EP1251395B1

EP1251395B1 - Silver halide photographic material containing a methine dye

Info

Publication number: EP1251395B1
Application number: EP01124350A
Authority: EP
Inventors: Tetsuo Nakamura; Takanori Hioki; Katsuhisa Ohzeki; Naoyuki Hanaki
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2001-04-17
Filing date: 2001-10-23
Publication date: 2010-09-29
Anticipated expiration: 2021-10-23
Also published as: DE60143154D1; ATE483182T1; EP1251395A1

Abstract

Disclosed is a silver halide photographic material which comprises at least one methine dye represented by the following formula (I): <CHEM> wherein Y represents a furan ring or a pyrrole ring, and Y may further be condensed with other 5- or 6-membered carbocyclic ring or heterocyclic ring, or may have a substituent; the bond between two carbon atoms in which Y is condensed may be a single bond or a double bond; Z represents an atomic group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, and Z may further be condensed with other 5- or 6-membered carbocyclic ring or heterocyclic ring; R represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group; D represents a group necessary to form a methine dye; L<1> and L<2> each represents a methine group; p represents 0 or 1; M represents a counter ion; and m represents a number of 0 or higher necessary to neutralize the charge in the molecule.

Description

FIELD OF THE INVENTION

The present invention relates to a silver halide photographic material and more particularly relates to a silver halide photographic material which is high sensitive and generates less residual colors after processing.

BACKGROUND OF THE INVENTION

Every endeavor has been made for higher sensitization and reduction of residual colors after processing of a silver halide photographic material. It is known that a sensitizing dye which is used for spectral sensitization exerts a great influence on the capabilities of a silver halide photographic material. A trace of structural difference of a sensitizing dye largely affects photographic capabilities such as sensitivity, fog, storage stability and residual colors after processing. Photographic performances are also largely influenced by the combined use of two or more kinds of sensitizing dyes but it is difficult to foresee its effect. Many engineers have hitherto synthesized various kinds of sensitizing dyes, examined the combined use of sensitizing dyes and endeavored to investigate photographic capabilities thereof, however, it is not possible to know photographic capabilities in advance yet.
For that reason, a technique of spectral sensitization capable of improving sensitivity of silver halide grains without causing adverse effects such as fog and residual colors has been required.
Also, it is known that the present durability is deteriorated by adsorbing onto the surface of silver halide grains the sensitizing dye used for the spectral sensitization. Accordingly, a sensitizing dye in which the pressure durability is not deteriorated is desired.
EP-A-341 958 describes a silver halide photographic material containing at least one cyanine dye with a *H-pyrrolopyridine, 4H-thienopyrrole, 6H-thienopyrrole, 4H-furopyrrole or 6H-furopyrrole nucleus.
EP-A-1139164 , which is prior art in accordance with Article 54(3) EPC, discloses a silver halide photographic material containing a methine dye represented by the formula

SUMMARY OF THE INVENTION

An object of the present invention is to provide a silver halide photographic material which is high speed and generates less residual colors after processing, and also is to provide a silver halide photographic material not deteriorating the pressure durability.
The present invention provides a silver halide photographic material which comprises at least one methine dye represented by the following formula (XX):
wherein Y⁵¹ represents an atomic group necessary to form a furan ring or a pyrrole ring, and represents a structure selected from formulae (3a), (3b) and (3c) together with the rings including X⁵¹ _:
wherein Xa represents an oxygen atom or a nitrogen atom (N-Rw); Rw represents a hydrogen atom or a monovalent substituent; Va represents a monovalent substituent selected from a methyl group, a methoxy group, a cyano group and a halogen atom; Vb represents a hydrogen atom; Vc and Vd each represents a hydrogen atom or a monovalent substituent, and at least one of Vc and Vd is a monovalent substituent selected from a methyl group, a methoxy group, a cyano group and a halogen atom; X⁵¹ and X⁵² each represents an oxygen atom, a sulfur atom or a nitrogen atom;
Y⁵² represents an atomic group necessary to form a benzene ring or a 5- or 6-membered unsaturated heterocyclic ring, which may further be condensed with other 5- or 6-membered carbocyclic or heterocyclic ring or may have a substituent, and two carbon atoms to which Y⁵² is condensed may be bonded by a single bond or a double bond; R⁵¹ and R⁵² each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group; L⁵¹, L⁵² and L⁵³ each represents a methine group; n⁵¹ represents 0, 1, 2, 3 or 4; M⁵¹ represents a counter ion; and m⁵¹ represents a number of 0 or higher necessary to neutralize the charge in the molecule,
with the proviso that the methine dye is not
Preferred embodiments of the invention are set forth in the sub-claims.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will be described in detail below. In the first place, the methine dye represented by formula (XX) will be described in detail below.
In formula (XX),
Y⁵¹ represents an atomic group necessary to form a furan ring or a pyrrole ring, and represents a structure selected from formulae (3a), (3b) and (3c) together with the rings including X⁵¹ _:
wherein Xa represents an oxygen atom or a nitrogen atom (N-Rw); Rw represents a hydrogen atom or a monovalent substituent; Va represents a monovalent substituent selected from a methyl group, a methoxy group, a cyano group and a halogen atom; Vb represents a hydrogen atom; Vc and Vd each represents a hydrogen atom or a monovalent substituent, and at least one of Vc and Vd is a monovalent substituent selected from a methyl group, a methoxy group, a cyano group and a halogen atom; X⁵¹ and X⁵² each represents an oxygen atom, a sulfur atom or a nitrogen atom;
Y⁵² represents an atomic group necessary to form a benzene ring or a 5- or 6-membered unsaturated heterocyclic ring, which may further be condensed with other 5- or 6-membered carbocyclic or heterocyclic ring or may have a substituent, and two carbon atoms to which Y⁵² is condensed may be bonded by a single bond or a double bond; R⁵¹ and R⁵² each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group; L⁵¹ L⁵² and L⁵³ each represents a methine group; n⁵¹ represents 0, 1, 2, 3 or 4; M⁵¹ represents a counter ion; and m⁵¹ represents a number of 0 or higher necessary to neutralize the charge in the molecule.
Rw represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom, a substituted alkyl group or an unsubstituted alkyl group. The substituents of the substituted alkyl group are preferably substituents having higher hydrophilicity than an iodine atom, more preferably substituents having the same or higher hydrophilicity than a chlorine atom, and particularly preferably substituents having the same or higher hydrophilicity than a fluorine atom. Rw more preferably represents a hydrogen atom or an unsubstituted alkyl group, and particularly preferably a hydrogen atom or a methyl group.
As the preferred substituents, an alkyl group (e.g., methyl), an aryl group (e.g., phenyl), an aromatic heterocyclic group (e.g., 1-pyrrolyl), an alkoxyl group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group, an acyl group (e.g., acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), and a halogen atom (e.g., fluorine, chlorine, bromine, iodine) are exemplified, the more preferred substituents are a methyl group, a methoxy group, a cyano group and a halogen atom, the still more preferred is a halogen atom, the particularly preferred are a fluorine atom, a chlorine atom and a bromine atom, and the most preferred is a chlorine atom.
Of (3a), (3b) and (3c), (3a) and (3b) are preferred. X⁵¹ and X⁵² each represents an oxygen atom, a sulfur atom, or a nitrogen atom, and preferably an oxygen atom or a sulfur atom.
Y⁵² represents an atomic group necessary to form a benzene ring or a 5- or 6-membered unsaturated heterocyclic ring, which may further be condensed with other 5- or 6-membered carbocyclic or heterocyclic ring or may have a substituent, and two carbon atoms to which Y⁵² is condensed may be bonded by a single bond or a double bond, preferably a double bond. Y⁵² represents an atomic group necessary to form a benzene ring or a 5- or 6-membered unsaturated heterocyclic ring.
Examples of the 5-membered unsaturated heterocyclic rings formed by Y⁵² include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a furan ring, an oxazole ring, an isooxazole ring, a thiophene ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a selenophene ring, a selenazole ring, an isoselenazole ring, a tellurophene ring, a tellurazole ring, and an isotellurazole ring, and examples of the 6-membered unsaturated heterocyclic rings formed by Y⁵² include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyran ring, and a thiopyran ring. Y⁵² may further be condensed with other 5- or 6-membered carbocyclic ring or heterocyclic ring to form, e.g., an indole ring, a benzofuran ring, a benzothiophene ring, or a thienothiophene ring. The preferred 5- or 6-membered unsaturated heterocyclic rings formed by Y⁵² are a pyrrole ring, a furan ring, a thiophene ring, and a pyridine ring, and particularly preferred is a pyrrole ring, a thiophene ring or a furan ring. Also, the bond between two carbon atoms in which Y⁵² is condensed may be a sigle bond or a double bond. Particularly, a double bond is preferred.
Y⁵² is preferably a benzene ring, a pyrrole ring, a furan ring, or a thiophene ring (as the pyrrole and furan rings, the above-described (3a), (3b), and (3c) can be exemplified and the similar ones are preferred), particularly preferably a benzene ring, a furan ring or a pyrrole ring, and most preferably a benzene ring. The substituents are not limited but preferably an alkyl group (e.g., methyl), an aryl group (e.g., phenyl), an aromatic heterocyclic group (e.g., 1-pyrrolyl), an alkoxyl group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group, an acyl group (e.g., acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), and a halogen atom (e.g.,fluorine,chlorine,bromine,iodine) are exemplified, more preferably a methyl group, a methoxy group, a cyano group and a halogen atom, still more preferably a halogen atom, particularly preferably a fluorine atom, a chlorine atom and a bromine atom, and most preferably a chlorine atom.
R⁵¹ and R⁵² each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. The case where at least one of R⁵¹ and R⁵² represents an alkyl group substituted with an acid radical is preferred, the case where R⁵¹ and R⁵² both represent an alkyl group substituted with an acid radical is more preferred, the case where at least one of R⁵¹ and R⁵², which are alkyl groups substituted with an acid radical, represents an alkyl group substituted with an acid radical other than a sulfo group is particularly preferred, and the case where one of R⁵¹ and R⁵² represents an alkyl group substituted with an acid radical other than a sulfo group and the other represents an alkyl group substituted with a sulfo group is most preferred.
The alkyl group represented by R⁵¹ or R⁵² may be substituted or unsubstituted, for example, an unsubstituted alkyl group having from 1 to 18, preferably from 1 to 7, and particularly preferably from 1 to 4, carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), and a substituted alkyl group having from 1 to 18, preferably from 1 to 7, and particularly preferably from 1 to 4, carbon atoms [examples of the substituents include, e.g. , an aryl group having from 6 to 12 carbon atoms (e.g., phenyl, p-chlorophenyl, p-tolyl), an unsaturated hydrocarbon group having from 2 to 6 carbon atoms (e.g., vinyl), a carboxyl group, a sulfo group, a sulfato group, a cyano group, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), a hydroxyl group, a mercapto group, an alkoxyl group having from 1 to 7 carbon atoms (e.g., methoxy, ethoxy, 2-methoxyethoxy, benzyloxy), an aryloxy group having from 6 to 12 carbon atoms (e.g., phenoxy, 1-naphthoxy), an alkylthio group having from 1 to 7 carbon atoms (e.g., methylthio), an arylthio group having from 6 to 12 carbon atoms (e.g., phenylthio, 1-naphthylthio), an acyl group having from 1 to 7 carbon atoms (e.g., acetyl, benzoyl), an alkoxycarbonyl group having from 2 to 8 carbon atoms (e.g., ethoxycarbonyl, benzyloxycarbonyl), an aryloxycarbonyl group having from 7 to 13 carbon atoms (e.g., phenoxycarbonyl), an acyloxy group having from 1 to 8 carbon atoms (e.g., acetyloxy), a carbamoyl group (e.g., morpholinocarbonyl), a sulfamoyl group (e.g., N,N-dimethylsulfamoyl), a heterocyclic group (e.g., tetrahydrofuryl), an alkylsulfonylcarbamoyl group (e.g., methanesulfonylcarbamoyl), an acylcarbamoyl group (e.g., acetylcarbamoyl), an acylsulfamoyl group (e.g., acetylsulfamoyl), and an alkylsulfonylsulfamoyl group (e.g., methanesulfonylsulfamoyl)] can be exemplified.
The aryl group represented by R⁵¹ or R⁵² may be substituted or unsubstituted, for example, an unsubstituted aryl group having from 6 to 20, preferably from 6 to 15, and more preferably from 6 to 10, carbon atoms (e.g., phenyl, 1-naphthyl), and a substituted aryl group having from 6 to 26, preferably from 6 to 21, and more preferably from 6 to 16, carbon atoms [examples of the substituents include each substituent described above in the substituted alkyl group (an aryl group, an unsaturated hydrocarbon group, a carboxyl group, a sulfo group, a sulfato group, a cyano group, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), a hydroxyl group, a mercapto group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a heterocyclic group, an alkylsulfonylcarbamoyl group, an acylcarbamoyl group, an acylsulfamoyl group, an alkylsulfonyl sulfamoyl group), and an alkyl group (which may be substituted) can be exemplified, and preferred is a phenyl group.
The heterocyclic group represented by R⁵¹ or R⁵² may be substituted or unsubstituted, for example, an unsubstituted heterocyclic group having from 1 to 20, preferably from 1 to 15, and more preferably from 1 to 10, carbon atoms (e.g., pyrrole, furan, thiophene), and a substituted azole group having from 1 to 26, preferably 1 to 21, and more preferably 1 to 16, carbon atoms [examples of the substituents include each substituent described above in the substituted alkyl group (an aryl group, an unsaturated hydrocarbon group, a carboxyl group, a sulfo group, a sulfato group, a cyano group, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), a hydroxyl group, a mercapto group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a heterocyclic group, an alkylsulfonylcarbamoyl group, an acylcarbamoyl group, an acylsulfamoyl group, an alkylsulfonylsulfamoyl group), and an alkyl group (which may be substituted)] can be exemplified.
R⁵¹ and R⁵² preferably represent, an alkyl group substituted with a group having an acid radical or a dissociable proton (specifically, a carboxyl group, a sulfo group, a phosphoric acid group, a boric acid group, an alkylsulfonylcarbamoyl group (e.g., methanesulfonylcarbonyl), an acylcarbamoyl group (e.g., acetylcarbamoyl), an acylsulfamoyl group (e.g., acetylsulfamoyl), or an alkylsulfonylsulfamoyl group (e.g., methanesulfonylsulfamoyl)), and more preferably represents a carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, or a methanesulfonylcarbamoylmethyl group.
L⁵¹, L⁵² and L⁵³ each represents a methine group, which may be a substituted or unsubstituted methine group. Example of the substituents include the substituents described above in the substituted alkyl group represented by R⁵¹ or R⁵². n⁵¹ represents 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and more preferably 0 or 1. When n⁵¹ represents 2 or more, L⁵² and L⁵³ are repeated but they may be or may not be the same. When n⁵¹ represents 0, L⁵¹ preferably represents an unsubstituted methine group, and when n⁵¹ represents 1, L⁵¹ and L⁵³ each preferably represents an unsubstituted methine group, and L⁵² preferably represents a methine group substituted with an unsubstituted alkyl group (e.g., methyl, ethyl, propyl). L⁵² more preferably represents a methine group substituted with an ethyl group.
M⁵¹ represents a counter ion, which is required for neutralizing the ion charge. M⁵¹ is included in the formula for showing the presence of cation or anion. It is depended on the substituent whether a dye is cation or anion, or the dye has a net ion charge or not.
Examples of the cation include inorganic ions such as a hydrogen ion, alkali metal ions (e.g., Na, K, and Li ions) and alkaline earth metal ions (e.g., Ca ion), organic ions such as ammonium ions (e.g., ammonium, tetraalkyl ammonium, pyridinium and ethylpyridinium ions) . Examples of the anion may be either of inorganic and organic ions, and include halide ions (fluoride, chloride, bromide and iodide ions), substituted arylsulfonic acid ions (e.g., p-toluene sulfonic acid ion, p-chlorobenzene sulfonic acid ion), aryldisulfonic acid ions (e.g., 1, 3-benzene sulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfonic acid ions (e.g., methyl sulfuric acid ion), a sulfonic acid ion, a thiocyanic acid ion, a perchloric acid ion, a tetrafluoroboric acid ion, a picric acid ion, an acetic acid ion, a trifluoromethane sulfonic acid ion.
Examples of the preferred cation include a sodium ion, a potassium ion, a triethylammonium ion, a tetraethylammonium ion, a pyridinium ion, an ethylpyridinium ion and a methylpyridinium ion. Examples of the preferred anion include a perchloric acid, a iodide ion, a bromide ion, and a substituted arylsulfonic acid ion (e.g., p-toluen sulfonic acid ion).
m⁵¹ represents a number of 0 or higher necessary to neutralize the charge in the molecule, and when an inner salt is formed, m⁵¹ represents 0. m⁵¹ preferably represents a number of from 0 to 4.
The methine dye represented by formula (XX) is more preferably represented by the following formula (XXI).
wherein Y⁷¹ represents an atomic group necessary to form a furan ring or a pyrrole ring as defined for Y⁵¹. X⁷¹ and X⁷² each represents an oxygen atom, a sulfur atom, or a nitrogen atom. R⁷¹ and R⁷² each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. L⁷¹, L⁷² and L⁷³ each represents a methine group. n⁷¹ represents 0, 1, 2, 3 or 4. M⁷¹ represents a counter ion, and m⁷¹ represents a number of 0 or higher necessary to neutralize the charge in the molecule. V⁷¹, V⁷², V⁷³ and V⁷⁴ each represents a hydrogen atom or a substituent.
Y⁷¹ has the same meaning as Y⁵¹ described above, and the similar ones are preferred, and two carbon atoms to which Y⁷¹ is condensed may be bonded by a single bond or a double bond, preferably a double bond. X⁷¹ and X⁷² each has the same meaning as X5¹ and X⁵² described above, and the similar ones are preferred. R⁷¹ and R⁷² each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, each has the same meaning as R⁵¹ and R⁵² described above, and the similar ones are preferred. L⁷¹, L⁷² and L⁷³ each represents a methine group, each has the same meaning as L⁵¹, L⁵² and L⁵³ described above, and the similar ones are preferred. n⁷¹ represents 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and more preferably 0 or 1. The case where the methine chain represented by =L⁷¹-(L⁷²=L⁷³)_n71- represents the following LLa or LLb is particularly preferred.

Preferred methine chain

LLa: =CH-

LLb:

-wherein A represents a methyl group, an ethyl group or a propyl group, preferably an ethyl group.
M⁷¹ represents a counter ion, and m⁷¹ represents a number of 0 or higher necessary to neutralize the charge in the molecule, and they have the same meaning as M⁵¹ and m⁵¹ described above. It is particularly preferred that M⁷¹ represents a cation, and preferred cations are a sodium ion, a potassium ion, a triethylammonium ion, a pyridinium ion and an N-ethylpyridinium ion.
V⁷¹, V⁷², V⁷³ and V⁷⁴ each represents a hydrogen atom or a substituent. Of these, two contiguous substituents may be linked to each other to form a saturated or unsaturated condensed ring but it is not preferred particularly to form an unsaturated condensed ring in view of photographic performances. Further, it is also preferred not to form a saturated condensed ring. It is preferred that both V⁷¹ and V⁷⁴ represent a hydrogen atom, and V⁷² and V⁷³ each represents a hydrogen atom, an alkyl group (e.g., methyl), an aryl group (e.g., phenyl), an aromatic heterocyclic group (e.g., 1-pyrrolyl), an alkoxyl group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group, an acyl group (e.g., acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), or a halogen atom (e.g., fluorine, chlorine, bromine, iodine) . V⁷² more preferably represents a hydrogen atom and V⁷³ more preferably represents a methyl group, a methoxy group, a cyano group, an acetyl group, a methoxycarbonyl group, or a halogen atom, still more preferably a halogen atom, particularly preferably a fluorine atom, a chlorine atom or a bromine atom, and most preferably a fluorine atom or a chlorine atom.
When the methine dye represented by formula (XXI) is used in a red-sensitive emulsion layer, it is preferred that the methine chain (L⁷¹, L⁷², L⁷³, n⁷¹) represents theabove-describedLLb (wherein Apreferably represents an ethyl group), either X⁷¹ or X⁷² represents an oxygen atom and the other represents a sulfur atom, and Y⁷¹ represents a pyrrole ring or a furan ring substituted with a halogen atom (preferably a chlorine atom or a bromine atom).
It is preferred that R⁷¹ and R⁷² each represents a sulfoalkyl group, a carboxyalkyl group or an alkanesulfonylcarbamoylalkyl group, all of V⁷¹, V⁷² and V⁷⁴ represent a hydrogen atom, V⁷³ represents an alkyl group (e.g., methyl), an alkoxyl group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group, an acyl group (e.g., acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), or a halogen atom (e.g., fluorine, chlorine, bromine, iodine), more preferably a methyl group, a methoxy group, a cyano group, an acetyl group, a methoxycarbonyl group or a halogen atom, particularly preferably a halogen atom, and most preferably a fluorine atom or a chlorine atom, M⁷¹ represents an organic or inorganic monovalent cation, and m⁷¹ represents 0 or 1.
When the methine dye represented by formula (XXI) is used in a green-sensitive emulsion layer, it is preferred that the methine chain (L⁷¹, L⁷², L⁷³, n⁷¹) represents the above-described LLb (wherein A preferably represents an ethyl group), both of X⁷¹ and X⁷² represent an oxygen atom, and Y⁷¹ represents a pyrrole ring or a furan ring substituted with a halogen atom (preferably a chlorine atom or a bromine atom).
It is preferred that R⁷¹ and R⁷² each represents a sulfoalkyl group, a carboxyalkyl group or an alkanesulfonylcarbamoylalkyl group, all of V⁷¹, V⁷² and V⁷⁴ represent a hydrogen atom, V⁷³ represents an alkyl group (e.g., methyl), an aryl group (e.g., phenyl), an aromatic heterocyclic group (e.g., 2-thienyl), an alkoxyl group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group, an acyl group (e.g., acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), or a halogen atom (e.g., fluorine, chlorine, bromine, iodine), more preferably a methyl group, a methoxy group, a cyano group, an acetyl group, a methoxycarbonyl group or a halogen atom, particularly preferably a halogen atom, and most preferably a fluorine atom or a chlorine atom, M⁷¹ represents an organic or inorganic monovalent cation, and m⁷¹ represents 0 or 1.
When the methine dye represented by formula (XXI) is used in a blue-sensitive emulsion layer, it is preferred that the methine chain (L⁷¹, L⁷², L⁷³, n⁷¹) represents the above-described LLa, both of X⁷¹ and X⁷² represent a sulfur atom, and Y⁷¹ represents a pyrrole ring or a furan ring substituted with a halogen atom (preferably a chlorine atom or a bromine atom).
It is preferred that R⁷¹ and R⁷² each represents a sulfoalkyl group, a carboxyalkyl group or an alkanesulfonylcarbamoylalkyl group, all of V⁷¹, V⁷² and V⁷⁴ represent a hydrogen atom, V⁷³ represents an alkyl group (e.g., methyl), an alkoxyl group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group, an acyl group (e.g., acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), or a halogen atom (e.g., fluorine, chlorine, bromine, iodine), more preferably a methyl group, a methoxy group, a cyano group, an acetyl group, a methoxycarbonyl group or a halogen atom, particularly preferably a halogen atom, and most preferably a fluorine atom or a chlorine atom, M⁷¹ represents an organic or inorganic monovalent cation, and m⁷¹ represents 0 or 1.
In general, sensitizing dyes which are less in residual colors are poor in J-associative property and low in sensitivity, but the sensitizing dyes used according to the present invention are remarkably high in J-associative property and high in sensitivity, although they generate less residual colors.

Only dyes S-66, S-106, S108, S-112, S-113, S-115, S-116, S-120, S-121, S-123, S-126, S-127, S-128, S-139, S-140, S-141, S-142, S-143, S-144, S-148, S-149, S-150, S-151, S-152, S-154 and S-157 are comprised by the formula (XX).

	R₁	R₂	V
S-98	CH₂CONHSO₂CH₃	(CH₂)₃SO₃ ^-	Br
S-99	"	" Cl
S-100	"	"	F
S-101	(CH₂)₃SO3^-	CH₂CO₂H	Cl
S-102	"	"	Br
S-103	"	"	F
S-104	CH₂CO₂H	(CH₂)₃SO₃ ^-	Br

	X	Y	Z₁	Z₂	R	M
S-105	F	Y	S	S	CH₂CO₂H	-
S-106	Br	O	O	S	(CH₂)₃SO3^-	$H \overset{+}{N} (C_{2} H_{5})_{3}$
S-107	Cl	S	O	S	CH₂CONHSO₂H₃	-
S-108	Cl	NH	O	O	CH₂CO₂H	-
S-109	Cl	S	S	O	(CH₂)₃SO₃ ^-	K⁺
S-110	Br	S	S	O	(CH₂)₃SO₃ ^-	K⁺
S-111	Cl	S	O	O	(CH₂)₃SO₃ ^-	Na⁺

	X	Y	Z₁	Z₂	R	M
S-112	Cl O		S	O	CH₂CO₂H	-
S-113	Br	O	S	S	(CH₂)₃SO₃ ^-	K⁺
S-114	H	NH	S	O	CH₂CO₂H	-
S-115	Cl	NH	S	O	CH₂CONHSO₂CH₃	-
S-116	Cl	N-CH₃	O	S	CH₂CO₂H	-

	R	M
S-117	(CH₂)₄SO₃ ^-	K⁺
S-118	CH₂CONHSO₂CH₃	-
S-119	CH₂CO₂H	-

	X	Y	Z₁	Z₂	R	M
S-120	Cl	O	S	S	CH₂CO₂H	-
S-121	Cl	NH	S	S	CH₂CONHSO₂CH₃	-
S-122	Bar	S	O	S	(CH₂)₃SO₃ ^-	$H \overset{+}{N} (C_{2} H_{5})_{3}$
S-123	Br	O	S	S	CH₂CO₂H	-

	X	Y	Z₁	Z₂	R	M
S-124	Cl	S	O	5	CH₂CO₂H	-
S-125	H	NH	S	S	(CH₂)₃SO₃ ^-	$H \overset{+}{N} (C_{2} H_{5})_{3}$
S-126	Cl	NH	S	S	CH₂SO₂NHCOCH₃	-
S-127	Br	O	S	S	CH₂CO₂H	-
S-128	Cl	N-CH₃	S	O	(CH₂)₄SO₃ ^-	$H \overset{+}{N} (C_{2} H_{5})_{3}$ H

	X	R	M
S-129	Cl	(CH₂)₃SO₃ ^-	$H \overset{+}{N} (C_{2} H_{5})_{3}$
S-130	Cl	CH₂CONHSO₂CH₃	-
S-131	Cl	CH₂CO₂H	-
S-132	Br	CH₂CO₂H	-

The methine dyes for use in the present invention can be synthesized according to the methods described in the following literature.

a) F.M. Hamer, Heterocyclic Compounds - Cyanine Dyes and Related Compounds, John Wiley & Sons, New York, London (1964)
b) D.M. Sturmer, Heterocyclic Compounds - Special Topics in Heterocyclic Chemistry, Chap. 8, Clause 4, pp. 482 to 515, John Wiley & Sons, New York, London (1977)
c) Rodd's Chemistry of Carbon Compounds, 2nd Ed., Vol. 4, Part B, Chap. 15, pp. 369 to 422, Elsevier Science Publishing Company Inc., New York (1977)

The synthesis of hetero ring as a raw material of the methine dyes for use in the present invention is disclosed
in literatures such as Bulletin de la Societe Chimique de France, Chap. II, p.150 (1980) and Journal of Heterocyclic Chemistry, Chap. 16, p.1563 (1979).
For the incorporation of the methine dyes into the silver halide emulsion used in the present invention, they may be directly dispersed in the emulsion, or they may be dissolved in water, a single or mixed solvent of methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N,N-dimethylformamide, and then added to the emulsion.
In addition, various methods can be used for incorporating dyes into the emulsion, for example, a method in which dyes are dissolved in a volatile organic solvent, the solution is dispersed in water or hydrophilic colloid and this dispersion is added to the emulsion as disclosed in U.S. Patent 3,469,987 , a method in which water-insoluble dyes are dispersed in a water-soluble solvent without being dissolved and this dispersion is added to the emulsion as disclosed in JP-B-46-24185 (the term "JP-B" as used herein means an "examined Japanese patent publication"), a method in which dyes are dissolved in acid and this solution is added to the emulsion, or dyes are added to the emulsion as an aqueous solution coexisting with acid or base as disclosed in JP-B-44-23389 , JP-B-44-27555 and JP-B-57-22091 , a method in which dyes are added to the emulsion as an aqueous solution or a colloidal dispersion coexisting with a surfactant as disclosed in U.S. Patents 3,822,135 and 4,006,026 , a method in which dyes are directly dispersed in a hydrophilic colloid and the dispersion is added to the emulsion as disclosed in JP-A-53-102733 and JP-A-58-105141 , or a method in which dyes are dissolved using a compound capable of red-shifting and the solution is added to the emulsion as disclosed in JP-A-51-74624 can be used. Further, ultrasonic waves can also be used for dissolution.
The time of the addition of the methine dyes to the silver halide emulsion used in the present invention may be at any stage of the preparation of the emulsion recognized as useful hitherto. For example, they may be added at any stage if it is before coating, i.e., before grain formation stage of silver halide grains and/or before desalting stage, during desalting stage and/or after desalting and before beginning of chemical ripening, as disclosed in U.S. Patents 2,735,766 , 3,628,960 , 4,183,756 , 4,225,666 , JP-A-58-184142 and JP-A-60-196749 , or immediately before or during chemical ripening, after chemical ripening and before coating as disclosed in JP-A-58-113920 . Also, as disclosed in U.S. Patent 4,225,666 and JP-A-58-7629 , the dyes can be used as a single compound alone or in combination with compounds having foreign structures, and they may be divided and added separately, for example, one part of them is added during grain formation stage and the remaining is added during chemical ripening or after the completion of chemical ripening, otherwise one part is added prior to chemical ripening or during ripening stage and the remaining after completion of chemical ripening. The kinds of compounds added separately and combinations of compounds may be varied.
The use amount of the methine dyes used according to the present invention varies in accordance with the shape and the size of silver halide grains, but is preferably from 1×10^-2 to 1×10^-8 mol per mol of the silver halide.
Other sensitizing dyes can be used in combination besides the methine dyes used according to the present invention. Sensitizing dyes are often used in combination, in particular, for the purpose of supersensitization. Representative examples thereof are disclosed in U.S. Patents 2,688,545 , 2,977,229 , 3,397,060 , 3,522,052 , 3,527,641 , 3,617,293 , 3,628,964 , 3,666,480 , 3,672,898 , 3,679,428 , 3,703,377 , 3,769,301 , 3,814,609 , 3,837,862 , 4,026,707 , British Patents 1,344,281 , 1,507,803 , JP-B-43-4936 , JP-B-53-12375 , JP-A-52-110618 and JP-A-52-109925 .
Any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride, and silver chloroiodobromide can be used as silver halide grains in the silver halide photographic material according to the present invention.
The silver halide grains contained in the silver halide emulsion for use in the present invention have an average grain size (the grain size herein refers to the diameter of the equivalent circle corresponding to the projected area of the grains, and the number average is taken as the average grain size) of preferably from 0.1 to 2 µm.
With respect to the distribution of sizes of these grains, a so-called monodispersed emulsion having a variation coefficient (the value obtained by dividing the standard deviation of the grain size distribution by the average grain size) of 20% or less, preferably 15% or less, and more preferably 10% or less, is preferred. For obtaining a wide latitude, it is also preferred to blend the above described monodispersed emulsions in the same layer or multilayer-coat the monodispersed emulsion.
The silver halide grains contained in a photographic emulsion may have a regular crystal form, such as cubic, octahedral or tetradecahedral form, an irregular crystal form, such as spherical or plate-like form, or a composite form of these forms. In the present invention, the grains having the above described regular crystal forms preferably account for 50% or more, preferably 70% or more, and more preferably 90% or more.
Further, an emulsion in which the proportion of tabular grains having an average aspect ratio (equivalent-circle diameter/thickness) of 5 or more, preferably 8 or more, to the entire grains exceeds 50% as a projected area can also be preferably used.
The emulsion for use in the present invention can be prepared according to the methods disclosed, for example, in P. Glafkides, Chimie et Physique Photographique, Paul Montel (1967), G. F. Duffin, Photographic Emulsion Chemistry, Focal Press (1966), V.L. Zelikman, et al., Making and Coating Photographic Emulsion, Focal Press (1964). That is, any process, such as an acid process, a neutral process, and an ammoniacal process, can be used. A single jet method, a double jet method, and a combination of them may be used for reacting a soluble silver salt with a soluble halide, and any of these methods can be used. A method in which silver halide grains are formed in the atmosphere of excessive silver ions (a so-called reverse mixing method) may also be used. Further, a so-called controlled double jet method, which is one form of a double jet method, in which the pAg of the liquid phase in which the silver halide is formed is maintained constant, may also be used. According to this method, a silver halide emulsion having a regular crystal form and substantially an almost uniform grain size can be obtained.
The silver halide emulsions for use in the present invention are generally chemically sensitized. In chemical sensitization, chemical sensitization using chalcogen sensitizers (typically, sulfur sensitization represented by the addition of labile sulfur compounds, selenium sensitization by selenium compounds, and tellurium sensitization by tellurium compounds can be exemplified), noble metal sensitization represented by gold sensitization, and reduction sensitization are used alone or in combination. The compounds disclosed in JP-A-62-215272 , from p. 18, right lower column to p. 22, right upper column are preferably used in the chemical sensitization.
Various compounds and precursors thereof can be added to the silver halide emulsions for the purpose of preventing generation of fog or stabilizing photographic performances during production, storage or photographic processing of the photographic material. The compounds disclosed in JP-A-62-215272 , from pp. 39 to 72 are preferably used. Further, 5-arylamino-1,2,3,4-thiatriazole compounds (the aryl residue has at least one electron attractive group) disclosed in European Patent 0447647 are also preferably used.
The silver halide emulsions used according to the present invention can be used in both color photographic materials, such as color papers, color films for photographing, and color reversal films , and black-and-white photographic materials, such as X-ray films, general films for photographing, and photographic films for printing, and preferably used as color photographic materials.
With respect to various techniques and inorganic and organic materials which can be used in the silver halide photographic emulsions, in general, those described in Research Disclosure, No. 308119 (1989), ibid., No. 37038 (1995) can be used.

In addition to these, more specifically, for example, techniques and inorganic and organic materials which can be used in the color photographic material to which the silver halide photographic emulsion used in the present invention is applicable are disclosed in the following places of EP-A-436938 and the patents cited in the following places.

	Item	Place
1)	Layer Constitution	line 34, page 146 to line 25, page 147
2)	Silver Halide Emulsion	line 26, page 147 to line 12, page 148
3)	Yellow Coupler	line 35, page 137 to line 33, page 146, lines 21 to 23, page 149
4)	Magenta Coupler	lines 24 to 28, page 149; line 5, page 3 to line 55, page 25 of EP-A- 421453
5)	Cyan Coupler	lines 29 to 33, page 149; line 28, page 3 to line 2, page 40 of EP-A- 432804
6)	Polymer Coupler	lines 34 to 38, page 149; line 39, page 113 to line 37, page 123 of EP-A-435334
7)	Colored Coupler	line 42, page 53 to line 34, page 137, lines 39 to 45, page 149
8)	Other Functional Coupler	line 1, page 7 to line 41, page 53, line 46, page 149 to line 3 page 150; line 1, page 3 to line 50, page 29 of EP-A-435334
9)	Preservative	lines 25 to 28, page 150
10)	Formalin Scavenger	lines 15 to 17, page 149
11)	Other Additives	lines 38 to 47, page 153; line 21, page 75 to line 56, page 84 of EP-A- 421453
12)	Dispersion Method	lines 4 to 24, page 150
13)	Support	line 32 to 34, page 150
14)	Film Thickness, Physical Properties of Film	lines 35 to 49, page 150
15)	Color Development Process	line 50, page 150 to line 47, page 151
16)	Desilvering Process	line 48, page 151 to line 53, page 152
17)	Automatic Processor	line 54, page 152 to line 2, page 153
18)	Washing and Stabilizing Processes	lines 3 to 37, page 153

In the photographic material of the present invention, it is preferred to color a hydrophilic colloid layer for the purpose of preventing irradiation and halation and improving safelight stability. As water-soluble dyes which can be used as such a coloring substance, the dyes capable of decoloration by processing (oxonol dyes and cyanine dyes, above all) disclosed in EP-A-0337490 , pages 27 to 76, can be exemplified.
A coloring substance disperses regardless of the position where it is added and pervades over the entire constitutional layers of the photographic material by such coloration.
Cyan, magenta and yellow couplers are preferably impregnated in a loadable latex polymer (e.g., disclosed in U.S. Patent 4, 203, 716 ) in the presence (or absence) of the high boiling point organic solvents described in the above table, or dissolved in a polymer insoluble in water but soluble in an organic solvent and emulsified and dispersed in a hydrophilic colloid aqueous solution.
Examples of polymers insoluble in water but soluble in an organic solvent which can preferably be used in the present invention include homopolymers or copolymers disclosed in U.S. Patent 4,857,449 , from pages 12 to 30. Methacrylate based or acrylamide based polymers are more preferred, in particular, acrylamide based polymers are preferred in the light of color image stability.
In the photographic material of the present invention, it is preferred to use color image preservability improving compounds disclosed in EP-A-0277589 in combination with the couplers. In particular, the use in combination with pyrazoloazole couplers or pyrrolotriazole couplers is preferred.
That is, the use of the compound disclosed in the above EP Patent which produces a chemically inactive and substantially colorless compound upon chemically bonding with an aromatic amine developing agent remaining after color development processing and/or the compound disclosed in the above EP Patent which produces a chemically inactive and substantially colorless compound upon chemically bonding with the oxidized product of an aromatic amine color developing agent remaining after color development processing, alone or in combination, is preferred for preventing the generation of stain due to the formation of a colored dye caused by the coupling reaction of the coupler with the color developing agent or the oxidized product thereof remaining in the film, or preventing other side reactions, during preservation after processing.
The present invention will be illustrated specifically with reference to examples below.

EXAMPLE 1

Synthesis of Methine Dye S-76

5-Bromo-2-methylthieno[3,2-d]thiazole was obtained at a yield of 34% by reacting 3-acetylamino-2,5-dibromothiophene (synthesized according to J. Am. Chem. Soc, 1954, 76, 2447) with phosphorous pentasulfide in toluene under heat-reflux.
5-Bromo-2-methylthieno[3,2-d]thiazole (2.58 g), 1.61 g of 1,3 -propane sultone and 6.4 ml anisole were mixed and stirred with heating at 150°C for 3 hours. After cooling the reaction mixture, the black precipitate generated was washed with acetone, the supernatant was removed by decantation, and 5.21 g of 4-(5-chloro-2-sulfobutylthio-3-benzothiazolio)butanesulfonate and 55 ml of acetonitrile were added thereto, followed by stirring with heating at 100°C.
Triethylamine (7.7 ml) was added to the reaction mixture and the mixture was refluxed under heating with stirring for 1.5 hours, thereby yellow precipitate was generated. The precipitate was filtered out by cooling with ice, washed with acetonitrile to thereby obtain 2.27 g of yellow powder. The yellow powder was dissolved in 150 ml of methanol, and then the solvent was distilled off to thereby obtain 1.34 g of Methine Dye S-76 as powder. The structure of S-76 was confirmed by ¹H-NMR, FAB-MS, and elemental analysis.
λ_max (MeOH) = 435.7 nm ( ε = 7.1×10⁴)

EXAMPLE 2

Synthesis of Methine Dye S-31

5-Bromo-2-methylthieno[3,2-d]thiazole (1.47 g), 0.93 g of 1,3-propanesultone and 3.7 ml of anisole were mixed and stirred with heating at 150°C for 3 hours. After cooling the reaction mixture, the black precipitate generated was washed with acetone. The supernatant was removed by decantation, and 3.28 g of 3-[5-chloro-2-(2-ethoxy-1-butenyl)-3-benzoxazolio]propane-sul fonate and 45 ml of dimethylsulfoxide were added thereto, followed by stirring at room temperature. 1,8-Diazabicyclo [5.4.0]-7-undecene (2.4 ml) was added to the reaction solution and the solution was stirred for 30 minutes, and then 6 ml of acetic acid and 600 ml of ethyl acetate were added thereto, thereby red precipitate was generated. The precipitate was purified by column chromatography, and 1.0 g of potassium acetate was added to methanol solution to distill off the solvent, thereby 1.03 g of Methine Dye S-31 was obtained as green powder. The structure of S-31 was confirmed by ¹H-NMR, FAB-MS, and elemental analysis.
λ_max (MeOH) = 524.3 nm ( ε = 7.8×10⁴)

EXAMPLE 3

Synthesis of Methine Dye S-85

5-Bromo-2-methylthieno[2,3-d]thiazole was obtained at a yield of 96% by adding dropwise bromine to 2-methylthieno[2,3-d]thiazole (synthesized according to J. Heterocyclic Chem., 1983, 20, 113) in the presence of sodium acetate in an acetic acid solvent.
5-Bromo-2-methylthieno[3,2-d]thiazole (9.37 g), 10.37 g of methanesulfonylcarbamoylmethyl bromide and 12 ml of cumene were mixed and stirred with heating at 150°C for 5 hours. The temperature of the reaction mixture was lowered to 80°C, acetone was added thereto, and the mixture was refluxed for 1 hour. The gray precipitate generated after cooling was filtered out, washed with acetone to thereby obtain 18.45 g of 5-bromo-3-methanesulfonylcarbamoylmethyl-2-methylthieno[2,3-d ]thiazolium bromide as powder. The above-obtained compound (1.80 g), 1.78 g of 4-(5-chloro-2-sulfopropylthio-3-benzothiazolio)propanesulfonate, and 16 ml of acetonitrile were mixed and stirred with heating at 40°C. Triethylamine in an amount of 2 ml was added thereto and the reaction mixture was heated for 1 hour to thereby generate yellow precipitate. After ice-cooling the reaction solution, the precipitate was filtered out, washed with acetonitrile, thereby 1.61 g of yellow powder was obtained. The obtained powder was dissolved in a mixed solvent of 20 ml of methanol, 20 ml of water and 1 ml of triethylamine, and then 3 ml of acetic acid was added thereto, thereby precipitate was generated. The precipitate was filtered out and washed with acetone to obtain 1.24 g of Methine Dye S-85 as powder. The structure of S-85 was confirmed by ¹H-NMR, FAB-MS, and elemental analysis.
λmax (MeOH) = 445.8 nm ( ε = 7.1×10⁴)

EXAMPLE 4

Synthesis of Methine Dye S-96

5-Chloro-2-methylthieno[2,3-d]thiazole was obtained by making trichloroisocyanuric acid act on the above 2-methylthieno[2,3-d]thiazole in a dichloromethane solvent. Yield: 98%.
5-Chloro-2-methylthieno[2,3-d]thiazole (15.2 g), 13.3 g of bromoacetic acid and 24 ml of cumene were mixed and stirred with heating at outer temperature of 135°C for 8 hours. After cooling the reaction mixture, 100 ml of acetone was added thereto. The crystals precipitated were filtered out by suction, washed with 50 ml of acetone, dried under reduced pressure, thereby 15.6 g of 3-carboxymethyl-5-chloro-2-methylthieno[2,3-d]thiazolium bromide (A) was obtained as yellow powder. To 7.4 g of (A), 18.5 g of 3-[5-chloro-2-(2-ethoxy-1-butenyl)-3-benzoxazolio]propanesulfonate and 70 ml of benzyl alcohol were added and stirred at room temperature. After that, 10.1 ml of 1,8-diazabicyclo[5.4.0]-7-undecene was added to the above mixture and stirred at outer temperature of 50°C for 20 minutes, 1,000 ml of ethyl acetate was then added thereto, a supernatant was removed by decantation to obtain a residue. The residue was dissolved in methanol and refined by Sephadex column chromatography. The refined product was dissolved in 150 ml of methanol, 3 g of potassium acetate was added thereto, after heating under reflux for 10 minutes, the mixture was allowed to be cooled, and the crystals precipitated were filtered out by suction. Methanol (300 ml) was added to the above-obtained powder, and the solution was heated under reflux for 50 minutes, then the solution was concentrated by distilling off 100 ml of the solvent. After cooling, the obtained crystals were recovered by suction filtration, the filtrate was washed with 50 ml of methanol and dried under reduced pressure, thereby 2.65 g of orange powder of S-96 was obtained. The structure of S-96 was confirmed by ¹H-NMFt, FAB-MS, and elemental analysis. λmax (MeOH) = 535 nm (e = 8.3×10⁴)

EXAMPLE 5

Synthesis of Methine-Dye S-97

Orange powder of S-97 was synthesized in the same manner as in Example 4 except for using 3-[5-fluoro-2-(2-ethoxy-1-butenyl)-3-benzoxazolio]propanesulfonate in place of 3-[5-chloro-2-(2-ethoxy-1-butenyl)-3-benzoxazolio]propanesulfonate. The structure of S-97 was confirmed by ¹H-Wm, FAB-MS, and elemental analysis. λmax (MeOH) = 534 nm (ε = 8.2×10⁴)

EXAMPLE 6

Synthesis of Methine Dye S-122

Synthesis of 2-Acetyl-3-hydroxythiophene

According to the description in Synth. Commun., 1996, 26, 1083, methyl 2-acetyl-3-hydroxythiophene-5-carboxylate was synthesized with chloroacetone, dimethyl acetylene dicarboxylate and sodium hydrosulfide as starting materials (yield: 60%).
The above-obtained methyl 2-acetyl-3-hydroxythiophene-5-carboxylate was hydrolyzed with an aqueous solution of sodium hydroxide, the hydrolyzate was heated with copper-quinoline to be decarboxylated, thereby the objective 2-acetyl-3-hydroxythiophene was obtained (yield: 58%).

Syntheses of 2-Methylthieno[2,3-d]oxazole

According to the description in Arch. Pharm., (Weinheim) 1987, 320, 837, oxime was prepared using 2-acetyl-3-hydroxythiophene and hydroxylamine (yield: 88%), and the oxime was further acetylated with acetic anhydride (yield: 69%). The oxime acetate was subjected to treatment with sodium hydroxide in an N, N-dimethylformamide solvent at room temperature, thereby the objective 2-methylthieno[2,3-d]oxazole was obtained (yield: 57%).

Synthesis of 5-Bromo-2-methylthieno[2,3-d]oxazole

Sodium acetate (1.4 g) and 2 g of 2-methylthieno[2,3-d]-oxazole were dissolved in 24 ml of an acetic acid solvent, and a solution comprised of 15.8 ml of bromine and 7.2 ml of acetic acid was dropwise added thereto with stirring at room temperature. After stirring at room temperature for 2.5 hours, the reaction solution was added to 150 ml of water, followed by further stirring at room temperature for 2 hours. The crystals precipitated were recovered by suction filtration, and dried under reduced pressure, thereby 1.7 g of 5-bromo-2-methylthieno[2,3-d]oxazole was obtained as pale yellow powder (yield: 54%).

Synthesis of Methine Dye S-122

5-Bromo-2-methylthieno[2,3-d]oxazole (1.53 g) (7 mmol) and 0.94 g of 1,3-propanesultone (7.7 mmol) were heated at 130°C with stirring for 6 hours. After cooling the mixture, 3.1 g of 3-[5-chloro-2-(3-sulfopropyl)thio-1-benzothiazolio]propanesulfonate (7 mmol), 5 ml of dimethyl sulfoxide and 5 ml of acetonitrile were added to the above reaction mixture, and 3.9 ml of triethylamine (28 mmol) was added with stirring at 60°C, and stirring was further continued for 1 hour. The solution was concentrated and refined by column chromatography, thereby 0.51 g of the objective Dye S-122 was obtained. Yield: 10%, λmax (MeOH) = 428.6 nm.

EXAMPLE 7

Synthesis of Methine Dye S-125

Synthesis of 2-Methylpyrrolo[3,2-d]thiazole

According to the description in J. Heterocyclic Chem., 1979, 16, 1563, 4-chloromethyl-2-methylthiazole was synthesized with 1,3-dichloroacetone and thioacetamide as starting materials. The above-obtained 4-chloromethyl-2-methylthiazole was converted to a 4-hydroxymethyl body by dilute sulfuric acid, and then introduced into a 4-formyl body by oxidation of manganese dioxide (yield to this point: 62%). 5-Ethoxycarbonyl-2-methylpyrrolo[3,2-d]thiazole was obtained by making ethyl azidoacetate act on the above product in the presence of sodium ethoxide and further heating in xylene (yield: 31%) .
Subsequently, according to the description in Synth.Commun., 1992, 2077, the above-obtained 5-ethoxycarbonyl-2-methylpyrrolo[3,2-d]thiazole was hydrolyzed with sodium hydroxide, and then heated in diphenylmethane at 230°C for 3.5 hours, thereby the objective decarboxylated2-methylpyrrolo[3,2-d]thiazole was obtained (yield: 63%).

Synthesis of Methine Dye S-125

2-Methylpyrrolo [3, 2-d] thiazole (0.70 g) (5 mmol) and 0.67 g of 1,3-propanesultone (5.5 mmol) were stirred with heating at 130°C for 6 hours. After cooling, the crystals precipitated were filtered out and washed with acetone, thereby 1.2 g of 3-[2-methyl-1-pyrrolo[3,2-d]thiazolio]propanesulfonate was obtained (yield: 92%).
3-[5-Chloro-2-(3-sulfopropyl)thio-1-benzothiazolio]propanesulfonate (0.45 g) (1 mmol), 2 ml of dimethyl sulfoxide and 2 ml of acetonitrile were added to 0.26 g of the quaternary salt of 3-[2-methyl-l-pyrrolo[3,2-d]thiazolio]propanesulfonate (1 mmol) and the mixture was stirred at 50°C with adding 0.56 ml of triethylamine (4 mmol), followed by further stirring for 1 hour. The solution was concentrated, and then refined with column chromatography, thereby 0.10 g of the objective Methine Dye S-125 was obtained. Yield: 15%, λmax (MeOH) = 447.5 nm.

EXAMPLE 8

Preparation of Sample No. 101

A multilayer color photographic material was prepared as Sample No. 101 by coating each layer having the following composition on an undercoated cellulose triacetate film support having a thickness of 127 µm. The numeral corresponding to each component indicates the addition weight per m². The functions of the compounds added are not limited to the use described.

First Layer: Antihalation Layer
Black Colloidal Silver silver amount:	0.28 g
Gelatin	2.20 g
Ultraviolet Absorber U-1	0.27 g
Ultraviolet Absorber U-3	0.08 g
Ultraviolet Absorber U-4	0.08 g
High Boiling Point Organic Solvent Oil-1	0.29 g
Coupler C-9	0.12 mg

Second Layer: Interlayer
Gelatin	0.38 g
Compound Cpd-K	5.0 mg
Ultraviolet Absorber U-2	3.0 mg
High Boiling Point Organic Solvent Oil-3	0.06 g
Dye D-4	10.0 mg

Third Layer: Interlayer
Yellow Colloidal Silver silver amount:	0.007 g
Gelatin	0.40 g

Fourth Layer: First Red-Sensitive Emulsion Layer
Emulsion A silver amount:	0.55 g
Emulsion B silver amount:	0.23 g
Surface Fogged Fine Grain silver amount: Silver Iodobromide Emulsion (average grain size: 0.11 µm)	0.07 g
Gelatin	1.11 g
Coupler C-1	0.04 g
Coupler C-2	0.09 g
Compound Cpd-A	1.0 mg
Compound Cpd-E	0.14 g
Compound Cpd-K	2.0 mg
Compound Cpd-H	4.4 mg
High Boiling Point Organic Solvent Oil-2	0.09 g

Fifth Layer: Second Red-Sensitive Emulsion Layer
Emulsion C silver amount:	0.14 g
Emulsion D silver amount:	0.28 g
Gelatin	0.65 g
Coupler C-1	0.05 g
Coupler C-2	0.11 g
Compound Cpd-E	0.10 g
High Boiling Point Organic Solvent Oil-2	0.09 g

Sixth Layer: Third Red-Sensitive Emulsion Layer
Emulsion E silver amount:	0.50 g
Gelatin	1.56 g
Coupler C-3	0.63 g
Compound Cpd-E	0.11 g
Additive P-1	0.16 g
High Boiling Point Organic Solvent Oil-2	0.04 g

Seventh Layer: Interlayer
Gelatin	0.50 g
Compound Cpd-D	0.04 g
High Boiling Point Organic Solvent Oil-3	0.08 g

Eighth Layer: Interlayer
Yellow Colloidal Silver silver amount:	0.01 g
Gelatin	1.56 g
Compound Cpd-A	0.12 g
Compound Cpd-1	0.04 mg
Compound Cpd-J	0.07 g
High Boiling Point Organic Solvent Oil-3	0.15 g

Ninth Layer: First Green-Sensitive Emulsion Layer
Emulsion F silver amount:	0.42 g
Emulsion G silver amount:	0.38 g
Emulsion H silver amount:	0.32 g
Surface Fogged Core/Shell Type silver amount: Fine Grain Silver Bromide Emulsion (average grain size: 0.11 µm)	0.08 g
Gelatin	1.53 g
Coupler C-7	0.07 g
Coupler C-8	0.17 g
Compound Cpd-B	0.30 mg
Compound Cpd-C	2.00 mg
Compound Cpd-K	3.0 mg
Polymer Latex P-2	0.02 g
High Boiling Point Organic Solvent Oil-2	0.10 g

Tenth Layer: Second Green-Sensitive Emulsion Layer
Emulsion I silver amount:	0.16 g
Emulsion J silver amount:	0.34 g
Gelatin	0.75 g
Coupler C-4	0.20 g
Compound Cpd-B	0.03 g
Polymer Latex P-2	0.01 g
High Boiling Point Organic Solvent Oil-2	0.01 g

Eleventh Layer: Third Green-Sensitive Emulsion Layer
Emulsion K silver amount:	0.44 g
Gelatin	0.91 g
Coupler C-4	0.34 g
Compound Cpd-B	0.06 g
Polymer Latex P-2	0.01 g
High Boiling Point Organic Solvent Oil-2	0.02 g

Twelfth Layer: Yellow Filter Layer
Yellow Colloidal Silver silver amount:	0.02 g
Gelatin	0.73 g
Microcrystal Dispersion of Dye E-1	0.24 g
Compound Cpd-G	0.02 g
Compound Cpd-J	0.04 g
High Boiling Point Organic Solvent Oil-3	0.08 g
Polymer M-1	0.23 g

Thirteenth Layer: First Blue-Sensitive Emulsion Layer
Emulsion L silver amount:	0.35 g
Gelatin	0.55 g
Coupler C-5	0.20 g
Coupler C-6	4.00 g
Coupler C-10	0.02 g
Compound Cpd-E	0.07 g
Compound Cpd-K	0.03 mg

Fourteenth Layer: Second Blue-Sensitive Emulsion Layer
Emulsion M silver amount:	0.06 g
Emulsion N silver amount:	0.10 g
Gelatin	0.75 g
Coupler C-5	0.35 g
Coupler C-6	5.00 g
Coupler C-10	0.30 g
Compound Cpd-E	0.04 g

Fifteenth Layer: Third Blue-Sensitive Emulsion Layer
Emulsion O silver amount:	0.20 g
Emulsion P silver amount:	0.02 g
Gelatin	2.40 g
Coupler C-6	0.09 g
Coupler C-10	0.90 g
Compound Cpd-E	0.09 g
Compound Cpd-M	0.05 mg
High Boiling Point Organic Solvent Oil-2	0.40 g
Additive P-2	0.10 g

Sixteenth Layer: First Protective Layer
Gelatin	1.30 g
Ultraviolet Absorber U-1	0.10 g
Ultraviolet Absorber U-2	0.03 g
Ultraviolet Absorber U-5	0.20 g
Compound Cpd-F	0.40 g
Compound Cpd-J	0.06 g
Dye D-1	0.01 g
Dye D-2	0.01 g
Dye D-3	0.01 g
Dye D-5	0.01 g
High Boiling Point Organic Solvent Oil-2	0.37 g

Seventeenth Layer: Second Protective Layer
Fine Grain Silver Iodobromide silver amount: Emulsion (average grain size: 0.06 µm, AgI content: 1 mol%)	0.05 g
Gelatin	1.80 g
Compound Cpd-L	0.8 mg
Polymethyl Methacrylate (average particle size: 1.5 µm)	5.00 g
Copolymer of Methyl Methacrylate/Methacrylic Acid in Proportion of 6/4 (average particle size: 1.5 µm)	0.10 g
Silicone Oil SO-1	0.030 g
Surfactant W-2	0.030 g

Additives F-1 to F-11 were further added to every emulsion layer in addition to the above components. Moreover, Gelatin Hardener H-1 and Surfactants W-1, W-3, W-4, W-5 and W-6 for coating and emulsifying were added to every layer in addition to the above components.

In addition, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-hydroxybenzoic acid butyl ester were added as antibacterial and antifungal agents. Photosensitive emulsions used in Sample No. 101 are shown in Table 1 below.

TABLE 1

Emulsion	Equivalent-Sphere Diameter (µm)	Variation Coefficient of Equivalent-Circle Diameter (%)	Average Aspect Ratio of Entire Grains	Iodide Content (mol%)	Sensitizing Dye		Sensitizing Dye		Sensitizing Dye
Emulsion	Equivalent-Sphere Diameter (µm)	Variation Coefficient of Equivalent-Circle Diameter (%)	Average Aspect Ratio of Entire Grains	Iodide Content (mol%)	Kind	Addition Amount (×10^-4mol/ mol-Ag)	Kind	Addition Amountv (×10^-4mol/ mol-Ag)	Kind	Addition Amount (×10^-4 mol/ mol-Ag)
A	0.20	16	1.6	4.0	Sen-1	8.1			Sen-3	0.3
B	0.25	15	3.0	4.0	Sen-1	8.9			Sen-3	0.3
C	0.22	14	2.5	4.0	Sen-1	8.8	Sen-2	0.2	Sen-3	0.2
D	0.35	10	3.6	4.0	Sen-1	9.8	Sen-2	0.3	Sen-3	0.2
E	0.49	16	5.0	2.0	Sen-1	6.7	Sen-2	0.5	Sen-3	0.2
F	0.15	15	1.0	3.5	Sen-4	15.1	Sen-5	1.5
G	0.23	14	1.9	3.5	Sen-4	10.4	Sen-5	2.0
H	0.32	11	2.4	3.5	Sen-4	7.5	Sen-5	1.4
I	0.28	11	4.5	3.3	Sen-4	7.7	Sen-5	1.4
J	0.40	16	4.0	3.3	Sen-4	7.2	Sen-5	1.4
K	0.59	20	5.9	2.8	Sen-4	6.4	Sen-5	1.2
L	0.24	14	3.4	4.6	Sen-6	6.5	Sen-7	2.5
M	0.30	10	3.0	4.6	Sen-6	6.2	Sen-7	2.0
N	0.40	9	4.5	1.6	Sen-6	5.6	Sen-7	1.8
O	0.60	15	5.5	1.0	Sen-6	4	Sen-7	1.5
P	0.80	18	2.5	1.0	Sen-6	3.4	Sen-7	1.1

Note 1) All of the above emulsions were silver iodobromide emulsions chemically sensitized using gold, sulfur and selenium.
Note 2) All of the above emulsions were added with sensitizing dyes before chemical sensitization.
Note 3) Appropriate amounts of Compounds F-5, F-7, F-8, F-9, F-10, F-11, F-12, F-13, F-14 and F-15 were respectively added to the above emulsions.
Note 4) Emulsions A, B, I and J comprise triple structure tabular grains having main planes comprising {100} faces and other emulsions comprise triple structure tabular grains having main planes comprising {111} faces.
Note 5) Emulsions A, B, E, F, I and P are emulsions whose internal sensitivity is higher than surface sensitivity.
Note 6) Emulsions E, I and P are emulsions comprising silver chloride grains epitaxially grown after chemical sensitization.
Note 7) Emulsions other than A, E and F comprise grains having 50 or more dislocation lines per one grain observed by a transmission electron microscope.

Preparation of Dispersion of Organic Solid Dispersion Dye

Dye E-1 shown below was dispersed according to the following method. That is, water and 70 g of W-4 were added to 1,400 g of a wet cake of the dye containing 30% of water,
and the mixture was stirred to obtain a slurry having 30% dye concentration. Next, 1,700 ml of zirconia beads having an average diameter of 0.5 mm was filled in an ultravisco mill (UVM-2) manufactured by Imex Co., the slurry was passed and pulverized at a peripheral speed of about 10 m/sec and discharge amount of 0.5 1/min for 8 hours. Beads were removed by filtration and the resulting dispersion was heated at 90°C for 10 hours for stabilization, then water and gelatin were added thereto to dilute the dispersion to dye concentration of 3%. The average grain size of the obtained fine grains of the dye was 0.4 µm and the extent of distribution of grain sizes [(standard deviation of grain sizes)/(average grain size) × 100] was 18%.

Preparation of Sample Nos. 100, 102 to 130

Sample Nos. 102 to 130 were prepared in the same manner as in the preparation of Sample No. 101 except that Sensitizing Dye Sen-2 or Sen-7 in the emulsions used in Sample No. 101 were replaced in equimolar amount as shown in Tables 2 and 3. Sample No. 100 (i.e., blank sample) was prepared by excluding Sen-2 and Sen-7. Each of the thus-obtained samples was subjected to 20 CMS white light exposure for 1/100 sec. through a gray wedge.
The exposed sample was processed according to the processing step shown below and sensitometry was carried out.
Further, residual colors were evaluated by subtracting the yellow stain density and magenta stain density of Sample No. 100, a dye-blank sample, from the yellow stain
density and magenta stain density of each processed sample. The stain density was measured with densitometer Status A manufactured by X-RITE Co., Ltd.

numerals indicate weight percentage
average molecular weight: about 25,000

Oil-1 Dibutyl Phthalate
Oil-2 Tricresyl Phosphate

W-1 H₂₅C₁₂-O-SO₃H·Na

P-2 Polybutyl acrylate/acrylic acid copolymer in proportion of 95/5

Processing

Processing Step	Processing Time	Processing Temperature	Tank Capacity	Replenishing Rate
	(min)	(°C)	(liter)	(ml/m²)
First Development	6	38	12	2,200
First Washing	2	38	4	7,500
Reversal	2	38	4	1,100
Color Development	6	38	12	2,200
Pre-bleaching	2	38	4	1,100
Bleaching	6	38	2	220
Fixing	4	38	8	1,100
Second Washing	4	38	8	7,500
Final Rinsing	1	25	2	1,100

The composition of each processing solution used was as follows.

First Developing Solution	Tank Solution	Replenisher
Pentasodium Nitrilo-N,N,N-	1.5 g	1.5 g
trimethylenephosphonate
Pentasodium Diethylene-	2.0 g	2.0 g
triaminepentaacetate
Sodium Sulfite	30 g	30 g
Potassium Hydroquinone-	20 g	20 g
monosulfonate
Potassium Carbonate	15 g	20 g
Sodium Bicarbonate	12 g	15 g
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone	1.5 g	2.0 g
Potassium Bromide	2.5 g	1.4 g
Potassium Thiocyanate	1.2 g	1.2 g
Potassium Iodide	2.0 mg
Diethylene Glycol	13 g	15 g
Water to make	1,000 ml	1,000 ml
pH (adjusted with sulfuric acid or potassium hydroxide)	9.60	9.60

Reversal Solution	Tank Solution	Replenisher
Pentasodium Nitrilo-N,N,N-trimethylenephosphonate	3.0 g	same as the tank solution
Stannous Chloride	1.0 g
Dihydrate
p-Aminophenol	0.1 g
Sodium Hydroxide	8 g
Glacial Acetic Acid	15 ml
Water to make	1,000 ml
pH (adjusted with acetic acid or sodium hydroxide)	6.00

Color Developing Solution	Tank Solution	Replenisher
Pentasodium Nitrilo-N,N,N-trimethylenephosphonate	2.0 g	2.0 g
Sodium Sulfite	7.0 g	7.0 g
Trisodium Phosphate	36 g	36 g
Dodecahydrate
Potassium Bromide	1.0 g	-
Potassium Iodide	90 mg	-
Sodium Hydroxide	3.0 g	3.0 g
Citrazinic Acid	1.5 g	1.5 g
N-Ethyl-N-(B-methanesulfonamidoethyl)-3-methyl-4-aminoaniline·Sesquisulfate· Monohydrate	11 g	11 g
3,6-Dithiaoctane-1,8-diol	1.0 g	1.0 g
Water to make	1,000 ml	1,000 ml
pH (adjusted with sulfuric acid or potassium hydroxide)	11.80	12.00

Pre-bleaching Solution	Tank Solution	Replenisher
Disodium Ethylenediamine-tetraacetate Dihydrate	8.0 g	8.0 g
Sodium Sulfite	6.0 g	8.0 g
1-Thioglycerol	0.4 g	0.4 g
Sodium Bisulfite Addition Product of Formaldehyde	30 g	35 g
Water to make	1,000 ml	1,000 ml
pH (adjusted with acetic acid or sodium hydroxide)	6.30	6.10

Bleaching Solution	Tank Solution	Replenisher
Disodium Ethylenediamine-tetraacetate Dihydrate	2.0 g	4.0 g
Ammonium Ethylenediamine-tetraacetato Ferrate (III)	120 g	240 g
Dihydrate
Potassium Bromide	100 g	200 g
Ammonium Nitrate	10 g	20 g
Water to make	1,000 ml	1,000 ml
pH (adjusted with nitric acid or sodium hydroxide)	5.70	5.50

Fixing Solution	Tank Solution	Replenisher
Ammonium Thiosulfate	80 g	same as the tank solution
Sodium Sulfite	5.0 g	"
Sodium Bisulfite	5.0 g	"
Water to make	1,000 ml	"
pH (adjusted with acetic acid or aqueous ammonia)	6.60

Stabilizing Solution	Tank Solution	Replenisher
1,2-Benzisothiazolin-3-one	0.02 g	0.03 g
Polyoxyethylene-p-monononylphenyl Ether (average polymerization degree: 10)	0.3 g	0.3 g
Polymaleic Acid (average molecular weight: 2,000)	0.1 g	0.15 g
Water to make	1,000 ml	1,000 ml
pH	7.0	7.0

The results of sensitometry and evaluation of residual colors are shown in the following Tables 2 and 3. Relative sensitivities of the blue-sensitive layer and the red-sensitive layer were compared based on the relative exposure amount giving density of minimum density plus 1.0.

TABLE 2

Sample No.	Replacement of Sensitizing Dye Sen-7 in Emulsions L to P	Relative Sensitivity of Blue-Sensitive Layer	Yellow Stain Density
100* (blank)	None		0 (control)
101*	Sen-7	100 (control)	0.073
102*	Comparative Dye Sen-12	92	0.055
103*	Comparative Dye Sen-13	109	0.088
104*	S-1	113	0.017
105*	S-2	114	0.028
106*	S-3	115	0.025
107*	S-5	115	0.015
108*	S-6	112	0.018
109*	S-7	116	0.012
110*	S-10	125	0.034
111*	S-15	111	0.020
112*	S-64	119	0.015
113 (invention)	S-66	124	0.012
114*	S-76	142	0.0260
115*	S-78	133	0.018
116*	S-79	135	0.019
117*	S-80	140	0.022
118*	S-81	123	0.013
119*	S-84	127	0.016
120*	S-85	125	0.017

* reference samples

TABLE 3

Sample No.	Replacement of Sensitizing Dye Sen-2 in Emulsions C to F	Relative Sensitivity of Red-Sensitive Layer	Magenta Stain Density
100*	None		0 (control)
101*	Sen-2	100 (control)	0.085
121*	Comparative Dye Sen-10	92	0.067
122*	Comparative Dye Sen-11	83	0.044
123*	S-31	118	0.031
124*	S-39	106	0.026
125*	S-65	117	0.030
126*	S-69	112	0.020
127*	S-87	110	0.026
128*	S-88	125	0.028
129*	S-89	115	0.021
130*	S-90	121	0.016

*) reference samples

As is apparent from the results in Tables 2 and 3, photographic materials showing less residual colors and having high sensitivity can be obtained by using the compounds and emulsions used according to the present invention. Thus, it is apparent that high sensitivity and less residual colors are compatible for the first time by using the constitution according to the present invention.

EXAMPLE 9

Preparation of Seed Emulsion a

An aqueous solution (1,164 ml) comprised of 0.017 g of KBr and 0.4 g of oxidation-processed gelatin having an average molecular weight of 20,000 was stirred with maintaining the temperature at 35°C. An aqueous solution containing 1.6 g of AgNO₃, an aqueous solution of KBr and an aqueous solution containing 2.1 g of oxidation-processed gelatin having an average molecular weight of 20,000 were added to the above solution by a triple jet method over 48 seconds. At this time, the silver potential was maintained at 13 mV to the saturated calomel electrode. An aqueous solution of KBr was added thereto, and the silver potential was adjusted to -66 mV, and the temperature was raised to 60°C. After 21 g of succinated gelatin having an average molecular weight of 100,000 was added to the above solution, an aqueous solution containing 5.1 g of NaCl was added. An aqueous solution containing 206.3 g of AgNO₃ and an aqueous solution containing KBr were added thereto by a double jet method over 61 minutes with accelerating the flow rate. At this time, the silver potential was maintained at -44 mV to the saturated calomel electrode. After desalting, succinated gelatin having an average molecular weight of 100 , 000 was added to the solution to adjust pH to 5.8 and pAg to 8.8 at 40°C, thus a seed emulsion was obtained. The seed emulsion was tabular grain emulsion containing 1 mol of Ag and 80 g of gelatin per kg of the emulsion, and having an average equivalent-circle diameter of 1.46 µm, an equivalent-circle diametyer variation coefficient of 28%, an average thickness of 0.046 µm, and an average aspect ratio of 32.

Formation of Core

An aqueous solution (1,200 ml) comprised of 134 g of the above-prepared Seed Emulsion a, 1.9 g of KBr and 22 g of succinated gelatin having an average molecular weight of 100,000 was stirred with maintaining the temperature at 75°C. An aqueous solution containing 43.9 g of AgNO₃, an aqueous solution containing KBr, and an aqueous solution containing gelatin having a molecular weight of 20,000 were mixed just before addition in another chamber equipped with a magnetic coupling induction stirrer disclosed in JP-A-10-43570 , and added to the above emulsion over 25 minutes. At this time, the silver potential was maintained at -40 mV to the saturated calomel electrode.

Formation of First Shell

After the formation of the above core grains, an aqueous solution containing 43.9 g of AgNO₃, an aqueous solution containing KBr, and an aqueous solution containing gelatin having a molecular weight of 20,000 were mixed just before addition in the same another chamber, and added to the above emulsion over 20 minutes. At this time, the silver potential was maintained at -40 mV to the saturated calomel electrode.

Formation of Second Shell

After the formation of the above first shell, an aqueous solution containing 42.6 g of AgNO₃, an aqueous solution containing KBr, and an aqueous solution containing gelatin having a molecular weight of 20,000 were mixed just before addition in the same another chamber, and added to the above emulsion over 17 minutes. At this time, the silver potential was maintained at -20 mV to the saturated calomel electrode, and then the temperature was lowered to 55°C.

Formation of Third Shell

After the formation of the above second shell, the silver potential was adjusted to -55 mV, and an aqueous solution containing 7.1 g of AgNO₃, an aqueous solution containing 6.9 g of KI, and an aqueous solution containing gelatin having a molecular weight of 20,000 were mixed just before addition in the same another chamber, and added to the above emulsion over 5 minutes.

Formation of Fourth Shell

After the formation of the above third shell, an aqueous solution containing 66.4 g of AgNO₃ and an aqueous solution containing KBr were added to the above emulsion by a double jet method over 30 minutes at constant flow rate. Potassium iridium hexachloride and yellow prussiate of potash were added en route. At this time, the silver potential was maintained at 30 mV to the saturated calomel electrode. The emulsion was subjected to ordinary washing, and then gelatin was added to adjust pH to 5.8 and pAg to 8.8 at 40°C. The thus-obtained emulsion was designated Emulsion b. Emulsion b was a tabular grain emulsion having an average equivalent-circle diameter of 3.3 µm, an equivalent-circle diameter variation coefficient of 21%, an average thickness of 0.090 µm and an average aspect ratio of 37. Tabular grains having an equivalent-circle diameter of 3.3 µm or more and a thickness of 0.090 µm or less accounted for 70% or more of the entire projected area of Emulsion b.
Emulsion b was heated at 56°C, and after the sensitizing dye shown in Table 4 was added in an amount of 1.1×10^-3 mol/mol Ag, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N,N-dimethylselenourea were added and the emulsion was optimally chemically sensitized, and stirred for 60 minutes.
The sensitizing dye was used as the solid fine particle dispersion prepared according to the method disclosed in JP-A-11-52507 . That is, 0.8 weight parts of sodium nitrate and 3.2 weight parts of sodium sulfate were dissolved in 43 parts of ion exchange water, 13 weight parts of the sensitizing dye was added to the above solution, and dispersed by means of dissolver blades at 2, 000 rpm for 20 minutes on the condition of 60°C, thereby a solid dispersion of the sensitizing dye was obtained.

Preparation of Coated Sample

On a triacetyl cellulose film support having an undercoat layer, the emulsion layer and the protective layer as shown in Table 4 below were coated, and Sample Nos . 201 to 214 shown in Table 5 were prepared.

TABLE 4

Coating Condition of Emulsion
(1)	Emulsion Layer
	Emulsion b (used dye are shown	2.1×10^-2 mol/m²
	in Table 5 below)	(silver amount)
	Coupler A, B or C shown below	1.5×10^-3 mol/m²
	Tricresyl phosphate	1.10 g/m²
	Gelatin	2.30 g/m²

(2)	Protective Layer
	Gelatin	1.80 g/m²
	2,4-Dichloro-6-hydroxy-s-triazine sodium salt	0.08 g/m²

Samples shown in Table 5 were subjected to sensitometric exposure for 1/100 sec. and to the following development process.

Processing Step
Processing Step	Processing Time	Temperature	Replenishment Rate*	Tank Capacity
		(°C)	(ml)	(liter)
Color Development	2 min 45 sec	38	33	20
Bleaching	6 min 30 sec	38	25	40
Washing	2 min 10 sec	24	1,200	20
Fixing	4 min 20 sec	38	25	30
Washing (1)	1 min 05 sec	24	countercurrent system from (2) to (1)	10
Washing (2)	1 min 00 sec	24	1,200	10
Stabilization	1 min 05 sec	38	25	10
Drying	4 min 20 sec	55

Replenishment rate: per 1 meter of 35 mm wide

The composition of each processing solution is described below.

Color Developing Solution
	Mother Solution	Replenisher
	(g)	(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
Potassium Iodide	1.5 mg	-
Hydroxylamine Sulfate	2.4	2.8
4-(N-Ethyl-N-β-hydroxyethylamino)-2-methylaniline Sulfate	4.5	5.5
Water to make	1.0 1	1.0 1
pH	10.05	10.05

Bleaching Solution
	Mother Solution	Replenisher
	(g)	(g)
Sodium Ethylenediaminetetra-acetato Ferrate Trihydrate	100.0	120.0
Disodium Ethylenediamine-tetraacetate	10.0	11.0
Ammonium Bromide	140.0	160.0
Ammonium Nitrate	30.0	35.0
Aqueous Ammonia (27%)	6.5 ml	4.0 ml
Water to make	1.0 1	1.0 1
pH	6.0	5.7

Fixing Solution
	Mother Solution	Replenisher
	(g)	(g)
Sodium Ethylenediaminetetra-acetate	0.5	0.7
Sodium Sulfite	7.0	8.0
Sodium Bisulfite	5.0	5.5
Aqueous Solution of Ammonium Thiosulfate (70%)	170.0 ml	200.0 ml
Water to make	1.0 1	1.0 1
pH	6.7	6.6

Stabilizing Solution
	Mother Solution	Replenisher
	(g)	(g)
Formalin (37%)	2.0 ml	3.0 ml
Polyoxyethylene-p-monononylphenyl Ether (polymerization degree: 10)	0.3	0.45
Disodium Ethylenediaminetetra-acetate	0.05	0.08
Water to make	1.0 1	1.0 1
pH	5.8-8.0	5.8-8.0

The density of each processed sample was measured, i.e., Sample Nos. 201 to 206 were measured through a red filter, Sample Nos. 207 to 209 were measured through a green filter, and Sample Nos. 210 to 214 were measured through a blue filter respectively and sensitivity was evaluated.
The reciprocal of the exposure amount giving density of fog density + 0.2 is taken as sensitivity, and sensitivity of each sample is shown in a relative value taking the value of Sample No. 201 as 100 with Sample Nos. 201 to 206, taking the value of Sample No. 207 as 100 with Sample Nos. 207 to 209, and taking the value of Sample No. 210 as 100 with Sample Nos. 210 to 214.
The sensitizing dye formed a J-association body having absorption maximum at about 605 nm in Sample No. 206, and at about 487 nm in Sample No. 213, and each sensitizing dye showed similar spectral sensitivity distribution to that of absorption.
For further evaluating residual colors of sensitizing dyes, samples in Table 5 were subjected to color development processing in the same manner as above (ordinarily processed samples) as one group, and the samples were subjected to sufficient washing processing (that is, the same processing was performed except that the time of washing (2) in the processing step was changed to 30 minutes) to completely remove the remaining sensitizing dyes (washing-processed samples) as the other group, each sample was not subjected to exposure. Since the samples did not undergo exposure, development did not occur and image-forming dyes were not formed.
After processing each sample, the spectrum by transmission mode of from 360 to 700 nm of each sample was recorded with a spectrophotometer. After that, for evaluating the remaining sensitizing dye of the ordinarily processed sample, the difference spectrum of the ordinarily processed sample and the washing-processed sample was taken. The absorption of the difference spectrum means the amount of the retained dye, i.e., the residual color of the sensitizing dye. The residual color of each sample is shown in a relative value of the absorbance of the peak wavelength of each sample taking the absorbance of the peak wavelength of Sample No. 201 as 100 with Sample Nos. 201 to 206, taking the absorbance of the peak wavelength of Sample No. 207 as 100 with Sample Nos. 207 to 209, and taking the absorbance of the peak wavelength of Sample No. 210 as 100 with Sample Nos. 210 to 214.
Further, pressure resistance test was performed as follows. A needle having a diameter of 0.1 mm was put on the above sample before exposure and 5 g of load was applied to the needle and the needle was moved at a rate of 600 mm/min. (pressure processing). The difference in density between the part where pressure processing was performed and the part where pressure processing was not performed (pressure marks) of the sample which had been development-processed without undergoing exposure was measured with a micro-densitometer having an aperture diameter of 10 µm.

The results of evaluation of sensitivity, residual color and pressure marks of each sample are shown in Table 5.

TABLE 5

Sample No.	Dye	Coupler	Sensitivity	Residual Color	Pressure Marks	Remarks
201	Sen-14	A	100 (criterion)	100 (criterion)	0.225	*
202	S-110	A	155	50	0.131	*
203	S-109	A	155	48	0.123	*
204	S-98	A	161	25	0.055	*
205	S-99	A	162	18	0.046	*
206	S-96	A	161	18	0.046	*
207	Sen-15	B	100 (criterion)	100 (criterion)	0.210	*
208	S-111	B	153	35	0.105	*
209	S-108	B	155	19	0.041	Invention
210	Sen-16	C	100 (criterion)	100 (criterion)	0.225	*
211	S-129	C	135	50	0.151	*
212	S-130	C	144	20	0.061	*
213	S-131	C	142	21	0.063	*
214	S-132	C	142	36	0.066	*

*) reference samples

It can be seen from the results in Table 5 that the sample containing the sensitizing dye used according to the present invention is high is sensitivity and conspicuously low in residual color. In particular, sensitivity is markedly improved in trimethyl cyanine dyes.
The sample containing the sensitizing dye used according to the present invention is also excellent in pressure marks (i.e., pressure resistance).

EXAMPLE 10

Preparation of (111) high silver chloride tabular grains (A)

To 1.2 liters of water were added 1.0 g of sodium chloride and 2.5 g of inert gelatin and the temperature of the reaction vessel was maintained at 27 °C. An aqueous solution of silver nitrate (75 ml) (containing 18 g of silver nitrate) and 75 ml of an aqueous solution of sodium chloride (containing 6.2 g of sodium chloride and 0.75 g of inert gelatin) were added to the reaction vessel by a double jet method with stirring over 1 minute. One minutes after the completion of addition, 18.6 ml of an aqueous solution containing 0.92 mmol of Crystal Phase Controlling Agent-1 was added to the reaction solution. One minute after that, 450 ml of a 10% aqueous solution of oxidation-processed gelatin was added thereto. Then, the temperature of the reaction vessel was raised to 55 °C over 28 minutes, and ripening was performed for 27 minutes.
After ripening, 2.35 mg of sodium benzylthiosulfate was added to the reaction solution. Thereafter, an aqueous solution of silver nitrate (containing 263 g of silver nitrate) and an aqueous solution of NaCl (containing 96 g of NaCl and 0.016 mg of K₂IrCl₆) were added to the reaction solution at an accelerated flow rate over 32 minutes. At the same time, 2.63 mmol of Crystal Phase Controlling Agent-1 was added at an accelerated flow rate (in proportion to the addition amount of silver nitrate). After that, an aqueous solution of silver nitrate (containing 71 g of silver nitrate) and an NaCl aqueous solution (containing 24.2 g of NaCl, 1.39 g of KI and 12 mg of yellow prussiate of potash) were added to the reaction mixture at an accelerated flow rate over 14 minutes. After addition was finished, the temperature of the reaction solution was raised to 75 °C over 20 minutes, and an aqueous solution of silver nitrate (containing 2.9 g of silver nitrate) and a KBr aqueous solution (containing 2.25 g of KBr) were added to the reaction solution at a constant flow rate over 1 minute.
The temperature was lowered to 40 °C and washing was performed according to ordinary flocculation method. After washing, 175 g of inert gelatin, 34 ml of phenoxyethanol (35%) and 700 ml of distilled water were added to the above mixture. pH and pAg were adjusted to 6.2 and 7.5 respectively using sodium hydroxide and an aqueous solution of sodium chloride. Thus, grains (A) was obtained, in which 99% of the entire projected area was occupied by tabular grains having an average equivalent-circle diameter of 0.85 µm and an average thickness of 0.146 µm. The variation coefficient of thickness was 16.8% and the variation coefficient of equivalent-circle diameter was 19.0%.

Crystal Phase Controlling Agent-1

Chemical sensitization

Emulsion A was optimally chemically sensitized at 60 °C using Sen-17, Sen-18, Sen-19, S-132 and S-78 shown in Table 6, sodium benzylthiosulfonate, sodium thiocyanate, 1-(5-methylureidophenyl)-5-mercaptotetrazole, sodium thiosulfate and chloroauric acid.

TABLE 6

Sample No.	Grains	Sensitizing Dye	Addition Mount of Sensitizing Dye		Remarks
Sample No.	Grains	Sensitizing Dye	Molar Ratio	Total Amount (mol/mol-Ag)	Remarks
301	A	Sen-17 and Sen-18	1/1	8×10^-4	*
302	A	Sen-19 and Sen-18	1/1		*
303	A	Sen-19 and S-132	1/1	8×10^-4	*
304	A	Sen-19 and S-78	1/1	8×10^-4	*

*) reference sample

Preparation of coated sample and evaluation of photographic properties and stability

The surface of a paper support both surfaces of which were laminated with polyethylene resin was subjected to corona discharge treatment. The support was provided with a gelatin undercoat layer containing sodium dodecylbenzenesulfonate, and further, photographic constitution layers, from the first layer to the seventh layer, described below were coated in order to prepare a silver halide color photographic material samples shown below. The coating solution of each photographic constitution layer was prepared as described below.

Preparation of coating solution

Each coupler, color image stabilizer and ultraviolet absorber were dissolved in a solvent and ethyl acetate. The solution was emulsified and dispersed in a 10 weight% gelatin aqueous solution containing a surfactant by means of a high speed dissolver, thus an emulsified dispersion was prepared.
The above emulsified dispersion and silver chlorobromide emulsion were mixed and dissolved to prepare a coating solution having the composition described below.
As the gelatin hardening agent in each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.
Further, Ab-1, Ab-2 and Ab-3 were added to each layer so that the total amount became 15.0 mg/m², 60.0 mg/m² and 5.0 mg/m², respectively.
High silver chloride emulsion used in each photosensitive emulsion layer was as follows.

Blue-Sensitive Emulsion Layer

See Table 6.

Green-Sensitive Emulsion Layer

To silver chlorobromide emulsion (a cubic form, a mixture in a ratio of 1/3 (silver molar ratio) of a large grain size emulsion having an average grain size of 0.45 µm and a small grain size emulsion having an average grain size of 0.35 µm, variation coefficients of the grain size distribution were 10% and 8% , respectively, emulsions of both sizes contained 0.4 mol% of silver bromide localized at a part of the grain surface and the remaining substrate was comprised of silver chloride), Sensitizing Dye D was added to the large grain size emulsion in an amount of 3.0×10^-4 mol per mol of the silver halide and to the small grain size emulsion in an amount of 3.6×10^-4 mol per mol of the silver halide, and Sensitizing Dye E was added to the large grain size emulsion in an amount of 4.0×10^-5 mol per mol of the silver halide and to the small grain size emulsion in an amount of 2.8×10^-4 mol per mol of the silver halide.

Red-Sensitive Emulsion Layer

To silver chlorobromide emulsion (a cubic form, a mixture in a ratio of 1/1 (silver molar ratio) of large grain size emulsion having an average grain size of 0.40 µm and small grain size emulsion having an average grain size of 0.30 µm, variation coefficients of the grain size distribution were 0.09 and 0.11, respectively, emulsions of both sizes contained 0.5 mol% of silver bromide localized at a part of the grain surface, and the remaining substrate was comprised of silver chloride), Sensitizing Dyes G and H were added to the large grain size emulsion each in an amount of 9.0×10^-5 mol per mol of the silver halide, and to the small grain size emulsion each in an amount of 1.2×10^-5 mol per mol of the silver halide.
Further, the following Compound I was added to a red-sensitive emulsion layer in an amount of 3.0×10^-3 mol per mol of the silver halide.
Further, 1-(3-methylureidophenyl)-5-mercaptotetrazole was added to a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer in an amount of 3.3×10^-4 mol, 1.0×10^-3 mol and 5.9×10^-4 mol, respectively, per mol of the silver halide.
Further, 1-(3-methylureidophenyl)-5-mercaptotetrazole was added to the second layer, the fourth layer, the sixth layer and the seventh layer in an amount of 0.2 mg/m², 0.2 mg/m², 0.6 mg/m² and 0.1 mg/m², respectively.
Further, 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene was added to a blue-sensitive emulsion layer and a green-sensitive emulsion layer in an amount of 1x10^-4 mol and 2x10^-4 mol respectively, per mol of the silver halide.
Copolymer of methacrylic acid and butyl acrylate (weight ratio: 1/1, average molecular weight: from 200,000 to 400,000) was added to a red-sensitive emulsion layer in an amount of 0.05 g/m². Further, disodium catechol-3,5-disulfonate was added to the second layer, the fourth layer and the sixth layer in an amount of 6 mg/m², 6 mg/m² and 18 mg/m², respectively.
Moreover, the following dyes were added to emulsion layers for preventing irradiation (the numerals in parentheses represent the coating amount).

Layer Constitution

The constitution of each layer is described below. The numeral represents the coating amount (g/m²). The numeral for an emulsion represents the coating amount in terms of silver.

Support

Polyethylene resin-laminated paper [a white pigment (TiO₂, content: 16 weight%, ZnO, content: 4 weight%), a brightening agent (13 mg/m² of 4,4'-bis (5-methylbenzoxazolyl) stilbene), and 96 mg/m² of a bluish dye (ultramarine) were added to the polyethylene resin of the first layer side].

First Layer (red-sensitive emulsion layer)
Emulsion (the above red-sensitive emulsion)	0.12
Gelatin	0.59
Cyan Coupler (ExC-1)	0.13
Cyan Coupler (ExC-2)	0.03
Color Image Stabilizer (Cpd-7)	0.01
Color Image Stabilizer (Cpd-9)	0.04
Color Image Stabilizer (Cpd-15)	0.19
Color Image Stabilizer (Cpd-18)	0.04
Solvent (Solv-5)	0.09

Second Layer (color mixing preventing layer)
Gelatin	0.60
Color Mixing Preventive (Cpd-1)	0.09
Color Image Stabilizer (Cpd-5)	0.007
Color Image Stabilizer (Cpd-7)	0.007
Ultraviolet Absorber (UV-C)	0.05
Solvent (Solv-5)	0.11

Third Layer (green-sensitive emulsion layer)
Emulsion (green-sensitive emulsion)	0.14
Gelatin	0.73
Magenta Coupler (ExM)	0.15
Ultraviolet Absorber (UV-A)	0.05
Color Image Stabilizer (Cpd-2)	0.02
Color Image Stabilizer (Cpd-7)	0.008
Color Image Stabilizer (Cpd-8)	0.07
Color Image Stabilizer (Cpd-9)	0.03
Color Image Stabilizer (Cpd-10)	0.009
Color Image Stabilizer (Cpd-11)	0.0001
Solvent (Solv-3)	0.06
Solvent (Solv-4)	0.11
Solvent (Solv-5)	0.06

Fourth Layer (color mixting preventing layer)
Gelatin	0.48
Color Mixing Preventive (Cpd-4)	0.07
Color Image Stabilizer (Cpd-5)	0.006
Color Image Stabilizer (Cpd-7)	0.006
Ultraviolet Absorber (UV-C)	0.04
Solvent (Solv-5)	0.09

Fifth Layer (blue-sensitive emulsion layer)
Emulsion (see Table 6)	0.24
Gelatin	1.25
Yellow Coupler (ExY)	0.57
Color Image Stabilizer (Cpd-1)	0.07
Color Image Stabilizer (Cpd-2)	0.04
Color Image Stabilizer (Cpd-3)	0.07
Color Image Stabilizer (Cpd-8)	0.02
Solvent (Solv-1)	0.21

Sixth Layer (ultraviolet absorbing layer)
Gelatin	0.32
Ultraviolet Absorber (UV-C)	0.42
Solvent (Solv-7)	0.08

Seventh Layer (protective layer)
Gelatin	0.70
Acryl-Modified Copolymer of Polyvinyl	0.04
Alcohol (modification degree: 17%)
Liquid Paraffin	0.01
Surfactant (Cpd-13)	0.01
Polydimethylsiloxane	0.01
Silicon Dioxide	0.003

number average molecular weight: 60,000

(UV-A)

A mixture of UV-1/UV-2/UV-3/UV-4 in the weight ratio of 4/2/2/3

(UV-C)

A mixture of UV-2/UV-3/UV-6/UV-7 in the weight ratio of 1/1/1/2
Coated Sample Nos. 301 to 304 were prepared by using emulsions shown in Table 6 in the blue-sensitive layer of the photographic material having the above layer constitution.

Exposure

Gradation exposure by three color separation was performed with laser beams of three colors of B, G and R using the following apparatus. At that time, laser output was modulated so that each sample could obtain appropriate improvement.

Exposure Apparatus

Three types of laser beams were used as light sources, that is, the wavelength of YAG solid state laser (oscillation wavelength: 946 nm) using a semiconductor laser GaAlAs (oscillation wavelength: 808.5 nm) as an excitation light source converted with SHG crystal of LiNbO₃ having reversal domain structure to 473 nm, the wavelength of YVO₄ solid state laser (oscillation wavelength: 1,064 nm) using a semiconductor laser GaAlAs (oscillation wavelength: 808.5 nm) as an excitation light source converted with SHG crystal of LiNbO₃ having reversal domain structure to 532 nm, andAlGaInP (oscillation wavelength: 680 nm, manufactured by Matsushita Densan Co., Ltd., Type No. LN9R20). Each of three laser beams was made to be able to successively scanning expose a color photographic paper transferring vertically to scanning direction by a polygonal mirror the intensity of which was modulated by AOM. For restraining the fluctuation of light amount due to the changes of temperature, the temperature of semiconductor laser was maintained constant using Peltier element. At this time, scanning exposure was performed at 600 dpi, and every beam diameter of B, G and R measured with a beam diameter meter (1180GP manufactured by Beam Scan Co., U.S.A.) was 65 µm (circular beams showing the difference in diameters in the main scanning direction/sub scanning direction of within 1%).

(Development process, dry to dry: 180 seconds)

The thus-exposed samples were processed by CP45X processing (manufactured by Fuji Photo Film Co., Ltd.).
The reflection density of each processed color sample was measured using a TCD type densitometer (manufactured by Fuji Photo Film Co., Ltd.). Sensitivity was expressed as the logarithm of the exposure amount required to give color density of fog density + 1.0. Sensitivity of the blue-sensitive layer of each sample is shown in Table 7. In Table 7, sensitivity of each sample is shown in a relative value taking the value of Sample No. 301 as 0.00. A positive value shows that sensitivity is high.

Test of pressure marks

Pressuremarks (i.e., pressure resistance) test was performed as follows. A needle having a diameter of 0.1 mm was put on each of the above samples and 10 g of load was applied to the needle and the needle was moved at a rate of 600 mm/min. (pressure processing).
The difference in density between the part where pressure processing was performed and the part where pressure processing was not performed (pressure marks) of the sample which had been development-processed without undergoing exposure was measured with a micro-densitometer having an aperture diameter of 10 µm. The results obtained are shown in Table 7. TABLE 7

Sample No. Grains Blue Light Exposure Pressure Marks Remarks

Fog Sensitivity

301 A 0.04 0.00 0.185 *

302 A 0.04 0.02 0 160 *

303 A 0.03 0.08 0.090 *

304 A 0.03 0.05 0.105 *

*) reference sample

EXAMPLE 11

A tabular silver iodobromide emulsion was prepared according to the method of preparing Emulsion D in Example 5 of JP-A-8-29904 and this was designated Emulsion Q.
Multilayer color photographic materials were prepared according to the method of preparation of Sample No. 101 in Example 5 of JP-A-8-29904 . Sample Nos. 401 and 402 were prepared by replacing Emulsion D in the fifth layer of Sample No. 101 in Example 5 of JP-A-8-29904 with Emulsion Q, and further replacing ExS-1, 2 and 3 with Sensitizing Dye Sen-10 (5.0×10^-4 mol/Ag mol) or Sensitizing Dye S-31 (5.0×10^-4 mol/Ag mol).
For examining the sensitivity of the thus-obtained samples, each sample was exposed for 1/100 sec. through an optical wedge and a red filter with Fuji FW type sensitometer (a product of Fuji Photo Film Co., Ltd.), color development processing was performed using the same processing step and processing solutions as in Example 1 of JP-A-8-29904 and cyan density was measured. Sensitivity was a reciprocal of exposure amount required to give density of fog density + 0.2 and expressed as a relative value.
As a result, Sample No. 402 showed high sensitivity of 113 as compared with sensitivity 100 (control) of Sample No. 401. Sample No. 402 also showed less residual colors after processing.

EXAMPLE 12

In Emulsion 1 in Example 1 of JP-A-7-92601 , the spectral sensitizing dyes were replaced with Sensitizing Dye Sen-10 (8×10^-4 mol/Ag mol) or Sensitizing Dye S-31 (8×10^-4 mol/Ag mol) to prepare tetradecahedral silver iodobromide emulsions, the thus-obtained emulsions were designated Emulsion R and Emulsion S. Further, in Emulsion 1 in Example 1 of JP-A-7-92601 , the silver potential during the second double jet was changed from +65 mV to +115 mV, further, the spectral sensitizing dyes were replaced with Sensitizing Dye Sen-12 (8×10^-4 mol/Ag mol) or Sensitizing Dye S-76 (8×10^-4 mol/Ag mol) to prepare cubic silver iodobromide emulsions, the thus-obtained emulsions were designated Emulsion T and Emulsion U.
Multilayer color photographic materials were prepared according to the method of preparation of Sample No. 401 in Example 4 of JP-A-7-92601 . Emulsion 1 in the ninth layer of Sample No. 401 in Example 4 of JP-A-7-92601 was replaced with Emulsion R or Emulsion S, the thus-obtained samples were designated Sample Nos. 411 and 412. Similarly, Emulsion 1 in the ninth layer of Sample No. 401 in Example 4 of JP-A-7-92601 was replaced with Emulsion T or Emulsion U, and these samples were designated Sample Nos. 413 and 414.
The sensitivity of the thus-obtained samples was evaluated. In the same manner as in Example 4 of JP-A-7-92601 , samples were subjected to exposure for 1/50 sec. and color reversal development processing, and magenta density was measured. Sensitivity was a reciprocal of exposure amount required to give density of minimum density +0.2 which was obtained with sufficient exposure and expressed as a relative value taking the sensitivity of Sample No. 411 as 100. As a result, Sample No. 412 showed high sensitivity of 129. Sample No. 412 also showed less residual colors after processing. Further, Sample No. 414 showed such high sensitivity of 133 taking the sensitivity of Sample No. 413 as 100. Sample No. 414 also showed less residual colors after processing.

EXAMPLE 13

Octahedral silver bromide internal latent image type direct positive emulsion and hexagonal tabular silver bromide internal latent image type direct positive emulsion were prepared in the same manner as in the preparation of Emulsions 1 and 5 in Example 1 of JP-A-5-313297 and these emulsions were named Emulsion V and Emulsion W.
Color diffusion transfer photographic films were prepared in the same manner as in the preparation of Sample No. 101 in Example 1 of JP-A-5-313297 . In the sixteenth layer of Sample No. 101 in Example 1 of JP-A-5-313297 , Emulsion-2 was replaced with Emulsion V and Sensitizing Dye (3) was replaced with Sensitizing Dye Sen-12 (9×10^-4 mol/Ag mol) or Sensitizing Dye S-76 (9×10^-4 mol/Ag mol), the thus-obtained samples were designated Sample Nos. 421 and 422. Also, in the eleventh layer of Sample No. 101 in Example 1 of JP-A-5-313297 , Emulsion-2 was replaced with Emulsion W and Sensitizing Dye (2) was replaced with Sensitizing Dye Sen-10(9×10^-4 mol/Ag mol) or Sensitizing Dye S-31 (9×10^-4 mol/Ag mol), the thus-obtained samples were designated Sample Nos. 423 and 424
For examining the sensitivity of the thus-obtained samples, processing was carried out using the same exposure, processing step and processing solutions as in Example 1 of JP-A-5-313297 and transfer density was measured using a color densitometer. Sensitivity was a reciprocal of exposure amount required to give density of 1.0 and expressed as a relative value. The sensitivity of Sample No. 422 was as high as 123 taking the sensitivity of Sample No. 421 as 100. Sample No. 422 also showed less residual colors after processing. Also, the sensitivity of Sample No. 424 was as high as 115 taking the sensitivity of Sample No. 423 as 100. Sample No. 424 also showed less residual colors after processing.

EXAMPLE 14

In the preparation of Emulsion F in Example 2 of JP-A-4-142536 , red-sensitive sensitizing dye (S-1) was not added before sulfur sensitization, in addition to sulfur sensitization using triethylthiourea, chloroauric acid was used in combination and optimally gold-sulfur sensitized, and after gold-sulfur sensitization, Sensitizing Dye Sen-10 (2×10^-4 mol/Ag mol) or Sensitizing Dye S-31 (2×10^-4 mol/Ag mol) was added, the thus-obtained silver chlorobromide emulsions were designated Emulsions X and Y.
Multilayer color photographic papers were prepared in the same manner as in the preparation of Sample No. 20 in Example 1 of JP-A-6-347944 . The emulsion in the fifth layer of Sample No. 20 in Example 1 of JP-A-6-347944 was replaced with Emulsion X or Y, these samples were designated Sample Nos. 431 and 432.
For examining the sensitivity of the thus-obtained samples, samples were exposed for 1/10 sec. through an optical wedge and a red filter with Fuji FW type sensitometer (a product of Fuji Photo Film Co., Ltd.), color development processing was carried out using the same processing step and processing solutions as in Example 1 of JP-A-6-347944 . As a result, Sample No. 432 showed such high sensitivity of 136 taking the sensitivity of Sample No. 431 as 100. Sample No. 432 also showed less residual colors after processing.

EXAMPLE 15

Tabular silver chloride emulsions were prepared in the same manner as in the preparation of Emulsion A in Example 1 of JP-A-8-122954 . In chemical sensitization (B) in Example 1 of the same patent, Sensitizing Dye-1 and Dye-2 were replaced with Sensitizing Dye Sen-10 (2×10^-4 mol/Ag mol) or Sensitizing Dye S-31 (2×10^-4 mol/Ag mol), the thus-obtained emulsions were designated Emulsion ZA and Emulsion ZB.
Coated samples were prepared by replacing the emulsion in Example 1 of JP-A-8-122954 with Emulsion ZA or Emulsion ZB and an emulsion layer and a surface protective layer were coated in combination on both sides of the support by a simultaneous extrusion method similar to in Example 1, these samples were designated Sample Nos. 441 and 442. The coated silver amount per one side was 1.75 g/m².
For examining the sensitivity of the thus-obtained samples, samples were exposed for 0.05 sec. from both sides through an X-ray ortho-screen HGM produced by Fuji Photo Film Co., Ltd. and processed with the same automatic processor and processing solutions as in Example 1 of JP-A-8-122954 . Sensitivity was a reciprocal of exposure amount required to give a density of fog + 0.1 and expressed as a relative value taking the sensitivity of Sample No. 441 as 100. As a result, Sample No. 442 showed such high sensitivity of 120, and also showed less residual colors after processing.
When exposure was performed using HR-4 or HGH in place of X-ray ortho-screen HGM, the same effects could be obtained.

EXAMPLE 16

Tabular silver chloride emulsion was prepared in the same manner as in the preparation of Emulsion D in Example 2 of JP-A-8-227117 except that Sensitizing Dye-2 and Dye-3 were not added. This emulsion was designated Emulsion ZC.
Coated samples were prepared in the same manner as in the preparation of Coated Sample No. F in Example 3 of JP-A-8-227117 . Emulsion F in Coated Sample No. F in Example 3 of JP-A-8-227117 was replaced with Emulsion ZC, and Sensitizing Dye-1 in Coated Sample No. F in Example 3 was replaced with Sensitizing Dye Sen-12 (5×10^-4 mol/Ag mol) or Sensitizing Dye S-76 (5×10^-4 mol/Ag mol), the thus-obtained samples were designated Sample Nos. 451 and 452.
For examining the sensitivity of the thus-obtained samples, samples were exposed for 1/100 second through an optical wedge and a blue filter using Fuji FW type sensitometer (a product of Fuji Photo Film Co., Ltd.), subjected to Fuji Photo Film CN16 processing and photographic characteristics were compared.
Sensitivity was a reciprocal of exposure amount required to give a density of fog + 0.2 and expressed as a relative value taking the sensitivity of Sample No. 451 as 100. Sample No. 452 showed such high sensitivity of 124, and also showed less residual colors after processing.

EXAMPLE 17

Octahedral silver chloride emulsion was prepared in the same manner as in the preparation of Emulsion F in Example 3 of JP-A-8-227117 , this was designated Emulsion ZD.
Coated samples were prepared in the same manner as in the preparation of Coated Sample No . F in Example 3 of JP-A-8-227117 . Emulsion F and Sensitizing Dye-1 in Coated Sample No. F in Example 3 of JP-A-8-227117 were replaced with Emulsion ZD and Sensitizing Dye Sen-12 (5×10^-4 mol/Ag mol) or Sensitizing Dye S-76 (5×10^-4 mol/Ag mol), the thus-obtained samples were designated Sample Nos. 461 and 462.
For examining the sensitivity of the thus-obtained samples, samples were subjected to exposure for 1/100 sec. through an optical wedge and a red filter using Fuji FW type sensitometer (a product of Fuji Photo Film Co. , Ltd.), subjected to Fuji Photo Film CN16 processing and photographic characteristics were compared. Sensitivity was a reciprocal of exposure amount required to give a density of fog + 0.2 and expressed as a relative value taking the sensitivity of Sample No. 461 as 100. Sample No. 462 showed such high sensitivity of 129, and also showed less residual colors after processing.

EXAMPLE 18

Tabular grain emulsions were prepared in the same manner as in the preparation of Emulsion CC disclosed in European Patent 0699950 , and in chemical sensitization Sensitizing Dye Sen-12 was added in an amount of 5×10^-4 mol/Ag mol and chemical sensitization was performed, then Sen-12 was added in an amount of 3×10^-4 mol/Ag mol, thereafter, further, Sen-12 was added in an amount of 3×10^-4 mol/Ag mol, this emulsion was designated Emulsion ZE, or S-76 was added in an amount of 5×10^-4 mol/Ag mol and chemical sensitization was performed, then S-76 was added in an amount of 3×10^-4 mol/Ag mol, thereafter, further, S-76 was added in an amount of 3×10^-4 mol/Ag mol, this emulsion was designated Emulsion ZF.
Coated samples were prepared in the same manner as in the preparation of the coated samples in the example of European Patent 0699950 , and a sample in which Emulsion ZE was used was designated Sample No. 471, and ZF was used was designated Sample No. 472. The thus-prepared samples were subjected to exposure and development in the same manner as in European Patent 0699950 and photographic characteristics were compared. Sensitivity was a reciprocal of exposure amount required to give a density of fog + 0.2 and expressed as a relative value taking the sensitivity of Sample No. 471 as 100. Sample No. 472 showed such high sensitivity of 136, and also showed less residual colors after processing.

EXAMPLE 19

Preparation of Sample No. 501

Sample No. 101 in Example 8 was prepared and designated Sample No. 501.

Preparation of Sample Nos. 500, 502 to 516

Sample Nos. 502 to 516 were prepared by replacing sensitizing dye Sen-2 or Sen-7 used in the emulsion of Sample No. 501 with equimolar amount of the dye shown in Table 8 and Table 9, and Sample No. 500 (blank sample) was prepared by excluding both dyes. Each piece of the samples thus obtained was subjected to 20 CMS white light exposure for 1/100 sec. through a gray wedge, then processed by the same processing step and same processing solutions as in Example 8, and sensitometry was performed.
The yellow stain density and the magenta stain density of blank Sample No. 500 were subtracted from the yellow stain density and magenta stain density of each piece of the samples after processing and residual color was evaluated. The stain density was measured using a densitometer Status A, a product of X-RITE Co.

Sensitometry and the results of evaluation of residual color are shown in Tables 8 and 9 below. BL relative sensitivity and RL relative sensitivity were compared on the basis of relative exposure amount giving minimum density + 1.0.

TABLE 8

Sample No.	Sensitizing Dye in Emulsions L to P and Replacement of Sen-7	Relative Sensitivity of Blue-Sensitive Layer	Yellow Stain Density
500*	None	-	0 (criterion)
501*	Sen-7	100 (criterion)	0.073
502*	Comparative Dye Sen-12	92	0.055
503*	Comparative Dye Sen-13	109	0.088
504 (Invention)	S-139	113	0.022
505*	S-145	126	0.032
506 (Invention)	S-148	124	0.035
507 (Invention)	S-154	122	0.017
508*	S-156	134	0.044
509 (Invention)	S-157	130	0.033
510*	S-158	125	0.036

*) reference samples

TABLE 9

Sample No.	Sensitizing Dye in Emulsions C to E and Replacement of Sen-2	Relative Sensitivity of Red-Sensitive Layer	Magenta Stain Density
500*	None	-	0 (criterion)
501*	Sen-2	100 (criterion)	0.085
511	Comparative Dye Sen-10	92	0.067
512*	omparative Dye Sen-11	83	0.044
513 (Invention)	S-150	118	0.025
514 (Invention)	S-151	128	0.038
515 (Invention)	S-152	125	0.026
516*	S-155	130	0.032

*) reference samples

As is apparent from the results in Tables 8 and 9, photographic materials exhibiting less residual color and high sensitivity can be obtained by using the compounds and emulsions used according to the present invention. Thus, high sensitivity is compatible with less residual color for the first time by using the constitution of the present invention.

EFFECT OF THE INVENTION

High sensitivity and excellent residual color effect can be obtained by the constitution of the present invention.

Claims

A silver halide photographic material which comprises at least one methine dye represented by the following formula (XX):
wherein Y⁵¹ represents an atomic group necessary to form a furan ring or a pyrrole ring, and represents a structure selected from formulae (3a), (3b) and (3c) together with the rings including X⁵¹:
wherein Xa represents an oxygen atom or a nitrogen atom (N-Rw); Rw represents a hydrogen atom or a monovalent substituent; Va represents a monovalent substituent selected from a methyl group, a methoxy group, a cyano group and a halogen atom; Vb represents a hydrogen atom; Vc and Vd each represents a hydrogen atom or a monovalent substituent, and at least one of Vc and Vd is a monovalent substituent selected from a methyl group, a methoxy group, a cyano group and a halogen atom; X⁵¹ and X⁵² each represents an oxygen atom, a sulfur atom or a nitrogen atom;
Y⁵². represents an atomic group necessary to form a benzene ring or a 5- or 6-membered unsaturated heterocyclic ring, which may further be condensed with other 5- or 6-membered carbocyclic or heterocyclic ring or may have a substituent, and two carbon atoms to which Y⁵² is condensed may be bonded by a single bond or a double bond; R⁵¹ and R⁵² each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted acryl group, or a substituted or unsubstituted heterocyclic group; L⁵¹, L⁵² and L⁵³ each represents a methine group; n⁵¹ represents 0, 1, 2, 3 or 4; M⁵¹ represents a counter ion; and m⁵¹ represents a number of 0 or higher necessary to neutralize the charge in the molecule,
with the proviso that the methine dye is not
The silver halide photographic material of claim 1, wherein R⁵¹ and R⁵² in the formula (XX) each represents an alkyl group substituted with, an acid radical.
The silver halide photographic material of claim 2, wherein one of R⁵¹ and R⁵² represents an alkyl group substituted with an acid radical other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group.
The silver halide photographic material of claim 1, wherein Y⁵² in the formula (XX) is an atomic group necessary to form a benzene ring.
The silver halide photographic material of any of claims 1 to 4, wherein Va represents a chlorine atom.