JPH10307358A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material high in light absorbance and sensitivity by incorporating at least one kind of specified compound. SOLUTION: This photographic sensitive material contains at least each one kind of compound represented by formulae I and II in which U is a compound represented by formula II; each of Z1 and Z3 is an atomic group necessary to form a 5- or 6-membered N-containing hetero ring; each of L1 -L5 and L11 -L15 is a methine group; n1 is 0 or 1; p1 is 0-3; L is a divalent bonding group; each of R1 -R3 and R7 and R8 is an alkyl group; each of V1 and V2 is a substituent; each of q1 and q2 is 0 or an integer of >=1; each of M1 and M2 is a charge balancing counter ion; and each of m1 and m2 is an integer of 1-10 necessary for neutralizing the charge in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material having high light absorption and high sensitivity.

[0002]

2. Description of the Related Art Conventionally, great efforts have been made to increase the sensitivity of silver halide photographic materials. It is considered that, in the sensitizing dye, the efficiency of transmitting light energy to silver halide is improved by increasing the light absorptivity, thereby achieving higher spectral sensitivity. But,
The amount of the sensitizing dye adsorbed on the surface of the silver halide grains is limited, and it is difficult to adsorb a sensitizing dye having a monolayer saturation adsorption or more. Therefore, at present, the absorptance of the incident light quantum of each silver halide grain in the spectral sensitization region is extremely low.

A method proposed to solve these points is described below. PBGilman, Jr., et al., Photographic Science and Engineering (Photographic S
cience and Engineering) Volume 20, Issue 3, Page 97 (1
976), the first layer adsorbed the cationic dye, and the second layer adsorbed the anionic dye using electrostatic force. GBBird et al., In U.S. Pat. No. 3,622,316, multiple dyes were adsorbed to silver halide in multiple layers and sensitized by the contribution of Forster-type excitation energy transfer. Sugimoto et al., JP-A-63-138,341 and JP-A-64-84,24.
In No. 4, spectral sensitization was performed by energy transfer from the luminescent dye. R. Steiger et al., Photographic Science and Engineering
Vol. 27, No. 2, p. 59 (1983), spectral sensitization by energy transfer from a gelatin-substituted cyanine dye was attempted. Ikegawa et al., JP-A-61-251842.
No. 2, spectral sensitization was performed by energy transfer from a cyclodextrin-substituted dye.

A so-called linked dye having two chromophores which are not separately conjugated but linked by a covalent bond is described, for example, in US Pat. Nos. 2,393,351 and 2,42.
5,772, 2,518,732, 2,52
1,944, 2,592,196, European Patent 56
No. 5,083 and the like. However, these were not aimed at improving the light absorption rate. G.B.B.D. (G.
B. Bird), AL Borror et al., U.S. Pat. Nos. 3,622,317 and 3,976,493.
In No. 2, the sensitizing dye molecules having a plurality of cyanine chromophores were adsorbed to increase the light absorption, and sensitization was achieved by the contribution of energy transfer. Ukai, Okazaki and Sugimoto have disclosed in Japanese Patent Application Laid-Open No. 64-91134 a spectrophotometer capable of adsorbing at least one substantially non-adsorbable dye containing at least two sulfo groups and / or carboxyl groups onto silver halide. It was proposed to attach to sensitizing dye. Also,
Proposed spectral sensitization with a cyanine dye polymer in US Pat. No. 4,950,587. As described above, many studies have been made to improve the light absorptance up to now, but none of them has a sufficient effect of increasing the sensitivity, and there have been problems such as an increase in intrinsic desensitization and suppression of development. For the above reasons, there has been a demand for a spectral sensitization technique for improving the light absorptance of a silver halide photosensitive material and increasing the sensitivity.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material having a high light absorption and a high sensitivity.

[0006]

The above objects of the present invention have been achieved by the following (1) as a result of intensive studies. (1) A silver halide photographic material comprising at least one compound represented by the following general formulas (I) and (III). General formula (I)

[0007]

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[In the formula (I), U represents a compound represented by the following general formula (II). General formula (II)

[0009]

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[Z₁And Z_TwoAre the same or different
Often, to form a 5- or 6-membered nitrogen-containing heterocycle, respectively.
Represents the required atomic group. L₁, L_Two, L_Three, L_Four, L_Five,
L₆, L₇, L₈, L₉, And L_TenRepresents a methine group.
n₁And n_TwoRepresents 0 or 1. p₁And p₁Is 0,
Represents 1, 2, or 3. L represents a divalent linking group;
And U are in the N-position (R_FourOr R_Fiveinstead of
Directly to a nitrogen atom), and L₆, L₇, L₈Represented by
May be bonded to any of the methine groups. R ₁, R
_Two, R_Three, R_Four, R_Five, And R₆Represents an alkyl group
You. V₁, V_Two, V_Three, And V_FourAre the same but different
And each represents a substituent. q₁, Q_Two, Q_Three,
And q_FourRepresents 0 or a positive integer. Where R₁,
R_Two, R_Three, R _Four, R_Five, R₆, (V₁) Q₁,
(V_Two) Q_Two, (V_Three) Q_Three, And (V_Four) Q _FourIs dissociated
Contains no functional groups,₁, R_Two, R_Three, (V₁) Q
₁, (V_Two) Q _TwoTotal number of dissociable groups and R_Four, R_Five,
R₆, (V_Three) Q_Three, (V_Four) Q_FourThe total number of dissociative groups
Numbers are assumed to be equal. M₁Represents the charge-balancing counterion
Then m₁Is from 0 to 10 necessary to neutralize the molecular charge.
Represents the following numbers. General formula (III)

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[In the formula (III), U is the same as the general formula (I)
Z represents a compound represented by I)_Two, L ₆, L₇,
L₈, L₉, L_Ten, N_Two, P_Two, L, R_Four, R_Five,
R₆, V_Three, V_Four, Q_Three, And q_FourIs the above general formula (I)
It is synonymous with the one described in Z_ThreeContains 5 or 6 members
Represents an atom group necessary for forming a nitrogen heterocycle. L and
U is U's L ₆, L₇, L₈Any of the methine groups represented by
Shall be combined with R₇, And R₈Are each
Represents a alkyl group. V_FiveAnd V₆Are the same but different
And each represents a substituent. q_FiveAnd q₆Is 0 or
Represents a positive integer. Where R _Four, R_Five, R₆, R₇, R
₈, (V_Three) Q_Three, (V_Four) Q_Four, (V_Five) Q_Five,as well as
(V₆) Q₆Contains no dissociable groups or R₇,
R₈, (V_Five) Q_Five, (V₆) Q₆Of the dissociative group of
Total number and R_Four, R_Five, R₆, (V_Three) Q_Three, (V_Four) Q_Four
Have the same total number of dissociable groups. L₁₁,
L₁₂, L₁₃, L₁₄, And L_FifteenRepresents a methine group. n_ThreeIs
Represents 0 or 1. p_ThreeRepresents 0, 1, 2, or 3
You. M_TwoRepresents a charge-balancing counter ion, m_TwoIs the molecular charge
Represents a number from 0 to 10 required to neutralize ]

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention will be described below in detail. Formulas (I), (II) and (III)
In the above, as the 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ₁ , Z ₂ and Z ₃ , a thiazoline nucleus, a thiazole nucleus,
Benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, Benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quinoxalin nucleus, oxadiazole nucleus, Examples thereof include a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus.

Z ₁ , Z ₂ and Z ₃ are preferably a benzoxazole nucleus, a benzothiazole nucleus, a benzimidazole nucleus and a quinoline nucleus, more preferably
A benzoxazole nucleus, a benzimidazole nucleus, and a benzothiazole nucleus, and particularly preferably a benzimidazole nucleus.

V ₁ , V ₂ , V ₃ , V ₄ , V ₅ , and V ₆
May be the same or different and each represents a substituent. The substituents represented by V ₁ , V ₂ , V ₃ , V ₄ , V ₅ , and V ₆ are not particularly limited, and include, for example, a halogen atom, (eg, chlorine, bromine, iodine, fluorine), a mercapto group, Cyano group, carboxyl group, phosphate group, sulfo group, hydroxy group, carbamoyl group having 1 to 10, preferably 2 to 8, more preferably 2 to 5 carbon atoms (for example, methylcarbamoyl, ethylcarbamoyl, morpholino Carbobonyl), having 0 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 5 carbon atoms.
(E.g., methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), a nitro group, having 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms
0, more preferably an alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy,
Phenylethoxy), an aryloxy group having 6 to 20, preferably 6 to 12, and more preferably 6 to 10 carbon atoms (eg, phenoxy, p-methylphenoxy, p-chlorophenoxy, naphthoxy),

An acyl group having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (eg acetyl, benzoyl, trichloroacetyl), 1 to 20 carbon atoms, preferably 2 to 20 carbon atoms 12, more preferably an acyloxy group having 2 to 8 carbon atoms (eg, acetyloxy, benzoyloxy);
It preferably has 2 to 12 carbon atoms, and more preferably 2 carbon atoms.
To 8 acylamino groups (eg, acetylamino), 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms, sulfonyl groups (eg, methanesulfonyl, ethanesulfonyl, benzenesulfonyl), 1 to 20, preferably 1 to 1 carbon atoms
0, more preferably a sulfinyl group having 1 to 8 carbon atoms (for example, methanesulfinyl, ethanesulfinyl, benzenesulfinyl), a sulfonylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms. Groups (eg, methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino),

An amino group, a substituted amino group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methylamino, dimethylamino, benzylamino, anilino, diphenylamino); An ammonium group having a number of 0 to 15, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms (eg, trimethylammonium, triethylammonium);
To 15, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, such as a trimethylhydrazino group, 1 to 15 carbon atoms, preferably 1 carbon atoms.
To 10, more preferably a ureido group having 1 to 6 carbon atoms (e.g., a ureido group, an N, N-dimethylureido group);
C1 to C15, preferably C1 to C10, more preferably C1 to C6 imide group (for example, succinimide group), C1 to C20, preferably C1 to C12, more preferably C1 to C12 1 to 8 alkylthio groups (eg methylthio, ethylthio, propylthio),
An arylthio group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio, p-chlorophenylthio, 2-pyridylthio, naphthylthio), 2 carbon atoms To 20, preferably 2 to 12, more preferably 2 to 8 alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, 2-benzyloxycarbonyl), 6 to 20 carbon atoms, preferably 6 to 20 carbon atoms 12, more preferably 6 to 10 carbon atoms
Aryloxycarbonyl group (for example, phenoxycarbonyl),

An unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, butyl), 1 to 18 carbon atoms, preferably A substituted alkyl group having 1 to 10, more preferably 1 to 5 carbon atoms {eg, hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, and here having 2 to 18 carbon atoms, preferably C3 to C10, more preferably C3 to C5 unsaturated hydrocarbon group (for example, vinyl group, ethynyl group, 1-cyclohexenyl group, benzylidine group, benzylidene group)
, A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenyl, naphthyl, p- Carboxyphenyl, p-
Nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl),

A substituted or unsubstituted heterocyclic group having 1 to 20, preferably 2 to 10, more preferably 4 to 6 carbon atoms (eg, pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydro Furfuryl). Further, a structure in which a benzene ring or a naphthalene ring is condensed can be used. Further, these substituents may be further substituted by the substituents described in the description of V _{1 and the} like described above. Preferred substituents are the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom and benzene ring condensation, more preferably methyl group, phenyl group, methoxy group chlorine atom, bromine atom, iodine atom, and benzene ring condensation. It is.

Formulas (I), (II) and (III)
In the formula, q ₁ , q ₂ , q ₃ , q ₄ , q ₅ , and q ₆ represent 0 or a positive integer, and q ₁ , q ₂ , q ₃ , q ₄ , q ₅ , and q ₆ are 2 or more. , V ₁ , V ₂ , V ₃ , V ₄ , V ₅ ,
And V ₆ may be present as a plurality of different substituents.

Formulas (I), (II) and (III)
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ in the above each represent an alkyl group. R ₁ , R ₂ , R ₃ ,
Examples of the alkyl group represented by R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ include, 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), having 1 to 18 carbon atoms, preferably 1 to 7,
Particularly preferred are 1 to 4 substituted alkyl groups,
Examples of the substituent include those described in the description of the above-described substituent V ₁ and the like.

In the general formula (I), R₁, R_Two, R_Three,
R_Four, R_Five, R₆, (V₁) Q₁, (V _Two) Q_Two, (V
_Three) Q_Three, And (V_Four) Q_FourContains no dissociable groups
Or R₁, R_Two, R_Three, (V₁) Q₁, (V_Two) Q_Twoof
Total number of dissociable groups and R_Four, R_Five, R₆, (V_Three)
q_Three, (V_Four) Q_FourWith the same total number of dissociable groups
And In the general formula (III), R_Four, R_Five, R₆,
R₇, R₈, (V_Three) Q_Three, (V_Four) Q_Four, (V_Five) Q
_Five, And (V₆) Q₆Contains no dissociable groups or R
₇, R₈, (V_Five) Q_Five, (V₆) Q₆Dissociative group of
Total number and R_Four, R_Five, R₆, (V_Three) Q_Three, (V_Four) Q
_FourHave the same total number of dissociable groups. That's all
The light absorption and sensitivity are improved by limiting the substituent
I was able to make it. The dissociable group referred to here is proton dissociation
A leaving group, that is, an acidic group,
Corresponds to this.

Preferred as the dissociative group are a hydroxy group, a carboxy group, a sulfo group, a sulfato group, a phosphono group, an alkylsulfonylcarbamoyl group (for example, methanesulfonylcarbamoyl group), an acylcarbamoyl group (for example, acetylcarbamoyl group), and an acyl group. A sulfamoyl group (eg, an acetylsulfamoyl group),
Examples include an alkylsulfonylsulfamoyl group (for example, a methanesulfonylsulfamoyl group). More preferably a carboxy group, a sulfo group, a sulfato group, a phosphono group, a methanesulfonylcarbamoyl group,
Particularly preferred are carboxy, sulfo and sulfato groups.

L represents a divalent linking group. This linking group is
It is composed of atoms or atomic groups containing at least one of carbon, nitrogen, sulfur and oxygen. Preferably, for example, an alkylene group having 1 to 20 carbon atoms (for example,
Ethylene, propylene, butylene, 1-methylethylene, 2-methylpropylene, etc., which may be substituted. Examples of the substituent include those described in the description of V ₁ and the like. A hetero atom (eg, an oxygen atom, a sulfur atom, a nitrogen atom), an aryl group (eg, 1,2-phenylene, 1,3-phenylene,
1,4-phenylene, 1,2 naphthylene), a heterocyclic ring (eg, 2,3-pyridylene) and the like may be present. ), An alkenylene group having 1 to 20 carbon atoms (for example,
1,2-ethenylene, 1-methyl-1,2-ethenylene, 1,2-dimethyl-1,2-ethenylene, 1,3- (1-propenylene), 1,4- (2-butenylene) and the like, which may be substituted. V ₁ as a substituent
And the like described in the description. ), An alkynylene group having 1 to 20 carbon atoms (e.g., ethynylene, propynylene, etc., which may be substituted. Examples of the substituent include those described in the description of V ₁ and the like). . L is more preferably a substituted or unsubstituted alkylene group, an alkylene group containing an ether bond at the terminal or inside, an alkylene group containing an ester bond at the terminal or inside, an alkylene group containing an amide bond at the terminal or inside, and a terminal or An alkylene group containing a thioether bond inside, particularly preferably an unsubstituted alkylene group having 1 to 10 carbon atoms, an alkylene group containing an ester bond at the terminal or inside, and an alkylene group containing an amide bond at the terminal or inside.

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
_{7, L 8, L 9,} L 10, L 11, L 12, L 13, L 14, and L ₁₅ each independently represents a methine group. The methine group represented by L _{1 to} L ₁₅ may have a substituent. Examples of the substituent include a substituted or unsubstituted C ₁ to C 15, preferably C ₁ to C 10, particularly preferably carbon An alkyl group of the formulas 1 to 5 (eg, methyl, ethyl, 2-carboxyethyl), a substituted or unsubstituted C 6 to C 20,
Preferably it has 6 to 15 carbon atoms, more preferably 6 carbon atoms.
To 10 aryl groups (e.g., phenyl, o-carboxyphenyl), substituted or unsubstituted 3 to 20 carbon atoms,
Preferably it has 4 to 15 carbon atoms, more preferably 6 carbon atoms.
To 10 heterocyclic groups (eg, N, N-dimethylbarbituric acid group), halogen atoms (eg, chlorine, bromine, iodine, fluorine), having 1 to 15 carbon atoms, preferably 1 carbon atom
To 10, more preferably an alkoxy group having 1 to 5 carbon atoms (eg, methoxy, ethoxy);
Preferably it has 2 to 10 carbon atoms, more preferably 4 carbon atoms.
To 10 amino groups (eg, methylamino, N, N-dimethylamino, N-methyl-N-phenylamino, N-
Methylpiperazino), an alkylthio group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methylthio, ethylthio), 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and Preferably, an arylthio group having 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio) and the like are mentioned.
Further, a ring may be formed with another methine group, or an auxochrome ring may be formed.

P ₁ , p ₂ and p ₃ each independently represent 0, 1, 2 or 3. It is preferably 0, 1, or 2, and more preferably 0 or 1. When p ₁ , p ₂ , and p ₃ are 2 or more, the methine group is repeated but need not be the same.

N ₁ , n ₂ and n ₃ are each independently 0
Or represents 1. Preferably it is 0.

M ₁ and M ₂ are included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the molecule. Typical cations include inorganic ions such as hydrogen ions (H ⁺ ), alkali metal ions (sodium ions, potassium ions, lithium ions), alkaline earth metal ions (eg, calcium ions), and ammonium ions (eg, ammonium ions). , Tetraalkylammonium ion, pyridinium ion, ethylpyridinium ion)
And other organic ions. The anion may be either an inorganic anion or an organic anion, and may be a halogen anion (eg, a fluorine ion, a chloride ion, a bromine ion, an iodine ion), a substituted arylsulfonate ion (eg, a p-toluenesulfonic acid ion, -Chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenedisulfonate ion, 1,5
-Naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion,
Examples include perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, and trifluoromethanesulfonate ion. Further, an ionic polymer or a molecule having a charge opposite to that of the molecule may be used. m ₁ and m ₂
Represents the number necessary to balance the charges, and is 0 when a salt is formed in the molecule.

The general formulas (I) and (II) of the present invention are described below.
Specific examples of I) will be shown, but the present invention is not limited thereto.

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[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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[0039]

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[0041]

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[0042]

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The compounds represented by the general formulas (I) and (III) of the present invention can be prepared by using FM Harmer.
By Heterocycling Compounds-Cyanine Soybeans and Related Compounds (Heterocycl
ic Compounds-Cyanine Dyes and Related Compound
s) ", John Wile and Sands
y & Sons), New York, London, 1964, DMSturmer, Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry (Hetero)
cyclic Compouds -Special Topics in Heterocyclic Ch
emistry) ", Chapter 18, Section 14, 482-515
Page, John Wiley & Sons
Sons)-New York, London, 1977,
"Rodd's Chemistry of Carbon Compouds" 2nd
Edition, Volume IV, Part B, Chapter 15, pp. 369-422 Elsevier Science Publishing Company, Inc.
Inc.), New York, 1977, and the like.

The methine compounds represented by formulas (I) and (III) of the present invention (hereinafter, methine compounds of the present invention) may be used alone or in combination with other sensitizing dyes in a silver halide photographic material. Can be.

The timing at which the methine compound of the present invention (and the same applies to other sensitizing dyes) is added to the silver halide emulsion of the present invention in any of the emulsion preparations which have been recognized to be useful. It may be during the process. For example,
U.S. Pat. Nos. 2,735,766 and 3,628,960
Nos. 4,183,756 and 4,225,666
JP-A-58-184142 and JP-A-60-19674.
As disclosed in No. 9, etc., the timing before silver halide grain forming step and / or before desalting, the timing during and / or after desalting and before the start of chemical ripening, 58
As disclosed in, for example, JP-A-113920, etc., it may be added at any time during the process just before or during the process of chemical ripening, or at any time before the application of the emulsion after the chemical ripening and before coating. No. 4,225,666.
As disclosed in JP-A-58-7629 or the like, the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step, during the chemical ripening step, or after the completion of the chemical ripening. Or may be divided and added before or during chemical ripening or during and after the process, or may be added by changing the kind of compound to be divided and added and the combination of compounds. .

The addition amount of the methine compound of the present invention is
Although it depends on the shape and size of the silver halide grains, it can be used in an amount of 1 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−6 to} 3.5 × 10 ⁻³ mol per mol of silver halide, and is preferably 7.5. An addition amount of × 10 ^{−6 to} 1.5 × 10 ⁻³ mol is more preferable.

The methine compound of the present invention can be directly dispersed in an emulsion. Also, these are first suitable solvents,
For example, it can be dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof and added to the emulsion in the form of a solution. At this time, additives such as a base, an acid, and a surfactant can be made to coexist. Also, ultrasonic waves can be used for dissolution. As a method for adding the methine compound, as described in US Pat. No. 3,469,987, the compound is dissolved in a volatile organic solvent,
This solution is dispersed in a hydrophilic colloid, and this dispersion is added to the emulsion. As described in JP-B-46-24185, the dispersion is dispersed in a water-soluble solvent, and this dispersion is added to the emulsion. Dissolving a methine compound in a surfactant, as described in US Pat. No. 3,822,135;
A method of adding the solution to an emulsion, JP-A-51-7462.
4, a method of dissolving with a compound that causes a red shift and adding the solution to an emulsion;
As described in JP-A-80826, a method of dissolving a methine compound in an acid substantially free of water and adding the solution to an emulsion is used. Other additions to emulsions include U.S. Pat. Nos. 2,912,343 and 3,342,605.
Nos. 2,996,287 and 3,429,835 can also be used.

Further, the methine compound of the present invention has sharpness,
It can be used as various filter dyes, irradiation prevention dyes or antihalation dyes for the purpose of improving color resolution and the like. This methine compound can be contained in a coating solution such as a silver halide photographic light-sensitive material layer, a filter layer and / or an antihalation layer by a conventional method. The amount of the dye used may be an amount sufficient to color the photographic layer, and those skilled in the art can easily select this amount according to the purpose of use. In general, it is preferable to use such that the optical density is in the range of 0.05 to 3.0. The timing of addition may be any step before coating. Alternatively, a polymer having a charge opposite to that of the dye ion may coexist in the layer as a mordant, and the dye may be localized in the characteristic layer by interaction with the dye molecule. As the polymer mordant, for example, US Pat.
8,564, 4,124,386, 3,62
5,694, 3,958,995, 4,16
Nos. 8,976 and 3,445,231.

Supersensitizers useful in the spectral sensitization of the present invention include, for example, US Pat. Nos. 3,511,664, 3,615,613, 3,615,632, and 3,615, Nos. 641, 4,596,767, 4,945,038, 4,965,182, 4,965,182, etc., pyrimidylamino compounds, triazinylamino compounds, azolium compounds, etc. The method described in the above-mentioned patent is also preferable as to its use.

The silver halide which can be used in the silver halide light-sensitive material of the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. Preferred silver halides are silver bromide, silver chlorobromide, silver iodochlorobromide, or high silver chloride described in JP-A-2-42. The composition and processing of the light-sensitive material will be described below. The composition and processing described in JP-A-2-42 are preferably used particularly in high silver chloride. Also, JP-A-63-2
The constitution and processing described in No. 64743 are particularly preferably used for silver chlorobromide.

The silver halide grains may have different phases between the inside and the surface layer, or may consist of a uniform phase. Also, particles whose latent image is mainly formed on the surface (for example, a negative photosensitive material), particles that are mainly formed inside the particle (for example, an internal latent image photosensitive material), or particles that have been previously fogged (For example, a direct positive photosensitive material). Silver halide grains having the various halogen compositions, crystal habits, intragrain structures, shapes and distributions described above,
Used in photosensitive photographic materials (elements) for various uses.

The silver halide grains in the photographic light-sensitive material are regular, such as cubic, tetradecahedral, and rhombodecahedral.
It may have an irregular crystal form, may have an irregular crystal form such as a sphere or a plate, or may have a complex form of these crystal forms. It may consist of a mixture of particles of different crystal forms.

In the photographic light-sensitive material of the present invention, the silver halide grains forming the emulsion layer have an aspect ratio of 3 or more and 1 or more.
The case where it is 00 or less is preferable. Here, the aspect ratio of 3 or more and 100 or less means that the silver halide grains having an aspect ratio (equivalent circle diameter of silver halide grains / grain thickness) of 3 or more and 100 or less correspond to all the silver halide grains in the emulsion. It means that there is at least 50% of the projected area. The aspect ratio is preferably 3 or more and 20 or less, and most preferably 4 or more.
It is 12 or less. Tabular grains are described in Gaft, Photographic Science and Engineering,
14, 248-257 (1970); US Pat.No. 4,434,226, 4,41
4,310, 4,433,048, 4,439,520 and GB 2,112,157
Can be easily adjusted by the method described in (1). In the photographic light-sensitive material of the present invention, its abundance is at least 70%, particularly preferably at least 85%.

The methine compound of the present invention is used for the following applications for sensitizers, sensitizing dyes, filters, antihalation or irradiation prevention. These dyes can be added to desired layers such as an intermediate layer, a protective layer and a back layer in addition to the photosensitive emulsion layer. The methine compound of the present invention is used for various color and black-and-white silver halide photographic materials. More specifically, a light-sensitive material for color positive, a light-sensitive material for color paper, a light-sensitive material for color negative, a light-sensitive material for color reversal (with or without a coupler), a silver halide photographic light-sensitive material for direct positive, Photographic materials for plate making (eg lith film, lith dupe film, etc.), cathode ray tube display materials, X-ray recording materials (especially materials for direct and indirect photography using a screen), silver salt diffusion transfer process (Silver Salt) diffusion transfer proces
s), the photosensitive material used in the color diffusion transfer process, the die transfer process (im
It is used as a light-sensitive material used in the inhibition process, a light-sensitive material used in the silver dye bleaching method, a light-sensitive material for heat development, and the like.

The silver halide photographic emulsion used in the present invention is described in Chimie et Physiqu by P. Glafkides.
e Photograhique "(Paul Montel, 1967), GF Deffein (GFDuff
in) "Photographic Emulsion Chemistry" (The FocalPress, 1966); Making and Coating by VLZelikman et al.・ Photographic ・
Emulsion (Making and Coating Photographic Emul
sion) "(The Focal Press)
Ed., 1964) and the like.

In the formation of silver halide grains, in order to control the growth of the grains, a silver halide solvent such as ammonia, rodankari, rodanammon, thioether compound (for example, US Pat. No. 3,271,157)
Nos. 3,574,628 and 3,704,130
Nos. 4,297,439 and 4,276,374) and thione compounds (for example, JP-A-53-14431).
9, No. 53-82408 and No. 55-77737), amine compounds (for example, JP-A-54-100717).
Number etc.) can be used. In the course of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be coexisted. As the internal latent image type silver halide emulsion used in the present invention, for example, US Pat. No. 2,592,250,
Conversion-type silver halide emulsions described in 3,206,313, 3,447,927, 3,761,276, and 3,935,014, etc., core / shell type halides Silver emulsions and silver halide emulsions containing different types of metals are included.

The silver halide emulsion is usually chemically sensitized. For chemical sensitization, for example, H. Frieser, “Die Grundlagen der Photographische”, edited by D. Grundlagen der Photographische.
n Prozesse mit Silberhalogeniden) ", Akademische Verlagsgesellsch
aft), (1968) pp. 675-734 can be used. That is, sulfur sensitization using a compound containing sulfur (e.g., thiosulfate, thioureas, mercapto compounds, rhodanines) that can react with active gelatin or silver; selenium sensitization; ,
Reduction sensitization method using stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); noble metal compounds (for example, gold complex salts, Pt, I
A noble metal sensitization method using a complex group VIII metal of the periodic table such as r or Pd) can be used alone or in combination.

The photographic light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. it can. That is, thiazoles such as benzothiazolium salts described in U.S. Pat. Nos. 3,954,478 and 4,942,721, JP-A-59-191332, and JP-B-59-26731. Ring-opened products thereof, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazole , Mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketonization Compounds such as oxazolinethione; azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and JP-A-62-87957. Many compounds known as antifoggants or stabilizers can be added, such as the acetylene compounds described, and the like.

The silver halide photographic light-sensitive material of the present invention may contain a color coupler such as a cyan coupler, a magenta coupler and a yellow coupler, and a compound dispersing the coupler. That is, in the color development processing, aromatic 1
It may contain a compound capable of developing color by oxidative coupling with a secondary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative). For example,
Examples of magenta couplers include 5-pyrazolone couplers, pyrazorobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (eg, benzoylacetoanilides, pivaloylacetoanilides). Some cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible couplers having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion. Further, a colored coupler having a color correcting effect or a coupler that releases a development inhibitor during development (a so-called DIR coupler) may be used. Also DI
In addition to the R coupler, a colorless DIR coupling compound which is colorless and releases a development inhibitor may be contained.

The photographic light-sensitive material of the present invention may be, for example, polyalkylene oxide or a derivative thereof such as ether, ester, or amine, a thioether compound, thiomorpholines, or quaternary ammonium for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may contain salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. The silver halide light-sensitive material of the present invention may contain various dyes other than the methine compound of the present invention as a filter dye or for various purposes such as prevention of irradiation. Such dyes include, for example, British Patent Nos. 506,385 and 1,17.
7,429, 1,311,884, 1,33
8,799, 1,385,371, 1,46
7,214, 1,433,102, 1,55
3,516, JP-A-48-85130, and JP-A-49-1
No. 14420, No. 52-117123, No. 55-16
No. 1233, No. 59-111640, Japanese Patent Publication No. 39-2
No. 2069, No. 43-13168, No. 62-2735
No. 27, U.S. Pat. Nos. 3,247,127 and 3,46.
Oxonol dyes having a pyrazolone nucleus or a barbituric acid nucleus described in US Pat. Nos. 9,985 and 4,078,933; U.S. Pat. Nos. 2,533,472 and 3,37;
Other oxonol dyes described in JP-A No. 9,533, UK Patent No. 1,278,621, JP-A Nos. 1-134447 and 1-183652, and UK Patent No. 575,6
Nos. 91, 680, 631, 599, 623, 786, 907, 907, 125, and 1,04
No. 5,609, U.S. Pat. No. 4,255,326, Japanese Patent Publication No. Sho 59-211043, azo dyes described in JP-A Nos. 50-100116 and 54-118247, and British Patent No. 2,014, Azomethine dyes described in US Pat. No. 2,865,598 and US Pat.
No. 752, anthraquinone dyes described in U.S. Pat. Nos. 2,533,009, 2,688,541 and 2,538,008, British Patent 584,609,
No. 1,210,252, JP-A-50-40625,
No. 51-3623, No. 51-10927, No. 54-
118247, JP-B-48-3286, and 59-3
Arylidene dyes described in No. 7303, etc.
Nos. 8-3082, 44-16594, 59-28
No. 898 and the like, British Patent No. 44
Nos. 6,583 and 1,335,422;
Triarylmethane dyes described in U.S. Pat. No. 2,228,250 and the like, British Patent Nos. 1,075,653 and 1,153,
No. 341, No. 1, 284, 730, No. 1, 475, 2
No. 28, No. 1,542,807, etc .; merocyanine dyes described in U.S. Pat.
294, 539 and JP-A-1-291247.

The following method can be used to prevent such dye diffusion. For example, a method of coexisting a hydrophilic polymer having a charge opposite to that of a dissociated anionic dye in a layer as a mordant and localizing the dye in a specific layer by interaction with dye molecules is disclosed in U.S. Pat.
8,564, 4,124,386, 3,62
No. 5,694 and the like. Further, a method of dyeing a specific layer using a dye solid insoluble in water is disclosed in
-12639, 55-155350, 55-1
No. 55351, No. 63-27838, No. 63-197
943, European Patent No. 15,601 and the like. Further, a method of dyeing a specific layer by using metal salt fine particles to which a dye is adsorbed is disclosed in U.S. Pat. Nos. 2,719,088, 2,496,841, and 2,496,843; No. 45237 and the like.

The photographic light-sensitive material of the present invention has various types of interfaces for various purposes such as coating aids, antistatic properties, improvement of slipperiness, emulsification / dispersion, prevention of adhesion and improvement of photographic properties (eg, development acceleration, high contrast, sensitization). An active agent may be included. In practicing the present invention, other additives are used together with the silver halide emulsion or other hydrophilic colloid, for example, an anti-fading agent, an inorganic or organic hardening agent, an anti-fog agent,
UV absorbers, mordants, plasticizers, latex polymers,
Matting agents and the like can be mentioned. Specifically, Research Disclosure Vol.
176 (1978, XI), D-17643, and the like. In the photographic light-sensitive material used in the present invention, a hydrophilic polymer such as gelatin is used as a protective colloid. Finished silver halide emulsions, etc.
Coated on a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic bases or glass plates.

Exposure for obtaining a photographic image may be performed using a usual method. That is, any of various known light sources such as natural light (daylight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, and cathode ray tube flying spot can be used. Exposure time is 1/1 which is usually used in cameras
Exposure time from 000 seconds to 1 second, of course, 1/1000
Exposure shorter than one second, for example, exposure of 1/10 ⁴ to 1/10 ⁶ seconds using a xenon flashlight or a cathode ray tube, or exposure longer than 1 second can be used. If necessary, the spectral composition of light used for exposure can be adjusted by a color filter. Laser light can also be used for exposure. Further, exposure may be performed by light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray, or the like. Photographic processing of photosensitive materials made using the present invention includes, for example, Research Disclosure (Research Disclosure).
Disclosure) 176, pp. 28-30 (RD-1764)
As described in 3), any of a known method and a known processing solution can be applied. This photographic processing may be either photographic processing for forming a silver image (black-and-white photographic processing) or photographic processing for forming a dye image (color photographic processing), depending on the purpose. Processing temperature is usually 1
The temperature is selected between 8 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C.

The silver halide photographic light-sensitive material carrying magnetic recording which may be used in the present invention (hereinafter also referred to as "light-sensitive material")
Are disclosed in JP-A-6-35118 and JP-A-6-17528.
No., a thin layer support of a pre-heat treated polyester described in detail in Hatsumei Kyokai Disclosure No. 94-6023, for example,
Polyethylene aromatic dicarboxylate polyester support, 50 μm to 300 μm, preferably 50 μm
Heat treatment (annealing) at a temperature of 40 ° C. or more and a glass transition temperature or less at a temperature of 40 to 200 μm, more preferably 80 to 115 μm, and particularly preferably 85 to 105 μm.
No. 43-2603, No. 43-2604
U.S. Pat. No. 5,326,689 by ultraviolet irradiation described in JP-B-45-3828, surface treatment such as corona described in JP-B-48-5043 and JP-A-51-131576.
No. described in US Pat. No. 2,761, if necessary
No. 791 described in JP-A-59-23.
No. 505, JP-A-4-195726, JP-A-6-59
357 may be applied. In addition,
The magnetic layer described above is disclosed in JP-A-4-124462,
It may be in the form of a stripe described in JP-A-124645.
Further, if necessary, an antistatic treatment described in JP-A-4-62543 is used, and finally a product coated with a silver halide emulsion is used. The silver halide emulsion used here is described in JP-A-4-166.
No. 932, JP-A-3-41436, JP-A-3-414
No. 37 is used.

The photographic material thus produced is disclosed in Japanese Patent Publication No. 4-86817.
No. 6-87146.
It is preferable to record the manufacturing data by the method described in the above item. Thereafter or before that, according to the method described in JP-A-4-125560, the film is cut into a narrower film than the conventional 135 size, and the perforation is reduced per small format screen so as to match the smaller format screen. Punch two holes per side. The film thus produced is the cartridge package of JP-A-4-157559, the cartridge shown in FIG. 9 of the embodiment of JP-A-5-210202, or US Pat. No. 4,221,479, film cartridge, US Pat. No. 4,834,306, US Pat. ,
No. 834,366, USP 5,226,613, US
It is used in a cartridge described in P4,846,418. The film cartridge or film cartridge used here is USP 4,848,693, USP
No. 5,317,355 is preferred from the viewpoint of light-shielding properties. Further, USP 5,29
A cartridge having a lock mechanism such as US Pat. No. 6,886, a cartridge displaying a use state described in US Pat. No. 5,347,334, and a cartridge having a double exposure prevention function are preferable. 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 laboratory device described below.
For example, JP-A-6-8886, JP-A-6-99908
No. 6-57398.
And Japanese Patent Application Laid-Open No. 6-101135, a camera capable of taking out and changing the type of film during photographing described in Japanese Patent Application Laid-Open No. 6-205690, and
No. 293138 and Japanese Patent Application Laid-Open No. 5-283382, for example, a camera capable of magnetic recording on a film a panoramic image, a high-vision image, and a normal image (magnetic recording capable of selecting a print aspect ratio). Use of a camera having a double exposure prevention function described in JP-A-6-101194 or a camera having a use state display function such as a film described in Japanese Patent Application Laid-Open No. 5-150577 fully demonstrates the function of a film cartridge (patrone). it can. The film photographed in this manner is disclosed in JP-A-6-22.
No. 2514 and Japanese Unexamined Patent Publication No. 6-222545.
The method of using magnetic recording on a film described in JP-A-95265 and 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, the film is spliced and processed according to the method described in JP-A-5-119461. Also, when or after the development processing,
Attachment described in No. 8805, detach processing is performed. After processing in this manner, Japanese Patent Application Laid-Open Nos.
The film information may be converted into a print through back printing and front printing on color paper by the methods described in JP-A-186335 and JP-A-6-79968.
Further, JP-A-5-11353, JP-A-5-2325
It may be returned to the customer together with the index print and return cartridge described in No. 94.

[0068]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 (1) Preparation of emulsion An aqueous solution containing gelatin having an average molecular weight of 15,000 (water 12
100 ml, gelatin 7.0 g, while stirring keeping the containing KBr4.5G) to 30 ° C., tabular added by 1.9MAgNO ₃ solution and 1.9MKBr aqueous double jet of 70 seconds at 25 ml / min Particle nuclei were obtained. 400 ml of this emulsion was used as seed crystals, and 650 ml of an inert gelatin aqueous solution (20 g of gelatin, KBr1.2
g) was added and the temperature was raised to 75 ° C., followed by aging for 40 minutes. Then, an AgNO ₃ aqueous solution (containing 1.7 g of AgNO ₃ ) was added over 1 minute and 30 seconds, and then NH ₄ NO ₃
(50 wt%) aqueous solution 7.0ml and NH ₃ (25wt%)
7.0 ml was added and aged for an additional 40 minutes.

Next, the emulsion was adjusted to pH 7 with HNO ₃ (3N), and 1.0 g of KBr was added. Then, 366.5 ml of a 1.9 MAg NO ₃ aqueous solution and an aqueous KBr solution were added, followed by 1.9 MAg NO ₃ aqueous solution.
gNO ₃ aqueous solution 53.6 ml and KBr (KI 33.3 m
An aqueous solution of 1.9% MAgNO ₃ and an aqueous solution of KBr were added while maintaining the pAg at 7.9 to obtain Emulsion 1.

Emulsion 1 obtained was a triple structure grain having a region having the highest silver iodide content in the intermediate shell, an average aspect ratio of 2.8, and a tabular grain having an aspect ratio of 3 or more. The ratio to the total projected area was 26%. The coefficient of variation of the particle size was 7%, and the average of the particle size was 0.98 μm in sphere equivalent diameter.

Emulsion 1 was desalted by a usual flocculation method, and a sensitizing dye was added to 1 mol of silver, and gold, sulfur and selenium sensitization was optimally performed in the presence of the sensitizing dye.

(2) Preparation of Coated Samples Emulsion layers and protective layers as shown in Table 1 were applied to a triacetyl cellulose film support provided with an undercoat layer to prepare samples 101 to 109.

[0073]

[Table 1]

The absorption spectrum of the prepared coated sample was measured using a spectrophotometer U-3410 manufactured by Hitachi, Ltd. with an integrating sphere. The value S obtained by integrating the absorption intensity on the longer wavelength side than 350 nm with respect to the horizontal axis (eV) was obtained. Sample 101
And 105 were expressed as relative values with the value S being 1.00. Table 2 shows the results. These samples were exposed to sensitometry (1/100 second) and subjected to the following color development processing.

Processing method Step Processing time Processing temperature Supplementary capacity Tank capacity Color development 2 minutes 45 seconds 38 ° C 33 ml 20 liter Bleaching 6 minutes 30 seconds 38 ° C 25 ml 40 liter Water wash 2 minutes 10 seconds 24 ° C 1200 ml 20 liters 4 minutes 20 seconds 38 ° C 25ml 30 liters Washing water (1) 1 minute 05 seconds 24 ° C 10 liters counter current piping from (2) to (1) Water washing (2) 1 minute 00 seconds 24 ° C 1200ml 10 liters Stability 1 Minutes 05 seconds 38 ° C 25ml 10 liters Drying 4 minutes 20 seconds 55 ° C Replenishment amount is 35mm width per 1m length Next, the composition of the processing solution is described.

(Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Iodide Potassium 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH 10.05 10.05 (bleach) Mother liquor (g) Replenisher (g) Sodium ferric ethylenediaminetetraacetate trihydrate 100.0 120.0 Disodium ethylenediaminetetraacetate 10.0 11.0 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml Add water 1.0 liter 1.0 liter pH 6.0 5.7

(Fixing solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid sodium salt 0.5 0.7 Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 Ammonium thiosulfate aqueous solution (70%) 170.0 ml 200.0 ml Add water 1.0 liter 1.0 Liters pH 6.7 6.6 (Stabilizer) Mother liquor (g) Replenisher (g) Formalin (37%) 2.0 ml 3.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 0.45 Disodium ethylenediaminetetraacetate 0.05 0.08 1.0 liter with water 1.0 liter pH 5.8-8.0 5.8-8.0

The density of the treated sample was measured with a green filter. The sensitivity is defined as the reciprocal of the exposure amount that gives a density 0.2 higher than the fog density.
The value was expressed as a relative value with the value of 05 as 100. The emulsion and methine compound species used for each sample and the sensitivity results for each sample are shown in Table 2 below.

[0079]

[Table 2]

[0080]

Embedded image

From Table 2, it can be seen that the sample of the present invention has high sensitivity and a high light absorption in the silver halide emulsion.

Example 2 (1) Preparation of Emulsion 2 An aqueous solution containing gelatin having an average molecular weight of 15,000 (water 12
1.9 M AgNO ₃ aqueous solution and 1.9 M KBr aqueous solution were added at 25 ml / min by a double jet method at 25 ml / min for 70 sec while stirring at 30 ° C. while maintaining the mixture at 00 ° C., containing 7.0 g of gelatin and 4.5 g of KBr. As a result, nuclei of tabular grains were obtained. 350 ml of this emulsion was used as seed crystals, and 650 ml of an inert gelatin aqueous solution (gelatin 20 g, KBr1.
(Including 2 g), and the mixture was heated to 75 ° C. and aged for 40 minutes. Then, an AgNO ₃ aqueous solution (including 1.7 g of AgNO ₃ ) was added over 1 minute and 30 seconds, and then NH ₄ NO
6.2 ml of ₃ (50 wt%) aqueous solution and NH ₃ (25 wt%)
6.2 ml were added and aged for an additional 40 minutes. Next, the emulsion was adjusted to pH 7 with HNO ₃ (3N), and 1.0 g of KBr was added. Then, 366.5 ml of a 1.9 M aqueous solution of AgNO ₃ and an aqueous solution of KBr were added thereto, followed by a 1.9 M aqueous solution of AgNO _3.
3.6 ml of an aqueous solution of KBr (containing 33.3 mol% of KI) and 160.5 ml of a 1.9 M aqueous solution of AgNO ₃
And an aqueous KBr solution were added while maintaining the pAg at 8.3 to obtain Emulsion 2. Emulsion 2 obtained is a triple structure grain having a region with the highest silver iodide content in the intermediate shell, an average aspect ratio of 6.7, and the total projected area of tabular grains having an aspect ratio of 6 or more. And the proportion of tabular grains having an aspect ratio of 3 or more and 100 or less to the total projected area was about 95%. The coefficient of variation of the particle size is 11%, and the average of the particle size is 1.0 in sphere equivalent diameter.
It was 0 μm. Emulsion 2 was desalted by the usual flocculation method, and then 5.4 × 10 ^-4 mol per mol of silver.
(80% of saturated coating) sensitizing dye was added, and gold / sulfur / selenium sensitization was optimally performed in the presence of the sensitizing dye.

(2) Preparation of Coated Samples Samples 201 to 209 were prepared by coating the same emulsion layer and protective layer as in Example 1 using Emulsion 2 on a triacetyl cellulose film support provided with an undercoat layer. did. For these samples, the integrated value S was determined from the absorption spectrum in the same manner as in Example 1. Further, exposure for sensitometry (1/100 second) was performed, and the same color development processing and density measurement as in Example 1 were performed. Emulsion used for each sample,
Table 3 shows the results of the methine compound species, S of each sample, and sensitivity. The sensitivity of each sample was represented by a relative value with the value of samples 201 and 205 being 100.

[0084]

[Table 3]

From Table 3, it can be seen that the samples of the present invention have higher sensitivity with emulsions having an aspect ratio of 3 or more and have high light absorption. Example 3 Emulsions 3 to 16 and samples 301 to 301 were prepared by the method described below.
340 were prepared, and the results of measuring the sensitivity are shown in Table 4.

Emulsion 3 Tabular silver iodobromide was prepared in the same manner as Emulsion D of Example 5 of JP-A-8-29904 to obtain Emulsion 3. The multilayer color photographic material is the sample 10 of Example 5 of JP-A-8-29904.
In the same manner as in Example No. 1, it was produced. Emulsion H of the ninth layer in Sample 101 of Example 5 of JP-A-8-29904 was replaced with Emulsion 3, and ExS-4, 5, 6 were replaced with S-1 or the sensitizing dye (I-3) of the present invention. Replaced sample is replaced with sample 301
To 304. In order to examine the sensitivity of the sample thus obtained, light from a Fuji FW type sensitometer (Fuji Film Co., Ltd.) was exposed to light for 1/100 second through an optical wedge and a green filter. The color development processing was performed using the process and the processing solution, and the magenta density was measured. The sensitivity is determined by calculating the reciprocal of the exposure amount necessary to give a density of fog density + 0.2, and setting the sensitivity of the sample 301 to 10
The value was indicated by a relative value of 0.

Emulsions 4 to 7 The emulsion 1 of Example 1 of JP-A-7-92601 is different from the emulsion 1 in that the spectral sensitizing dye is S-1 or the sensitizing dye of the present invention (I-3).
A tetradecahedral silver iodobromide emulsion was prepared which was different only in that the emulsions were replaced with the above. Also, JP-A-7-9
The emulsion 1 of Example 1 of No. 2601 was prepared by changing the silver potential in the second double jet from +65 mV to +115 mV, and changing the spectral sensitizing dye to S-1 or the sensitizing dye of the present invention (I-3). A) cubic silver iodobromide emulsion was prepared, which was different from the above-mentioned emulsions. 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. JP-A-7-926
Samples Nos. 305 to 308 were prepared by changing Emulsion 1 of the ninth layer of Sample 401 of Example 4 of Example No. 01 to Emulsion 4 or Emulsion 5.
And Similarly, Samples 309 to 312 were obtained by changing Emulsion 1 of the ninth layer to Emulsion 6 or Emulsion 7 in the same Example. The sample thus obtained was evaluated for sensitivity. JP-A-7-
In the same manner as in Example 4 of No. 92601, exposure was performed for 1/50 second and color reversal development was performed to measure magenta density. 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 samples 305 and 309 taken as 100.

Emulsions 8, 9 As in Emulsions 1 and 5 of Example 1 of JP-A-5-313297, octahedral silver bromide internal latent image type direct positive emulsions and hexagonal tabular silver bromide internal latent image type direct Positive emulsions were prepared and used as Emulsions 8 and 9. The color diffusion transfer photographic film is a sample 101 of Example 1 of JP-A-5-313297.
In the same manner. Emulsion 8 of the eleventh layer and sensitizing dye (2) in Sample 101 of Example 1 of JP-A-5-313297 were prepared by using emulsion 8 and S-1 or the sensitizing dye (I) of the present invention.
Samples 313 to 316 were used instead of -3). Similarly, Samples 317 to 320 of Sample 101 of Example 101 were prepared by replacing Emulsion-2 and sensitizing dye (2) in the eleventh layer with Emulsion 9 and S-1 or the sensitizing dye (I-3) of the present invention. And
To examine the sensitivity of the sample thus obtained, see Japanese Patent Application Laid-Open No.
Processing was performed using the same processing steps and processing liquid as in Example 1 of No. 13297, and the transfer density was measured with a color densitometer. The sensitivity was calculated as the reciprocal of the exposure required to give a density of 1.0, and was shown as a relative value with the sensitivity of samples 313 and 317 as 100.

Emulsions 10, 11 Emulsion F of Example 2 of JP-A-4-142536 was prepared by adding no red-sensitizing dye (S-1) before sulfur sensitization, and adding sulfur-sensitizing dye of triethylthiourea. In addition to the sensation, chloroauric acid was also used in combination to optimize gold-sulfur sensitization, and after gold-sulfur sensitization,
A silver chlorobromide emulsion was prepared which differs only in that S-1 or the sensitizing dye (I-3) of the present invention was added.
0 and Emulsion 11. Multilayer color photographic paper is disclosed in
A sample was similarly prepared according to Sample 20 of Example 1 of 347944. Sample 20 of Example 1 of JP-A-6-347944
Samples 321 to 324 were obtained by changing the emulsion of the third layer in Example 1 to Emulsion 10 or Emulsion 11. In order to examine the sensitivity of the sample thus obtained, the light of a Fuji FW type sensitometer (Fuji Film Co., Ltd.) was exposed for 1/10 second through an optical wedge and a green filter.
Example 1 of No. 4 A color developing process was performed using the processing step and the processing solution, and the magenta density was measured. Sensitivity is fog density +
Find the reciprocal of the exposure required to give a density of 0.2,
The relative value is represented by setting the sensitivity of the sample 321 to 100.

Emulsions 12 and 13 A tabular silver chloride emulsion was prepared in the same manner as in Emulsion A of Example 1 of JP-A-8-122954, and the chemical sensitization (B) in this example was defined as sensitizing dye- Chemical sensitization was performed in the same manner except that S1 and S2 were replaced with S-1 or the sensitizing dye (I-3) of the present invention. The coated sample was prepared by replacing the emulsion of Example 1 in JP-A-8-122954 with Emulsion 12 or Emulsion 13, and combining both emulsion layers and surface protective layers on a support in the same manner as in Example 1 to simultaneously coat both sides by the extrusion method. Then, this is sampled 325 to 328
And The amount of silver applied per side was 1.75 g / m ² . To examine the sensitivity of the sample thus obtained, exposure was performed for 0.05 seconds from both sides using an X-ray orthoscreen HGM manufactured by Fuji Photo Film Co., Ltd.
Processing was carried out in the same manner as in Example 1 of JP-A-122954 using an automatic developing machine and a processing solution. The sensitivity is represented by the logarithm of the reciprocal of the amount of exposure necessary to give a density of fog density + 0.1.
Was expressed as a relative value with the sensitivity of 100 as 100.

Emulsion 14 A tabular silver chloride emulsion was prepared which was different from Emulsion D of Example 2 of JP-A-8-227117 only in that no sensitizing dyes 2 and 3 were added. The coated sample was prepared in the same manner as in the coated sample F of Example 3 of JP-A-8-227117. Emulsion F of coating sample F of Example 3 of JP-A-8-227117, sensitizing dye-1 and emulsion 14 and S-1
Alternatively, samples 329 to 332 were used instead of the sensitizing dye (I-3) of the present invention. In order to examine the sensitivity of the sample thus obtained, light from a Fuji FW type sensitometer (Fuji Film Co., Ltd.) was passed through an optical wedge and a green filter.
Exposure was performed for 100 seconds, and a magenta density was measured by performing Fuji Photo Film CN16 processing. Sensitivity is fog density +
It was expressed as the logarithm of the reciprocal of the exposure required to give a density of 0.2, and was expressed as a relative value with the sensitivity of sample 329 as 100.

Emulsion 15 An octahedral silver chloride emulsion was prepared in the same manner as Emulsion F in Example 3 of JP-A-8-227117, and this was designated as Emulsion 15. The coated sample was prepared in the same manner as in the coated sample F of Example 3 of JP-A-8-227117. Emulsion F of coating sample F of Example 3 of JP-A-8-227117 and sensitizing dye-1 in emulsion 15
Were replaced with S-1 or the sensitizing dye (I-3) of the present invention to prepare Samples 333 to 336. In order to examine the sensitivity of the sample thus obtained, the light of a Fuji FW type sensitometer (Fuji Film Co., Ltd.) was exposed to light for 1/100 second through an optical wedge and a green filter.
After the treatment, the magenta density was measured. The sensitivity is represented by the logarithm of the reciprocal of the exposure required to give a density of fogging density + 0.2, and is expressed as a relative value with the sensitivity of sample 333 being 100.

Emulsion 16 A tabular grain emulsion was prepared in the same manner as Emulsion CC of EP-0699950, and this was designated as Emulsion 16. Upon chemical sensitization, S-1 or the sensitizing dye (I-3) of the present invention is added instead of Dye 1 and Dye 2, and EP 0699 A1.
The coated samples produced in the same manner as in the example of No. 950 were designated as samples 337 to 340, respectively. Exposure and development were performed in the same manner as in the patent, and the sensitivities were compared. The sensitivity was represented by the logarithm of the reciprocal of the exposure required to give a density of fog +0.2, and was represented by a relative value with the sensitivity of sample 337 being 100.

[0094]

[Table 4]

[0095]

[Table 5]

From Table 4, it can be seen that the samples of the present invention have high sensitivity with various emulsions.

In samples 325 to 328, instead of the X-ray orthoscreen HGM used at the time of exposure, HR-
Exposure with HGH 4 or 4 gave the same effect.

[0098]

According to the present invention, a silver halide photographic material having a high light absorption and a high sensitivity can be obtained.

Claims (1)

[Claims] 1. The following general formula (I) and general formula (III)
Characterized by containing at least one compound represented by
Silver halide photographic material. General formula (I)[In the formula (I), U is a compound represented by the following general formula (II)
Represents an object. General formula (II)[In the formula (II), Z₁And Z_TwoAre the same but different
To form a 5- or 6-membered nitrogen-containing heterocyclic ring, respectively.
Represents the group of atoms required for L₁, L_Two, L_Three, L_Four,
L_Five, L₆, L₇, L₈, L₉, And L_TenRepresents a methine group
Represent. n₁And n_TwoRepresents 0 or 1. p₁And p_Two
Represents 0, 1, 2, or 3. L represents a divalent linking group
And L and U are in the N-position (R_FourOr R_Fiveof
Instead of a direct nitrogen atom), and L₆, L₇, L₈
May be bonded to any of the methine groups represented by R
₁, R_Two, R_Three, R_Four, R_Five, And R₆Is each alkyl
Represents a group. V₁, V_Two, V_Three, And V_FourAre the same
May also be different and each represents a substituent. q₁, Q_Two,
q_Three, And q_FourRepresents 0 or a positive integer. However,
R₁, R_Two, R_Three, R_Four, R_Five, R₆, (V₁) Q₁,
(V_Two) Q_Two, (V_Three) Q_Three, And (V_Four) Q_FourIs dissociated
Contains no functional groups,₁, R_Two, R_Three, (V₁) Q
₁, (V_Two) Q_TwoTotal number of dissociable groups and R_Four, R_Five,
R₆, (V_Three) Q_Three, (V_Four) Q_FourThe total number of dissociative groups
Numbers are assumed to be equal. M₁Represents the charge-balancing counterion
Then m₁Is from 0 to 10 necessary to neutralize the molecular charge.
Represents the following numbers. General formula (III)[In the formula (III), U is represented by the above general formula (II)
Represents a compound, Z_Two, L ₆, L₇, L₈, L₉, L_Ten,
n_Two, P_Two, L, R_Four, R_Five, R₆, V_Three, V_Four,
q_Three, And q_FourIs the same as that described in the general formula (I).
It is synonymous. Z_ThreeForms a 5- or 6-membered nitrogen-containing heterocyclic ring
Represents the group of atoms necessary for L and U are L of U ₆,
L₇, L₈Is bonded to any of the methine groups
Shall be. R₇And R₈Each represents an alkyl group.
V_FiveAnd V₆May be the same or different
Represents a substituent. q_FiveAnd q₆Represents 0 or a positive integer
You. Where R_Four, R_Five, R₆, R₇, R₈, (V_Three) Q
_Three, (V_Four) Q_Four, (V_Five) Q_Five, And (V₆) Q₆
Contains no dissociable groups or R₇, R₈, (V_Five) Q
_Five, (V ₆) Q₆Total number of dissociable groups and R_Four, R_Five,
R₆, (V_Three) Q_Three, (V_Four) Q _FourThe total number of dissociative groups
Numbers are assumed to be equal. L₁₁, L₁₂, L₁₃, L₁₄,as well as
L _FifteenRepresents a methine group. n_ThreeRepresents 0 or 1. p_Three
Represents 0, 1, 2, or 3. M_TwoIs the charge balance versus Io
And m_TwoIs zero or more required to neutralize the molecular charge
Represents a number of 10 or less. ]