt, an iridium salt, a rhodium salt, or an iron salt is more preferable. Any of these can be added as needed, for example, an iridium salt (for example, Na ₃ IrCl ₆ ,
Na ₂ IrCl ₆ , Na ₃ Ir (CN) _6, etc.) in an amount of 1 × 10 ⁻⁸ or more and 1 × 10 ⁻⁵ or less per mole of silver,
Rhodium salts (eg, RhCl ₃ , K ₃ Rh (CN)
₆ ) is preferably in the range of 1 × 10 ⁻⁸ or more and 1 × 10 ⁻⁶ or less per mol of silver.

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. 17643, VII-CG and N
o. 307105, VII-CG, etc., are described in the patents and the like. However, a non-diffusible one having a hydrophobic group called a ballast group or a polymerized one is desirable. The coupler has 4 equivalents or 2
Equivalence may be used. Further, a colored coupler having a color correcting effect or a coupler which releases a development inhibitor during development (a so-called DIR coupler) may be included. Also, the product of the coupling reaction is colorless,
A colorless DIR coupling compound that releases a development inhibitor may be included. Examples of the coupler preferably used in the present invention include, for example, naphthol couplers and phenol couplers as cyan couplers.
U.S. Patents 2,369.929, 2,772,162, 2,801,171
Nos. 2,895,826, 3,446,622, 3,758,308
Nos. 3,772,002, 4,052,212, 4,126,396
Nos. 4,146,396, 4,228,233, 4,254,212
Nos. 4,296,199, 4,296,200, 4,327,173
No. 4,333,999, 4,334,011, 4,343,011
Nos. 4,427,767, 4,451,559, 4,690,889
No. 4,775,616, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, JP-A-61-42,658
And the like. As magenta couplers, imidazo [1,2-b] pyrazoles described in U.S. Pat.No. 4,500,630 and the like, and pyrazolo [1,5-b] [1,2,4] triazoles described in U.S. Pat. Particularly preferred. Further, pyrazolotriazole couplers in which a branched alkyl group is directly linked to the 2-, 3- or 6-position of the pyrazolotriazole ring as described in JP-A-61-65,245, described in JP-A-61-65,246 Pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147,254 and European Patent It is preferable to use pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position as described in 226,849 and 294,785. In addition, U.S. Pat.
3,725,067, 4,310,619, 4,351,897,
4,556,630, European Patent 73,636, JP-A-55-118,034
Nos. 60-35,730, 60-43,659, 60-185,951
No. 61-72,238, International Publication WO88 / 04795, and Research Disclosure No. 24220, N
o. The couplers described in Patent No. 24230 and the like are more preferable. As yellow couplers, for example, U.S. Pat.Nos. 3,933,501, 3,973,968, 4,022,620,
4,248,961, 4,314,023, 4,326,024,
4,401,752, 4,511,649, European Patent 249,473A
No. 58-10,739, UK Patent 1,425,020,
The couplers described in 1,476,760 and the like are more preferred, and the use of pivaloylacetoanilides is more preferred. The 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 2-248,945, pp. 22-29.

Typical examples of polymerized dye-forming couplers include US Pat. Nos. 3,451,820 and 4,080,211;
Nos. 4,367,282, 4,409,320, 4,576,910, EP 341,188A, and UK Patent 2,102,137, and the use thereof is more preferable. U.S. Pat.
6,237, European Patent 96,570, UK Patent 2,125,570
And those described in West German Patent Publication No. 3,234,533 are preferred. A colored coupler for correcting unnecessary absorption of a coloring dye is described in Research Disclosure No. 176
43, section VII-G, ibid. No. 307105, patents described in section VIIG, U.S. Pat. Nos. 4,004,929 and 4,138,258
No. 4,163,670; British Patent No. 1,146,368;
Preferred are those described in JP-A-7-39413. US Patent
No. 4,774,181 discloses a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling, or a dye precursor group capable of forming a dye by reacting with a developing agent described in U.S. Pat. It is also preferable to use a coupler.

Compounds which release a photographically useful residue upon coupling can also be preferably used in the present invention.
The DIR coupler releasing the development inhibitor is described in RD.
No. 17643, section VII-F, ibid. 30710
5, Patents described in Section VII-F, JP-A-57-151944
No. 57-154234, No. 60-184248, No. 63-37346
Nos. 63-37350, U.S. Pat.Nos. 4,248,962 and 4,78
Those described in 2,012 are preferred. Couplers which release a nucleating agent or a development accelerator imagewise during development are disclosed in JP-A-59-157638, JP-A-59-170840, and British Patent
Those described in 2,097,140 and 2,131,188 are preferred. Further, by a redox reaction with an oxidized form of the developing agent described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-45687, a fogging agent, development acceleration Also, compounds which release agents, silver halide solvents and the like are 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 the like, and US Pat.
No. 93, 4,310,618, etc., and DIR described in JP-A-60-185950, JP-A-6-24252, etc.
Redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, EP 17
No. 3,302A, No. 313,308A, etc., couplers which release dyes which recolor after release, RD. No. 11449,
No. Patent No. 24241 and Japanese Patent Application Laid-Open No.
Bleaching accelerator releasing couplers described in 201247, etc., U.S. Patent
Examples thereof include a ligand releasing coupler described in 4,555,477, a coupler releasing leuco dye described in JP-A-63-75747, a coupler releasing a fluorescent dye described in US Pat. No. 4,774,181 and the like.

The couplers and the like can be used in combination of two or more in the same layer in order to satisfy the characteristics required for the light-sensitive material. Of course, the same compound can be added to 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.
0.5 mol is contained. 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 protection method, and after being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. Further, the alkali-soluble coupler can be dispersed by a so-called Fisher dispersion method. After removing the low-boiling organic solvent from the coupler dispersion by a method such as distillation, noodle washing or ultrafiltration, it may be mixed with a photographic emulsion. As a dispersion medium of such a coupler, a dielectric constant (2 to 20 at 25 ° C, a refractive index (1.5 to 25 ° C)
It is preferred to use a high boiling organic solvent and / or a water-insoluble polymer compound having a molecular weight of -1.7. As the preferred high-boiling organic solvent, a solvent as described on page 30 of JP-A-2-248,945 is used, but the solvent having a melting point of 100 ° C or less and a boiling point of 140 ° C or more is immiscible with water. 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 organic solvents, see JP-A-62-21527.
No. 2 is described in the lower right column on page 137 to the upper right column on page 144.
These couplers may be impregnated with a loadable latex polymer (for example, US Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvent, or dissolved in a water-insoluble and organic solvent-soluble polymer. And emulsified and dispersed in a hydrophilic colloid aqueous solution. Homopolymers or copolymers described in WO 88/00723, pages 12 to 30, are preferably used, and the use of an acrylamide polymer is particularly preferred for stabilizing a color image.

Further, it is particularly preferable to use the following compounds together with the above-mentioned coupler. That is, a compound that is chemically bonded to an aromatic amine-based developing agent remaining after color development to form a chemically inert and substantially colorless compound and / or an aromatic amine-based color development remaining after color development. Simultaneous or sole use of a compound which forms a chemically inert and substantially colorless compound in combination with the oxidized form of the active ingredient can be achieved, for example, by remaining color development in the film during storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the main drug or its oxidized product and the coupler. Regarding such compounds and their preferable conditions, see JP-A-2-248,945 31
Pp. 32 to 32, and preferred examples of the former compound are described in JP-A-63-158,545 and JP-A-62-283,338.
No. 64-2042, European Patent Publication EP 277,589, No. 2
No. 98,321 and the like, and preferred specific examples of the latter compound are described in JP-A-62-143,048.
No. 62-229,145, European Patent Publication EP 255,722,
JP-A 64-2042, JP-A-1-57259, JP-A-1-230039
And European Patent Publications 277,589 and 298,321. The details of the combination of the former compound and the latter compound are described in EP-A-277,589.

In the silver halide photographic light-sensitive material containing the emulsion according to the present invention, the halogenated emulsion layer and / or the other hydrophilic colloid layer may have higher image sharpness and safelight safety, and may have better color mixture. Dyes may be used for such purposes as prevention. The dye may be a layer containing the emulsion or a layer not containing the above-mentioned emulsion, but is preferably fixed to a specific layer. For this purpose, a dye is contained in the colloid layer in a diffusion-resistant state, and is used so that it can be decolorized in the course of development processing. The first is to use a fine particle dispersion of a dye which is substantially insoluble in water having a pH of 7 and is soluble in water having a pH of 7 or more. Second, the use of an acid dye with a polymer or polymer latex that provides cationic sites. In the first and second methods, dyes represented by formulas (VI) and (VII) described in JP-A-63-197,947 are useful. In particular, a dye having a carboxy group is useful for the first method.

In the light-sensitive material of the present invention, phenethyl alcohol and JP-A-62-272248, JP-A-63-257747, JP-A
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 fungicides such as 2-phenoxyethanol and 2- (4-thiazolyl) benzimidazole.

The other additives of the photographic light-sensitive material of the present invention are not particularly limited. For example, Research Disclosure, Vol.
(RD18716) and 308 volume item 308119 (RD30811
9) can be referred to. The places where various additives are described in RD17643 and RD18716 are listed below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23, page 648, right column, page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, supersensitizer 23 to 24, page 648, right column, page 996 right column 649Page 649 right column 998998 page right column 4 Brightener 24 page 998 page right column 5 Antifoggant, stabilizer 24 to 25 page 649 page right column 998 page right column 10001000 page right column 6 Light absorber, Filter Dye, page 25-26 page 649 right column page 1003 left column Ultraviolet absorber 頁 page 650 left column 100page 1003 right column 7 Stain inhibitor 25 page right column 650 page left column 1002 page right column right column 8 dye image Stabilizer 25 page 1002 right column 9 Hardener 26 page 651 left column 1004 right column to 1005 left column 10 Binder 26 same as above 1003 right column to 1004 right column 11 Plasticizer, lubricant 27 page 650 Page right column, page 1006 left column 100page 1006, right column 12 Coating aids, surfactants, pages 26-27 Same as above, page 1005 left column 頁 page 1006, left column 13 Static inhibitor, page 27 Same as above, page 1006 right column 100page 1007 left column 14 Matting agent 1008 pages Column

The photographic light-sensitive material of the present invention includes, for example, black-and-white and color negative films for photography (for general use and movies), color reversal films (for slides and movies), black-and-white and color photographic paper, and color positive films (for movies) , Color reversal photographic paper, black-and-white and color photographic materials for thermal development, black-and-white and color photographic materials for plate making (lith film, scanner film, etc.), black-and-white and color medical and industrial photosensitive materials, black-and-white and color diffusion transfer photosensitive materials It can be applied to (DTR) and the like, but can be particularly preferably used for color paper.

Suitable supports that can be used in the present invention, for example, those described in the above-mentioned RD. No. 17643, page 28, RD. Have been.

In the photographic processing of the photosensitive material using the present invention,
Any of the known methods can be used, and a known treatment solution can be used. The processing temperature is usually selected between 18 ° C and 50 ° C.
Lower temperatures or temperatures above 50 ° C. may be used. Depending on the purpose, any of a developing process for forming a silver image (black-and-white photographic process) and a color photographic process including a developing process for forming a dye image can be applied. Black-and-white developers include dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-3
Publicly known developing agents such as -pyrazolidone) and aminophenols (for example, N-methyl-p-aminophenol) can be used alone or in combination. The color developer 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, etc.) can be used. In addition, LFA Meson, "Photographic Processing Chemistry", Focal Press (1966), 226-
229. And U.S. Pat. Nos. 2,193,015 and 2,592,364 and JP-A-48-64933 may be used.

The developing solution may further include a pH buffer such as a sulfite, a carbonate, a borate and a phosphate of an alkali metal;
It may contain a development inhibitor or antifogging agent such as bromide, iodide, and organic antifogging agent. Also, if necessary, a water softener, a preservative such as hydroxyamine,
Benzyl alcohol, organic solvents such as diethylene glycol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competing couplers, covering agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, polycarboxylic acid-based compounds described in U.S. Pat. Chelating agents and antioxidants described in West German Patent 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 may be performed simultaneously with the fixing process, or may be performed individually. As a bleach, for example,
Iron (III), cobalt (III), chromium (IV), copper (II)
Compounds of polyvalent metals such as peracids, quinones, nitroso compounds and the like are used. For example, organic complex salts of ferricyanide, dichromate, iron (III) or cobalt (III), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid Complex salts of organic acids such as acid, tartaric acid and malic acid, persulfates, permanganates, nitrosophenols and the like can be used. Of these, potassium ferricyanide and iron ethylenediaminetetraacetate (II
I) Sodium complex salt and iron ethylenediaminetetraacetate (II
I) Ammonium complex salts are particularly useful. The iron (III) complex salt of ethylenediaminetetraacetate, even in an independent bleaching solution,
It is also useful in a single bath bleach-fix solution. In addition to the thiol compounds described in U.S. Pat. Nos. 3,042,520, 3,241,966, JP-B-45-8,506 and JP-B-45-8,836, various additives can be added to the bleaching or bleach-fixing solution. After the bleaching or the bleaching / fixing treatment, a washing treatment or a stabilizing bath treatment alone may be used.

The present invention can be preferably applied to a silver halide photographic material having a transparent magnetic recording layer. The silver halide light-sensitive material supporting the magnetic recording layer used in the present invention is disclosed in
-35118, JP-A-6-17528, Hatsumei Kyokai Disclosure No. 94-6023, a thin layer support of a pre-heat treated polyester, for example, a polyethylene aromatic dicarboxylate-based polyester support having a thickness of 50 μm.
To 300 μm, preferably 50 μm to 200 μm, more preferably 80 to 115 μm, particularly preferably 85 to 1 μm.
05 µm is heat-treated (annealed) at a temperature not lower than 40 ° C and not higher than the glass transition temperature for 1 to 1500 hours.
2603, JP-B-43-2604, JP-B-45-382
8 irradiation, JP-B-48-5043, JP-A-5
Corona discharge described in 1-1131576, etc.
7578, surface treatment such as glow discharge described in JP-B-46-43480, undercoating described in US Pat. No. 5,326,689, and providing an undercoat layer described in US Pat. No. 2,761,791 if necessary. -23505, JP-A-4-
195726, the ferromagnetic particles described in JP-A-6-59357 may be applied. The magnetic layer described above may have a stripe shape described in JP-A-4-124462 and JP-A-4-124645.

Further, if necessary, see JP-A-4-62543.
, And finally coated with a silver halide photographic emulsion. The silver halide photographic emulsion used here is described in JP-A-4-16632, JP-A-3-41436, and JP-A-3-41437. It is preferable that the photosensitive material thus produced is manufactured by the manufacturing management 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. Thereafter or before that, Japanese Patent Application Laid-Open No. 4-125
In accordance with the method described in U.S. Pat.

The film thus produced is disclosed in
7459 cartridge package or JP-A-5-21020
The cartridge shown in FIG. 9 of the two embodiments, 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
Use in the cartridge described in 8. The film cartridge or film cartridge used herein is disclosed in U.S. Pat. No. 4,848,693 and U.S. Pat. No. 5,317,355.
The type that can store the tongue as described above is preferable from the viewpoint of light shielding properties. Further, a cartridge having a lock mechanism as disclosed in U.S. Pat. No. 5,296,886 or U.S. Pat.
It is preferable to use a cartridge in which the use 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 mounted by simply inserting the film into the cartridge may be used.

The film cartridge thus produced can be used for photographing, developing, and various ways of enjoying a photograph by using a camera, a developing machine, and a lab described below.
For example, a simple loading camera described in JP-A-6-8886 and JP-A-6-99908, an automatic winding camera described in JP-A-6-57398 and JP-A-6-101135, and a photographing camera described in JP-A-6-205690 are disclosed. Camera that can take out and replace the type of film with
8. A camera capable of magnetically recording on a film magnetic recording information described in JP-A-5-283382, for example, panoramic shooting, high-vision shooting, and normal shooting (a print aspect ratio can be selected) or JP-A-6-1011.
The function of a film cartridge (patrone) can be sufficiently exhibited by using a camera having a double exposure prevention function described in No. 94 or a camera having a use state display function such as a film described in JP-A-5-150577.

The film photographed in this manner is processed by a self-developing machine described in JP-A-6-222514 and JP-A-6-212545, or before, during or after the processing. 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,
And splicing according to the method described in -119461.
Further, when or after the development processing,
5. Attach and detach processing described in 5. After processing in this manner, Japanese Patent Application Laid-Open Nos. 2-184835 and 4-1863.
35, the film information may be converted to 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.

The evaluation of the amount of the sensitizing dye adsorbed on the emulsion grains was performed as follows.
A method in which the dye-adsorbed emulsion is centrifuged to separate the emulsion particles and the supernatant gelatin aqueous solution, the unadsorbed dye concentration is determined from the spectral absorption measurement of the supernatant, and the amount of the adsorbed dye is subtracted from the added dye amount. And drying the precipitated emulsion particles, dissolving a fixed weight of the precipitate in a 1: 1 mixture of an aqueous solution of sodium thiosulfate and methanol, and measuring the amount of the adsorbed dye 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, Journal of Physical, W. West et al.
Chemistry (Journal of Physica)
l Chemistry, vol. 56, p. 1054 (1952). Under conditions where the amount of dye added is large, even unadsorbed dye may precipitate, and the method of measuring the dye concentration in the supernatant may not always provide the correct amount of dye. On the other hand, if the method of measuring the amount of dye adsorbed by dissolving the precipitated silver halide particles, the emulsion particles have an overwhelmingly high sedimentation speed, so that the particles can be easily separated from the sedimented dye, and the dye adsorbed on the particles can be easily separated. It has been found that only the quantity can be measured accurately. The light absorption intensity per unit area of the particle surface can be determined using a microspectrophotometer. A microspectrophotometer is a device that can measure an absorption spectrum of a small area, and can measure a transmission spectrum of one particle. For the measurement of the absorption spectrum of a single particle by the microspectroscopy method, reference can be made to the report by Yamashita et al. From this absorption spectrum, the absorption intensity per particle is determined. However, since the light passing through the particle is absorbed by the upper surface and the lower surface, the absorption intensity per unit area of the particle surface is obtained by the method described above. It can be determined as 1/2 of the obtained absorption intensity per particle.

[0072]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. <Example 1> Preparation of pure silver bromide side plate grain emulsion and silver iodobromide tabular grain emulsion 6.4 g of potassium bromide and low molecular weight gelatin 6 having an average molecular weight of 15,000 or less in 1.2 liters of water Dissolving 0.2 g and keeping the temperature at 30 ° C. with a 16.4% aqueous silver nitrate solution 8.1.
ml and 7.2 ml of a 23.5% aqueous potassium bromide solution were added by the double jet method over 10 seconds. Next, 11.7
% Gelatin aqueous solution, and heated to 75 ° C.
After aging for 3 minutes, 370 ml of a 32.2% silver nitrate aqueous solution
And a 20% aqueous potassium bromide solution were added over 10 minutes while maintaining the silver potential at -20 mV, and the temperature was lowered to 35 ° C after physical ripening for 1 minute. Thus, the average projected area diameter is 2.32 μm, the thickness is 0.09 μm, and the diameter variation coefficient is 1
A 5.1% monodispersed pure silver bromide tabular emulsion (specific gravity: 1.15) was obtained. Thereafter, soluble salts were removed by the coagulation sedimentation method.
The temperature was again maintained at 40 ° C., and 45.6 g of gelatin and 1 mol
10 ml of an aqueous sodium hydroxide solution having a concentration of
167 ml of water and 10 ml of 5% phenol were added and p
Ag was adjusted to 6.88 and pH to 6.16 to obtain Emulsion A. In the preparation of Emulsion A, Emulsion B was prepared by using a 20% aqueous potassium bromide solution at the time of tabular grain growth and a mixed aqueous solution of 17% potassium bromide and 3% potassium iodide. Thereafter, the emulsions A and B were added with potassium thiocyanate, chloroauric acid and sodium thiosulfate so as to obtain the optimum sensitivity, and ripened at 55 ° C. for 50 minutes. While maintaining the emulsion obtained as described above at 50 ° C., the first dye shown in Table 1 was added, the mixture was stirred at 50 ° C. for 30 minutes, the second dye was added, and the mixture was further stirred at 50 ° C. for 30 minutes. . Samples 101 to 109 shown in Table 1 were prepared as described above.

[0073]

[Table 1]

[0074]

Embedded image

The amount of dye adsorbed was determined as follows.
After centrifugation at 000 rpm for 10 minutes, the precipitate was freeze-dried, and 0.05 g of the precipitate was made up to 50 ml by adding 25 ml of a 25% aqueous sodium thiosulfate solution and methanol. This solution was analyzed by high performance liquid chromatography, and the dye concentration was quantified and determined.

Measurement of the light absorption intensity per unit area
Apply the thin emulsion to a glass slide
Using Ice Microscope MSP65
The transmission spectrum and the reflection of each particle are
The emission spectrum was measured to determine the absorption spectrum. Transparent
The hyperspectral reference is the particle-free part
And the reflection spectrum is a silicon camera whose reflectance is known.
The carbide was measured and used as a reference. Measurement part is diameter
1μm circular aperture, with aperture on particle outline
Adjust the position so that the char section does not overlap and 14000
cm^-1(714 nm) to 28000 cm^-1(357n
Transmission spectrum and reflection spectrum in the wave number range up to m)
1-T (transmittance) -R (reflectance)
The absorption spectrum was determined as A. Silver halide absorption
Is subtracted to obtain an absorption rate A ′, and −Log (1-A ′) is
Wave number (cm^-1), Halving the integrated value
The light absorption intensity per surface area was used. Integration range is 1400
0cm^-1From 28000cm ^-1Up to. At this time,
The source is a tungsten lamp and the light source voltage is 8V
Was. Primary to minimize dye damage from light irradiation
Using the monochromator on the side, the wavelength interval is 2 nm,
The cut width was set to 2.5 nm.

A gelatin hardening agent and a coating aid are added to the obtained emulsion, and a gelatin protective layer is coated on a cellulose acetate film support so that the coated silver amount is 3.0 g-Ag / m ^2. At the same time. The resulting film was exposed to a tungsten bulb (color temperature 2854K) for 1 second through a continuous wedge color filter.
As a color filter, a wavelength range of 330 is obtained by combining a UVD33S filter and a V40 filter (manufactured by Toshiba Glass Co., Ltd.) as blue exposure for exciting silver halide.
The sample was irradiated with light from 400 nm to 400 nm. Further, the light was passed through a Fuji Gelatin Filter SC-52 (manufactured by Fuji Film Co., Ltd.) as minus blue exposure to excite the dye side.
The light of 20 nm or less was blocked and the sample was irradiated. The exposed sample was developed at 20 ° C. for 10 minutes using the following surface developer MAA-1.

Surface developer MAA-1 Metol 2.5 g L-ascorbic acid 10 g Nabox (Fuji Film Co., Ltd.) 35 g Potassium bromide 1 g 1 liter with water, pH 9.8 The optical density is measured by using the following formula.
The reciprocal of the amount of light required to give the optical density of is shown as a relative value based on Comparative Example 1. Table 2 and Table 3 show the results.
Shown in As shown in Table 2, the use of the silver halide photographic emulsion of the present invention allows multilayer adsorption on the grain surface, and the light absorption intensity per unit area of the grain surface (1/1 / the light absorption intensity of one grain). 2) has increased dramatically. Further, as shown in Table 3, the color sensitization sensitivity was dramatically increased.

[0079]

[Table 2]

[0080]

[Table 3]

<Example 2> Example 5 of JP-A-8-29904
A tabular silver iodobromide emulsion was prepared in the same manner as in Emulsion D of Emulsion D to prepare Emulsion 2A. The multi-layer color photographic material was prepared in the same manner as in Sample 101 of Example 5 of JP-A-8-29904. JP Hei 8
Fifth layer emulsion D in sample 101 of Example 5 of No. 29904
Was replaced with Emulsion 2A, and instead of ExS-1, 2, and 3, H-3 was added at 1.1 × 10 ⁻³ mol / Ag mol, and then H-4 was added at 1.0 × 10 ⁻³ mol / Ag mol. The sample obtained was 201 or S-7 was 1.1 × 10 ⁻³ m
ol / Ag mol, H-4 was added 1.0 × 10
^The sample to which ^-3 mol / Ag mol was added was designated as 202.
In order to examine the sensitivity of the sample thus obtained, light from a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was exposed to light for 1/100 second through an optical wedge and a red filter, and Example 1 of JP-A-8-29904 was used. Color development was performed using the same processing steps and processing solution as described above, and cyan density was measured. The results are shown in Table 4. The sensitivity was represented by the reciprocal of the exposure amount giving a density of fog density + 0.2, and was indicated by a relative value based on the sample 201.

[0082]

[Table 4]

[0083]

Embedded image

It was found that the use of the silver halide photographic emulsion of the present invention increased the amount of dye adsorbed and increased the sensitivity even in a negative type multilayer color light-sensitive material. <Example 3> Emulsion 3A was prepared by adding a mixture of H-1 and H-5 in place of spectral sensitizing dye S-1 in Emulsion 1 of Example 1 of JP-A-7-92601. The addition amounts of H-1 and H-5 were 3.25 × 10 ⁻³ mol / A, respectively.
g mol, 3.0 × 10 ⁻³ mol / Ag mol. Similarly, an emulsion to which a mixture of S-13 and S-49 was added was designated as Emulsion 3B. The addition amounts of S-13 and S-49 were 3.25 × 10 ⁻³ mol / Ag mol, respectively.
3.0 × 10 ⁻³ mol / Ag mol. 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 +115 mV.
v, and H- in place of the spectral sensitizing dye S-1.
Emulsion to which a mixture of 1 and H-5 was added was designated as Emulsion 3C.
The added amount of H-1 and H-5 was 3.25 × 10
^-3 mol / Ag mol, 3.0 × 10 ^-3 mol / Ag
mol. Similarly, an emulsion to which a mixture of S-13 and S-49 was added was designated as Emulsion 3D. S-13 and S-
The amount of addition of each was 3.25 × 10 ⁻³ mol / Ag.
mol, 3.0 × 10 ⁻³ mol / Ag mol. The multilayer color photosensitive material is described in Example 4 of JP-A-7-92601.
Was prepared in the same manner according to Sample 401. Samples 301 and 302 were prepared by replacing emulsion 1 of the ninth layer of sample 401 of Example 4 of JP-A-7-92601 with emulsion 3A or emulsion 3B. Similarly, Samples 303 and 304 were obtained by changing Emulsion 1 of the ninth layer of Example 1 to Emulsion 3C or Emulsion 3D. The sample thus obtained was evaluated for sensitivity. 1/5 as in Example 4 of JP-A-7-92601.
The magenta density was measured after exposure for 0 second and color reversal development. Table 5 shows the results. The sensitivity was calculated as the reciprocal of the amount of exposure necessary to give a density of +0.2 of the minimum density obtained by giving sufficient exposure, and was shown as a relative value with the sensitivity of sample 301 being 100.

[0085]

[Table 5]

[0086]

Embedded image

It was found that the use of the silver halide emulsion of the present invention increased the amount of dye adsorbed and increased the sensitivity even in a reversal multilayer color photographic material. <Example 4> An octahedral silver bromide internal latent image type direct positive emulsion and a hexagonal tabular silver bromide internal latent image type direct positive emulsion in the same manner as in Emulsions 1 and 5 of Example 1 of JP-A-5-313297. Was prepared and used as Emulsion 4A and Emulsion 4B. A color diffusion transfer photographic film was prepared in the same manner as in Sample 1 of Example 1 of JP-A-5-313297. Emulsion 2 in the 16th layer of Sample 101 of Example 1 of JP-A-5-313297 was replaced with Emulsion 4A, and 4.5 × 10 ^-3 mol of H-6 was used instead of the addition of sensitizing dye (3). / Hg after adding Ag mol
7 was added to 4.0 × 10 ⁻³ mol / Agmol of the sample 401, and S-52 was added to 4.5 × 10 ⁻³ mol / Ag.
After addition of H-7, 4.0 × 10 ⁻³ mol / A of H-7 was added.
The sample to which g mol was added was designated as Sample 402. Similarly, Emulsion-2 in the 16th layer of Sample 101 of the same Example was replaced with Emulsion 4B, and H-6 was added at 4.5 × 10 ^-3 mol / Ag mol instead of the addition of sensitizing dye (3). Later H-
7 was added to 4.0 × 10 ⁻³ mol / Ag mol of the sample 403, and S-52 was added to 4.5 × 10 ⁻³ mol / Ag.
After addition of H-7, 4.0 × 10 ⁻³ mol / H-7 was added.
The sample to which Ag mol was added was used as Sample 404. In order to examine the sensitivity of the sample thus obtained, the same exposure and processing steps as in Example 1 of JP-A-5-313297, and processing were performed using a processing solution, and the transfer density was measured with a color densitometer. The results are shown in Table 6. The sensitivity was represented by the reciprocal of the exposure amount giving a density of 1.0, and was represented by a relative value with respect to the sample 401.

[0088]

[Table 6]

[0089]

Embedded image

It was found that the use of the silver halide photographic emulsion of the present invention increased the amount of dye adsorbed and increased the sensitivity even in a color diffusion transfer photographic film. Example 5 In the preparation of Emulsion F of Example 2 of JP-A-4-142536, the red-sensitizing sensitizing dye (S-1) was not added before the sulfur sensitization, and the sulfur sensitization of triethylthiourea was carried out. In addition, chloroauric acid is also used for optimal gold-sulfur sensitization, and after gold-sulfur sensitization,
3.5 × 10 ⁻⁴ mol / Ag mol of H-8 and H-9
Was mixed with 3.5 × 10 ⁻⁴ mol / Ag mol in advance and then added to emulsion 5A and S-3 to 3.5 × ^10-4 mol / Ag mol.
3.5 × 10 ^{−4 of} 10 ⁻⁴ mol / Agmol and S-53
Emulsion 5B was obtained by adding mol / Ag mol in advance after mixing. Multilayer color photographic paper is
It was prepared in the same manner according to Sample 20 of Example 1 of No. 6-347944. Samples 501 and 502 were obtained by changing the emulsion of the first layer in Sample 20 of Example 1 of JP-A-6-347944 to Emulsion 5A or Emulsion 5B. 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 to light for 1/10 second through an optical wedge and a blue filter, and Example 1 of JP-A-6-347944 was used. Color development was performed using the same processing steps and processing solution as described above, and the yellow density was measured. The results are shown in Table 7. The sensitivity is represented by the reciprocal of the exposure amount required to give a density of fog +0.1, and is represented by a relative value based on the sensitivity of the sample 501.

[0091]

[Table 7]

[0092]

Embedded image

It was found that the use of the silver halide photographic emulsion of the present invention increased the amount of dye adsorbed and increased the sensitivity even in a multilayer color printing paper. <Example 6> A tabular silver chloride emulsion was prepared in the same manner as in Emulsion A of Example 1 of Japanese Patent Application No. 7-232320, and sensitizing dye-1 and sensitizing dye-1 were used in the chemical sensitization (B) of the same example. H instead of 2
-1 was added at 1.0 × 10 ⁻³ mol / Ag mol, and then gold-sulfur selenium was sensitized.
^-3 mol / Ag mol and H-2 at 2.2 × 10 ^-3 mol
1 / Ag mol and 3.8 × 10 ⁻⁵ mol / A of H-4
gmol of the mixed solution was added to Emulsion 6A, S-
13 was added at 1.0 × 10 ⁻³ mol / Ag mol, and then sensitized with gold-sulfur selenium.
0 ⁻³ mol / Ag mol and S-55 are 2.2 × 10 ^−3.
mol / Ag mol and S-49 are 3.8 × 10 ⁻⁵ mo
1 / Ag mol mixed solution was added to Emulsion 6B
And The coated sample was prepared by replacing the emulsion of Example 1 of Japanese Patent Application No. 7-232320 with Emulsion 6A or Emulsion 6B, and combining an emulsion layer and a surface protective layer on a support in the same manner as in Example 1 by simultaneous extrusion. And these were designated as Sample 601 and Sample 602. 1.75 g / m2 coated silver per side
^{And 2} . To examine the sensitivity of the sample thus obtained, an X-ray orthoscreen H manufactured by Fuji Photo Film Co., Ltd. was used.
Exposure was performed for 0.05 seconds from both sides using GM, and processing was performed using an automatic developing machine and a processing solution in the same manner as in Example 1 of Japanese Patent Application No. 7-232320. The results are shown in Table 8. Sensitivity +
It was represented by the reciprocal of the exposure required to give a density of 0.1, and was represented by a relative value based on the sensitivity of the sample 601.

[0094]

[Table 8]

It was found that the use of the silver halide photographic emulsion of the present invention increased the amount of dye adsorbed and also increased the sensitivity of the Xray sensitive material. HR-4 or HGH instead of X-ray orthoscreen HGM used during exposure
The same effect was obtained even when the exposure was performed. <Example 7> A tabular silver chloride emulsion different from Emulsion D of Example 2 of Japanese Patent Application No. 7-146891 in that sensitizing dyes 2 and 3 were not added was prepared, and this was mixed with Emulsion 7A. did.
The coated sample was prepared in the same manner as in the coated sample F of Example 3 of Japanese Patent Application No. 7-146891. The sensitizing dye-1 was prepared by replacing the emulsion F of the coating sample F of Example 3 of Japanese Patent Application No. 7-146891 with the emulsion 7A.
Instead of H-2 is 3.0 × 10 ^-3 mol / Ag mo
After addition of H-1, 2.0 × 10 ⁻³ mol / Ag of H-1 was added.
Sample 701, H
Sample 702 was prepared by adding 3.0 × 10 ⁻³ mol / Ag mol of -2 and then replacing the emulsion with S-11 of 2.0 × 10 ⁻³ mol / Ag mol. 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 to the light for 1/100 second through an optical wedge and a green filter. Compared. The results are shown in Table 9. The sensitivity is represented by the reciprocal of the exposure amount required to give a density of fog + 0.2, and is represented by a relative value based on the sensitivity of the sample 701.

[0096]

[Table 9]

It was found that the use of the silver halide photographic emulsion of the present invention increased the amount of dye adsorbed and increased the sensitivity even in a silver chloride tabular emulsion having the (111) plane as the outer surface. <Example 8> An octahedral silver chloride emulsion was prepared in the same manner as in Emulsion F of Example 3 of Japanese Patent Application No. 7-146891, and this was designated as Emulsion 8A. The coated sample was prepared in the same manner as in the coated sample F of Example 3 of Japanese Patent Application No. 7-146891. Example 3 of Japanese Patent Application No. 7-146891
Coating Sample F was replaced with Emulsion 8A of Emulsion F, and 3.0 × 10 ^-3 mol / Ag of H-10 was used instead of Sensitizing Dye-1.
After addition of H-11, 2.0 × 10 ⁻³ mol of H-11 was added.
Sample 8 replaced with the emulsion containing the
01 and S-5 were added at 3.0 × 10 ⁻³ mol / Ag mol, and then H-11 was added at 2.0 × 10 ⁻³ mol / Ag m.
The sample replaced with the emulsion added was designated as Sample 802. To check the sensitivity of the sample thus obtained, Fuji FW
A 1/100 second exposure was given to the light of a type sensitometer (Fuji Photo Film Co., Ltd.) through an optical wedge and a blue filter, and processed by Fuji Photo Film CN16 to compare the photographic properties. The results are shown in Table 10. The sensitivity is represented by the reciprocal of the amount of exposure required to give a density of fog + 0.2,
It was expressed as a relative value based on the sensitivity of.

[0098]

[Table 10]

[0099]

Embedded image

As described above, it was found that the use of the silver halide photographic emulsion of the present invention increased the amount of dye adsorbed and increased the sensitivity of the octahedral silver chloride emulsion. <Example 9> A tabular grain emulsion was prepared in the same manner as the emulsion CC of EP-0699950, and at the time of chemical sensitization, 2.0 × 10 ⁻³ mol of H-6 was used instead of Dye 1 and Dye 8.
After adding / Ag mol and chemically sensitizing, H-6 was added to 4.
0 × 10 ⁻³ mol / Ag mol and H-7 at 5.5 × 1
The emulsion containing 0 ^-3 mol / Ag mol was added to Emulsion 9A, S
After adding 2.0 × 10 ⁻³ mol / Ag mol of S-2 and performing chemical sensitization, 4.0 × 10 ⁻³ mol / Ag of S-2 was added.
mol and S-52 at 5.5 × 10 ⁻³ mol / Ag mo
The emulsion to which 1 was added was designated as Emulsion 9B. The coated sample was prepared in the same manner as the coated sample of the example of European Patent No. 0699950, and a sample using the emulsion 9A was designated as a sample 901, and a sample using the emulsion 9B was designated as a sample 902. Exposure and development were performed in the same manner as in the patent, and the photographic properties were compared. The results are shown in Table 11. The sensitivity was represented by the logarithm of the reciprocal of the exposure amount required to give a density of fog + 0.2, and was represented by a relative value based on the sensitivity of the sample 901.

[0101]

[Table 11]

Thus, it was found that the use of the silver halide photographic emulsion of the present invention increased the amount of dye adsorbed and increased the sensitivity of tabular grain emulsions.

[0103]

According to the present invention, it is possible to provide a silver halide emulsion having a high light absorption rate per unit area of a grain surface and a high-sensitivity photographic material using the emulsion.

Claims (4)

[Claims] 1. A silver halide photographic emulsion comprising an anionic dye and a cationic dye, wherein the charge of either the anionic dye or the cationic dye is divalent or higher. 2. A silver halide photographic material having at least one silver halide emulsion layer containing the silver halide emulsion according to claim 1. 3. A silver halide emulsion layer containing at least one silver halide photographic emulsion, wherein the total amount of the anionic dye and the cationic dye is 160% or more of the saturated coating amount. Item 7. The silver halide photographic light-sensitive material according to Item 1, and a method for producing the same. 4. A silver halide photographic material having at least one silver halide emulsion layer containing the silver halide emulsion according to claim 3.