JPH0234832A - Direct positive silver halide emulsion - Google Patents

Abstract

PURPOSE:To obtain a direct positive silver halide emulsion having high spectral sensitivity by incorporating at least one kind of specified metine pigment constituted of a azulene nucleus wherein at least one C atom of 10C atoms is substituted by a chalcogen atom or a N atom, and at lest one kind of org. desensitizer in the silver halide emulsion. CONSTITUTION:The title direct positive silver halide emulsion contains at lest one kind of methine pigment constituted of a heterocyclic azulene nucleus wherein at least one C atom of an azulene nucleus which has 10 C atoms is substituted by a chalcogen atom such as O, S, Se and Te, or N atom, and a 7-membered ring moiety of the nucleus is substituted by a methine linkage having an auxochrome which forms a conjugate resonance chromophore together with a 10pi electron system of the nucleus. The emulsion contains also at least one kind of org. desensitizer having -1.0 or more positive reduction potential. The org. desensitizer is defined as a material having a capacity or capturing free electrons generated in silver halide particles by the irradiation with radiant rays and being adsorbed with silver halide. By this constitution, a direct positive silver halide emulsion having high spectral sensitivity is obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a prefogged direct positive halogenated emulsion containing a methine dye and an organic desensitizer. It relates to prefogged direct positive silver halide emulsions exhibiting photographic properties.

(Prior art) The spectral sensitization technology of pre-fogged direct positive type silver halide emulsion is an important technology in manufacturing high-sensitivity photographic materials.Pre-fogged direct positive type halogenated The dyes used for spectral sensitization of silver emulsions are generally called desensitizing dyes, and a large number of compounds have been known so far, such as HoJames W.
Author, “The Theory of the Photographic
Process J (The Theory of
the Photographic Processes
s) (3rd edition), 1966, Macmillan
Examples include cyanine dyes and merocyanine dyes, which are described in 1985-228, published by Ilan) Co., Ltd., N, Y, pages 198 to 228. It is preferable to have a value of .

It is known that these desensitizing dyes can be used alone or in combination (for example, as organic desensitizers).

[Problem to be solved by the invention]

The conditions that desensitizing dyes used in such photographic materials must satisfy are not only high spectral sensitivity, but also no increase in the minimum density (Dmin) of the inversion (n tip); Examples include small changes in sensitivity and minimum concentration (Dmin) during storage of raw samples.

However, even with the use of conventional desensitizing dyes and organic desensitizers, fully satisfactory performance could not be obtained. The present inventors discovered that methine dye satisfies the above conditions as a desensitizing dye or an organic desensitizing agent, and previously published II.
I (Japanese Patent Application No. 62-44868), and the present invention relates to an improvement thereof.

Therefore, the object of the present invention is to achieve even higher sensitivity and minimum concentration (
It is an object of the present invention to provide a prefogged direct positive type silver halide emulsion which exhibits no increase in Dmin (Dmin) and small changes in sensitivity and minimum density (Dmin) upon raw storage.

[Means for solving problems]

The above aspects of the present invention include a nucleus in which at least one of the ten carbon atoms of the azulene nucleus is replaced with a chalcogen atom (for example, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom) or a nitrogen atom (a complex azulene nucleus). ), and the seven-membered ring part of the cough nucleus is substituted with a methine bond having an auxochrome at the end that forms a conjugated resonance chromophore with the 10π electron system of 3111, at least one methine dye, and the reduction potential is -1,0 (vvssc
This was achieved by a prefogged direct positive silver halide emulsion characterized in that it contains at least one organic 15 agent having a value of E) or more positive.

This methine dye acts as a desensitizing dye or an organic desensitizing agent.

The present invention will be explained in more detail below.

In the methine dye containing a hetero azulene nucleus used in the present invention, a preferable hetero azulene nucleus is a nucleus in which at least one of the carbon atoms at the 1st and 3rd positions is replaced with a chalcogen atom or a nitrogen atom. This nucleus will be explained.

The dye of the present invention can be expressed in an alternating resonance form as shown in the following general formula (1).

V5 V4 Ml! I ↓ V5 V4 Mm In the formula, E represents an auxochrome, L represents a methine bond, and v, , v, , v, , v, , and V each represent a hydrogen atom, a halogen atom, an alkyl group, or an acyl group. group, acyloxy group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, carboxy group, cyano group, hydroxy group, amino group, acylamino group, alkoxy group,
represents an alkylthio group, an alkylsulfonyl group, a sulfonic acid group, or an aryl group, or two of (1) to (2) bonded to adjacent carbon atoms may form a fused ring with each other; These may further have a substituent.

■ Y and Z! is a carbon atom (-C=, where ■ is v,
, Vj, Vj, v, and ■), a chalcogen atom (for example, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, etc.) or a nitrogen source R3 (-N=, R1 is synonymous with forming a nucleus) may or may not be necessary, but when necessary, R1 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted 7-aryl group, or a heterocyclic group),
However, both Y and Z are not carbon atoms,
Furthermore, when Y and Z are represented by a chalcogen atom or a nitrogen atom, one of them is a nitrogen atom.

Further, when one represents a chalcogen atom and the other represents a carbon atom or a nitrogen atom, Z represents a chalcogen atom and Y represents a carbon atom or a nitrogen atom.

M represents a charge-balancing counterion, and m is a number greater than or equal to 0 necessary to balance the charges.

In formula (1), the bonding position of the methine bond is represented as the 6th position as a representative, but the other positions (4th, 5th, 7th, and 8th positions) are also represented in the same way. However, preferably the 4th, 6th, and 8th positions, and more preferably the 4th and 6th positions.

I will explain Sukeki Danmi in detail.

E can take any common form found in methine dyes. Typically, auxochromes are composed of nitrogen or chalcogen atoms that resonate between charged and uncharged states in the dye. For example, cyanine, merocyanine, oxonol, pyrylium or thiapyrylium dyes. It can be any form of the auxochrome found in . however,
There is no need to limit auxochromes to these categories.

To a lesser extent, auxochromes formed by other atoms, such as phosphorus or boron, are conceivable.For example, 2-triphenylphosphoro-1°3-cyclopentadien-5-yl may be mentioned. .

Among the dyes represented by the general formula (1), preferred are those represented by the following general formulas (n) to (IX).

General formula (n) V5 V4 Mm In the formula, V, ~V, , Y, Z, , MSm are the general formula (
It is synonymous with 1). Furthermore, as in general formula (1), the methine bond may be located at any of the 4th, 5th, 6th, 7th, and 8th positions.

Q represents an atomic group necessary to form a 5- or 6-membered nitrogen-containing ring; L represents an optionally substituted methine group; Table R1 represents a substituted or unsubstituted alkyl group.

2 represents an integer of 0 to 3, and n represents 0 or 1.

General formula (III) ■5 ■4 MI! 1 In the formula, V+''-Vs, Y, Zt, M, and m have the same meanings as in the general formula (1). Also, as in the general formula (1), the positions of the methine bond are the 4th, 5th, and 6th positions. , 7th or 8th place is fine.

Q! represents an atomic group necessary to form a 5- or 6-membered nitrogen-containing ring; LA, Lt, Ls, L-, and Lta are L
t, Lx, Lx, L4, and.

is synonymous with

R3 represents a substituted or unsubstituted alkyl group.

12 represents an integer of 0 to 3, and R2 represents 0 or l.

General formula (It/) V5 V4 Mm y, t '115/In the formula, Vl ~ V5, Y, Zz, M, m are general formula (1)
is synonymous with Y' and Zx' are synonymous with Y and Z. Also, as in -S formula (1), the position of the methine bond is 4
1st place, 5th place, 6th place, 7th place, or 8th place.

■O~■,' are synonymous with v1~■.

Ll, L12, and L12 are Lt, Lx, Ls,
Synonymous with LA and LS. ! , represents an integer from 0 to 3.

General formula (V) V5 V4 Mm In the formula, V, ~V, , Y, Zz, M, and m are the general formula (
It is synonymous with 1). Further, as in general formula (I), the methine bond may be located at any of the 4th, 5th, 6th, 7th, and 8th positions.

D and D+' represent an atomic group necessary to form an acidic nucleus, and may be acyclic or cyclic.

Ja, LIS% Ll4 and Llt beam,, Lt, R
It is synonymous with 2, La, and ri. 24 represents an integer of 0 to 3; n is 0 or 1;

General formula (Vl) is synonymous with Ll, LI, beam, SLt, L, , R4, and beam. ff1s represents an integer from O to 3.

General formula (■) In the M formula, V+ to Vs, Y, Zz, M, and m have the same meanings as in the general formula (1). Furthermore, as in general formula (1), the methine bond may be located at any of the 4th, 5th, 6th, 7th, and 8th positions.

R&,R? represents a substituent known in general tertiary amines; Rh and R1 may form a ring.

where E and E' are E+ or R2.

However, at least one of E and E'' is E.

Vl to V5, Y, Zz, M, and m have the same meanings as in general formula (1). Furthermore, as in general formula (1), the methine bond may be located at any of the 4th, 5th, 6th, 7th, and 8th positions.

Wl represents an atomic group necessary to form a 5- or 6-membered heterocycle.

R1 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group.

Qx and Rv have the same meanings as Q, , and R6 in general formula (It), respectively.

Lzo, L! 1% L0% Synonymous with Lzx, LI4, Lzs and Lh, , L, , L, , L, and LS.

! h and 2. is an integer from O to 3.

R4 is 0 or 1.

General Formula (■) R+θ In the formula, V+ to Vs, Ys 22 , M-, and m have the same meanings as in General Formula (1). Furthermore, as in general formula (1), the methine bond may be located at any of the 4th, 5th, 6th, 7th, and 8th positions.

W2 is synonymous with Wl. IRI. is synonymous with R6. Dt and D2' are DI and D+ of general formula (V)
' is synonymous with '.

Lit, L-is, Lxq, Lea, Ls+ and l-
3Z has the same meaning as Ll, R2, 1, R4, and RI.

18 and 2. is an integer from 0 to 3.

n represents 0 or 1.

General formula (IXa) V5 V4 Mm General formula (IXb) In the formula, V, ~Vs, Y, Z, , M, m are the general formula (
It is synonymous with 1). Furthermore, as in general formula (1), the methine bond may be located at any of the 4th, 5th, 6th, 7th, and 8th positions.

L22 and L3a are L+, Lx, Ls, L4,
It is synonymous with and.

Ar represents an aromatic group.

11° represents an integer from 0 to 3.

General formulas (1) to (IX) will be explained in detail below.

R1 is preferably a hydrogen atom, an unsubstituted alkyl group having 18 or less carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group), or a substituted alkyl group ( Examples of substituents include carboxy group, sulfo group, cyano group,
Halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms).

), hydroxy group, alkoxycarbonyl group having 8 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, fenoquine carbonyl group, benzyloxycarbonyl group), alkoxy group having 8 or less carbon atoms (e.g. methoxy group, ethoxy group, benzyloxy group, phenethyloxy group), monocyclic aryloxy group having IO or less carbon atoms (e.g. phenoxy group, p-tolyloxy group), acyloxy group having 3 or less carbon atoms (e.g. acetyloxy group, propionyloxy group), Acyl groups having 8 or less carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, mesyl group), carbamoyl groups (e.g. carbamoyl group, N, N
-dimethylcarbamoyl group, morpholinocarbonyl group,
piperidinocarbonyl group), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group), aryl group having 10 or less carbon atoms (e.g. phenyl group, -Chlorphenyl group, 4-methylphenyl group, α-
Alkyl group having 18 or less carbon atoms substituted with naphthyl group), aryl group (e.g. phenyl group, 2-naphthyl group)
, a substituted aryl group (e.g., 4-carboxyphenyl group, 4-sulfophenyl group, 3-chlorophenyl group, 3-
methylphenyl group), and heterocyclic groups (for example, 2-pyridyl group, 2-thiazolyl group).

Particularly preferred are unsubstituted alkyl groups (e.g. methyl group,
ethyl group), a sulfoalkyl group (eg, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfoptyl group), and more preferably a methyl group.

Furthermore, as the metal atom that can form a salt with R1, an alkali metal is particularly preferable, and as the organic compound that can form a salt with R1, pyridines, amines, etc. are preferable.

V+, V! , Vs, Va, Vs, V+ 'VZ■,
゛, ■4', and Vs' are hydrogen atom, halogen atom (e.g., chlorine atom, fluorine atom, bromine atom), unsubstituted alkyl group having 10 or less carbon atoms (e.g., methyl group, ethyl group), carbon number Under 18! Substituted alkyl groups (e.g. benzyl group, α-naphthylmethyl group, 2-phenylethyl group, trifluoromethyl group), acyl groups having 10 or less carbon atoms (e.g. acetyl group, benzoyl group, mesyl group), 10 or less carbon atoms Acyloxy group (e.g. acetyloxy group), alkoxycarbonyl group having 10 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), substituted or unsubstituted carbamoyl group (e.g. carbamoyl group, N, N
-dimethylcarbamoyl group, morpholinocarbonyl group,
piperidinocarbonyl group), substituted or unsubstituted sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group), carboxy group, cyano group, hydroxy group, amino group, acylamino group having 8 or less carbon atoms (
acetylamino group), alkoxy groups having 10 or fewer carbon atoms (e.g. methoxy, ethoxy, benzyloxy), alkylthio groups (e.g. ethylthio), alkylsulfonyl groups (e.g. methylsulfonyl), sulfonic acid groups, aryl groups. (e.g. phenyl group, tolyl group)
is preferable, and (2) two bonded to adjacent carbon atoms in 1 to V may be bonded to each other to form a benzene ring, or may be bonded to each other to form a heterocyclic ring (e.g. ring, thiophene ring, furan ring, pyridine ring, imidazole ring, triazole ring, thiazole ring).

Preferred as V, , V3, V, , V, , V, , V, , V' and 5 is a hydrogen atom. ■
, and (1) are preferably a hydrogen atom, a chlorine atom, an alkoxy group (for example, a methoxy group), an alkylthio group (for example, a methylthio group), or an atomyl group (for example, a phenyl group).

M is included in the formula to indicate the presence or absence of a cation or anion when necessary to neutralize the ionic charge of the dye. Whether a dye is cationic, anionic, or has a net ionic charge depends on its auxochromes and substituents. Counterions can be easily exchanged after the dye is manufactured.

Typical cations are ammonium ions and alkali metal ions, while anions may specifically be either inorganic or organic anions, such as halogen anions (e.g. fluoride, chloride,
Bromine ion, iodine ion), substituted arylsulfonate ion (e.g. p-)luenesulfonate ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (e.g. 1.3-benzenedisulfonate ion, 1.5- naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (
Examples include methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, and trifluoromethanesulfonate ion. Preferably it is an iodine ion.

The nucleus formed by Q and Q includes a thiazole nucleus (e.g. thiazole, 4-methylthiazole, 4-methylthiazole,
-phenylthiazole, 4,5-dimethylthiazole,
4.5-diphenylthiazole), benzothiazole nucleus (e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5- Methylbenzothiazole, 6
-Methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole,
5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5.6-dimethylbenzothiazole, 5.6-Simethoxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4
-phenylbenzothiazole), naphthothiazole nucleus (
For example, naphtho[2,1-d]thiazole, naphtho(1
,2-d]thiazole, naphtho[2,3-d)thiazole, 5-methoxynaphtho(1,2-d)thiazole, 7
-nitoxynaphtho(2,1-d)thiazole, 8-methoxynaphtho(2,1-d)thiazole, 5-methoxynaphtho(2,3-d)thiazole, etc.), thiazoline nucleus (
For example, thiazoline, 4-methylthiazoline, 4-nitrothiazoline), oxazole nucleus (e.g. oxazole, 4-methyloxazole, 4-nitrooxazole, 5-methyloxazole, 4-phenyloxazole, 4,5- diphenyloxazole,
4-ethyloxazole), benzoxazole core (e.g., benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5
-Phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6 -Nitrobenzoxazole, 6-ethoxybenzoxazole, 6-hydroxybenzoxazole, 5.6-dimethylbenzoxazole, 4.6
-dimethylbenzoxazole, 5-ethoxybenzoxazole), naphthoxazole nuclei (e.g., naphtho(2,1-d)oxazole, naphtho[1°2-d]oxazole, naphtho(2,3-d)oxazole, 5 −
nitronaphtho(2,1-d)oxazole, etc.), oxazoline cores (e.g., naphtho(4,4-dimethyloxazoline), selenazole cores (e.g., 4-methylselenazole, 4-nitroselenazole,
4-phenylselenazole), benzoselenazole nucleus (
Examples Eva, benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-
nitrobenzoselenazole, 5,6-dimethylbenzoselenazole, etc.), naphthoselenazole core (e.g., naphtho(2,1-d)selenazole, naphtho(1,2-d)
] Selenazoline)), selenazoline core (e.g. selenazoline, 4-methylselenazoline), tellurazole core (
tellurazole core (e.g. telllazole, 4-methyltelllazole, 4-phenyltelllazole), penzotelllazole core (e.g. penzotelllazole, 5-chlorobenzotelllazole, 5-methylbenzotelllazole,
5.6-dimethylbenzotelllazole, 6-medoxybenzotelllazole), naphthotellazole core (e.g.
naphtho(2,1-d)tellazole, naphtho(1,2-
d) telllazoline core (e.g.
tellazoline, 4-methylselenazoline), 3,3-dialkylindolenine core (e.g., 3,3-dimethylindolenine, 3゜3-diethylindolenine, 3.3-
Dimethyl-5-cyanoindolenine, 33-dimethyl-
6-nitroindolenine, 33-dimethyl-5=nitroindolenine, 3.3-dimethyl-5-methoxyindolenine, 3,3.5-trimethylindolenine, 3,3.
5-dimethyl-5-chloroindolenine), imidazole nucleus (e.g., 1-alkylimidazole, 1-alkyl-4-phenylimidazole), benzimidazole (e.g., 1-alkylbenzimitazole, 1- Alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole,
1-Alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-
Alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, l-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-aryl-imidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, ■-aryl-5-cyanobenzo imidazole), naphthoimidazole core (e.g. 2-alkylnaphtho(1,2-d)imidazole, 1-arylnaphtho(
(1,2-d) imidazole), the aforementioned alkyl groups have 1 to 8 carbon atoms, such as unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and hydroxyalkyl groups (e.g., 2-hydroxy ethyl,
3-hydroxypropyl) is preferred, and methyl and ethyl groups are particularly preferred. The aforementioned aryl groups represent phenyl, halogen (e.g. chloro) substituted phenyl, alkyl (e.g. methyl) substituted phenyl, alkoxy (e.g. methoxy) substituted phenyl), pyridine nuclei (e.g. 2-pyridine, 4- Pyridine, 5-methyl-2-
pyridine, 3-methyl-4-pyridine), quinoline nucleus (
Quinoline core (e.g. 2-quinoline, 3-methyl-2-
Quinoline, 5ethyl-2-quinoline, 6-methyl-2-
Quinoline, 6-nitro-2-quinoline, 8-fluoro-
2-quinoline, 6-medoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 4
-quinoline, 6-nitoxy-4-quinoline, 6-nitro-4-quinoline, 8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 8-
methoxy-4-quinoline, 6-methyl-4-quinoline, 6-medoxy-4-quinoline, 6-chloro-4-quinoline), isoquinoline nuclei (e.g. 6-nitro-1-isoquinoline, 3,4-dihydroquinoline), -1-isoquinoline, 6
-nitro-3-isoquinoline)), imidazo(4,5-
b) Quinoxaline core (e.g. 1,3-diethylimidazo(4,5-b)quinoxaline, 6-chloro-1,3-
diallylimidazo(4,5-b)quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus,
Mention may be made of pyrimidine nuclei.

More preferred are benzothiazole core, benzoxazole core, and indolenine core.

R,, Rs and R1 can take the form of quaternizing substituents of the basic core of any cyanine dye.

For example, preferably an unsubstituted alkyl group having 18 or less carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a decyl group, a dodecyl group,
octadecyl group) or a substituted alkyl group (for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom).

), hydroxy group, alkoxycarbonyl group having 8 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group), alkoxy group having 8 or less carbon atoms (e.g. methoxy group, ethoxy group, benzyloxy group, phenethyloxy group), monocyclic aryloxy group having up to 10 carbon atoms (e.g. phenoxy group, p-)lyloxy group), acyloxy group having up to 3 carbon atoms (e.g. acetyloxy group,
propionyloxy group), acyl group having 8 or less carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, mesyl group), carbamoyl group (e.g. carbamoyl group, N,
N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), sulfamoyl group (e.g. sulfamoyl!i, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group), carbon number 10 or less aryl group (e.g. phenyl group, 4-chlorophenyl group, 4-methylphenyl group,
An alkyl group having 18 or less carbon atoms substituted with an α-naphthyl group is preferable.

D, , D,' and Dt, , Dz'' represent atomic groups necessary to form an acidic nucleus, but they can take the form of an acidic nucleus of any general merocyanine dye.

In a preferred form Dl and D2 are cyano, sulfo or carbonyl groups;

Dt' represents the remaining atomic group necessary to form an acidic nucleus.

When the acidic nucleus is acyclic, that is, D, and Dl
When 'or D□ and Dt' are independent groups, the terminus of the methine linkage is a group such as malononitrile, alkylsulfonylacetonitrile, cyanmethyl benzofuranyl ketone or cyanomethyl phenyl ketone.

D, ,D,' or , ,D,' - together with carbon, nitrogen and chalcogen (typically oxygen, sulfur,
It forms a 5- or 6-membered heterocycle consisting of (selenium, tellurium) atoms. Preferably, ,D,' or Dz
, Dz' together complete the next nucleus.

2-pyrazolin-5-one, pyrazolidine-35-dione, imidacillin-5-one, hydantoin, 2- or 4-thiohydantoin, 2-iminooxazolidine-4
-one, 2-oxazolin-5-one, 2-thioxazolidine-2,4-dione, isoxazolin-5-one, 2-thiazolin-4-one, thiazolidin-4-one, thiazolidine-2,4-dione , rhodanine, thiazolidine-2,4-dithione, isorhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indoline-2-
one, indolin-3-one, indacillin-3-one, 2-oxoindacillinium, 3-oxoindacillinium, 5.7dioxo67-cyhydrothiazolo(3
,2-a]pyrimidine, cyclohexane-1,3-dione, 3.4-dihydroisoquinolin-4-one, 1.3
-dioxane-4,6-dione, barbylic acid, 2-
A core of thiobarviric acid, chroman-24-dione, indacillin-2-one, or pyrido(1,2-a)pyrimidine-1,3-dione.

More preferably, 1,3-dialkylbarbylic acid, 1,3-dialkyl-2-thiobarbylic acid, 3-
It is an alkylrhodanine (the alkyl group is preferably an unsubstituted alkyl group).

The substituent bonded to the nitrogen atom contained in the nucleus is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, particularly preferably 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, Isopropyl group, butyl group, isobutyl group,
hexyl group, octyl group, dodecyl group, octadecyl group), substituted alkyl group (e.g. aralkyl group (e.g. benzyl group, 2-phenylethyl group), hydroxyalkyl group (e.g. 2-hydroxyethyl group, 3-hydroxypropyl group) , carboxyalkyl group (e.g. 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, carboxymethyl group), alkoxyalkyl group (e.g. 2methoxyethyl group, 2-(2-
methoxyethoxy)ethyl group), sulfoalkyl group (e.g. 2-sulfoethyl group, 3-sulfopropyl group, 3
-sulfobutyl group, 4-sulfobutyl group, 2-[3-sulfopro-poxy]ethyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfopropoxyethoxyethyl group), sulfatoalkyl group (e.g. 3-sulfopropoxyethoxyethyl group), 10 biru group, 4-sulfatobutyl group), heterocyclic monosubstituted alkyl group (e.g. 2(pyrrolidin-2-one-1-yl)ethyl group, tetrahydrofurfuryl group, 2-morpholinoethyl group), 2-acetoxy ethyl group, carbomethoxymethyl group, 2-methanesulfonylaminoethyl group),
Allyl group, aryl group (e.g. phenyl group, 2-naphthyl group), substituent aryl group (e.g. 4-carboxyphenyl group, 4-sulfophenyl group, 3-chlorophenyl group,
3-methylphenyl d), heterocyclic groups (eg 2-pyridyl group, 2-thiazolyl group) are preferred.

R4, R? is a substituent of the tertiary amine used in the synthesis, so tFp! of a general tertiary amine! , any base is acceptable.

Rh and Rq may be the same or different from each other, and are preferably unsubstituted alkyl groups having 18 or less carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl). , octadecyl group) or substituted alkyl group (substituents include, for example, carboxy group, sulfo group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom), hydroxy group, alkoxycarbonyl having 8 or less carbon atoms) groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group), alkoxy groups having 8 or less carbon atoms, (e.g. methoxy group, ethoxy group, benzyloxy group, phenethyloxy group), 10 or less carbon atoms monocyclic aryloxy groups (e.g. phenoxy group, p-tolyloxy group), acyloxy groups having 3 or less carbon atoms (e.g. acetyloxy group, propionyloxy group), acyl groups having 8 or less carbon atoms (e.g. acetyl group,
propionyl group, benzoyl group, mesyl group), carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfonyl group), moyl group, morpholinosulfonyl group, piperidinosulfonyl group) carbon number of 18 or less substituted with an aryl group of carbon number of 10 or less (e.g., phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group) Preferable alkyl groups include) cyano group, alkoxy group (eg, methoxy group, ethoxy group), aryloxy group (eg, phenoxy group), alkoxycarbonyl group (eg, ethoxycarbonyl group).

Further, R6 and R1 can be combined with each other to form a heterocycle excluding an aromatic heterocycle.

For example, pyrrolidine, piperidine, morpholine, piperazine, tetrahydropyridine, dihydropyridine and tetrahydroquinoline are preferred.

More preferably R4 and R1 are ethyl groups.

Examples of the heterocycle formed by Q2 include a pyrrole nucleus, a carbazole nucleus, an indole nucleus, a pyrazole nucleus,
Preferred are pyrazolo(1,5-a)benzimidazole nucleus, pyrazolo(1,5-b)quinazolone nucleus, and indazole nucleus.

In addition, the 5- or 6-membered heterocycle formed by W, , W, is an oxo group or a thioxo group at an appropriate position from the cyclic heterocycle represented by D, , D,' and Di, Dz. The base is removed.

R3 and R+o are preferably the same as those mentioned above as substituents bonded to the nitrogen atom contained in the nucleus of the cyclic heterocycle represented by Dl, DI', and D'.

Ar represents an aromatic group, preferably an aryl group (eg, phenyl group, 3-chlorophenyl group, naphthyl group).

L, ,L□,Ll ,L, ,L, ,L, ,L, ,
L,,L,,L,. , Lll, L1□, Ll3, Ll4
,L15%LI4%LlffsLI8%LIqsL20
%Lx'5LzzsLza, Lta, L, zs, Lzh
, LZ? ,Lo,shi,L,. , R31, L)Z, Lj
ffs and R34 are substituted with a methine group (substituted or unsubstituted alkyl group (e.g. methyl group, ethyl group), substituted or unsubstituted aryl group (e.g. phenyl group), or halogen atom (e.g. chlorine atom, bromine atom) ), and may also form a ring with another methine group, or may form a ring with an auxochrome.

The organic desensitizer used in the present invention is a substance that has the ability to capture free electrons generated in silver halide grains by radiation irradiation, and is a substance that adsorbs to silver halide. Furthermore, it is defined as a substance having the lowest vacant electron energy level, which is lower than the electron energy level of the conduction band of silver halide grains. Preferably, the compound has a highest occupied electron energy level lower than the valence band of the particles.

The evaluation of the lowest unoccupied electron energy level here can be performed by measuring the reduction potential. Measurement of reduction potential is
This was performed using phase-discriminative second-harmonic AC polarography. Details are described below. 4A-1 as a solvent
Acetonitrile (spectral grade) dried in /16 molecular sieves was used as the supporting electrolyte, and normal tetrapropylammonium verchlorate (special reagent for polarography) was used. The sample solution was 0. 1M
organic desensitizer in acetonitrile containing supporting electrolyte of 10
-3 to 10-S mol/l of ultra-high-purity argon gas (99, 100,000
A mercury dropping electrode was used as the working electrode, a saturated calomel electrode (SCE) was used as the reference electrode, and platinum was used as the counter electrode. 0 between the reference electrode and the sample solution
．． They were connected using a Luggin tube filled with acetonitrile containing 1M supporting electrolyte, and Vycor glass was used for the liquid junction. Measurements were taken at 25° C. with the tip of the Luggin tube and the tip of the mercury capillary separated by 8M from the 5-point tube. Measurement of reduction potential by phase-discriminative oni-harmonic alternating current portammetry using platinum as a working electrode is described in the Journal of Imaging Science J (Journal of Imaging Science J).
Imaging 5science), Volume 30, 2
7-35 (1986).

The organic desensitizer used in the present invention has a reduction potential of -1,0 (
V, , 5CE) or a more positive value. Many of such organic desensitizers (2), which do not function as desensitizers when the reduction potential is -1.0 (VysSCE) or lower, are disclosed in, for example, U.S. Pat.
No. 14,796, No. 2.901,351, No. 3,
357,779, British Patent No. 723,019, British Patent No. 698°575, British Patent No. 698,576, British Patent No. 834
No. 839, No. 667.206, No. 748.68
No. 1, No. 796.873, No. 875°887,
Same No. 905,237, Same No. 907゜367, Same No. 9
No. 40,152, Temple Patent No. 1.520.824, No. 1,518,094, No. 1,518,095, No. 1,520,819, No. 1,520.823,
Belgian Patent No. 1.520.821, Belgian Patent No. 1.523,626, Belgian Patent No. 722,457, Belgian Patent No. 722,59
4 specifications, Japanese Patent Publication No. 43-13167, No. 43-
These are described in various publications such as No. 14500.

More preferred organic desensitizers are compounds represented by general formula (X), general formula (X I ''), or general formula (Xn).

General Formula (X) In the formula, Z represents an atomic group necessary to form a nitrogen-containing heterocycle.

T-G! , halogen atom, alkyl group, halogen atom,
Acyl group, acyloxy group, acylamino group, alkoxy group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, carboxy group, cyano group, hydroxy group, amino group, alkylthio group, alkylsulfonyl group,
Sulfonic acid group, sulfonamide group, aryl group or
Represents a condensed ring, which may further have a substituent.

ql represents 1.2 or 3.

r represents 0, 1.2 or 3.

General formula (XI) (T2)T2 1 In the formula, R1 represents a hydrogen atom, an alkyl group, a ring group, or a heterocyclic group, which may further have a substituent.

T! is synonymous with T1.

qt represents 1.2 or 3.

T8 represents 0, 1.2 or 3.

General formula (Xn) In the formula, Ro has the same meaning as R+.

T is synonymous with T1.

q2 represents 1.2 or 3.

T3 represents 0.1.2 or 3.

General formulas (X), (XI) and (Xn) will be explained in more detail. Specific examples of the nitrogen-containing heterocyclic nucleus completed by Assignment,
Triacinden, benzothiazole, penzimitazole, benzoxazole, pyrimidine, triazine,
Examples include pyridine, quinoline, quinazoline, phthalazine, quinoxaline, imidazo[4,5-1]quinoxaline, tetrazole, and 1,3-diasazulene, and these rings may further have substituents. may be condensed.

T, ,'rt and T are halogen atoms (T
3) r3 (for example, chlorine atom, fluorine atom, bromine atom), unsubstituted alkyl group having 10 or less carbon atoms (for example, methyl group, ethyl group), substituted alkyl group having 18 or less carbon atoms (for example,
cyclohexyl group, allyl group, benzyl group, α-naphthylmethyl group, 2-phenylethyl group, trifluoromethyl group), acyl group with 10 or less carbon atoms (e.g. acetyl group, benzoyl group, mesyl group), 10 carbon atoms The following acyloxy group (e.g. acetyloxy group), carbon number 10
The following alkoxycarbonyl groups (e.g., methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), substituted or unsubstituted carbamoyl groups (e.g., carbamoyl group, N%N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group) carbonyl group), substituted or unsubstituted sulfamoyl group (e.g., sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group), carboxy group, cyano group, hydroxy group, Amino group, acylamino group having 8 or less carbon atoms (e.g. acetylamino group), alkoxy group having 10 or less carbon atoms (methoxy group, ethoxy group, benzyloxy group), alkylthio group (e.g. ethylthio group), alkylsulfonyl group ( For example, methylsulfonyl group), sulfonic acid group, sulfonamide group, and tolyl group (e.g., phenyl group, tolyl group) are preferable, and two bonded to adjacent carbon atoms are bonded to each other and benzene It may form a ring.

In addition, heterocycles (e.g., virol ring, thiophene ring, furan ring, lysine ring, imidazole ring,
triazole ring, thiazole ring) may be formed.

R1 and Rt are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, particularly preferably 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, hexyl group, octyl group,
dodecyl group, octadecyl group), IF-substituted alkyl group, e.g., aralkyl group (e.g., benzyl group, 2-phenylethyl group), hydroxyalkyl group (e.g., 2-hydroxyethyl group, 3-hydroxypropyl group), carboxyalkyl group (For example, 2-carboxyethyl group,
3-carboxypropyl group, 4-carboxybutyl group,
carboxymethyl group), alkoxyalkyl group (e.g., 2-methoxyethyl group, 2-(2-methoxyethoxy)ethyl group), sulfoalkyl group (e.g., 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group) , 4-sulfobutyl group, 2-[3-sulfopropoxy]
Ethyl group, 2-hydroxy-3-sulfopropyl group, 3
-sulfopropoxyethoxyethyl group), sulfatoalkyl group (e.g., 3-sulfatopropyl group, 4-sulfatobutyl group), heterocyclic-substituted alkyl group (e.g.,
2-(pyrrolidin-2-one-1-yne)ethyl group, tetrahydrofurfuryl group, 2-morpholinoethyl group)2
-acetoxyethyl group, carbomethoxymethyl group, 2-
methanesulfonylaminoethyl group), allyl group, aryl group (e.g. phenyl group, 2-naphthyl group), substituted aryl group (e.g. 4-carboxyphenyl group, 4-sulfophenyl group, 3-chlorophenyl group, 3-methyl phenyl group), heterocyclic group (e.g. 2-pyridyl group, 2-
thiazolyl group) is preferred.

Next, the methine dye used in the present invention and the organic fI
Although specific examples of i-sensitizers are shown below, the present invention is not limited to these only.

Examples of compounds represented by general formula (I[) (blank below) Compound Y (ff-1) (U-2) (II-3) (II-4) -CH3 -CH3 -CH3 -CH5 (n- 6) N (n-7) N -C2H5 -CH5 (n-10) (n-11) (Il-12) (II-13) (II-14) (U-15) -CH3 -CH3 -CH3 e (n-17) CH (n-18) CH (II-19) CH -CH3 2' CH3 cl CH3 2H5 2H5 2H5 2H5 2H5 SCH3N-C2H5C2H5 SCH30C2H3 CH2C02H ■ CH3 H CH3 CH3 -cl 5 -cl S-c 1 0 2H5 CH3 CH3 2H5 CH3 CH3 CH3 2H5 2H5 2H5 X -NO2 -NO2 H 15,6-CI2 5-cl -NO2 -c1 vl Compound ■! (n-27) CH3 CH3 (n-28) CH3 (CH2)3S03 2H5 I2+ ■ Compound (m-1) -CH3 [Phase] (m-2) -C2H5 CH3 (m-3) -CH3 (m-4 ) (CH2)asO3 CH3 (Iff-5) -CH3 CH3 (III-6) CH3 (m-7) -CH3 ◎ Example compound represented by general formula (EV) Compound Z2 t (■-1) N N -CH5HOI f(
■-2) N N-CH55CHs OI
1(rV”3) N N-CH5SCH31I
1 (IV-6) N.

CH3 (1'/-11) N-012C02H (IV-12) Mm Acidic nucleus v-7) 5CHs 2 + 2H5 (CH2)sSO3- Mm E Z2 4M Acidic nucleus 2H5 2H5 C5H9 2H5 2H5 Acidic nucleus 2H5 2H5 (C) (2) 20CH3 E Y M m Acidic nucleus csH7 -i Side compound of the compound represented by formula (VI) CH8)N -C2H5 - (C) I2) Evil (Gloss 2)? Br''! (■-3) r- Examples of compounds represented by the general formula (■) (■-1) (■-2) CH2CH=CH2 2H5 ■1 Compound (VI-4)N N-CH33CH3 C2) (5 2H5 -(Vlr-5)N N-(O(2)4503--+◎-(CH2) 4-(
VI-6)N CHs -(CH2) 5- ■- Example of compound represented by general formula (■) (■-3) (W-1) (IX-2) (,;I'13 (IX- 3) S CH3 The methine dye of the present invention can be synthesized by the method described in Japanese Patent Application No. 62-24375 and Japanese Patent Application No. 62-44868.

Examples of organic sterilizing agents are shown below.

(X-1) (X-2) (X-7) n-CI2H25 (X-8) (X-9) (Knee 3) (X-5) (X-6) (X-10) N)( SO2CH3 (X-11) (X-12) 03H (X-13) (X-14) (X-15) 03H (X-21) (X-22) (X-16”) (X-17) ( X-18) O2 (X-23) (X-24) O2 (X-25) (X-26) 0H (X-27) H3 (X-28) Hs (X-32) (X-33) ( X-34) (X-29) (X-30) (X-31) (X-35) (X-36) (X-37) (X-38) NO2 (X-39) (X-40) (X-45) (X-46) (X-47) (X-48) i Ririshi (X-41) (X-42) (X-43) (X-44) ■ (X-50) (X -51) O2 (X-52) (X-53) (X-54) (X-55) (X-59) (X-60) (X-61) (X-56) (X-57) ( X-58) (X-”63) 03Na O2 (XI-5) CX I-7) -a Synthesis example of the compound represented by formula (X) is disclosed in JP-A-49
-84639.

Next, general formulas (XI) and (Xll) are shown.

<Xl-1) (Xl-3) (If-6) (XI-8) H3 (If-2) <Xl-4) H3 (XIr-ri(XI[-2) (In-3) (XI -4) (XI-5) (In-6) (Xll-7) (III-8) The methine dye of the present invention (preferably represented by general formula (+), more preferably general formula (II), ( 1 [[), (I
V), (V), (represented by 1, (■), (■), (IX)) as photographic desensitizing dyes or j! 2 When used as a sensitizer, when added to a silver halide photosensitive material layer, 5X10-' to IX1.0 per mole of silver halide.
-" mol, preferably 5 x 104 to 5 x 10-3 mol. The optimum amount depends on the chemical structure of the methine dye used, the crystal habit of the silver halide photosensitive material, and the grain size. , may be added during any process of preparing silver halide photosensitive materials such as grain formation, physical ripening, chemical ripening, etc., may be added to the coating solution before coating, or may be added in combination with the above-mentioned addition method. good.

The methine dye used in the present invention can be directly dispersed into a photosensitive material or a hydrophilic colloid solution. They can also be used in suitable solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve,
Dissolved in a halogenated alcohol, acetone, water, pyridine, etc., or a mixed solvent thereof, as described in JP-A-48-9715 and U.S. Pat. No. 3,756,830, and attached to a photosensitive material in the form of a solution. You can also do that.

Other addition methods include Japanese Patent Publication No. 46-24185, U.S. Patent No. 3,822,135, U.S. Patent No. 3,660゜101,
The methods described in No. 2,912,343, No. 2,996.287, No. 3,429.835, and No. 3658.546 can be used. Also, German patent issued @2.1
04.283, U.S. Pat. No. 3.649,2
The method described in No. 86 can also be used.

The organic desensitizer of the present invention (preferably general formula (X) and (
XI) (Compound represented by XI) is a halogenated tJ
It is preferably contained in an amount of 1XIO-' mole to 5X10-' mole per mole of W, and particularly preferably in a range of 1XIO-' mole to 2X10-' mole.

When the compound represented by the general formula (X) and (XI) (XI) is incorporated into a photographic light-sensitive material, it may be contained in an aqueous solution if it is water-soluble, or an alcohol (e.g. methanol, ethanol) if it is water-insoluble. Silver halide emulsion solutions as solutions of water-miscible organic solvents such as esters (e.g. ethyl acetate) and ketones (e.g. acetone);
Alternatively, it may be added to a hydrophilic colloid solution.

When added to a silver halide emulsion solution, it can be added at any time from the start of chemical ripening to coating, but it is preferable to add it after chemical ripening, especially in the coating prepared for coating. It is preferable to add it to the liquid.

The silver halide emulsion used in the present invention can be prepared by an acid method, a neutral method,
Alternatively, it may be produced by a method such as the ammonia method, and silver halides include silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver iodochlorobromide, etc. When handling is important, silver chlorobromide with a high C2 content is preferred, and when high sensitivity is important, silver bromide or silver iodobromide is preferred.

The silver halide grains used in the present invention preferably have an average grain diameter of 0.01 to 2 microns, preferably 0.02 to 1 micron.

Further, the particle size frequency distribution may be wide or narrow, but a narrower one is preferable. In particular, so-called monodisperse emulsions are preferred, in which 90%, preferably 95% of the total number of grains fall within a grain size range of ±40%, preferably ±20% of the average grain size. Further, the silver halide grains may have a single crystal habit or a mixture of various crystal habits, but a single crystal habit is preferable.

The direct positive silver halide used in the present invention is an inorganic desensitizer (i.e., noble metal atoms contained in silver halide grains, etc.)
It can also contain a freezing agent or a sterilizing dye, which is adsorbed on the silver halide surface, singly or in combination.

In order to incorporate the inorganic desensitizer used in the present invention into silver halide grains, water-soluble noble metal compounds such as chlorides of Group 8 metals of the periodic table such as iridium and rhodium must be halogenated! I! It may be added in an amount of 10<-7> to 10<4 >mol per mole, preferably 10<->S to 10<-> mole, as an aqueous solution when preparing silver halide grains.

Examples of organic desensitizers or desensitizing dyes that can be used in the present invention include dimethine cyanine dyes containing a 2-(nitrosubstituted phenyl)-indole nucleus, bis-(1-
Alkyl-2-phenyl)indole-3-trimethine cyanine dyes, cyanine dyes containing an aromatic substituted indole nucleus, imidazoquinoxaline dyes, asymmetric cyanine dyes containing a carbazole nucleus, trimethine cyanine dyes containing a 2-aromatic substituted indole nucleus, 2-3-3-) Cyanine dyes containing a realkyl-3H-nitroindole nucleus, cyanine dyes containing a complex fused pyrimidinedione nucleus, 2-isoxazoline 5-one nucleus, 2-pyrazoline-
Quaternized merocyanine dyes containing a 5-one nucleus or a complex fused pyrimidinedione nucleus, 2-allylimino (or alkylimino)-4-allyl (or alkyl)
-Cyanine dye containing a 3-thiazoline nucleus, 3-allyl-
Amino or 3-lower fatty acid amide substituted 2-pyrazoline-
Merocyanili quaternary ammonium salt dyes with 5-one, biryllium, thiavirylium, selenapyrylium salt dyes, cyanine dyes with nitro-substituted 2-7 arylindole nuclei, bipyridinium salt dyes, pyrrole bonded at the 2-position carbon atom Cyanine dyes containing nuclei, 1.2-
Diaryltrimethine indole dye, cyanine dye containing a 4-pyrazole nucleus, polymethine dye containing an imidazole nucleus, dimethine cyanine dye containing a 2-phenyl substituted indole nucleus, trimethine cyanine dye consisting of two indole nuclei, 1-cyanoalkyl- Cyanine dyes containing a 2-arylindole nucleus, cyanine and merocyanine dyes in which two nuclei have desensitizing substituents such as nitro groups, cyanine dyes containing a 1-alkyl-2-phenyl substituted indole nucleus, 1-alkoxy- Cyanine dyes containing a 2-arylindole nucleus, cyanine dyes having an imidazo(4,5,6]quinoxaline nucleus, dyes containing a cyclohenatanetriene ring, indole-conjugated dimethine cyanine dyes, pyrazolo(1,5-a) Cyanine dyes containing a pyrzoimitazole nucleus, cyanine dyes containing a pyrazolo(5,1-b) quinazolone nucleus, dimethine cyanine dyes containing a pyrrolo(2,3-b) pyridine nucleus, and cyanine dyes containing a roll nucleus, Dyes containing a pyrrolo(2,1-b)thiazole nucleus, cyanine dyes containing an indole or indolenine nucleus containing a benzoyl or phenylsulfonyl substituent Nitrostyryl-type compounds described in US Pat. No. 2,669,515, Pinacryptol Yellow, 5 -metanitrobenzylidene rhodanine, bis-pyridinium compounds described in Japanese Patent Publication No. 48-13059, phenazine compounds described in Japanese Patent Publication No. 47-8746, and the like are useful.

Fog can be applied to the direct positive type silver halide used in the present invention by a conventionally known technique after the silver halide is precipitated and water-soluble salts generated are removed. Fog can be applied by using a fogging agent (reducing agent) alone.
The fogging agent may be used in combination with a gold compound or a useful metal compound that is more electrically positive than silver.

Representative fogging agents useful in making such emulsions include, for example, formalin, hydrazine, polyamines (e.g., triethylenetetramine, tetraethylenepentamine, etc.), thiourea dioxide, tetra(hydroxymethyl)phosphonium chloride, acineborane hydrogen. These include boron compounds, stannous chloride, tin (■) chloride, etc. Typical useful metal compounds that are more electrically positive than silver include gold, rhodium, platinum, palladium, iridium, etc. Examples include soluble salts of potassium chloroaurate, chloroauric acid, ammonium palladium chloride, sodium iridium chloride, and the like.

Fogging agents are generally used at 1.0% per mole of silver halide. o
Xlo-6 to 1.0XIO-'-1:/l/(used in the 7+ range).

Typical gold compounds include chloroauric acid, sodium chloroaurate, sulfur compounds, selenium compounds, etc., and -a contains 1.0XIO-' to 1.0X10-' per mole of silver halide.
It is preferable to contain it in a molar range.

The degree of fogging of the pre-coupled direct positive silver halide emulsions used in this invention can vary over a wide range. The degree of fogging depends on the silver halide composition, grain size, etc. of the silver halide emulsion used, the type and concentration of the gasplase agent used, and the time at which fogging is applied, as well known to those skilled in the art. It is related to the emulsion's PH, PAg, temperature and time, etc.

The direct positive silver halide photographic material of the present invention contains a selenium compound as described in JP-A No. 46-4282, and a sensitizing dye such as a dimethine trimethine cyanine dye or a halogen-substituted hydroxyphthalein dye. , phenazine dyes, benzothiazole, cyanine dyes containing a benzoselenazole nucleus, cyanine dyes containing a naphthoxazole nucleus, triphenylmethane dyes, cyanine dyes containing an indolenine nucleus, cyanine dyes containing a 2-pyridine-rhodanine nucleus, Cyanine dye containing thiazole nucleus,
High sensitivity can be provided by containing a substance such as at least one sensitizing dye selected from asymmetric cyanine, quinoline, meso-substituted cyanine dye, cyanine dye containing a rhodanine nucleus, and polymethine dye having three nuclei. be.

The direct positive silver halide photographic light-sensitive material of the present invention may contain various other commonly used photographic additives. As stabilizers, for example, triazoles, azaindenes, quaternary benzothyls? , a thorium compound, a mercapto compound, or a water-soluble inorganic salt such as cadmium, cobalt, zinc, manganese, gold, lithium, or zinc. In addition, hardening agents such as formalin, glyoxal, aldehydes such as mucochloric acid, S-tria-Sifuni/s, evoquins, aziridines, vinylsulfonic acid, etc., and coating aids such as saponin, sodium polyalkylene sulfonate, etc. The gel may contain lauryl or oleyl monoether of polyethylene glycol, aluminized alkyl taurine, fluorine-containing compounds, and the like. Furthermore, it is also possible to contain a car'no coupler. In addition, a whitening agent, an ultraviolet absorber, a preservative, a man-1 agent, an antistatic agent, etc. can also be contained as necessary.

Further, the direct positive silver oxide photographic light-sensitive material of the present invention contains a so-called filter dye, which absorbs and cuts visible light so that it can be handled under a fluorescent lamp that cuts off ultraviolet light using an ultraviolet light source. be able to.

The dye used in the present invention has a main absorption in the visible wavelength range of the wavelength range of inherent sensitivity of the silver halide emulsion used. There are no particular restrictions on the chemical structure of the dye, and oxonol dyes, hekioxonol dyes, melonanine dyes, shea, dino dyes, azo dyes, etc. can be used, but water-soluble dyes are recommended to eliminate residual color after processing. Color dyes are useful.

Specifically, for example, pyrazolone dyes described in Japanese Patent Publication No. 58-12576, pyrazolone oxonol dyes described in U.S. Pat. No. 2,274°782, and U.S. Pat.
, 879, U.S. Patent No. 3, U.S. Pat.
．． No. 423,207, U.S. Patent No. 3,384,487;
27.583, merocyanine dyes and ochipafnol dyes described in U.S. Pat. No. 3.486.897, U.S. Pat. 976.661 and British Patent No. 5
No. 84.609, No. 1,177゜429 - Japanese Unexamined Patent Publication No. 1977
-85130, 4999620, 49-114
No. 420, U.S. Pat. No. 2.533,472, U.S. Patent No. 3.1
No. 48,187, No. 3,177.078, No. 3,
No. 247.127, No. 3.540,887, No. 3
．． The dyes described in No. 575,704 and No. 3,653,905 are used.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic agents, shearability improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., enhancement of phenomena, high contrast, etc.). Various surfactants may be included for various purposes such as oxidation, sensitization, etc.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene dalicol condensates, polyethylene glycol alkyl enals or polyethylene glycol alkylaryl enals, polyethylene glycol esters, polyethylene glycol sorbitan esters) , polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Nonionic surfactants; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulcophochloride Contains acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate groups, phosphoric acid ester groups, etc., such as acid esters, sulfoalkyl polyoxyethylene alkylphenyl enals, polyoxyethylene alkyl phosphate esters Anionic surfactants; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts Cationic surfactants such as heterocyclic quaternary ammonium salts such as , pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more and described in Japanese Patent Publication No. 5B-9412.

The polyalkylene oxide compound used in the present invention is a polyalkylene oxide compound consisting of at least 10 units of an alkylene oxide having 2 to 4 carbon atoms, such as ethylene oxide, propylene-1,2-oxide, butylene-1,2-oxide, preferably ethylene oxide. Includes condensates of alkylene oxide and compounds having at least one active hydrogen atom, such as water, aliphatic alcohols, aromatic alcohols, fatty acids, organic amines, and hexitol derivatives, or block polymers of two or more types of polyalkylene oxides. do. Specifically, the polyalkylene oxide compounds include: polyalkylene glycols polyalkylene glycol alkyl ethers realkylene glycol aryl ethers polyalkylene glycol (alkylaryl) ethers polyalkylene glycol esters polyalkylene glycol fatty acid amide Polyalkylene glycol amines, polyalkylene glycol block copolymers, polyalkylene glycol graft polymers, and the like can be used. The molecular weight must be 600 or more.

The number of polyalkylene oxides in the molecule is not limited to one, but may be two or more. In that case, each polyalkylene oxide may consist of less than 10 alkylene oxide units, but the number of alkylene oxide units in the molecule The sum of oxide units must be at least 100
When having two or more polyalkylene oxides in the molecule, each of them may consist of different alkylene oxide units, such as ethylene oxide and propylene oxide. The polyalkylene oxide compound used in the present invention is preferably It contains 14 or more and up to 100 alkylene oxide units.

Specific examples of the polyalkylene oxide compounds used in the present invention are as follows.

Polyalkylene oxide compound example m-t 1m-2 1m-3 1m-4 1■-5 XI[r-6 HO(CH2CH20)90H C4HQO(CH2CH20)+5H CI2H250(CH2CH20)+5HCI8837
0 (CH2CH20)+5HCI8H370(CH2
CH20)40)(CaHI7CH=CHCeH+rs
O(CH2CH20)+5HXm-40Cl1H23C
OO(CH2CH20) soHXm-IT Cl1
H23COO(CH2CH20) 240CC1lH2
3Xm-! 3 Cl1H23COOH(CH2CH2
0) +5Hxm-Is C14HC14H29N(
CH3)(CH2CH20)24HX
CH2-0-CH-CH20CII823H (OCH
2CH2) tao-CH-CH-CH-(CH2CH
20) +4HO(CH2CH20)14H Xm-17H(CH2CH20) a (CH2H20
) b (CH2CH20) cHHs a+b+c=50 b:a+c=10:9 Xm-20HO(CH2CH20)a(CH2CH2C
H2CH20)b(CH2CH20)cHa+c=30
, b=14 b=8 , a+c=50 1 m-22 m-22
Polyalkylene oxide compounds described in JP-A-53-3217 and JP-A-53-3217 can be used. These polyalkylene oxide compounds may be used alone or in combination of two or more.

When the polyalkylene oxide compound of cholera is added to a silver halide emulsion, it is dissolved in an aqueous solution of an appropriate concentration or in a low boiling point organic solvent that is miscible with water.
It can be added to the emulsion at any suitable time before coating, preferably after chemical ripening. Instead of being added to the emulsion, it may be added to a photosensitive hydrophilic colloid layer, such as an intermediate layer, a protective layer, a filter layer, etc.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide, polymethyl methacrylate, etc. in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, (meth) ) acrylamide, vinyl esters (e.g. vinyl acetate),
Acrylonitrile and the like can be used alone or in combination.

The emulsion used in the present invention mainly uses gelatin as a protective colloid, and it is particularly advantageous to use inert gelatin. Instead of gelatin, photographically inert gelatin derivatives (eg, phthalated gelatin), water-soluble synthetic polymers (eg, polyvinyl acrylate, polyvinyl alcohol, polyvinylpyrrolidone) are used. The novel emulsions of this invention may be employed on any suitable photographic support such as glass, film bases such as cellulose acetate, cellulose acetate butyrate, polyesters such as poly(ethylene terephthalate).

The developer used in the present invention may be a so-called Lith type developer with a low sulfite ion concentration, or a developer containing a sufficient amount of sulfite ions as a preservative (particularly 0.15 mol/1 or more). can be used, and also has a pH of 9,
A developer having an IQ of 5 or more, especially 5 to 12.3 can also be used.

There are no particular limitations on the developing agents that can be used in the method of the present invention, such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone, 44-dimethyl-1-phenyl-
3-pyrazolidone), aminophenol! ! (For example, N
-methyl p-aminophenol) can be used alone or in combination.

The developer also contains alkali metal sulfites, carbonates,
Contains pH buffering agents such as borates and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic anticaprilants (particularly preferably nitroindazoles or benzotriazoles). I can do it.

If necessary, water softeners, solubilizing agents, color toning agents, development accelerators, surfactants (especially preferably the above-mentioned polyalxine oxides), antifoaming agents, hardeners, and film silver stain preventive agents may be added. (for example, 2-mercaptobenzimidazole sulfonic acids).

Specific examples of these additives are listed in Research Disclosure 1.
It is described in No. 76, No. 17643, etc.

The treatment temperature is usually selected between 18°C and 50°C, but 1
The temperature may be lower than 8°C or higher than 50°C.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, functional sulfur compounds known to be curing as fixing agents can be used. The fixing solution may also contain a water-soluble aluminum salt or the like as a hardening agent.

The direct positive silver halide photographic light-sensitive material of the present invention can be applied to various uses, such as dubbing,
Various photosensitive materials for printing such as reproductions and offset masters, special photographic photosensitive materials such as X-ray, flash photography, and electron beam photography, or for general copying, microcopying, direct positive color use, and quick stabilized materials. It is used in various types of direct positive photographic light-sensitive materials, such as those for use in photocoating, diffusion transfer, color diffusion transfer, and general development and fixing.

[Effect]

In general, direct positive silver halide emulsions are those in which the surfaces of silver halide grains are pre-fogged with a fogging agent, and the fogging nuclei are bleached with holes generated during exposure. In this direct positive silver halide emulsion, the spectral sensitization effect of the methine dye is enhanced by the addition of an organic desensitizer. It was discovered that this method provides superchromatic sensitization, which not only provides high spectral sensitivity, but also eliminates the increase in the minimum density (Dmin) of the exposed area, and also reduces the sensitivity and minimum density during preservation of raw samples. (D
It is possible to reduce the change in (min).

The present invention will be explained in more detail with reference to Examples below, but the embodiments of the present invention are not limited thereto.

[Example 1] In an aqueous gelatin solution kept at 50°C, 1 mol of silver was added.
In the presence of Xl0-' moles of rhodium chloride, an aqueous solution of silver sulfate and a mixed aqueous solution of sodium chloride and potassium bromide were simultaneously added at a constant rate for 30 minutes to form a monodisperse silver chlorobromide with an average particle size of 0.2μ. The emulsion was prepared. <ci composition 90 mol%) This emulsion was desalted by the flocculation method, and 2 mg of thiourea dioxide and 0.9 mg of potassium chloroaurate were added per 1 mole of IL.
Ripening was allowed to occur at 65°C until maximum performance was achieved.

After dividing these emulsions and adding the methine dye of the present invention and an organic desensitizer as shown in Table 1 below, 111 moles of
X10-' moles of polyalkylene oxide compound X'
1ll-7,10% KBr aqueous solution and 2-hydroxy-4,6-dichloro-1,3,5- as a hardening agent.
An emulsion is prepared by adding triazine sodium salt and 1,3-divinylsulfonyl-2-propanol, gelatin containing a dispersion of silica and ethyl acrylate as a matting agent, and sodium dodecylbenzenesulfonate as a surfactant. Simultaneously with the protective layer, coating was carried out on a polyethylene terephthalate film at an SR amount of 3.0 g/m8. The obtained sample was exposed to light using a tungsten light source through a light pattern, and then developed with a developer having the following composition.
The results of developing at 38° C. for 20 seconds, stopping, fixing, washing with water, and drying are shown in Table 1 as Photographic Properties 1.

Photographic properties 2 were evaluated in the same way as photographic properties 1 after each film was left at 50° C. and 75% relative humidity for 3 days.

Here, the relative sensitivity is a density of 1.0 when developed at 38°C for 20 seconds.
It is the relative value of the reciprocal of the exposure amount that gives 5, and sample 1
The relative sensitivity of sample 2.3.4 was determined by setting the value of photographic property 1 to 100. Similarly, Sample Demon 5.9.13.17
．． 2L25.2933.37.41.45.49.53
The relative sensitivity was determined by setting the value of photographic property 1 to 100.

In the development, a developer having the following formulation was used.

Developer formulation Hydroquinone 35.0g N-methyl-2-aminophenol 1/2 sulfate 0.8g Sodium hydroxide 9.0g Potassium triphosphate
74.0g potassium sulfite 9
0.0g Disodium ethylenediaminetetraacetate 1.0g 3.Diethyl-amino-1-propatol 15.0g5.Methylbenzotriazole 0.5g Sodium bromide
Add 3.0g water and lfi PH=11
．． Adjust to 60.

2H5 [Example 2] A gelatin aqueous solution containing 0.8 g of sodium bromide was maintained at 70°C, and the concentration was 5 x 101 mol/Ag per 1 mol of silver.
In the presence of mol of rhodium salt and 5 x 10-' mol/mol of Ag of iridium salt, the average particle size was reduced by adding aqueous silver nitrate and potassium bromide simultaneously at a constant rate over 85 min, while maintaining the potential at +60 mV. Size 0.2
A 5μ silver bromide cubic monodisperse emulsion was prepared. This emulsion was desalted by the furochelecitane method, 10 mg of thiourea dioxide and 8 mg of potassium chloroaurate per mole of silver were added, and the emulsion was aged at 65°C until the highest performance was obtained. Closed.

These emulsions were divided into 6X per mole of silver to which the methine dye of the present invention and an organic desensitizer were added as shown in Table 2 below.
10-' mol of the compound (14) described in JP-A-49-29828 was added, and 8XIO-' mol of polyalkylene oxide compound Xm-7 and 1
pAg with 0% KBr! 1.3 as a knot hardening agent
- After adding divinylsulfonyl-2-propatur,
Amount of silver of 3 ml on the polyethylene terephthalate film at the same time as a protective layer containing silica matte and gelatin with sodium dodecylbenzenesulfonate added as a surfactant.
．． 2 g/m'' (coating was performed).

A banking layer and a back protective layer were coated on the opposite side of the emulsion layer and protective layer with the support in between.

The backing layer contains 4-[5-oxo-3-
Methyl-4(4-N,N-dimethylaminophenyl)methylene-2-pyrazolinyl]benzenesulfonic acid potassium salt and 4-[3-carboxy-5-hydroxy-4-(
5-(3-carboxy-5-oxo-1-(4-sulfophenyl)2-pyrazoline-4-ylidene l-1,3-
It contains potassium salt of (pendagenyl)-1-pyrazolyl]benzenesulfonate, contains a polymer of ethyl acrylate to improve film quality, and is coated with a surfactant, a charge control agent, and a hardening agent together with gelatin.

In the back protective layer, a polymer of polymethyl methacrylate was added in gelatin as a surfactant and a matting agent and was coated on top of the back layer (on the opposite side of the support).

After exposing the obtained sample to light using a tungsten light source through a light wedge, the same evaluation as in Example 1 was performed. The results are shown in Table 2. As in Example 1, sample N11
57.61.65.69.73.77.81.85.8
9.93.97.101.105 photographic property 1 value is 1
00, relative sensitivity was determined.

(Hereinafter in the margin) Preferred implementation of the present invention l! 1) A photosensitive material according to the claims, characterized in that: 1) rhodium and/or iridium is contained in the emulsion grains;

2) The light-sensitive material according to 1) above, characterized in that the emulsion grains contain rhodium in an amount of 101 to 10-3 mol/mol AgX.

3) A photosensitive material according to the claims, characterized in that it contains a polyalkylene oxide compound in the emulsion layer or an adjacent layer.

4) The photosensitive material described in 3) above, wherein the polyalkylene oxide has a molecular weight of 600 or more.

5) A photosensitive material according to the claims, characterized in that it contains a benzylidene dye in the emulsion layer or an adjacent layer.

〔Effect of the invention〕

The present invention provides a direct positive silver halide emulsion comprising a nucleus in which at least one of the ten carbon atoms of the azulene nucleus is replaced with a chalcogen atom or a nitrogen atom, and the seven-membered ring portion of the nucleus is At least one methine dye substituted with a methine bond having an auxochrome at the end that forms a conjugated resonance group with the 10π electron system, and a reduction potential of -1,0.
(Vv.

By containing at least one organic desensitizer having a value of VS) or more positive, the spectral sensitization effect of the methine dye is supersensitized, which not only provides high spectral sensitivity but also reduces exposure to light. There is no increase in the minimum concentration (Dmin) of
Dmin) can be reduced.

Applicant: Fuji Photo Film Co., Ltd. Agent
Patent attorney: 1) Quantity (other 4 people) Principal proceeding author (spontaneous) Yoshi, Commissioner of the Japan Patent Office 1) Indication of the case of Takeshi Moon 1985 Patent Application No. 185250 2, Title of invention Direct positive halogenation Silver Emulsion 3, Relationship with the Amended Person Case Patent Applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name
Minoru Ohnishi, Representative of Fuji Photo Film Co., Ltd. 4. The description of the "Detailed Description of the Invention" in the agent's specification is amended as follows.

(1) Page 40, general formula (X) " (T) of " section of Target of correction Detailed description of the invention (T)r.

and correct it.

(2) "113.4-thiadiazole J" on page 42, line 9 is corrected to "1.3.4 thiadiazole."

(3) Correct "Penta Asainden" on page 42, line 1 O to "Penta Asainden J."

(4) "Triazainden" on page 42, line 10 is corrected to "triazainden".

(5) On page 42, line 14, change “Imitazo [4,5-1] J to “Imidazo [4,5-1]
b) Correct with J.

(6) "1.3-Diazaazulene" on page 42, line 15 is corrected to "1.3-Diazaazulene".

(7) Page 83 (XI-5) " C)-f.

and correct it.

(8) Page 84 (X　n　-6) of " of (Margin below) and correct it.

(9) Correct "r2-3-3-tri" on the 9th line of page 89 to "2.3.3-tri".

(10) Page 89, line 11, and lines 13 to 1 of the same page
Delete "complex fusion" in the 4th line.

(11) Correct "4th grade merocyanine ball J" in lines 19 to 20 of page 89 to be "merocyanine grade 4."

(12) "Bipyridinium" in the third line of page 90 is corrected to "bispyridinium."

(I3) Page 90, line 8 Ru.

(14) Page 90, line 12 ``Correct substituent J to ``substituent.''

(15) Page 90, line 16 rE4.5.6) Correct J to '(4,5-b)J.

(I6) Change “cycloheptatriene” on page 90, line 17 to “cycloheptatriene J
and correct it.

(I7) Page 93, line 1 Correct ``equal work'' to r ordinary skill j.

(18) Page 93, line 10 ``Correct chintorino to ``chin or tori.''

(19) Correct “containing cyanine dye” on page 93, line 16 to “containing merocyanine dye J.”

(20) Correct "Containing cyanine dye J" on page 93, lines 18 to 19 as "Containing merocyanine dye J."

(21) Page 94, line 6 Correct "asaindens" to "asaindens".

(22) “Quaternary benzothiazolium” on page 94, lines 6 to 7 is corrected to “quaternary benzothiazolium j.”

(23) Page 95, line 10 Correct "Heki" to "Hemi".

(24) Page 95, line 19 Correct "styrin" to "styrill".

(25) Page 96, line 5 Correct "Enamiki" to "Enamin".

(26) Page 97, line 5 Correct "ether" to "ether".

(27) "IN-acyl" on page 97, line 17 is corrected to "RU, N-acyl."

(28) Page 97, line 18 Correct ``succinic acid'' to ``succinic acid J.''

(29) Page 97, line 18 Correct "Suruhor" to "Sulho".

(30) Page 97, line 19 Correct "ether" to "ether".

(31) Page 98, line 1 Correct "carboxy" to "carboxy".

(32) "Phospho group sulfate ensulfate group" on page 98, lines 1 to 2 is corrected to "rphosphosulfate group".

(33) Page 103, line 5 Correct “using” to “using”.

(34) Page 104, line 17 Correct "polyester" to "polyester".

(35) Page 106, line 11 Correct "hard" to "effective".

(36) r2933 on page 109, lines 17 to 18
Correct J to "29.33".

(37) Page 110, line 1 O Correct "3-diethyl" to "3-diethyl".

(38) Page 110, line 12 Correct "5-methyl" to "5-methyl".

(39) Page 115, line 15 r4-ylidene" is corrected to "4-ylidene J.

(40) Page 115, line 16 Correct "Dadienyl" to "Dadienyl J."

(4I) Insert "or oxonol dye J" after "dye" on page 120, line 13.

Claims (1)

[Claims] It consists of a nucleus in which at least one of the 10 carbon atoms of the azulene nucleus is replaced with a chalcogen atom or a nitrogen atom, and the 7-membered ring part of the nucleus helps form a conjugated resonance chromophore with the 10π electron system of the nucleus. Contains at least one methine dye substituted with a methine bond with a chromophore at the end, and at least one organic desensitizer having a reduction potential of −1, 0 (V_v_sSCE) or more positive. A prefogged direct positive silver halide emulsion characterized by: