JPH0789207B2 - Direct positive silver halide emulsion - Google Patents

Description

TECHNICAL FIELD The present invention relates to a pre-fogged direct positive type silver halide emulsion containing a methine dye and an organic desensitizer, and more specifically, it has been improved. It relates to a pre-fogged direct positive silver halide emulsion exhibiting photographic properties.

[Conventional technology]

The spectral sensitization technique of a directly fogged direct positive type silver halide emulsion is an important technique for producing a highly sensitive photographic light-sensitive material. Dyes used for spectral sensitization of pre-fogged direct positive type silver halide emulsions are generally called desensitizing dyes, and many compounds have been known so far, for example, edited by TH James. , The Theory of the Photographic Process (3rd Edition), 1966, Macmillan, NY, 1st
Cyanine dyes, merocyanine dyes, etc. described on pages 98 to 228, but with a reduction potential of -1.2
Those having (V _vs SCE) or a more positive value are preferred.

It is known that these desensitizing dyes are used alone or in combination (for example, an organic desensitizer).

[Problems to be Solved by the Invention]

The conditions that must be satisfied as a desensitizing dye used for such photographic materials are that not only high spectral sensitivity can be obtained, but also the minimum density (Dmin) of inversion (exposed portion) does not increase, For example, there is little change in sensitivity and minimum density (Dmin) during storage.

However, even with the conventional desensitizing dyes and organic desensitizers, satisfactory performance was not obtained. The present inventors have found that a methine dye also satisfies the above conditions as a desensitizing dye or an organic desensitizer, and previously filed an application (Japanese Patent Application No. 62-44868). It is about improvement.

Therefore, an object of the present invention is to provide a pre-fogged direct positive type silver halide emulsion having higher sensitivity and no increase in the minimum density (Dmin), and a small change in the sensitivity and the minimum density (Dmin) due to raw storage. Is to provide.

[Means for solving problems]

The above objects of the present invention include a nucleus (heteroazulene nucleus) in which at least one of the 10 carbon atoms of the azulene nucleus is replaced by a chalcogen atom (for example, oxygen atom, sulfur atom, selenium atom, tellurium atom) or a nitrogen atom. ), Wherein the 7-membered ring portion of the nucleus is substituted with at least one methine dye having a methine bond terminated with an auxochrome forming a conjugated resonance chromophore with the 10π electron system of the nucleus. ,
And a prefogged direct positive silver halide emulsion characterized by containing at least one organic desensitizer having a reduction potential of -1.0 (V _vs SCE) or more positive.

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

The present invention will be described in more detail below.

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

The dye of the present invention can be represented by alternating resonance forms as in the following general formula (I).

General formula (I) In the formula, E represents an auxochrome, L represents a methine bond, V ₁ , V ₂ , V ₃ , V ₄ and V ₅ are a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an acyloxy group, Alkoxycarbonyl group, carbamoyl group, sulfamoyl group, carboxy group, cyano group, hydroxy group, amino group, acylamino group, alkoxy group, alkylthio group,
Two, which represent an alkylsulfonyl group, a sulfonic acid group, or an aryl group, or which are bonded to adjacent carbon atoms in V _{1 to} V ₅ may form a condensed ring with each other. Further, these may further have a substituent.

Y and Z ₂ are carbon atoms However, V is synonymous with V ₁ , V ₂ , V ₃ , V ₄ and V ₅ ),
Chalcogen atom (eg oxygen atom, sulfur atom, selenium atom, tellurium atom, etc.) or nitrogen atom R ₃ may or may not be necessary to form a nucleus, but when necessary, R ₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a heterocycle. Represents a group). However, Y and Z are not both carbon atoms. Also, Y and Z
When is represented by a chalcogen atom or a nitrogen atom, at least one is a nitrogen atom. 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 of 0 or greater required to balance the charge.

In the formula (I), the bonding position of the methine bond L is represented as the 6th position as a representative, but the other positions (4th position, 5th position, 7th position, 8th position) are also similarly expressed. However, preferably 4th, 6th and 8th
Positions, more preferably 4th and 6th positions.

The auxiliary chromophore E will be described in detail.

E can take any of the common forms found in methine dyes. Typically, the auxochrome is composed of nitrogen or chalcogen atoms and resonates in the dye between charged and uncharged states. For example, it can be in the form of any of the auxochromes found in cyanine, merocyanine, oxonol, pyrylium or thiapyrylium dyes. However,
It is not necessary to limit the auxochrome to this category. Less commonly, auxochromes composed of other atoms are conceivable, for example phosphorus or boron. For example, 2-
Triphenylphosphoro-1,3-cyclopentagen-5
-Ill.

Preferred dyes represented by the general formula (I) are those represented by the following general formulas (II) to (IX).

General formula (II) _{Wherein, V 1 ~V 5, Y,} Z 2, M, m has the same meaning as in formula (I). Further, the position of the methine bond may be any of the 4-position, 5-position, 6-position, 7-position and 8-position as in the general formula (I).

Q ₁ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing ring. L ₁ , L ₂ , L ₃ , L ₄ , and L ₅ represent an optionally substituted methine group.

R ₄ represents a substituted or unsubstituted alkyl group. l ₁ is 0
Represents an integer of 3. n ₁ represents 0 or 1.

General formula (III) _{Wherein, V 1 ~V 5, Y,} Z 2, M, m has the same meaning as in formula (I). Further, the position of the methine bond may be any of the 4-position, 5-position, 6-position, 7-position and 8-position as in the general formula (I).

Q ₂ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing ring. L ₆ , L ₇ , L ₈ , L ₉ , and L ₁₀ are L ₁ , L ₂ , L ₃ ,
Synonymous with L ₄ and L ₅ .

R ₅ represents a substituted or unsubstituted alkyl group.

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

General formula (IV) _{Wherein, V 1 ~V 5, Y,} Z 2, M, m has the same meaning as in formula (I). Y ', Z _2' have the same meaning Y, and Z _2. Further, as in the general formula (I), the position of the methine bond is the 4-position, 5-position, 6-position,
Either 7th or 8th place is acceptable.

V ₁ ′ to V ₅ ′ are synonymous with V _{1 to} V ₅ .

L ₁₁ , L ₁₂ and L ₁₃ are synonymous with L ₁ , L ₂ , L ₃ , L ₄ and L ₅ . l ₃ represents an integer of 0 to 3.

General formula (V) _{Wherein, V 1 ~V 5, Y,} Z 2, M, m has the same meaning as in formula (I). Further, the position of the methine bond may be any of the 4-position, 5-position, 6-position, 7-position and 8-position as in the general formula (I).

D ₁ and D ₁ ′ represent an atomic group necessary for forming an acidic nucleus and may be acyclic or cyclic.

L ₁₄ , L ₁₅ , L ₁₆ and L ₁₇ are synonymous with L ₁ , L ₂ , L ₃ , L ₄ and L ₅ . l ₄ represents an integer of 0 to 3. n ₃ is 0 or 1
Is.

General formula (VI) _{Wherein, V 1 ~V 5, Y,} Z 2, M, m has the same meaning as in formula (I). Further, the position of the methine bond may be any of the 4-position, 5-position, 6-position, 7-position and 8-position as in the general formula (I).

R ₆ and R ₇ represent substituents known in general tertiary amines. R ₆ and R ₇ may form a ring.

L ₁₈ and L ₁₉ are synonymous with L ₁ , L ₂ , L ₃ , L ₄ , and L ₅ . l ₅ represents an integer of 0 to 3.

General formula (VII) In the formula, E and E ′ are E ₁ or E ₂ . However, at least one of E and E'is E ₁ .

V _{1 to} V ₅ , Y, Z ₂ , M, and m have the same meaning as in formula (I).
In addition, the position of the methine bond is the 4-position as in the general formula (I),
It may be 5th, 6th, 7th or 8th.

W ₁ represents an atomic group necessary for forming a 5- or 6-membered heterocycle.

R ₈ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group.

Q ₃ and R ₉ have the same meanings as Q ₁ and R _{6 in} formula (II), respectively.

L ₂₀ , L ₂₁ , L ₂₂ , L ₂₃ , L ₂₄ , L ₂₅ and L ₂₆ are L ₁ , L ₂ ,
Synonymous with L ₃ , L ₄ , and L ₅ .

l ₆ and l ₇ are integers from 0 to 3.

n ₄ is 0 or 1.

General formula (VIII) _{Wherein, V 1 ~V 5, Y,} Z 2, M, m has the same meaning as in formula (I). Further, the position of the methine bond may be any of the 4-position, 5-position, 6-position, 7-position and 8-position as in the general formula (I).

W ₂ is synonymous with W ₁ . R ₁₀ is synonymous with R ₈ . D ₂ and D
₂ 'D ₁ and D ₁ of the general formula (V)' is synonymous with.

L ₂₇ , L ₂₈ , L ₂₉ , L ₃₀ , L ₃₁ and L ₃₂ are L ₁ , L ₂ , L ₃ , L ₄ ,
And L ₅ are synonymous.

l ₈ and l ₉ is an integer of 0 to 3.

n ₅ represents 0 or 1.

General formula (IXa) General formula (IXb) _{Wherein, V 1 ~V 5, Y,} Z 2, M, m has the same meaning as in formula (I). Further, the position of the methine bond may be any of the 4-position, 5-position, 6-position, 7-position and 8-position as in the general formula (I).

L ₃₃ and L ₃₄ are synonymous with L ₁ , L ₂ , L ₃ , L ₄ , and L ₅ .

Ar represents an aromatic group.

l ₁₀ represents an integer of 0 to 3.

The general formulas (I) to (IX) will be described in detail below.

R ₃ is preferably a hydrogen atom, an unsubstituted alkyl group having 18 or less carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, decyl group, dodecyl group, octadecyl group) or substituted alkyl group {As a substituent, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, an alkoxycarbonyl group having 8 or less carbon atoms (eg, a methoxycarbonyl group, ethoxy). Carbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group), alkoxy group having 8 or less carbon atoms, (for example, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group), monocyclic aryloxy group having 10 or less carbon atoms (For example, a phenoxy group, a p-tolyloxy group), an acyl group having 3 or less carbon atoms. A xy group (for example, an acetyloxy group,
A propionyloxy group), an acyl group having 8 or less carbon atoms (eg acetyl group, propionyl group, benzoyl group, mesyl group), carbamoyl group (eg carbamoyl group, N, N)
-Dimethylcarbamoyl group, morpholinocarbonyl group,
Piperidinocarbonyl group), sulfamoyl group, (eg, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group), aryl group having 10 or less carbon atoms (eg, phenyl group) ,
4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group) substituted alkyl group having 18 or less carbon atoms},
Aryl group (eg, phenyl group, 2-naphthyl group), substituted aryl group (eg, 4-carboxyphenyl group, 4
-Sulfophenyl group, 3-chlorophenyl group, 3-methylphenyl group), heterocyclic group (for example, 2-pyridyl group,
2-thiazolyl group).

Particularly preferably, an unsubstituted alkyl group (for example, a methyl group,
And an sulfoalkyl group (eg, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group). More preferably, it is a methyl group.

Further, the metal atom capable of forming a salt with R ₃ is particularly preferably an alkali metal, and the organic compound capable of forming a salt with R ₃ is preferably pyridines, amines and the like.

V ₁ , V ₂ , V ₃ , V ₄ , V ₅ , V ₁ ′, V ₂ ′, V ₃ ′, V ₄ ′, and V ₅ ′ are a hydrogen atom and a halogen atom (for example, chlorine atom, fluorine atom). , Bromine atom), unsubstituted alkyl groups having 10 or less carbon atoms (eg methyl group, ethyl group), 18 carbon atoms
The following substituted alkyl groups (eg, benzyl group, α-naphthylmethyl group, 2-phenylethyl group, trifluoromethyl group), acyl groups having 10 or less carbon atoms (eg, acetyl group,
Benzoyl group, mesyl group), acyloxy group having 10 or less carbon atoms (for example, acetyloxy group), alkoxycarbonyl group having 10 or less carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group),
Substituted or unsubstituted carbamoyl group (for example, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), substituted or unsubstituted sulfamoyl group (for example, 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 (eg, acetylamino group), 10 carbon atoms The following alkoxy groups (eg methoxy group, ethoxy group, benzyloxy group), alkylthio groups (eg ethylthio group), alkylsulfonyl groups (eg methylsulfonyl group), sulfonic acid groups, aryl groups (eg phenyl group, tolyl group) Is preferred. Two of V _{1 to} V ₅ which are bonded to adjacent carbon atoms may be bonded to each other to form a benzene ring. Further, they may be bonded to each other to form a heterocycle (for example, a pyrrole ring, a thiophene ring, a furan ring, a pyridine ring, an imidazole ring, a triazole ring, a thiazole ring).

_{V 2, V 3, V 4} , V 5, V 2 ', V 3', Preferable V ₄ 'and V _5' is a hydrogen atom. Preferred as V ₁ and V ₁ ′ are a hydrogen atom, a chlorine atom, an alkoxy group (eg methoxy group), an alkylthio group (eg methylthio group) and an aryl group (eg phenyl group).

M _m is included in the formula to indicate the presence or absence of a cation or anion, as required to neutralize the ionic charge of the dye. Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents. Counterions can be easily exchanged after the dye is manufactured.
Typical cations are ammonium ions and alkali metal ions, while the anions can be either inorganic or organic anions, for example halogen anions (eg fluoride, chloride, bromide). , Iodide ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulphonate ion (for example, 1,3-benzene sulfonate ion, 1,5-
Naphthalene disulfonate ion, 2,6-naphthalene disulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, Examples include trifluoromethanesulfonate ion. Iodine ion is preferred.

The nucleus formed by Q ₁ and Q ₃ includes a thiazole nucleus (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole), a benzothiazole nucleus (for example,
Benzothiazole, 4-chlorobenzothiazole, 5-
Chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzo Thiazole,
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-dimethoxybenzothiazole, 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-ethoxynaphtho [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 (Oxazole nucleus (for example, oxazole, 4-methyloxazole, 4-nitroxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (for example, benzo Oxazole, 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 -Methoxybenzoxazole, 6-
Hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5
-Ethoxybenzoxazole), naphthoxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 5-nitronaphtho [2,1-] d] oxazole etc.)}, oxazoline nucleus (for example, naphtho [4,4-dimethyloxazoline), selenazole nucleus {selenazole nucleus (for example, 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), benzo Selenazole nucleus (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-
Methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole, etc., naphthoselenazole nucleus (for example, naphtho [ 1,2-d] selenazole)}, selenazoline nucleus (for example, selenazoline, 4-methylselenazoline), tellurazole nucleus {terrazole nucleus (for example, tellurazole, 4-methylterrazole, 4-phenylterrazole), benzoterrazole Nucleus (for example, benzoterrazole, 5-chlorobenzoterrazole, 5-methylbenzotelrazole, 5,6-dimethylbenzoterrazole, 6-methoxybenzoterrazole), naphthoterrazole nucleus (for example, naphtho [2, 1-d] terrazole, naphtho [1,2-d] terrazo Le etc.)}, Terurazorin nucleus (e.g., Terurazorin, 4-methyl shine ethylbenzthiazoline), 3,3-dialkylindolenine nucleus (e.g., 3,3
-Dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-6-nitroindolenine, 3,3-dimethyl-5
-Nitroindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3,5-trimethylindolenine, 3,3,5
-Dimethyl-5-chloroindolenine), imidazole nucleus (imidazole nucleus (e.g. 1-alkylimidazole, 1-alkyl-4-phenylimidazole), benzimidazole nucleus (e.g. 1-alkylbenzimidazole, 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, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-arylimidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1-aryl-5-cyano Benzimidazole), naphthoimidazole nuclei (for example, 2-alkylnaphtho [1,2-d] imidazole, 1-arylnaphtho [1,2-d] imidazole), said alkyl group having 1 to 8 carbon atoms. , For example, methyl, ethyl, propyl, isopropyl, butyl, etc. Conversion alkyl group or hydroxyalkyl group (e.g., 2-hydroxyethyl,
3-hydroxypropyl) is preferred. Particularly preferred are methyl group and ethyl group. The aforementioned aryl group represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl. }, A pyridine nucleus (for example, 2-pyridine, 4-pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine), a quinoline nucleus (a quinoline nucleus (for example, 2-quinoline, 3-methyl-2-pyridine) Quinoline, 5-ethyl-2-quinoline, 6-methyl-2-
Quinoline, 6-nitro-2-quinoline, 8-fluoro-
2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 4
-Quinoline, 6-ethoxy-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-methoxy-4-quinoline, 6-chloro-4-quinoline), isoquinoline nucleus (for example, 6-nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline)}, Imidazo [4,5-b] quinoxaline nuclei (eg 1,3-diethylimidazo [4,5-
Examples thereof include b] quinoxaline, 6-chloro-1,3-diallylimidazo [4,5-b] quinoxaline, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus and pyrimidine nucleus.

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

R ₄ , R ₅ and R ₉ are 4 of the chlorine nucleus of any cyanine dye.
It can take the form of a graded substituent.

For example, preferably, an unsubstituted alkyl group having 18 or less carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, decyl group, dodecyl group,
Octadecyl group) or a substituted alkyl group (as a substituent, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, an alkoxycarbonyl group having 8 or less carbon atoms. (For example, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group), alkoxy group having 8 or less carbon atoms, (for example, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group), 10 or less carbon atoms A monocyclic aryloxy group (eg, phenoxy group, p-tolyloxy group), an acyloxy group having 3 or less carbon atoms (eg, acetyloxy group, propionyloxy group), an acyl group having 8 or less carbon atoms (eg, acetyl group, propionyl group) Group, benzoyl group,
Mesyl group), carbamoyl group (eg carbamoyl group,
N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group), carbon number 10 The following aryl groups (eg phenyl groups,
An alkyl group having 18 or less carbon atoms, which is substituted with a 4-chlorophenyl group, a 4-methylphenyl group, an α-naphthyl group) is preferable. } Can be mentioned.

D ₁ , D ₁ ′ and D ₂ , D ₂ ′ represent the atomic groups necessary to form an acidic nucleus, but can take the form of the acidic nucleus of any common merocyanine dye. In preferred form D ₁
And D ₂ is a cyano, sulfo or carbonyl group,
D ₁ ′ and D ₂ ′ represent the remaining atomic groups necessary for forming an acidic nucleus.

When the acidic nucleus is acyclic, that is, when D ₁ and D ₁ ′ or D ₂ and D ₂ ′ are independent groups, the terminal of the methine bond is malononitrile, alkylsulfonylacetonitrile, cyanomethylbenzofuranyl ketone or cyano. A group such as methyl phenyl ketone.

D ₁ , D ₁ ′ or D ₂ , D ₂ ′ are together a 5- or 6-membered heterocycle consisting of carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms. Form. Preferably D ₁ , D ₁ ′ or D ₂ , D ₂ ′ together complete the next nucleus.

2-pyrazolin-5-one, pyrazolidin-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4
-One, 2-oxazoline-5-one, 2-thiooxazolidin-2,4-dione, isoxazoline-5-one, 2-thiazolin-4-one, thiazolidin-4-one, thiazolidine-2,4-dione , Rhodanine, thiazolidine-2,4-dithione, isorhodanine, indane-
1,3-dione, thiophen-3-one, thiophen-3
-One-1,1-dioxide, indoline-2-one, indoline-3-one, indazoline-3-one, 2-oxoindazolinium, 3-oxoindazolinium,
5,7-Dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6 A nucleus of dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, indazolin-2-one, or pyrido [1,2-a] pyrimidin-1,3-dione.

More preferably, 1,3-dialkyl barbituric acid,
These are 1,3-dialkyl-2-thiobarbituric acid and 3-alkylrhodaninate (preferably an unsubstituted alkyl group as the 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, and particularly preferably 1 to 4 (e.g., methyl group, ethyl group, propyl group, Isopropyl group, butyl group, isobutyl group,
Hexyl group, octyl group, dodecyl group, octadecyl group), substituted alkyl group (eg aralkyl group (eg benzyl group, 2-phenylethyl group), hydroxyalkyl group (eg 2-hydroxyethyl group, 3-hydroxypropyl group)) , A carboxyalkyl group (for example, 2-
Carboxyethyl group, 3-carboxypropyl group, 4-
Carboxybutyl group, carboxymethyl group), alkoxyalkyl group (eg, 2-methoxyethyl group, 2-
(2-methoxyethoxy) ethyl group), sulfoalkyl group (for example, 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 (eg, 3-sulfatopropyl group, 4-sulfatobutyl group), heterocyclic-substituted alkyl group (eg, 2- (pyrrolidine-2) -On-
1-yl) ethyl group, tetrahydrofurfuryl group, 2-
Morpholinoethyl group), 2-acetoxyethyl group, carbomethoxymethyl group, 2-methanesulfonylaminoethyl group}, allyl group, aryl group (for example, phenyl group, 2
-Naphthyl group), substituted aryl group (for example, 4-carboxyphenyl group, 4-sulfophenyl group, 3-chlorophenyl group, 3-methylphenyl group), heterocyclic group (for example, 2-pyridyl group, 2-thiazolyl group) Is preferred.

Since R ₆ and R ₇ are the substituents of the tertiary amine used in the synthesis, any general substituents of the tertiary amine may be used.

R ₆ and R ₇ may be the same or different from each other, and preferably an unsubstituted alkyl group having 18 or less carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, decyl group, Dodecyl group, octadecyl group) or substituted alkyl group (as a substituent, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group,
Alkoxycarbonyl group having 8 or less carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group), carbon number 8
The following alkoxy groups (eg methoxy group, ethoxy group, benzyloxy group, phenethyloxy group), carbon number
10 or less monocyclic aryloxy group (eg, phenoxy group, p-tolyloxy group), acyloxy group having 3 or less carbon atoms (eg, acetyloxy group, propionyloxy group), acyl group having 8 or less carbon atoms (eg, acetyl group, Propionyl group, benzoyl group, mesyl group), carbamoyl group (eg carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), sulfamoyl group (eg sulfamoyl group,
N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group), aryl groups having 10 or less carbon atoms (eg, phenyl group, 4-chlorophenyl group, 4
An alkyl group having 18 or less carbon atoms, which is substituted with a -methylphenyl group or an α-naphthyl group) is preferable. } A cyano group, an alkoxy group (for example, a methoxy group, an ethoxy group), an aryloxy group (for example, a phenoxy group), and an alkoxycarbonyl group (for example, an ethoxycarbonyl group).

Further, R ₆ and R ₇ can be bonded to each other to form a heterocycle other than the aromatic heterocycle.

Preferred are, for example, pyrrolidine, piperidine, morpholine, piperazine, tetrahydropyridine, dihydropyridine and tetrahydroquinoline.

More preferably, R ₆ and R ₇ are ethyl groups.

Examples of the heterocycle formed by Q ₂ include a pyrrole nucleus, a carbazole nucleus, an indole nucleus, a pyrazole nucleus, a pyrazolo [1,5-a] benzimidazole nucleus, a pyrazolo [1,5-b] quinazolone nucleus, and an indazole nucleus. preferable.

The 5- or 6-membered heterocycle formed by W ₁ and W ₂ is an oxo group at an appropriate position from the cyclic heterocycle represented by D ₁ , D ₁ ′ and D ₂ , D ₂ ′. , Or a thioxo group is excluded.

R ₈ and R ₁₀ are the same as those described above as the substituent bonded to the nitrogen atom contained in the nucleus of the cyclic heterocycle represented by D ₁ , D ₁ ′ and D ₂ , D ₂ ′. preferable.

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

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L ₇ , L ₈ , L ₉ , L ₁₀ , L ₁₁ ,
L ₁₂ , L ₁₃ , L ₁₄ , L ₁₅ , L ₁₆ , L ₁₇ , L ₁₈ , L ₁₉ , L ₂₀ , L ₂₁ ,
L ₂₂ , L ₂₃ , L ₂₄ , L ₂₅ , L ₂₆ , L ₂₇ , L ₂₈ , L ₂₉ , L ₃₀ , L ₃₁ ,
L ₃₂ , L ₃₃ , and L ₃₄ represent a methine group (substituted or unsubstituted alkyl group (eg, methyl group, ethyl group), substituted or unsubstituted aryl group (eg, phenyl group) or halogen atom (eg, chlorine atom, It may be substituted with a bromine atom). }, And may form a ring with another methine group, or may form a ring with an auxiliary chromophore.

The organic desensitizer used in the present invention is a substance capable of trapping free electrons generated in the silver halide grains by irradiation with radiation and adsorbing to silver halide. Furthermore, it is defined as a substance having a lowest unoccupied electron energy level lower than the electron energy level of the conduction band of silver halide grains. A compound having a highest occupied electron energy level lower than the valence band of the particle is preferable.

The evaluation of the lowest unoccupied electron energy level can be performed by measuring the reduction potential. The measurement of reduction potential is
Phase discrimination second harmonic AC polarography was performed. The details are described below. As a solvent 4A-1 /
Acetonitrile (spectral grade) dried in 16 molecular sieves was used as a supporting electrolyte of normal tetrapropylammonium perchlorate (special polarographic reagent). The sample solution is 10 ^-3 to 10 ^-5 mol of organic desensitizer in acetonitrile containing 0.1 M supporting electrolyte.
It was prepared by dissolving / l, and before measurement, it was deoxygenated for 15 minutes or more with a highly alkaline aqueous solution of pyrogallol and with ultrahigh-purity argon gas (99.999%) that had passed through calcium chloride. The working electrode was a mercury dropping electrode, the reference electrode was a saturated calomel electrode (SCE), and the counter electrode was platinum. The reference electrode and the sample solution were connected by a Luggin tube filled with acetonitrile containing 0.1 M supporting electrolyte, and Vycor glass was used for the liquid junction. The tip of the Lugin tube and the tip of the mercury capillary
The measurement was carried out at 25 ° C. with a distance of 5 mm to 8 mm. In addition, the measurement of reduction potential by phase discrimination type oni harmonic AC voltammetry using platinum as the working electrode is described in "Journal
Of Imaging Science "(Journal of Imagi
ng Science), Vol. 30, pp. 27-35 (1986).

The organic desensitizer used in the present invention has a reduction potential of -1.0 (V _vs.
SCE) or more positive. If the reduction potential is −1.0 (V _vs SCE) or less, it does not function as a desensitizer. Many of such organic desensitizers are described, for example, in US Pat.
3,023,102, 3,314,796, 2,901,351, 3,367,779, British Patent 723,019, 698,575.
No. 698,576, 834,839, 667,206,
No. 748,681, No. 796,873, No. 875,887, No. 9
05,237, 907,367, 940,152, French patent 1,
No. 520,824, No. 1,518,094, No. 1,518,095, No.
1,520,819, 1,520,823, 1,520,821, 1,523,626, Belgian Patents 722,457, 722,59
No. 4 and Japanese Patent Publication Nos. 43-13167 and 43-14500.

The organic desensitizer is more preferably a compound represented by the general formula (X), the general formula (XI) or the general formula (XII).

General formula (X) In the formula, Z ₁ represents an atomic group necessary for forming a nitrogen-containing heterocycle.

T ₁ is a halogen atom, an alkyl group, a halogen atom, an acyl group, an acyloxy group, an acylamino group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a carboxy group, a cyano group, a hydroxy group,
It represents an amino group, an alkylthio group, an alkylsulfonyl group, a sulfonic acid group, a sulfonamide group, an aryl group or a condensed ring, and these may further have a substituent.

q ₁ represents ₁ , 2 or 3.

r ₁ represents 0, ₁ , 2 or 3.

General formula (XI) In the formula, R ₁ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. These may have a substituent further.

T ₂ is synonymous with T ₁ .

q ₂ represents 1, 2 or 3.

r ₂ represents 0, 1, 2 or 3.

General formula (XII) In the formula, R ₂ has the same meaning as R ₁ .

T ₃ is synonymous with T ₁ .

q ₃ represents 1, 2 or 3.

r3 represents 0, 1, 2 or 3.

The general formulas (X), (XI) and (XII) will be described in more detail. Specific examples of the nitrogen-containing heterocyclic nucleus completed by Z ₁ include 1,2,4-triazole,
1,3,4-oxadiazole, 1,3,4-thiadiazole, tetraazaindene, pentaazaindene, triazaindene, benzothiazole, benzimidazole, benzoxazole, pyrimidine, triazine, pyridine, quinoline, quinazoline, phthalazine , Quinoxaline, imidazo [4,5-b] quinoxaline, tetrazole, 1,3-diazaazulene, and these rings may further have a substituent, and the ring may be further condensed. .

T ₁ , T ₂ and T ₃ include a halogen atom (eg, chlorine atom, fluorine atom, bromine atom), an unsubstituted alkyl group having 10 or less carbon atoms (eg, methyl group, ethyl group), carbon number
Substituted alkyl groups of 18 or less (for example, cyclohexyl group,
Allyl group, benzyl group, α-naphthylmethyl group, 2-phenylethyl group, trifluoromethyl group), acyl group having 10 or less carbon atoms (eg, acetyl group, benzoyl group, mesyl group), acyloxy having 10 or less carbon atoms Group (eg, acetyloxy group), alkoxycarbonyl group having 10 or less carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), substituted or unsubstituted carbamoyl group (eg, carbamoyl group,
N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), substituted or unsubstituted sulfamoyl group (for example, 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 (eg, acetylamino group), 10 or less carbon atoms An alkoxy group (methoxy group, ethoxy group, benzyloxy group), an alkylthio group (for example, an ethylthio group), an alkylsulfonyl group (for example, a methylsulfonyl group),
A sulfonic acid group, a sulfonamide group, and an aryl group (for example, a phenyl group and a tolyl group) are preferable. Two bonded to adjacent carbon atoms may bond to each other to form a benzene ring. Heterocycles that are bonded to each other (eg, pyrrole ring, thiophene ring, furan ring, pyridine ring, imidazole ring, triazole ring, thiazole ring)
May be formed.

R ₁ and R ₂ are a hydrogen atom, having 1 to 18 carbon atoms, preferably 1
To 7, particularly preferably 1 to 4 alkyl groups (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, dodecyl group, octadecyl group), substituted alkyl groups { For example, an aralkyl group (for example, a benzyl group, a 2-phenylethyl group), a hydroxyalkyl group (for example, a 2-hydroxyethyl group, a 3-hydroxypropyl group), a carboxyalkyl group (for example, a 2-carboxyethyl group, 3- Carboxypropyl group, 4-carboxybutyl group, carboxymethyl group), alkoxyalkyl group (for example, 2-methoxyethyl group, 2- (2-methoxyethoxy) ethyl group), sulfoalkyl group (for example, 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 (for example, 3-sulfatopropyl group, 4-sulfate) Fattobutyl group), a heterocyclic-substituted alkyl group (for example, 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 (Eg, phenyl group, 2-naphthyl group), substituted aryl group (eg, 4-carboxyphenyl group, 4-sulfophenyl group, 3-chlorophenyl group, 3-methylphenyl group), heterocyclic group (eg, 2- Pyridyl group and 2-thiazolyl group) are preferred.

Next, specific examples of the methine dye and the organic desensitizer used in the present invention are shown, but the present invention is not limited to these.

Examples of compounds represented by general formula (II) Examples of compounds represented by general formula (III) Examples of compounds represented by general formula (IV) Examples of compounds represented by general formula (V) Examples of compounds represented by general formula (VI) Examples of compounds represented by general formula (VII) Examples of compounds represented by general formula (VIII) Examples of compounds represented by general formula (IX) The methine dye of the present invention is disclosed in Japanese Patent Application Nos. 62-24375 and 62-44868.
Can be synthesized by the method described in 1.

Next, examples of compounds of the organic desensitizer are shown.

Synthesis examples of the compound represented by the general formula (X) are described in JP-A-49-8.
4639.

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

The methine dye of the present invention (preferably represented by the general formula (I), more preferably the general formulas (II), (III), and (I)
V), (V), (VI), (VII), (VIII), and (IX). ) As a photographic desensitizing dye or desensitizing agent, when added to the silver halide light-sensitive material layer,
5 × 10 ⁻⁷ to 1 × 10 ⁻² mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻³ mol, is used per mol of silver halide. The optimum amount is
It depends on the chemical structure of the methine dye used, the crystal habit of the silver halide light-sensitive material, and the grain size. Further, these methine dyes may be added in any process of preparing a silver halide light-sensitive material such as grain formation, physical ripening and chemical ripening, or may be added to a coating solution before coating. You may use together with the method.

The methine dye used in the present invention can be directly dispersed in a light-sensitive material or a hydrophilic colloid solution. These are also suitable solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve,
JP-A-48-9715, halogenated alcohols described in US Pat. No. 3,756,830, acetone, water, pyridine, etc., or
It may be dissolved in these mixed solvents or the like and attached to the light-sensitive material in the form of a solution. Other addition methods include JP-B-46-24185, U.S. Patents 3,822,135 and 3,660,101.
No., No. 2,912,343, No. 2,996,287, No. 3,429,835,
The method described in No. 3,658,546 can be used. In addition, the method described in German Patent Application No. 2,104,283, US patent
The method described in 3,649,286 can also be used.

The organic desensitizer of the present invention (preferably compounds represented by the general formulas (X) and (XI) (XII)) is a silver halide 1
The amount added is preferably 1 × 10 ^-6 mol to 5 × 10 ^-1 mol, and particularly preferably 1 × 10 ^-5 mol to 2 × 10 ^-2 mol.

When the compounds represented by the general formulas (X) and (XI) (XII) are contained in the photographic light-sensitive material, they are aqueous solutions when they are water-soluble, and alcohols (for example, methanol and ethanol) when they are water-insoluble. It may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as esters (eg, ethyl acetate) and ketones (eg, acetone).

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

The silver halide emulsion used in the present invention includes an acidic method, a neutral method,
Alternatively, it may be produced by a method such as an ammonia method, and as the silver halide, there are silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver iodochlorobromide, etc. When handling is important, silver chlorobromide having a high Cl content is preferable, and when high sensitivity is important, silver bromide or silver iodobromide is preferable.

The silver halide grains used in the present invention have an average grain diameter of
0.01 to 2 microns is good, but preferably 0.
It is desirable to use the one of 02 to 1 micron. The particle size frequency distribution may be wide or narrow, but is preferably narrow. Especially ± 40% of the average particle size, preferably ± 20%
A so-called monodisperse emulsion in which 90% of the total number of grains, preferably 95%, falls within the grain size range is preferable. The silver halide grains may have a single crystal habit or a mixture of various crystal habits, but a single crystal habit is preferred.

The direct positive type silver halide used in the present invention is an inorganic desensitizer (that is, a noble metal atom contained in silver halide grains).
And an organic desensitizer adsorbed on the surface of the silver halide or a desensitizing dye alone or in combination.

In order to incorporate the inorganic desensitizer used in the present invention into silver halide grains, a water-soluble noble metal compound such as iridium or rhodium such as a chloride of a Group 8 metal of the periodic law is added to the silver halide grain at a concentration of 10 ^-7 per mol of silver halide. ~ 10 ^-2 mol, preferably 10 ^-5 ~ 10
^-3 mol, may be added as an aqueous solution at the time of preparation of silver halide grains.

Examples of the organic desensitizer or desensitizing dye that can be used in the present invention include, for example, dimethine cyanine dye containing a 2- (nitro-substituted phenyl) -indole nucleus) and bis- (1
-Alkyl-2-phenyl) -indole-3-trimethine cyanine dye, aromatic substituted indole nucleus-containing cyanine dye, imidazoquinoxaline dye, asymmetric cyanine dye containing carbazole nucleus, trimethine cyanine containing 2-aromatic substituted indole nucleus Dyes, cyanine dyes containing 2,3,3-trialkyl-3H-nitroindole nuclei, cyanine dyes containing pyrimidinedione nuclei, 2-isoxazolin-5-one nuclei, 2-pyrazolin-5-one nuclei or pyrimidinediones Quaternized merocyanine dyes having a nucleus, 2-allylimino (or alkylimino) -4-allyl (or alkyl) -3-thiazoline cyanine dyes having a nucleus, 3-allyl-amino or 3-lower fatty acid amide substituted 2- Merocyanine quaternary ammonium salt with pyrazolin-5-one Dyes, pyrylium, thiapyrylium, serenapyrylium salt dyes, cyanine dyes having a nitro-substituted 2-arylindole nucleus, bispyridinium salt dyes, cyanine dyes containing a pyrrole nucleus bonded at a 2-position carbon atom, 1,2-diaryls Trimethine indole dye, cyanine dye containing 4-pyrazole nucleus, polymethine dye containing imidazole nucleus, dimethine cyanine dye containing 2-phenyl-substituted indole nucleus, trimethine cyanine dye consisting of two indole nuclei, 1-cyanoalkyl- Cyanine dyes containing 2-arylindole nuclei, cyanine and merocyanine dyes having two desensitizing substituents such as nitro groups, cyanine dyes containing 1-alkyl-2-phenyl substituted indole nuclei, 1-alkoxy-2 A sheer containing an arylindole nucleus Nin dye,
Cyanine dye having imidazo [4,5-b] quinoxaline nucleus, dye containing cycloheptatriene ring, dimethinecyanine dye containing indole nucleus, cyanine dye containing pyrazolo [1,5-a] bayazoimitazole nucleus, pyrazolo 〔5,1
-B] Cyanine dye containing a quinazolone nucleus, pyrrolo [2,3
-B] Dimethine cyanine dye containing pyridine nucleus, cyanine dye containing pyrrole nucleus, dye containing pyrrolo [2,1-b] thiazole nucleus, cyanine dye containing indole or indolenine nucleus containing benzoyl or phenylsulfonyl substituents Nitrostyryl type compounds described in U.S. Pat. No. 2,669,515, pinacryptol yellow, 5-metanitrobenzylidene rhodanine and the like, bis-type compounds described in JP-B-48-13059.
Pyridinium compounds and phenazine compounds described in JP-B-47-8746 are useful.

Fog can be imparted to the direct positive type silver halide used in the present invention by a conventionally known technique after removing the water-soluble salts generated after the precipitation of the silver halide described above. Fog can be applied with a fogging agent (reducing agent) alone,
A fogging agent may be combined with a gold compound and 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 (eg, triethylenetetramine, tetraethylenepentamine, etc.) thiourea dioxide, tetra (hydroxymethyl) phosphonium chloride, asymborane hydrogen. Examples of useful metal compounds that include boron compounds, stannous chloride, tin (II) chloride, etc., and are more electrically positive than silver include gold, rhodium, platinum, palladium,
Soluble salts such as iridium, such as potassium chloroaurate, chloroauric acid, palladium ammonium chloride, sodium iridium chloride and the like are included.

Fogging agent is generally 1.0 × 1 per mol of silver halide.
It is used in the range of 0 ^{-6 to} 1.0 × 10 ^-1 mol.

Typical examples of the gold compound include chloroauric acid, sodium chloroaurate, gold sulfide, gold selenide, etc., and generally in the range of 1.0 × 10 ^{-6 to} 1.0 × 10 ^-4 mol per mol of silver halide. It is preferable to include in.

The degree of fog of the pre-fogged direct positive type silver halide emulsion used in the present invention can be varied within a wide range. The degree of fog depends on the type and concentration of the fogging agent used, the concentration, and the fog at the time of application, as well as the silver halide composition and grain size of the silver halide emulsion used as well known to those skilled in the art. It is related to pH, pAg, temperature and time of emulsion.

The direct positive silver halide photographic light-sensitive material of the present invention includes a selenium compound as described in JP-A-46-4282,
And sensitizing dyes such as dimethine or trimethine cyanine dyes, halogen-substituted hydroxyphthalein dyes, phenazine dyes, benzothiazole, cyanine dyes containing a benzoselenazole nucleus, cyanine dyes containing a naphthoxazole nucleus, triphenylmethane dyes, India From a cyanine dye containing a renin nucleus, a merocyanine dye containing a 2-pyridine-rhodanine nucleus, a cyanine dye containing a thiazole nucleus, an asymmetric cyanine, a quinoline, a meso-substituted cyanine dye, a merocyanine dye containing a rhodanine nucleus, and a polymethine dye having three nuclei High sensitivity can be imparted by incorporating at least one selected substance such as a sensitizing dye.

The direct positive silver halide photographic light-sensitive material of the present invention may contain various other photographic additives generally used. As the stabilizer, for example, triazoles, azaindenes, quaternary benzothiazolium compounds, mercapto compounds, or water-soluble inorganic salts such as cadmium, cobalt, nickel, manganese, gold, thallium, and zinc may be contained. As a hardening agent, for example, formalin, glyoxal, aldehydes such as mucochloric acid,
S-triazines, epoxies, aziridines, vinyl sulfonic acids, etc. or coating aids such as saponin, sodium polyalkylene sulfonate, lauryl or oleyl monoether of polyethylene glycol, aluminized alkyl taurine, fluorine-containing compounds, etc. You may make it contain. Further, it is possible to contain a color coupler. In addition, a whitening agent, an ultraviolet absorber, an antiseptic, a matting agent, an antistatic agent, etc. may be added, if necessary.

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

The dye used in the present invention has a main absorption in the visible wavelength region of the intrinsic light-sensitive wavelength region of the silver halide emulsion used. There is no particular limitation on the chemical structure of the dye, and oxonol dyes, hemioxonol dyes, merocyanine dyes, cyanine dyes, azo dyes, etc. can be used, but water-soluble dyes are useful in terms of eliminating residual color after processing. Is.

Specifically, for example, pyrazolone dyes described in JP-B-58-12576, pyrazolone oxonol dyes described in U.S. Pat.No. 2,274,782, diarylazo dyes described in U.S. Pat.No. 2,956,879, U.S. Pat. 3,384,487
Dyes and butadienyl dyes described in U.S. Pat.
2,527,583 merocyanine dyes, U.S. Pat.
86,897, 3,652,284, merocyanine dyes and oxonol dyes described in 3,718,472, U.S. Pat.
6,661, enaminohemioxonol dyes and British Patent Nos. 584,609, 1,177,429, JP-A-48-85130
No. 49-99620, No. 49-114420, U.S. Pat.
No. 3,148,187, No. 3,177,078, No. 3,247,12
No. 7, No. 3,540,887, No. 3,575,704, No. 3,653,9
The dye described in 05 is used.

For a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example,
Various surfactants may be included for various purposes such as accelerating the phenomenon, increasing the contrast, and sensitizing.

For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, poly Alkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidyl derivatives (eg alkenylsuccinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactant; alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfonic acid , Alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phosphosulfate groups, phosphate groups, etc .; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines , Amine amphoteric amphoteric surfactants; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium and other heterocyclic quaternary ammonium salts, and phosphonium containing an aliphatic or heterocyclic ring or It can be used cationic surfactants such as sulfonium salts.

In particular, the surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412.

The polyalkylene oxide compound used in the present invention is a polyalkylene oxide compound having 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, and preferably ethylene oxide. Includes condensates of alkylene oxides with water, aliphatic alcohols, aromatic alcohols, fatty acids, organic amines, compounds having at least one active hydrogen atom such as hexitol derivatives, and block polymers of two or more polyalkylene oxides. To do. That is, as the polyalkylene oxide compound, specifically, polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers, polyalkylene glycol (alkylaryl) ethers, polyalkylene glycol esters, polyalkylene glycol fatty acid amides. Polyalkylene glycol amines Polyalkylene glycol / block copolymers Polyalkylene glycol graft polymers and the like can be used. The molecular weight should be 600 or more.

The number of polyalkylene oxides is not limited to one in the molecule, and two or more may be contained in the molecule. The individual polyalkylene oxides may then consist of less than 10 alkylene oxide units, but the total number of alkylene oxide units in the molecule must be at least 10. When having more than one polyalkylene oxide 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 preferably contains 14 to 100 alkylene oxide units.

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

Polyalkylene oxide compound example XIII-1 HO (CH ₂ CH ₂ O) ₉₀ H XIII-2 C ₄ H ₉ O (CH ₂ CH ₂ O) ₁₅ H XIII-3 C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₅ H XIII-4 C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₁₅ H XIII-5 C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₄₀ H XIII-6 C ₈ H ₁₇ CH = CHC ₈ H ₁₆ O (CH ₂ CH ₂ O) ₁₅ H XIII-10 C ₁₁ H ₂₃ COO (CH ₂ CH ₂ O) ₈₀ H XIII-11 C ₁₁ H ₂₃ COO (CH ₂ CH ₂ O) ₂₄ OCC ₁₁ H ₂₃ XIII-13 C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₁₅ H XIII-15 C ₁₄ H ₂₉ N (CH ₃ ) (CH ₂ CH ₂ O) ₂₄ H XIII-20 HO (CH ₂ CH ₂ O) _a (CH ₂ CH ₂ CH ₂ CH ₂ O) _b (CH ₂ CH ₂ O) _c H a + c = 30, b = 14 The polyalkylene oxide compounds described in JP-A-50-156423, JP-A-52-108130 and JP-A-53-3217 such as XIII-24 HOCH ₂ CH ₂ O ₃₄ H can be used. These polyalkylene oxide compounds may be used alone or in combination of two or more.

When adding these polyalkylene oxide compounds to the silver halide emulsion, as an aqueous solution of a suitable concentration or dissolved in a low boiling organic solvent miscible with water,
It can be added to the emulsion at a suitable time before coating, preferably after chemical ripening. Instead of being added to the emulsion, it may be added to a non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer and a filter layer.

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

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

In the emulsion used in the present invention, it is advantageous to use mainly gelatin as a protective colloid, particularly inert gelatin. Instead of gelatin, photographic-inert gelatin derivatives (for example, phthalated gelatin, water-soluble synthetic polymers (for example, polyvinyl acrylate, polybonyl alcohol, polyvinylpyrrolidone) are used.) The novel emulsion of the present invention can be used in any suitable manner. Photographic support,
For example, glass, film bases such as cellulose acetate, cellulose acetate butyrate, polyester [for example, poly (ethylene terephthalate)] are used.

The developer used in the present invention may be a so-called lith type developer having a low sulfite ion concentration, or a developer containing sufficient sulfite ion as a preservative (especially 0.15 mol / l or more) is used. Can also be pH 9.5 or above, especially 1
It is also possible to use a developing solution of 0.5 to 12.3.

There is no particular limitation on the developing agent that can be used in the method of the present invention, and examples thereof include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-).
3-pyrazolidone), aminophenols (eg N-
Methyl-p-aminophenol) may be used alone or in combination.

Other developers include alkali metal sulfites, carbonates,
A development inhibitor such as a pH buffer such as borate and phosphate, bromide, iodide, and an organic antifoggant (particularly preferably nitroindazoles or benzotriazoles) or an antifoggant You can Further, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant (particularly preferably the above-mentioned polyalkylene oxides) defoaming agent, a hardener, and a silver stain preventive agent for the film ( For example, 2-mercaptobenzimidazole sulfonic acids) and the like may be included. Specific examples of these additives are described in Research Disclosure No. 176, 17643 and the like.

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

As the fixer, a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. Further, the fixing solution may 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 is applied to various uses. For example, for duplicating,
Various photographic light-sensitive materials for printing such as reproduction and offset master, special photographic light-sensitive materials such as X-ray, flash photography, electron beam photography or general copying, micro copying, direct positive color, quick stapled for,
It is used for various direct positive photographic light-sensitive materials for diffusion transfer, color diffusion transfer, general development and fixing.

[Action]

In general, a direct positive type silver halide emulsion is one in which the surface of silver halide grains is fogged in advance with a fogging agent and the fog nuclei are bleached with holes generated by the exposure. The part is not developed, but the unexposed part is developed to directly obtain a positive image. The present invention has found that the spectral sensitization effect of the methine dye in this direct positive type silver halide emulsion is supersensitized by the addition of an organic desensitizer, whereby a high spectral sensitivity can be obtained. Not only the minimum density (Dmin) of the exposed area does not increase, but also the sensitivity and minimum density (Dmin) for storage of raw samples
The change in can be reduced.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the embodiments of the present invention are not limited thereto.

[Example 1] 1 x 10 per mol of silver in a gelatin aqueous solution kept at 50 ° C.
-A silver chlorobromide dispersion emulsion with an average grain size of 0.2μ was prepared by simultaneously adding a silver sulfate aqueous solution and a mixed aqueous solution of sodium chloride and potassium bromide in the presence of ^-5 mol of rhodium chloride at a constant rate for 30 minutes. did. (Cl composition 90 mol%) This emulsion was desalted by the flocculation method to give 2 mg of thiourea dioxide and 0.9 mg per mol of silver.
After adding potassium chloroaurate, the mixture was aged at 65 ° C until the best performance was obtained.

These emulsions were divided and the methine dye of the present invention and an organic desensitizer were added as shown in Table 1 below, and 4 × per mol of silver was added.
10 ^-4 mol of polyalkylene oxide compound XIII-7, 10
% KBr aqueous solution, and 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt as a hardener,
Polyethylene terephthalate was prepared at the same time as a gelatin protective layer containing 1,3-divinylsulfonyl-2-propanol to prepare an emulsion, containing a dispersion of silica and ethyl acrylate as a matting agent, and containing sodium dodecylbenzenesulfonate as a surfactant. 3.0g silver on film
/ m ² was applied as much as possible. After exposing the obtained sample through a light wedge using a tungsten light source, it is developed with a developer having the following composition for 20 seconds at 38 ° C., stopped, fixed, washed with water,
The results of drying are shown in Table 1 as Photographic Properties 1.

Photographic property 2 is the same evaluation as photographic property 1 after each film was left under conditions of 50 ° C. and 75% relative humidity for 3 days.

Here, the relative sensitivity is the relative value of the reciprocal of the exposure amount that gives a density of 1.5 at 38 ° C. for 20 seconds development. I asked. Similarly, sample Nos. 5, 9, 13, 17, 21, 25, 29,
The relative sensitivity was determined by setting the value of the photographic characteristic 1 of 33, 37, 41, 45, 49, 53 to 100. In developing, the developer having the following formulation was used.

Developer formulation Hydroquinone 35.0 g N-methyl-p-aminophenol 1/2 sulfate 0.8 g Sodium hydroxide 9.0 g Potassium triphosphate 74.0 g Potassium sulfite 90.0 g Ethylenediaminetetraacetic acid disodium 1.0 g 3-Diethyl-amino- 1-Propanol 15.0g 5-Methylbenzotriazole sodium bromide 3.0g Add water and adjust to 1PH = 11.60.

Example 2 In a gelatin aqueous solution containing 0.8 g / l sodium bromide,
Keeping the temperature at 70 ° C., the silver nitrate aqueous solution and the calcium bromide aqueous solution are kept constant at the same time in the presence of 5 × 10 ^-6 mol / Ag mol of rhodium salt and 5 × 10 ^-7 mol / Ag mol of iridium salt per mol of silver. A silver bromide cubic monodisperse emulsion having an average grain size of 0.25 μm was prepared by applying the solution at a rate of 85 minutes for 85 minutes and maintaining the potential at +60 mV. The emulsion was desalted by the flocculation method, 10 mg of thiourea dioxide and 8 mg of potassium chloroaurate were added per 1 mol of silver, and ripening froth was produced at 65 ° C. until maximum performance was obtained.

These emulsions were divided and the methine dye of the present invention and an organic desensitizer were added to each emulsion as shown in Table 2 below.
10 ^-4 mol of the compound (14) described in JP-A-49-29828 was added, and the pAg was adjusted with 8 × 10 ^-4 mol of polyalkylene oxide compound XIII-7 and 10% KBr per mol of silver. After adding 1,3-divinylsulfonyl-2-propanol as a film agent, a silica mat and a protective layer containing gelatin to which sodium dodecylbenzenesulfonate was added as a surfactant, and 3.2 g of silver on a polyethylene terephthalate film simultaneously with a protective layer containing gelatin. The coating was performed so that it became / m ² .

A backing layer and a back protective layer were coated on the side opposite to the emulsion layer and protective layer and the support.

The backing layer contains 4- [5-oxo-3- as a dye.
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-pyrazolin-4-ylidene} -1,3-pentadienyl) -1-pyrazolyl] benzenesulfonic acid potassium salt, and improved film quality For this purpose it contained a polymer of ethyl acrylate and was coated with gelatin with surfactants, charge control agents and hardeners. A polymer of polymethylmethacrylate as a surfactant and a matting agent was added to gelatin in the back protective layer, and it was coated on the upper portion of the back layer (opposite side of the support).

After the obtained sample was exposed through a light wedge using a tungsten light source, the same evaluation as in Example 1 was performed. The results are shown in Table 2. Sample No. 5 as in Example 1
7, 61, 65, 69, 73, 77, 81, 85, 89, 93, 97, 101, 10
The relative sensitivity was determined by setting the value of Photographic property 1 of 5 to 100.

Preferred embodiments of the present invention are as follows: 1) The light-sensitive material according to the claims, characterized in that emulsion grains contain rhodium and / or iridium.

2) The light-sensitive material according to 1) above, wherein the emulsion grains contain 10 ⁻⁷ to 10 ⁻³ mol / mol of Agx rhodium.

3) A light-sensitive material according to claim 1, wherein the emulsion layer or the adjacent layer contains a polyalkylene oxide compound.

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

5) The light-sensitive material according to claim 1, wherein the emulsion layer or the adjacent layer contains a benzylidene dye or an oxonol dye.

〔The invention's effect〕

The present invention provides a direct positive type silver halide emulsion with an azulene nucleus.
At least one of the 10 carbon atoms comprises a nucleus in which at least one is replaced by a chalcogen atom or a nitrogen atom, and a 7-membered ring portion of the nucleus terminates an auxochrome that forms a conjugated resonance group with the 10π electron system of the nucleus. At least one methine dye substituted with a methine bond and having a reduction potential of -1.0 (V _vs VS)
Alternatively, by containing at least one organic desensitizer having a positive value, the spectral sensitization effect of the methine dye is supersensitized, whereby not only high spectral sensitivity can be obtained, but No increase in minimum density (Dmin)
In addition, changes in sensitivity and minimum concentration (Dmin) during storage of raw samples can be reduced.

Continuation of the front page (56) Reference JP-A-49-84640 (JP, A) JP-A-49-29828 (JP, A) JP-A-52-133210 (JP, A) JP-A-54-4118 (JP , A) JP 62-198636 (JP, A) JP 63-210922 (JP, A) JP 39-11766 (JP, B1)

Claims (1)

[Claims] 1. An azulene nucleus comprising a nucleus in which at least one of the 10 carbon atoms is replaced by a chalcogen atom or a nitrogen atom, and the 7-membered ring portion of the nucleus forms a conjugate resonance color with the 10π electron system of the nucleus. At least one methine dye substituted with a methine bond having a auxochrome forming a chromophore at the end,
And at least one organic desensitizer having a reduction potential of -1.0 (V _vs SCE) or a more positive value, a pre-fogged direct positive type silver halide emulsion.