JPH11222481A - New benzimidazole derivative, silver halide emulsion containing the same, silver halide-based photographic photosensitive material and silver halide-based color photographic photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound subject to spectral sensitization and useful as a photosensitive coloring matter capable of affording highly sensitive silver halide-based photosensitive materials improved in photographic characteristics such as residual color contamination. SOLUTION: This new compound is shown by formula I (R<1> and R<2> are each an aliphatic group; V<1> to V<4> are each H or the like; A<1> is an atom group necessary for forming amethyne dye through coupling via a conjugated chain; X is an ion necessary for neutralizing intramolecular electric charge; (n) is a number necessary for neutralizing intermolecular electric charge; with a proviso that V<1> and V<4> are neither H at the same time nor form a ring together with other substituent (s)), e.g. a compound of formula II. The compound of formula I can be synthesized based on a conventionally known method; for example, for the compound of formula II, it is obtained by reaction between compound of formula III and a compound of formula IV in diemthyl sulfoxide in the presence of 1,8-diazabicyclo[5, 4, 0]undec-7-ene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel benzimidazole derivative and a silver halide photographic light-sensitive material having improved photographic characteristics over time such as fog fluctuation and sensitivity fluctuation by using the same as a photosensitive dye.

[0002]

2. Description of the Related Art When a certain dye is added to a photosensitive silver halide emulsion (hereinafter, also referred to as a silver halide emulsion or simply an emulsion), the photosensitive wavelength range of the silver halide emulsion is expanded.
It is well known that it is optically sensitized.

A large number of dyes used for this purpose have been known in the art. For example, T. James, The Theory of the Photographic Process, 4th Edition (1977, Macmillan, N.M.
Y. ) P. 194-234, Francis M. Hammer, "The Cyanine Soy and Related Compounds" (1964, John Willy and
Sands, N. Y. ), Dem Sturmer, "The Chemistry of Heterocyclic Compounds, Vol. 30," p. 441- (1977, John Willy and Sons, NY) and other various dyes such as styryl dyes, hemicyanine dyes, cyanine dyes, merocyanine dyes, and xanthene dyes are known. By selecting and combining the length of the nucleus, the aromatic ring, the conjugated chain, and the substituent, a dye having an arbitrary absorption maximum wavelength from the near ultraviolet to the near infrared region is derived.

[0004] These spectral sensitizing dyes must not only extend the photosensitive wavelength range of the silver halide emulsion but also satisfy the following conditions.

(1) The spectral sensitization range is appropriate.

(2) High spectral sensitization efficiency.

(3) There is no bad interaction with other additives such as stabilizers, antifoggants, coating aids, high boiling solvents and the like.

(4) Does not adversely affect the characteristic curve, such as fogging and gamma change.

(5) When a silver halide photographic light-sensitive material containing a sensitizing dye is allowed to age (especially when stored under high temperature and high humidity), photographic performance such as fog does not change.

(6) The added photosensitive dye does not diffuse into layers having different photosensitive wavelength ranges to cause color turbidity.

(7) Developing and fixing After washing with water, the photosensitive dye does not come off and does not cause color contamination.

However, the spectral sensitizing dyes disclosed hitherto have not yet reached a level which sufficiently satisfies all of these conditions.

Furthermore, conventional dyes having an imidazole nucleus are more likely to flow out than other dyes having an azole ring nucleus. When this was done, there was a tendency for fog to easily occur.

In order to improve the storage performance, it is effective to lower the basicity. In many dyes having an imidazole nucleus, an electron-withdrawing group is substituted on the benzimidazole ring. However, since many electron-withdrawing groups have a bulky molecular size, the state of adsorption of a dye on silver halide grains or the state of formation of a dye aggregate changes depending on the type or position of the substituent, and as a result, The photographic characteristics fluctuated over time, and even the originally excellent residual color contamination characteristics tended to deteriorate.

An imidazolocarbocyanine dye in which an electron-withdrawing group has been introduced into the N-position alkyl group of the imidazole nucleus has been disclosed as a photosensitive dye which improves storage stability with time without causing a large change in photographic characteristics with time. 59-181338
No., No. 60-175939, No. 61-32840,
Research Disclosure 37312 (1995)
May, May). However, the dyes disclosed in the above-mentioned documents are still insufficient in the effect of improving storage stability, and further improvement has been demanded.

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SUMMARY OF THE INVENTION It is a first object of the present invention to provide a novel compound and a silver halide photosensitive material which is spectrally sensitized by using it as a photosensitive dye and has improved photographic characteristics. The second object is to provide a silver halide light-sensitive material having improved photographic characteristics such as high-sensitivity and residual color contamination by using a novel photosensitive dye, and a third object is to provide a new light-sensitive material. An object of the present invention is to provide a silver halide photographic material having a silver halide photographic emulsion layer sensitized by a photosensitive dye and having improved photographic characteristics.

[0017]

The object of the present invention has been attained by the following items.

1. A benzimidazole derivative represented by the following general formula (1) or (2).

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In the formula, R ¹ and R ² each represent an aliphatic group;
V ^{1 to} V ⁴ each represent a hydrogen atom, a halogen atom or a substituent, and may form a condensed ring between V ² and V ³ . A ¹ represents an atom group necessary for forming a methine dye by bonding through a conjugated chain. X represents an ion required to neutralize the intramolecular charge, and n represents a number required to neutralize the intramolecular charge. However, V ¹ and V ⁴ do not simultaneously become hydrogen atoms, and V ¹ and V ⁴ do not form a ring with other substituents.

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In the formula, R ¹ and R ² each represent an aliphatic group;
V ^{1 to} V ⁴ each represent a hydrogen atom, a halogen atom or a substituent, and may form a condensed ring between V ² and V ³ . A ² represents an atom group necessary for forming a methine dye by bonding through a conjugated chain. However, V ¹ and V ⁴ do not simultaneously become hydrogen atoms, and V ¹ and V ⁴ do not form a ring with other substituents.

2. The general formula (1) is the following general formula (3)
2. The benzimidazole derivative according to the above 1, wherein the general formula (2) is a derivative represented by the following general formula (4).

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In the formula, R ¹ , R ² and R ³ each represent an aliphatic group, V ¹ -V ⁴ each represent a hydrogen atom, a halogen atom or a substituent, and each of the groups between V ² and V ³ And a condensed ring may be formed. L ^{1 to} L ³ each represent a nitrogen atom or a methine group, n ¹ represents an integer of 0 to 3, and n ² represents 0 or 1. Z represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic group, and may be condensed with a saturated carbon ring, a benzene ring, a naphthalene ring or a heterocyclic ring. X represents an ion necessary for neutralizing an intramolecular charge, and n represents a number required for neutralizing an intramolecular charge. However, V ¹
And V ⁴ are not simultaneously hydrogen atoms, V ¹ and V 4
⁴ does not form a ring with other substituents.

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Wherein R ¹ and R ² each represent an aliphatic group;
V ^{1 to} V ⁴ each represent a hydrogen atom, a halogen atom, or a substituent, L ⁴ and L ⁵ each represent a nitrogen atom or a methine group, and n ³ represents an integer of 0 to 3. Q represents an atomic group necessary for forming a 5- or 6-membered carbocyclic or heterocyclic ring, and may be condensed with a saturated carbocyclic ring, a benzene ring, a naphthalene ring or a heterocyclic ring. However, V ¹ and V ⁴ do not simultaneously become hydrogen atoms, and V ¹ and V ⁴ do not form a ring with other substituents.

3. Substituent V of the general formulas (1) to (4)
Benzimidazole derivative as described in 1 or 2 ¹ represents a halogen atom or a substituent, V ⁴ is characterized in that a hydrogen atom.

4. Substituent V of the general formulas (1) to (4)
³ is a halogen atom, a cyano group, a trifluoromethyl group,
4. The benzimidazole derivative according to the above 1, 2, or 3, which is a substituent selected from the group consisting of an aryl group, a sulfamoyl group, a carbamoyl group, and an alkoxy group.

5. Substituent R of the above general formulas (1) to (4)
^{2. The} benzimidazole derivative according to the above 1, 2, 3 or 4, wherein 2 is an aliphatic group having 3 or less carbon atoms.

6. A silver halide emulsion comprising at least one of the benzimidazole derivatives represented by the general formulas (1) to (4).

7. A halide comprising at least one light-sensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers contains the silver halide emulsion described in 6 above. Silver photographic photosensitive material.

8. A halide comprising at least one light-sensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers contains the silver halide emulsion described in 6 above. Silver color photographic light-sensitive material.

Hereinafter, the present invention will be described in more detail.

In the benzimidazole derivatives represented by the general formulas (1) to (4), the aliphatic groups represented by R ¹ and R ² may be, for example, a branched or straight-chain having 1 to 10 carbon atoms. Chain alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, iso-pentyl, 2-ethylhexyl, octyl, decyl, etc.), 3 carbon atoms
To 10 alkenyl groups (for example, 2-propenyl, 3-
Butenyl, 1-methyl-3-propenyl, 3-pentenyl, 1-methyl-3-butenyl, 4-hexenyl, etc.), aralkyl groups having 7 to 10 carbon atoms (eg, benzyl, phenethyl, etc.) ).

The groups represented by R ¹ and R ² further include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.),
Alkoxy group (for example, methoxy group, ethoxy group, etc.),
Aryloxy group (eg, phenoxy group, p-tolyloxy group, etc.), cyano group, carbamoyl group (eg, carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (eg, sulfamoyl) Group, N, N-3-oxapentamethyleneaminosulfonyl group, etc.), methanesulfonyl group, alkoxycarbonyl group (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.), aryl group (eg, phenyl group, carboxyphenyl group, etc.) A substituent such as an acyl group (eg, acetyl group, benzoyl group, etc.), an acylamino group (eg, acetylamino, benzoylamino group, etc.), a sulfonamide group (eg, methanesulfonamide group, butanesulfonamide group, etc.) May be substituted with a hydrophilic group. Preferably it is.

Examples of the hydrophilic group include a sulfo group, a carboxy group, a carbamoyl group, a sulfamoyl group, a phosphono group, a sulfate group, a hydroxy group, a sulfino group, and a sulfonylaminocarbonyl group (for example,
Methanesulfonylaminocarbonyl group, ethanesulfonylaminocarbonyl group, etc.), acylaminosulfonyl group (eg, acetamidosulfonyl group, methoxyacetamidosulfonyl group, etc.), acylaminocarbonyl group (eg, acetamidocarbonyl group, methoxyacetamidocarbonyl group, etc.), And a sulfinylaminocarbonyl group (for example, a methanesulfinylaminocarbonyl group, an ethanesulfinylaminocarbonyl group, and the like).

As the aliphatic group having a hydrophilic group,
Carboxymethyl, carboxyethyl, sulfoethyl,
Sulfopropyl, sulfobutyl, sulfopentyl, 3-
Sulfobutyl, 6-sulfo-3-oxahexyl, ω-
Sulfopropoxycarbonylmethyl, ω-sulfopropylaminocarbonylmethyl, 3-sulfinobutyl, 3
Each group such as -phosphonopropyl, hydroxyethyl, N-methanesulfonylcarbamoylmethyl, 4-sulfo-3-butenyl, 2-carboxy-2-propenyl, o-sulfobenzyl, p-sulfophenethyl and p-carboxybenzyl; No.

R ¹ and R ² may independently form a fused heterocyclic ring (preferably having 5 or 6 members) together with A ¹ or A ² .

Examples of the substituent represented by V ¹ , V ² , V ³ and V ⁴ include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom) and an aryl group (for example,
Phenyl group, 2-hydroxyphenyl group, 4-bromophenyl group, etc.), heterocyclic group (eg, imidazolyl group, thiazolyl group, benzoxazolyl group, pyridyl group, pyrrolyl group, indolyl group, pyrimidinyl group, etc.), Alkenyl group (2-propenyl group, 1-propenyl group, 1-methyl-3-butenyl group and the like), alkynyl group (for example, 1
-Propynyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propoxy group, etc.), alkylthio group (for example, methylthio group, trifluoromethylthio group, etc.), trifluoromethyl group, aralkyl group (for example,
Benzyl group, 3-chlorobenzyl group, etc.), cyano group, carboxyl group, acylamino group (eg, acetylamino group, benzoylamino group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), sulfonylamino Group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), sulfonyl group (eg, methanesulfonyl group, trifluoromethanesulfonyl group, etc.), carbamoyl group (eg, Carbamoyl group, N, N-dimethylcarbamoyl group, N-morpholinocarbonyl group, etc., sulfamoyl group (sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfamoyl group, etc.), groups such as hydroxyl group, etc. But When the sum of the Hammett σp values of Ruga該 substituent, the sum preferably is 0.12 to 1.4.

Further, as the substituent V ^{3 in the} general formulas (1) to (4), a halogen atom, a cyano group, a trifluoromethyl group, an aryl group, a sulfamoyl group, a carbamoyl group and an alkoxy group are preferably used. Is particularly preferably used, a halogen atom, a cyano group,
A trifluoromethyl group, an aryl group, a sulfamoyl group or a carbamoyl group.

The Hammett σp value is a substituent constant determined by Hammett et al. From the electronic effect of the substituent on the hydrolysis of ethyl benzoate.
Of Organic Chemistry 23, 420-4
27 (1958), Experimental Chemistry Course 14 (Maruzen Publishing Co.), Physical Organic Chemistry (Mc
(Graw Hill Book: 1940), Drag Design VII (Academic Press)
New York: 1976) and the structure-activity relationship of drugs (Nankodo: 1979).

Examples of the condensed ring which can be formed between V ² and V ³ include a 6-membered saturated or unsaturated carbocyclic group, and 5- and 6-membered heterocyclic groups, and an imidazole ring Together with naphtho [2,1-d] imidazole, naphtho [1,2-d] imidazole, naphtho [2,3-d] imidazole, 1-aza-4,5,6-
To form trihydrobenzo [h, i] indolizine and the like. The on these condensed rings may be substituted for any of the groups mentioned in the V ¹ ~V ^4.

In the benzimidazole derivative represented by the general formula (3), Z represents a 5- or 6-membered nitrogen-containing heterocyclic group, and forms a condensed ring with a saturated carbon ring, a benzene ring and a naphtho ring. You may. Specific examples of these azole rings include, for example, pyridine (2-, 4-), quinoline (2-, 4-), isoquinoline, oxazolidin, oxazoline, oxazole, 4,5-trimethyleneoxazole, 4,5, 6,7-tetrahydrobenzoxazole, benzoxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, thiazolidine, thiazoline, thiazole, 4,5-trimethylenethiazole, 4,5,6 , 7-tetrahydrobenzothiazole, benzothiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, selenazole, selenazoline, benzoselenazole, naphtho [1,2-d] selenazole, imidazole, Benzimidazole, naphthoimidazole, indole, Ndorenin, benzotellurazole, and the like. These azole rings may have a substituent at any position,
For example, an alkyl group (for example, each group such as methyl, ethyl, n-propyl, t-pentyl, isobutyl, and benzyl), an alkynyl group (for example, a group such as 1-propynyl), a halogen atom (for example, fluorine atom, chlorine) atom,
Bromine atom, iodine atom, trifluoromethyl group, alkoxy group (for example, methoxy, ethoxy, butoxy, 2-
Methoxyethoxy, benzyloxy, etc.), alkyl mercapto group (eg, methyl mercapto, ethyl mercapto, etc.), hydroxy group, cyano group, aryloxy group (eg, phenoxy, tolyloxy, etc., substituted or unsubstituted) Each group), an aryl group (eg, phenyl, p-chlorophenyl, etc.), a styryl group, a heterocyclic group (eg, furyl, thienyl, pyrrolyl, imidazolyl, etc.), a carbamoyl group (eg, carbamoyl, N-ethylcarbamoyl, etc.) , A sulfamoyl group (for example, sulfamoyl, N, N-dimethylsulfamoyl and the like),
Acylamino groups (eg, acetylamino, propionylamino, benzoylamino, etc.), acyl groups (eg,
Acetyl, benzoyl, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl group), sulfonamide group (eg, methanesulfonylamide, benzenesulfonamide, etc.), sulfonyl group (eg, methanesulfonyl, butanesulfonyl, p-toluenesulfonyl) ), And any group such as a carboxy group can be substituted.

In the general formulas (3) and (4), L ¹ to
L ⁴ each independently represents a nitrogen atom or a methine carbon,
Examples of the group substituted on the methine carbon include a lower alkyl group (eg, methyl, ethyl, trifluoromethyl, benzyl, etc.), an alkoxy group (eg, methoxy, ethoxy, etc.), an alkylthio group (eg, methylthio, ethylthio) Etc.), acyl group (eg, acetyl group etc.), halogen atom (eg, fluorine atom, chlorine atom,
A bromine atom, an iodine atom, etc.), a cyano group, an aryl group (e.g., phenyl, carboxyphenyl, etc.), a heterocyclic group (e.g., 2-thienyl, 2-furyl, 1,3-bis (2-methoxyethyl) ) -6-Hydroxy-2,4-dioxo-1,2,3,4-tetrahydro-5-pyrimidyl, 5-hydroxy-3-methyl-1-phenyl-4-
Pyrazolyl, etc.). In addition, methine carbon is adjacent methine carbon or methine carbon separated,
It may be bonded through an alkylene group to form a 5- or 6-membered carbocyclic ring, or may be bonded to a substituent on the nitrogen atom forming an azole ring bonded to the methine chain to form a 5- or 6-membered carbon ring. A nitrogen-containing heterocyclic ring may be formed. The following are specific examples.

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In the formula, Z ^A has the same meaning as Z in formula (3). R ^A and R ^B each represent a hydrogen atom, an alkyl group or an aryl group; R ^C represents a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an aryl group, an amino group, a heterocyclic group or a halogen atom; Represents an atom, and t is an integer of 2 or 3. Examples of the alkyl group represented by R ^A , R ^B and R ^C include, for example, methyl, ethyl,
Lower groups such as propyl and isopropyl; examples of aryl groups include groups such as phenyl and p-tolyl; examples of alkoxy groups include groups such as methoxy and ethoxy; Examples of the group include groups such as methylthio; examples of the aralkyl group include groups such as benzyl, phenethyl and m-bromobenzyl; examples of the heterocyclic group include morpholino, piperidino, pyrrolidino, imidazolyl, Each group such as pyrrolyl is exemplified.

Examples of the amino group represented by R ^C include groups such as N, N-dimethylamino and N, N-diethylamino. Examples of the halogen atom include atoms such as fluorine and chlorine. Can be

In the general formula (4), Q represents 5
Represents an atom group necessary for forming a 6-membered or 6-membered carbon ring or a heterocyclic ring, and specific examples of the formed ring include the following.

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[0051]

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In the formula, R ^a , R ^b and R ^c each represent a hydrogen atom or a substituent, and the substituent may be an alkyl group (eg, methyl, ethyl, octyl, sec-octyl, carboxymethyl, hydroxy Ethyl, etc.), an aralkyl group (eg, o-sulfobenzyl, etc.), an allyl group (eg, allyl group, etc.), an aryl group (eg, phenyl, p-tolyl, p-methanesulfonylaminophenyl, etc.) or a heterocyclic group ( For example, thienyl, furyl, pyridyl and the like) and the like. Further, when substituted on a carbon atom, R ^a and R ^b are a halogen atom (fluorine atom, chlorine atom, etc.), a trifluoromethyl group, an alkoxy group (each group such as methoxy, ethoxy, etc.), a hydroxy group,
Cyano group, aryloxy group (such as phenoxy), styryl group, carbamoyl group, sulfamoyl group, acylamino group (such as acetylamino group), acyl group (such as acetyl group), alkoxycarbonyl group (such as ethoxycarbonyl group), and sulfone It represents groups such as an amide group (such as a methanesulfonylamide group), a sulfonyl group (such as a methanesulfonyl group), a carboxy group, and an amino group (such as an N, N-dimethylamino group).

In the above general formula (3), X represents a cation or an acid anion.
Examples thereof include a proton, an organic ammonium ion (for example, each ion such as triethylammonium and triethanolammonium) and an inorganic cation (for example, each cation such as lithium, sodium, and potassium). Specific examples of the acid anion include a halogen ion. (Eg, chloride ion, bromine ion, iodine ion, etc.), p-toluenesulfonic acid ion, perchlorate ion, boron tetrafluoride ion, sulfate ion and the like. n is 0 when an internal salt is formed and the charge is neutralized.

The benzimidazole derivatives represented by the above general formulas (1) to (4) are polymethine dyes having a benzimidazole nucleus, and cyanine dyes and merocyanine dyes having two heterocyclic nuclei linked via a methine group. In addition to a complex cyanine dye having a plurality of heterocycles bonded thereto, a complex merocyanine dye, a hemicyanine dye, a styryl dye, an azacyanine dye, an azamerocyanine dye, and a holopolar dye can be used.

Further, the general formulas (1) to (4) of the present invention
The benzimidazole derivative represented by the formula (1) preferably has at least one hydrophilic group in the molecule. Examples of the hydrophilic group include a sulfo group, a carboxy group, a carbamoyl group, a sulfamoyl group, a phosphono group, a sulfate group, a hydroxy group, a sulfino group, and a sulfonylaminocarbonyl group (for example, a methanesulfonylaminocarbonyl group, an ethanesulfonylaminocarbonyl group etc),
Acylaminosulfonyl group (eg, acetamidosulfonyl group, methoxyacetamidosulfonyl group, etc.), acylaminocarbonyl group (eg, acetamidocarbonyl group, methoxyacetamidocarbonyl group, etc.), sulfinylaminocarbonyl group (eg, methanesulfinylaminocarbonyl group, ethane It preferably has a hydrophilic group such as a sulfinylaminocarbonyl group.

Further, the above-mentioned general formulas (1) to (4) of the present invention
The novel photosensitive dye represented by formula (1) can have an imidazolidene structure or an imidazolium ion structure in the ultimate structure of the resonance system.

The novel photosensitive dyes represented by the general formulas (1) to (4) of the present invention are different from conventionally known dyes having a benzimidazole ring in that they exhibit photographic properties such as fog and relative sensitivity after storage over time. It is characterized by good performance and little residual color contamination.

The reason is that at least one of the carbon atoms adjacent to the condensed position of the benzene ring condensed with the imidazole nucleus has a substituent, so that the adsorption state on silver halide grains and the formation of aggregates are reduced. It is presumed that the influence of the above is reduced, so that the photographic characteristics over time are improved and the residual color contamination is also reduced.

Hereinafter, specific examples of the benzimidazole derivative of the present invention will be shown, but the present invention is not limited thereto.

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The benzimidazole derivatives represented by the general formulas (1) to (4) are described, for example, in F.I. M. HAMER
"Cyanine Soybeans and Related Compounds" (John Wiley & Sons, N.
ew York, London 1964, published by Inter Science Publishers); M. S
TURMER, Heterocyclic Compounds.
Special Topics In Heterocyclic Chemistry "(John Wiley & Sons,
New York, London 1977) and the like, and can be synthesized with reference to a conventionally known method.

The benzimidazole derivatives represented by the general formulas (1) to (4) of the present invention can be added to a silver halide emulsion by a conventionally known method. For example, the protonated dissolution addition method described in JP-A-50-80826 and 50-80827, U.S. Pat.
No. 35, JP-A-50-11419, a method of dispersing and adding together with a surfactant, US Pat.
6,147, 3,469,987, 4,24
No. 7,627, JP-A-51-59942, and JP-A-51-59942.
No. 16624, No. 53-102732, No. 53-1
No. 02733, 53-137131, the method of dispersing and adding to a hydrophilic substrate, East German Patent No. 143,3
No. 24, the method of adding as a solid solution, or Research Disclosure 21, 802,
No. 40659, and a water-soluble solvent dissolving a dye represented by JP-A-59-148053 (for example, low-boiling solvents such as water, methanol, ethanol, propyl alcohol, acetone and fluorinated alcohol, dimethylformamide, methyl) High-boiling solvents such as cellsolve and phenylcellsolve) alone or in the form of a mixture thereof dissolved in a solvent. The benzimidazole derivative of the present invention represented by the general formulas (1) to (4) may be added at any stage during the emulsion production process from physical ripening to completion of chemical ripening. It is preferably added during the period from to the end of chemical ripening.

The addition of the benzimidazole derivative of the present invention during the physical ripening, prior to the chemical sensitizer in the chemical ripening step, or immediately after the addition of the chemical sensitizer, provides higher spectral sensitivity. It has an effect and is preferably used. The amount of the benzimidazole derivative of the present invention varies greatly depending on the conditions used and the type of emulsion, but the coverage of the monolayer on the surface of the photosensitive grains in the silver halide emulsion is from 40% to 90%. , And more preferably in the range of 50% to 80%. still,
The monolayer coverage is determined relative to the saturated adsorption amount when an adsorption isotherm is created at 50 ° C., as an amount corresponding to a coverage of 100%.

The silver halide emulsion used in the present invention may be used in combination with a conventionally known methine dye, and the ratio of the used methine dyes can be arbitrarily selected in an amount giving a desired sensitivity. Further, a dye which does not itself have a spectral sensitizing effect, or a benzimidazole derivative which does not substantially absorb visible light, and which contains a supersensitizer which enhances the sensitizing effect of the sensitizing dye is contained in the emulsion. You may. Examples of the sensitizing dye include a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, a hemioxonol dye, and a polymethine dye including oxonol, merostyril, and streptocyanin. it can.

The silver halide emulsion of the present invention can be chemically sensitized by chalcogen sensitization such as sulfur sensitization, selenium sensitization and tellurium sensitization, reduction sensitization and noble metal sensitization either alone or in an appropriate combination. The conditions of the chemical sensitization step, for example, p
There are no particular restrictions on H, pAg, temperature, time, etc.
It can be performed under conditions generally performed in the art.

In sulfur sensitization, an unstable sulfur compound can be used, and specifically, 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3- (2-thiazolyl) thiourea Preferred are thiourea derivatives, rhodanine derivatives, dithicarbamic acids, polysulfide organic compounds, thiosulfates, and sulfur alone. In addition, as the elemental sulfur, α-sulfur belonging to the orthorhombic system is preferable.

Other US Pat. No. 1,574,944,
No. 2,410,689, No. 2,278,947, No. 2,728,668, No. 3,501,313, No. 3,656,955, etc., and West German application publication (OL
S) 1,422,869, JP-A-56-24937
And the sulfur sensitizers described in JP-A-55-45016 and the like can be used.

For selenium sensitization, an unstable selenium compound can be used. For example, US Pat. No. 1,574,
No. 944, No. 1,602,592, No. 1,623,4
No. 99, JP-A-60-150046, JP-A-4-25
No. 832, No. 4-109240, No. 4-147250
No. etc. Useful selenium sensitizers include
Colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N ′)
-Triethylselenourea, N, N, N'-trimethyl-
N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketone (Eg, selenoacetone, selenoacetophenone, etc.), selenoamide (eg, selenoacetamide,
N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophos) Fate), selenides (dimethyl selenide, triphenylphosphine selenide, pentafluorophenyl-diphenylphosphine selenide, etc.)
Is mentioned. Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenides.

Specific examples of techniques for using these selenium sensitizers are disclosed in the following patent publications. US Patent 1,57
4,944, 1,602,592, 1,62
No. 3,499, No. 3,297,466, No. 3,29
7,447, 3,320,069, 3,40
8,196, 3,408,197, 3,44
2,653, 3,420,670 and 3,59
1,385, French Patent 2,693,038,
2,093,209, JP-B-52-34491,
Nos. 52-34492, 53-295, 57-2
No. 2090, JP-A-59-180536 and JP-A-59-1
Nos. 85330, 59-181337, 59-18
Nos. 7338, 59-192241, 60-150
No. 046, No. 60-151637, No. 61-2467
No. 38, JP-A-3-4221 and JP-A-3-24537,
3-1-111838, 3-116132, 3-
148648, 3-237450, 4-168
No. 38, No. 4-25832, No. 4-32831, No. 4-96059, No. 4-109240, No. 4-14
No. 0738, No. 4-140739, No. 4-14725
No. 0, No. 4-184331, No. 4-190225,
Nos. 4,191,729 and 4,195,035; British Patent Nos. 255,846; 861,984;
E. FIG. The Journal of Pho by Spencer et al.
toographic science, Vol. 31, 15
8 to 169 (1983).

In tellurium sensitization, an unstable tellurium compound can be used. For tellurium sensitizers and sensitization methods, see US Pat. Nos. 1,623,499 and 3,32.
Nos. 0,069, 3,772,031, 3,53
Nos. 1,289 and 3,655,394, British Patent No. 2
35,211, 1,121,469, 1,29
Nos. 5,462, 1,396,696, Canadian Patent No. 800,958, and JP-A-4-20464. Specifically, phosphine tellurides (eg, butyl-diisopropylphosphine telluride, tributylphosphine telluride, etc.), telluroureas (eg, N, N-dimethylethylene tellurourea, N, N-)
Diphenylethylene tellurourea), telluramides and the like.

In the noble metal sensitization, Research
Gold, platinum, palladium, iridium, and the like described in Disclosure Magazine Vol.
Noble metal salts such as osmium can be used. Examples of useful gold sensitizers include chloroauric acid, gold thiosulfate, gold thiocyanate, and the like, as well as U.S. Pat.
And organic gold compounds disclosed in JP-A Nos. 049,485, JP-B-44-15748, JP-A-1-147375 and JP-A-4-70650, and the like, and preferably combined with other chalcogen sensitization.

Depending on the properties of the compound to be used, the above-mentioned various sensitizers may be added by dissolving them in water or an organic solvent such as methanol, alone or in a mixed solvent, or by adding them to a gelatin solution in advance. As a method of mixing and adding, a method disclosed in JP-A-4-140739,
That is, a method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer may be used.

The emulsion used in the present invention may be subjected to chemical sensitization in the presence of a silver halide solvent. As the silver halide solvent used in the present invention, US Pat.
Nos. 1,157 and 3,574,628;
Organic thioethers described in JP-A Nos. 1019 and 54-158917, JP-A-53-82408,
Thiourea derivatives described in JP-A-55-77737 and JP-A-55-2982, JP-A-53-144319;
A silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A No.
Examples thereof include imidazoles, sulfites, and thiocyanates described in JP-A-54-100717.

In the reduction sensitization, Research D
The reducing compounds described in the publications of Isukurosu, Vol. 307, No. 307105 and JP-A-7-78685 can be used. Specifically, aminoiminomethanesulfinic acid (also called thiourea dioxide), borane compounds (for example, dimethylamine borane, etc.), hydrazine compounds (for example, hydrazine, p-tolylhydrazine, etc.),
Examples include polyamine compounds (eg, diethylenetriamine, triethylenetetramine, etc.), stannous chloride, silane compounds, reductones (eg, ascorbic acid, etc.), sodium sulfite, aldehyde compounds, hydrogen gas, and the like. Also, Japanese Patent Application Nos. 8-277938 and 8-25
The reduction sensitization may be performed in an atmosphere having a high pH or an excess of silver ions as disclosed in, for example, Nos. 1486 and 8-182035.

As a stabilizer for a silver halide photographic emulsion containing silver halide grains subjected to reduction sensitization, the following general stabilizers can be used.
Antioxidants disclosed in U.S. Pat. S. Gahler's paper [Zeithlift
fur wissenschaftliche Ph
autographie Bd. 63, 133 (196
9)] and thiosulfonic acids described in JP-A-54-1019 can often give good results. These compounds may be added at any stage of the emulsion production process from the crystal growth to the preparation process immediately before coating.

The silver halide emulsion used in the present invention is:
Fine grain silver iodide may be added during the process from chemical ripening to coating. Here, the process from chemical ripening to coating includes during chemical ripening and means that fine grain silver iodide is added to the process from coating to coating.

The fine grain silver iodide used in the present invention may be cubic γ-AgI or hexagonal β-AgI.
Or any of these crystal structures,
These mixtures may be used.

The addition timing of the fine grain silver iodide used in the present invention may be any of the steps from the chemical ripening step to immediately before coating, but is preferably the chemical ripening step.

The term "chemical ripening step" used herein refers to a step of adding a chemical sensitizer after completion of physical ripening and desalting of the emulsion used in the present invention, and then performing an operation for stopping the chemical ripening. Point to the time. The addition of the fine grain silver iodide may be carried out several times at intervals, or another chemically-ripened emulsion may be added after the addition of the fine grain silver iodide. The temperature of the emulsion used in the present invention at the time of adding fine grain silver iodide is preferably in the range of 30 to 80C, more preferably 40 to 65C.

The silver halide grains of the silver halide emulsion used in the present invention include silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride. Although silver particles can be used arbitrarily, it is particularly preferably silver iodochlorobromide, silver chlorobromide or silver chloride having a silver chloride content of 60 mol% or more.

The shape of the silver halide grains used in the present invention may be any shape. For example, cube, octahedron,
The shape may be a tetrahedron, a sphere, a flat plate, a potato, or the like.

Particularly preferred shapes of silver halide grains are tabular grains.

Hereinafter, tabular grains will be described as typical examples of the silver halide grains used in the present invention.

The tabular silver halide grains preferably used in the invention are crystallographically classified as twins. Twins are silver halide crystals having one or more twin planes in one grain, and the classification of twin morphology is based on the report by Klein and Moiser in Photographies Correspondents (Photographisches Korresp).
ondenz), Vol. 99, p. 99, and Vol. 100, p. 57.

The tabular silver halide grains preferably used in the present invention mainly have an even number of parallel twin planes, and these twin planes may or may not be parallel to each other. However, it is particularly preferable to have two twin planes.

The tabular silver halide grains used in the present invention have an average ratio (average aspect ratio) of grain diameter / thickness (aspect ratio) of 2 or more. The average aspect ratio of the tabular silver halide grains used in the present invention is preferably from 2 to 12, more preferably from 3 to 8.
It is.

The outer wall of the crystal of the tabular silver halide grains used in the present invention may be substantially composed of {111} planes or substantially {100} planes. In addition, it may have both the {111} plane and the {100} plane. In this case, 50% or more of the particle surfaces are {111} planes, more preferably 60% to 90%.
% Is {111} plane, particularly preferably 70 to 95%
Is the {111} plane. It is preferable that the plane other than the {111} plane is mainly the {100} plane. This surface ratio utilizes the difference in the adsorption dependency between the {111} plane and the {100} plane in the adsorption of the sensitizing dye [T. Tani, J .; I
imaging Sci. 29,165 (1985)]
Can be obtained by

The tabular silver halide grains used in the present invention may be polydisperse or monodisperse, but are preferably monodisperse.

Specifically, (standard deviation of particle size / average particle size)
× 100 = 25% when the width of the distribution is defined by the relative standard deviation (coefficient of variation) that can be expressed by the width (%) of the particle size distribution
The following are preferred, more preferably 20% or less, and particularly preferably 15% or less.

In the present invention, the tabular silver halide grains are preferably hexagonal. Hexagonal tabular grains (hereinafter also referred to as hexagonal tabular grains) are defined as the main plane (｛1
(11 ° plane) is hexagonal, and the maximum adjacency ratio is 1.0 to 2.0. Here, the maximum adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. In the present invention, the hexagonal tabular grains have a maximum adjacent side ratio of 1.0 to 1.0.
If it is 2.0, the corner may be rounded. The length of a side having a rounded corner is represented by the distance between the intersection of the extended straight line portion of the side and the extended straight line portion of the adjacent side. In addition, the corner is further removed,
It may be a circular tabular grain.

In the present invention, it is preferable that at least one half of each side forming the hexagon of the hexagonal tabular grain is substantially a straight line. In the present invention, the adjacent side ratio is 1.
More preferably, it is 0 to 1.5.

The silver halide grains used in the present invention may have dislocation lines. The dislocation is described, for example, in J. Mol. F. Ha
Milton, Photo. Sci. Eng, 57
(1967) and T.W. Shiozawa, J .; So
c. Photo. Sci. Japan, 35, 213
(1972) can be observed by a direct method using a low-temperature transmission electron microscope. In other words, the silver halide grains taken out so as not to apply enough pressure to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscopic observation, and the sample is prepared so as to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a state of cooling. At this time, since the electron beam is more difficult to penetrate as the thickness of the particles is larger, it is more clear to use a high-pressure electron microscope (200 KV or more for particles having a thickness of 0.25 μm) to observe more clearly. it can.

From the photographs of the particles obtained by such a method, the position and number of dislocations for each particle can be determined. The dislocation position of the silver halide grains used in the present invention is preferably generated in a region from 0.58 L to 1.0 L from the center of the silver halide grains toward the outer surface, and more preferably 0%. .80L to 0.98L. The direction of the dislocation line is approximately from the center toward the outer surface, but often meanders.

In the present invention, the center of the silver halide grains is defined by dispersing silver halide microcrystals in a methacrylic resin in the same manner as in the method described in the abstract of Inoue et al. Solidified, ultrathin sections with a microtome, with the largest cross-sectional area and 90%
Focusing on the sliced sample having the above cross-sectional area, this is the center of a circle when a circumscribed circle that is the smallest with respect to the cross section is drawn. In the present invention, the distance L from the center to the outer surface is defined as the distance between the point at which the line intersects the outer periphery of the particle when a straight line is drawn outward from the center of the circle and the center of the circle.

Regarding the number of dislocations in the silver halide grains used in the present invention, 50% of the grains containing one or more dislocations
The number (number) is desirably at least (number), and the higher the ratio (number) of the number of tabular grains having dislocation lines, the more preferable.

In the present invention, the particle diameter is a diameter when a projected image of a particle is converted into a circular image having the same area. The projected area of a grain can be determined from the sum of the grain areas. In each case, a silver halide crystal sample distributed on a sample table to such an extent that no grain overlap occurs can be obtained by observing the sample with an electron microscope.

The average projected area diameter of the tabular silver halide grains in the present invention is represented by a circle-equivalent diameter of the projected area of the grains, and is preferably 0.30 μm or more, more preferably 0.30 μm to 5 μm. More preferably 0.40μ
m to 2 μm.

The particle size can be obtained by projecting the particles at a magnification of 10,000 to 70,000 times with an electron microscope and actually measuring the projected area on the print.

Further, the average particle diameter (φi) is expressed by n
And when the frequency of particles having a particle size φi is ni, it can be obtained by the following equation.

Average particle size (φi) = Σnidi / n (The number of measured particles is indiscriminately 1000 or more.) The particle thickness can be obtained by obliquely observing the sample with an electron microscope. . The preferred thickness of the tabular grains preferably used in the present invention is 0.03 to 1.0.
μm, and more preferably 0.05 to 0.5 μm.

The ratio (b / a) of the longest distance (a) between two or more parallel twin planes of the silver halide grains of the present invention and the thickness (b) of the grains is preferably 5 or more. ,
It is preferable that the ratio is 50% (number) or more.

The tabular silver halide grains preferably used in the present invention may have a uniform composition, but may contain at least two silver halide grains having substantially different halogen compositions.
Grains having a core / shell structure having a two-layer structure may be contained in the photosensitive silver halide emulsion layer.

The silver halide grains used in the present invention are:
So-called halogen conversion type (conversion type) particles may be used. The halogen conversion amount is 0.1 to silver amount.
It is preferably from 2 mol% to 2.0 mol%, and the conversion may be performed either during physical ripening or after physical ripening. As a method of halogen conversion, an aqueous halogen solution or fine silver halide particles having a smaller solubility product with silver than the halogen composition of the grain surface before the halogen conversion is usually added. The particle size at this time is preferably 0.2 μm or less, more preferably 0.02 to 0.1 μm.

The silver halide grains used in the present invention are:
For example, it is preferable to grow the seed crystal by a method of precipitating silver halide on a seed crystal as described in Examples of JP-A-60-138538.

In the method for producing a silver halide photographic emulsion, a water-soluble silver salt solution and a water-soluble halide solution are supplied to a protective colloid in order to obtain a tabular silver halide emulsion used in the present invention. , (A) silver iodide content 0
A step of forming a core grain in which the pBr of the mother liquor is maintained at 2.5 to -0.7 for a period of 1/2 or more from the beginning of the formation of a silver halide precipitate of .about.5 mol%; continue,
A silver halide solvent is added to the mother liquor at a rate of
0 ^-5 mol to 2.0 mol content to or substantially provided seed grain formation step of forming a silver halide seed grains are twinned crystal monodisperse spherical, or subsequent to the nucleic particle generation step, the mother liquor A seed grain forming step of raising the temperature to 40 to 80 ° C. to form silver halide twin seed grains is provided; (c) a water-soluble silver salt solution, a water-soluble halide solution and / or silver halide fine particles Is preferably used to provide a growth step for enlarging seed particles. Here, the mother liquor is a liquid (including a silver halide emulsion) which is used for preparing a silver halide emulsion up to a completed photographic emulsion.

The silver halide grains formed in the grain forming step are twin grains composed of 0 to 5 mol% of silver iodide.

A water-soluble silver salt may be added for the purpose of adjusting ripening during the seed particle forming step used in the present invention. The seed grain growing step for enlarging the silver halide seed grains is carried out during the precipitation of silver halide and during the Ostwald ripening.
It is achieved by controlling Ag, pH, temperature, concentration of silver halide solvent and silver halide composition, and addition rate of silver salt and halide solution.

In preparing the emulsion used in the present invention, a known silver halide solvent such as ammonia, thioether, thiourea or the like can be present during the step of forming seed grains and growing the seed grains.

In order to obtain tabular silver halide grains used in the present invention, conditions for enlarging the produced seed grains include, for example, JP-A-51-39027 and JP-A-55-14.
No. 2329, No. 58-113928, No. 54-485
As described in JP-A Nos. 21 and 58-49938, a water-soluble silver salt solution and a water-soluble halide solution were added by a double jet method, and the addition rate was adjusted according to the enlargement of the particles. Alternatively, a method of gradually changing the change within a range in which the occurrence does not occur may be used. As another condition for enlarging the seed grains, a method of adding silver halide fine grains, dissolving and recrystallizing the grains, as shown in Item 88 of the Abstracts of the 58th Annual Meeting of the Photographic Society of Japan, may be used.

For growth, an aqueous silver nitrate solution and an aqueous halide solution can be added by a double jet method, but the iodine can also be supplied into the system as silver iodide.
The addition rate is such that no new nuclei are generated, and the rate at which the size distribution does not spread due to Ostwald ripening,
That is, it is preferable to add in a range of 30 to 100% of the rate at which new nuclei are generated.

In the production of the silver halide emulsion used in the present invention, stirring conditions during production are extremely important. As the stirrer, an apparatus disclosed in JP-A-62-160128 in which an additive liquid nozzle is installed in the liquid near the mother liquor suction port of the stirrer is particularly preferably used. In this case,
The rotation speed of the stirring is preferably set to 400 to 1200 rpm.

The silver iodide content and the average silver iodide content of the silver halide grains used in the present invention are determined by the EPMA method (El
electron Probe Micro Analyz
er). According to this method, a sample in which emulsion grains are well dispersed so as not to be in contact with each other is prepared, and elemental analysis of a part smaller than X-ray analysis by electron beam excitation in which an electron beam is irradiated can be performed. By this method, the halogen composition of each grain can be determined by determining the characteristic X-ray intensity of silver and iodine emitted from each grain. EP for at least 100 particles
If the silver iodide content is determined by the MA method, the average silver iodide content is determined from the average thereof.

In the preparation of the photosensitive silver halide emulsion used in the present invention, the seed emulsion has a total projected area of 50% of the seed grains.
% Or more have two or more parallel twin planes, and both the coefficient of variation of the thickness of the seed grains and the coefficient of variation of the longest distance (at) between the twin planes of the seed grains are 35% or less. It is preferred that

Even if the variation coefficient of only the thickness of the seed grains or only (at) is set to 35% or less, it is not possible to suppress the variation coefficient of the twin plane distance (a) of the grown grains to 35% or less. No, it is necessary that both be established at the same time.

This is probably because twin planes are generally formed at the stage of nucleation, but some are formed during growth.

Further, the silver halide grains used in the present invention may be used in the course of forming and / or growing grains, in the form of cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts. (Including complex salts) and iron salts (including complex salts) by adding at least one kind of metal ion, so that these metal elements can be contained inside the particles and / or in the particle surface layer. By placing in a reducing atmosphere, a reduction sensitizing nucleus can be provided inside the grain and / or on the grain surface.

The effect of the reducing agent added at a desired point in time of particle formation can be improved by adding an oxidizing agent such as hydrogen peroxide (water) and its adduct, peroxoacid salt, ozone, and I2 at a desired point in time. It is preferable to deactivate and suppress or stop the reducing agent.

The time of addition of the oxidizing agent can be arbitrarily selected from the time of silver halide grain formation to the time of chemical sensitization.

In the silver halide emulsion of the silver halide photographic light-sensitive material of the present invention, unnecessary soluble salts may be removed at the end of the growth of silver halide grains, or may be kept contained. Research to remove the salts
Disclosure (hereinafter abbreviated as RD) No. 1764
It can be carried out based on the method described in No. 3, paragraph II.

The silver halide emulsion layer containing the group of grains in the present invention may contain grains of various shapes as long as the effects of the present invention are not impaired.

The silver halide emulsion used in the present invention is:
Various antifoggants and stabilizers can be contained for the purpose of preventing fogging during the production process, storage or processing of the photographic material and stabilizing photographic performance. Specifically, tetrazaindenes, azoles, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, thioketo compounds, benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonamide, hydroquinone derivatives, aminophenol derivatives, gallic acid Derivatives and ascorbic acid derivatives.

In the silver halide light-sensitive material of the present invention, various photographic additives can be used. Known additives include, for example, Research Disclosure (RD) N
o. No. 17643 (December 1978); 187
16 (November 1979) and No. 16 308119
(December 1989). The types of compounds and the locations described in these three RDs are listed below.

[0140]

[Table 1]

The silver halide photographic light-sensitive material of the present invention contains a developing agent such as aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone in the emulsion layer or other layers. May be.

The support usable in the silver halide photographic light-sensitive material of the present invention includes, for example, RD-1 described above.
7643 and RD-308119, page 1009. A suitable support is a polyethylene terephthalate film or the like, and the surface of these supports may be provided with an undercoat layer for improving the adhesion of the coating layer, or may be subjected to corona discharge, ultraviolet irradiation, or the like.

The following are specific examples of the present invention, but the present invention is not limited thereto.

[0144]

EXAMPLES Example 1 Synthesis of Compound D-29

[0145]

Embedded image

In 5 g of dimethyl sulfoxide (hereinafter referred to as DMSO), 2.5 g of compound 29A and 2.5 g of compound 29B
1.6 g, and mixed with 1,8-diazabicyclo [5,4,
0] Add 1.8 g of undec-7-ene (DBU) to obtain 1
The mixture was heated and stirred at 00 ° C. for 15 minutes. After cooling to room temperature, 15 ml of ethyl acetate was added to precipitate the reaction product. The mixture was decanted and separated from the supernatant, and ethanol was added to the remaining precipitate, dispersed and filtered. The obtained crude crystals were recrystallized from a mixed solution of methanol and dichloromethane to give orange crystals.
g was obtained.

The product was identified as the target product (Compound D-29) by NMR spectrum and mass spectrum.

Example 2 Synthesis of Compound D-31

[0149]

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In 5 g of dimethyl sulfoxide (hereinafter referred to as DMSO), 2.5 g of compound 31A and 2.5 g of compound 31B
After mixing 2.2 g, 1,8-diazabicyclo [5,4,
0] Add 1.6 g of undec-7-ene (DBU) and add 1
The mixture was heated and stirred at 00 ° C. for 5 minutes. After cooling to room temperature, 15 ml of ethyl acetate was added to precipitate the reaction product. The mixture was decanted and separated from the supernatant, and ethanol was added to the remaining precipitate, dispersed and filtered. The obtained crude crystals were recrystallized from a mixed solution of methanol and dichloromethane to give 1.6 g of orange crystals.
Obtained.

The product was identified as the target compound (Compound D-31) by NMR spectrum and mass spectrum.

Example 3 Synthesis of Compound D-68

[0153]

Embedded image

Compound 68A in 60 ml of methanol
5 g and 1.1 g of Compound 68B were mixed, 1.0 g of triethylamine was added, and the mixture was heated under reflux for 40 minutes, and the generated crystals were collected by filtration. 1.8 g recrystallized from methanol
Was obtained.

The product was identified as the target compound (Compound D-68) by NMR spectrum and mass spectrum.

Example 4 A high-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, on the side to be coated with the emulsion layer, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce a reflective support. Each layer having the following constitution was coated on this reflective support to prepare a silver halide photographic material. The coating solution was prepared as follows.

Magenta coupler (M-1) 12.14
g, additive (ST-1) 12.14 g, (ST-2) 1
0.32 g, and high boiling organic solvent (DIDP) 7.9
g, (DBP) 7.9 g, ethyl acetate 60 ml was added and dissolved, and this solution was added with 20% surfactant (SU-1) 12 m
The resulting mixture was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 1 using an ultrasonic homogenizer to prepare a magenta coupler dispersion.

This dispersion was mixed with a silver halide emulsion (containing 8.5 g of silver) prepared under the following conditions to prepare a first layer coating solution. The second layer coating solution was prepared in the same manner as the first layer coating solution. (H-1) was added to the second layer as a hardener. Surfactants (SU-2), (S
U-3) was added to adjust the surface tension.

Using the coating solution prepared as described above,
A silver halide photographic light-sensitive material was prepared. The layer structure is shown in Table 2 below.

[0160]

[Table 2]

[0161]

Embedded image

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sulfosuccinate
Sodium salt SU-3: sulfosuccinic acid di (2,2,3,3,4
4,5,5-octafluoropentyl) sodium salt DIDP: di-i-decyl phthalate DBP: dibutyl phthalate H-1: tetrakis (vinylsulfonylmethyl) methane (Preparation of silver halide emulsion) The following (Solution A) and (Solution B) were simultaneously added to one liter of a 1% aqueous solution of gelatin while controlling the pAg at 7.3 and the pH at 3.0, and the following (Solution C), (Solution D) and (Solution E) and (Solution F) were added simultaneously while controlling pAg = 8.0 and pH = 5.5. At this time, the pAg is controlled by Japanese Patent Laid-Open No. 59-45.
The pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10.0 g Water was added to 200 ml (Solution C) Sodium chloride 92.1 g Potassium bromide 87g Water was added and 538ml (D solution) Silver nitrate 269g Water was added and 538ml (Solution E) Sodium chloride 10.6g Potassium bromide 0.13g Water was added and 62ml (Solution F) Silver nitrate 31g Water was added and 62ml was added. Thereafter, desalting was carried out using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co. and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle diameter of 0.43 μm.
m, coefficient of variation (S / R) = 0.08, silver chloride content 9
A 9.5 mol% monodisperse cubic emulsion (EMP-11) was obtained.

Next, the following compounds were optimally chemically sensitized at 60 ° C. to give a green-sensitive silver halide emulsion (Em-G1).
01).

In the above Em-G101, GS-1
Was replaced by the sensitizing dyes shown in Table 3 to obtain a green-sensitive silver halide emulsion.

Sodium thiosulfate 3.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX stabilizer (STAB-2) 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye (GS- Aqueous solution of solid dispersion of 1) 4 × 10 ⁻⁴ mol / mol AgX

[0167]

Embedded image

STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole

[0169]

Embedded image

Each of these emulsions was divided into two, and one of them was coated with a dispersant and other additives as described above to prepare a coated sample. The other is once cooled and gelled, stored in a low-temperature oven for 2 days, and then redissolved to disperse and disperse other additives (HS-
5 etc.) to prepare a coated sample. (Sample No. I-
1 to I-22) Next, each of the obtained coated samples was tested for storage stability over time under the following two conditions.

Condition I: Left at 23 ° C., 55% RH for 3 days Condition II: Left at 30 ° C., 90% RH for 3 days Each sample was subjected to a three primary color separation filter using a sensitometer KS-7 (manufactured by Konica Corporation). After performing green light wedge exposure, the following development processing was performed.

It should be noted that Konica Color QA paper type A5 was printed and run until the processing solution was replenished with a replenisher twice the tank capacity of the color developing solution in advance.

The developing process and the composition of the processing solution are shown below. The replenishment amount was expressed as an amount per 1 m ² of the photographic material.

(Processing Step) Processing Step Processing Temperature Time Replenishment Color Development 39.0 ± 0.3 ° C. 45 seconds 40 ml Bleaching and Fixing 35.0 ± 0.5 ° C. 45 seconds 51 ml Stabilization 30-34 ° C. 45 seconds 250 ml ( (3 tank cascade) Drying 60 to 80 ° C. for 30 seconds The compositions of the tank solution and the replenisher of the developing solution are shown below.

(Color developer tank solution and replenisher) (Tank solution) (Replenisher) Pure water 800 ml 800 ml triethanolamine 10 g 14 g N, N-diethylhydroxylamine 3.6 g 5 g potassium chloride 4.5 g-diethylenetriaminepentaacetic acid 5.0 g-potassium sulfite 0.4 g-N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 12.0 g potassium carbonate 25 g 35 g 1 liter, tank liquid pH = 1
At 0.10, the replenisher is adjusted to pH = 11.50.

(Bleaching and Fixing Solution Tank Solution and Replenisher) Ethylenediaminetetraacetate ammonium dihydrate 53 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 123 ml Ammonium sulfite (40% aqueous solution) 51 ml Adjust to 1 liter and adjust to pH = 5.4 with potassium carbonate or glacial acetic acid.

(Stabilizing solution tank solution and replenisher) o-phenylphenol 0.1 g Ubitex (manufactured by Ciba Geigy) 1.0 g zinc sulfate heptahydrate 0.1 g ammonium sulfite (40% solution) 5.0 ml 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 g Ethylenediaminetetraacetic acid 1.5 g Water is added to make up to 1 liter, and the pH is adjusted to 7.8 with glacial acetic acid or aqueous ammonia.

Performance Evaluation A processed sample was used as a PDA-65 type densitometer (Konica Corporation)
The density of the magenta dye was measured and the characteristic curve was determined, and then the sensitivity was determined by the reciprocal of the exposure required to give a density of fog + 0.5.

<Aged Storage> The silver halide emulsion was immediately coated without setting, and the obtained samples were stored under storage conditions I and II.
And SOII, sample No. Green light sensitivity SO of I-1
The relative values were shown with I as 100.

<Emulsion low-temperature stagnation> The sensitivity obtained after storing a silver halide emulsion under cooling conditions and then aging (approximately 12 hours) and storing the coated sample under storage condition I was defined as SSI. From the obtained sensitivities, the sensitivity fluctuation value in the emulsion set was determined as the low-temperature stagnation of the emulsion by the following formula.

ΔS = (SOI / SSI) The closer the ΔS value is to 1, the better the stability over time during setting. Table 3 shows the obtained results.

[0182]

[Table 3]

A *: (solid dispersion addition)
, And a predetermined amount of a dispersion aqueous solution obtained by stirring at a high speed with a dissolver was adjusted to a concentration of 0.5 w / v%.

B *: (solution added) D-methanol and 2,
The dye was adjusted to a 0.5% concentration in a 1: 1 mixed solvent of 2,3,3-fluoropropanol and a predetermined amount was added.

As is clear from Table 3, the comparative samples using the dyes having similar structures (GS-2, GS-3 and GS-4) showed large fluctuations in sensitivity when aged, and the size of the samples was It's changing in different ways. Like the control sample, the sample of the present invention suppresses fluctuation in sensitivity over time irrespective of the method of adding the dye, and obtains high green light sensitivity.

The control sample had good photographic performance, but was inferior in that strong residual color contamination having a maximum absorption at 510 to 515 nm was observed on a white background.

On the other hand, in the sample of the present invention, clear coloring was not observed in the white background portion, and the sample was excellent without residual color contamination.

When used in combination with the control dye GS-1, a higher sensitivity was obtained than in the case of using the individual dye alone, and a favorable effect was obtained. When a comparative dye is similarly combined, high sensitivity is obtained and storage stability over time is improved, but it is still insufficient.

[0189] The amount of Example 5 silver halide photographic light-sensitive material is particularly shows the number of grams per 1 m ² unless otherwise noted. Incidentally, silver halide and colloidal silver are shown in terms of silver, and photosensitive dyes are shown in moles per mole of silver halide in the same layer.

(Preparation of silver halide photographic emulsion) <Preparation of seed emulsion-1> Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 100 g potassium bromide 2.05 g 11.5 l with water B1 ossein gelatin 55 g potassium bromide 65 g potassium iodide 1.8 g 0.2N sulfuric acid 38.5 ml 2.6 liters with water C1 ossein Gelatin 75 g Potassium bromide 950 g Potassium iodide 27 g 3.0 liters with water D1 95 g silver nitrate 2.7 liters with water E1 1410 g silver nitrate 3.2 liters with water A1 solution kept at 60 ° C. in a reaction vessel, B1 solution and D1 The liquid was added over 30 minutes by the control double jet method, and then the C1 and E1 liquids were added over 105 minutes by the control double jet method. Stirring is 50
Performed at 0 rpm.

The flow rate was such that no new nuclei were generated with the growth of the particles and so-called Ostwald ripening was performed, and the flow rate was such that the particle size distribution did not widen. At the time of adding the silver ion solution and the halide ion solution, pAg was adjusted to 8.3 ± 0.05 using an aqueous potassium bromide solution, and pH was adjusted to 2.0 ± 0.1 using sulfuric acid.

After the addition was completed, the pH was adjusted to 6.0, and then extraneous salts were removed to remove extraneous salts.
A desalting treatment was performed by the method described in No. 6.

When this seed emulsion was observed with an electron microscope, it was found to be a tetrahedral monodisperse emulsion having a cubic shape with an average grain size of 0.27 μm and a grain size distribution of 17% and a slightly chipped corner.

<Preparation of Em-C> A monodisperse core / shell emulsion was prepared using Seed Emulsion-1 and the following seven kinds of solutions.

A2 ossein gelatin 10 g ammonia water (28%) 28 ml glacial acetic acid 3 ml seed emulsion-1 0.119 mole equivalent 11.5 liter with water B2 ossein gelatin 0.8 g potassium bromide 5 g potassium iodide 3 g with water 110 ml C2 ossein gelatin 2.0 g potassium bromide 90 g with water 240 ml D2 silver nitrate 9.9 g ammonia water (28%) 7.0 ml with water 110 ml E2 silver nitrate 130 g ammonia water (28%) 100 ml with water 240 ml F2 potassium bromide 94 g 165 ml of G2 silver nitrate 9.9 g with water 7.0 ml of ammonia water (28%) 110 ml of A2 solution was kept at 40 ° C. with water, and stirred at 800 rpm with a stirrer. The pH of Solution A2 was adjusted to 9.90 using acetic acid, and Seed Emulsion-1 was collected and dispersed and suspended. Then, Solution G2 was added at a constant speed over 7 minutes to adjust the pAg to 7.3. Further, solution B2 and solution D2 were added simultaneously over 20 minutes. At this time, the pAg was kept constant at 7.3. Further, pH = 8.8 using an aqueous solution of potassium bromide and acetic acid over 10 minutes.
3. After adjusting the pAg to 9.0, the C2 solution and the E2 solution were simultaneously added over 30 minutes.

At this time, the flow ratio between the start of addition and the end of addition was 1:10, and the flow rate was increased with time.
Further, the pH was lowered from 8.83 to 8.00 in proportion to the flow rate ratio. Further, when the C2 solution and the E2 solution were added in only ／ of the total amount, the F2 solution was additionally injected and added at a constant speed over 8 minutes. At this time, the pAg was 9.0 to 11.
It has risen to zero. Further, acetic acid was added to adjust the pH to 6.0.

After the addition, to remove excess salts, precipitation and desalting were carried out using an aqueous solution of Demol (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate.
5, an emulsion having an average silver iodide content of about 2.0 mol% at pH 5.85 was obtained at 40 ° C.

When the obtained emulsion was observed with an electron microscope, the average particle size was 0.55 μm, and the particle size distribution was 14%.
This was a rounded tetradecahedral monodisperse core / shell emulsion.

<Preparation of Seed Emulsion-2> Seed Emulsion-2 was prepared as follows.

A3 Ossein gelatin 24.2 g Water 9657 ml Polypropylene oxy-polyethylene oxy-disuccinate Na salt (10% aqueous ethanol) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml B3 2.5 N silver nitrate aqueous solution 2825 ml C3 odor Potassium iodide 824 g Potassium iodide 23.5 g Water 2825 L D3 1.75 N Potassium bromide aqueous solution The following silver potential control amount at 35 ° C: JP-B-58-58288 and 58-5828
The solution B3 was added to the solution A3 using the mixing stirrer shown in No. 9.
Then, 464.3 ml of each of the solution C3 and the solution C3 were added by the simultaneous mixing method over 2 minutes to form nuclei.

After stopping the addition of the solution B3 and the solution C3, it takes 60 minutes to raise the temperature of the solution A3 to 60 ° C., adjust the pH to 5.0 with a 3% KOH aqueous solution, and then again. The solution B3 and the solution C3 were added at a flow rate of 55.4 ml / min for 42 minutes by the simultaneous mixing method. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise from 35 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B3 and C3 was +8 mV using the solution D3. And +16 mV.

After the addition is completed, p
H was adjusted to 6, and immediately desalting and washing were performed. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0,
It was confirmed with an electron microscope that the average thickness of the hexagonal tabular grains was 0.06 μm and the average particle size (in terms of salt diameter) was 0.59 μm.

<Preparation of Em-D> A tabular emulsion was prepared using Seed Emulsion-2 and the following three kinds of solutions.

A4 ossein gelatin 5.26 g Polypropylene oxy-polyethylene oxy-disuccinate Na salt (10% aqueous solution of ethanol) 1.4 ml seed emulsion-2 equivalent to 0.094 mol 569 ml with water B4 ossein gelatin 15.5 g potassium bromide 114 g Potassium iodide 3.19 g 658 ml with water C4 166 g with silver nitrate 889 g with water 10 ml of B4 and C4 solutions in A4 solution stirred vigorously at 60 ° C
It was added by the double jet method in 7 minutes. During this time, the pH was kept at 5.8 and the pAg was kept at 8.7 throughout. B4 liquid and C4
The addition rate of the liquid was linearly increased so as to be 6.4 times at the beginning and at the end.

After completion of the addition, precipitation and desalting were carried out using an aqueous solution of Demol (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate to remove excess salts.
5, an emulsion having an average silver iodide content of about 2.0 mol% at pH 5.85 was obtained at 40 ° C.

When the obtained emulsion was observed with an electron microscope, a tabular halide having an average grain size of 0.98 μm, a grain size distribution of 15%, and an average aspect ratio of 4.5 was obtained for 82% of the projected area. It was silver particles. The average of the ratio (t / l) of the distance between twin planes (l) to the thickness (t) of tabular grains is 11
Met. The crystal plane was composed of a (111) plane and a (100) plane, the main planes were all (111) planes, and the ratio of the (111) plane to the (100) plane in the edge plane was 78:22.

These emulsions were adjusted to pH 5.8 and pAg to 7.0 with citric acid and sodium chloride.
The dyes or additives shown in Table 4 were added, and after optimal chemical ripening at 60 ° C. using ammonium thiocyanate, sodium thiosulfate pentahydrate and chloroauric acid, 4-hydroxy-6-methyl-1 was added. The ripening was stopped by adding 1.0 g of 3,3,3,7-tetrazaindene per mole of silver.

(Preparation of a silver halide photographic light-sensitive material) One side (surface) of a triacetyl cellulose film support is subjected to an undercoating process, and the surface opposite to the undercoated process is sandwiched between the supports. On the (back side), layers having the following compositions were sequentially formed from the support side.

Back surface first layer Alumina sol AS-100 (aluminum oxide) (manufactured by Nissan Chemical Industries, Ltd.) 0.8 g Back surface second layer Diacetyl cellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle diameter 0.2 μm) 50 mg Under On the surface of the triacetyl cellulose film support having been subjected to the drawing process, each layer having the following composition was sequentially formed from the support side to form a color photographic light-sensitive material (sample Nos. II-1 to II-).
44) was produced.

First layer: Antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Dye (CC-1) 0.02 g High boiling solvent (Oil-1) 0.20 g High boiling point solvent (Oil-2) 0.20 g Gelatin 1.6 g Second layer: Intermediate layer (IL-1) Gelatin 1.3 g Third layer: Silver halide photosensitive layer Silver halide emulsions C and D 0.9 g Dye (described in Tables 4 and 5) 3.4 × 10 ⁻⁴ mol / mol AgX Magenta coupler (M-1a) 0.30 g Magenta coupler (M-2a) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-1) 0.004 g High-boiling point solvent (Oil-2) 0.35 g Gelatin 1.0 g Fourth layer: first protective layer (Pro-1) Fine grain silver iodobromide emulsion (average grain size: 0,1). 08 μm 0.3 g UV absorber (UV-1) 0.07 g UV absorber (UV-2) 0.10 g Additive 1 (HS-1) 0.2 g Additive 2 (HS-2) 0.1 g High boiling solvent (Oil-1) 0.07 g High boiling solvent (Oil-3) 0.07 g Gelatin 0.8 g Fifth layer: Second protective layer (Pro-2) Additive 3 (HS-3) 0.04 g Additive 4 (HS-4) 0.004 g polymethyl methacrylate (average particle size 3 μm) 0.02 g methyl methacrylate: ethyl methacrylate: methacrylic acid copolymer (3: 3: 4 weight ratio) (average particle size 3 μm) 0.13 g gelatin 0.5g In addition, the above-mentioned applied sample further contains activators SA-2 and SA-
3, viscosity modifier, hardener H-1, H-2, stabilizer ST-
3, ST-4, ST-5 (weight average molecular weight 10,000)
And 1,100,000) dyes F-4, F
-5 and the additive HS-5 (9.4 mg / m ² ).

[0212]

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[0213]

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[0214]

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[0215]

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[0216]

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Each of the prepared samples was divided into two parts, one of which was left as it was, and the other was left for 3 days in an atmosphere of 80% RH and 40 ° C. in order to evaluate the stability under high temperature, and then forcibly. Deteriorated.

[Evaluation of photographic performance] Each of the obtained samples was exposed to a wedge with white light for 1/100 second, and then subjected to development, bleaching and fixing according to the following processing steps. The density of the processed sample was measured using an optical densitometer (PDA-65 manufactured by Konica), and the sensitivity was defined as the reciprocal of the exposure at fog density +0.03 as usual. The fog increase (ΔF) with respect to the sample immediately after application and drying of the sample after the forced deterioration treatment
og) and the relative sensitivity (S ') of the sample after forced deterioration when the sensitivity of the sample immediately after coating and drying was set to 100.

The results are shown in Tables 4 and 5.

(Processing step) Step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 seconds 38 ± 2.0 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 60 seconds 55 ± 5.0 ° C.-* The replenishing amount is a value per 1 m ² of the photosensitive material.

<Preparation of Processing Agent> (Developer Composition) Water 800 ml Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g 4 -Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetetraaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to make up to 1.0 liter, Adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

(Composition of developing replenisher) Water 800 ml Potassium carbonate 35 g Sodium bicarbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl- N- (β-hydroxyethyl) aniline sulfate 6.3 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 2.0 g Water was added to make up to 1.0 liter, and the pH was adjusted to 10 with potassium hydroxide or 20% sulfuric acid. Adjust to .18.

(Bleach liquid composition) Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Adjust to pH 4.4 with water or glacial acetic acid.

(Bleach replenisher composition) Water 700 ml 1,3-Diaminopropanetetraacetate ammonium (III) ammonium 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g Adjust to pH 4.0 with aqueous ammonia or glacial acetic acid.

(Formulation of Fixing Solution) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g Water was added to make up to 1.0 liter, and the pH was adjusted to 6.2 with aqueous ammonia or glacial acetic acid.

(Formulation of Fixing Replenisher) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Add water to make up to 1.0 liter, and adjust to pH 6.5 with aqueous ammonia or glacial acetic acid. .

(Preparation of Stabilizing Solution and Stabilizing Replenishing Solution) Water 900 ml p-octylphenol / ethylene oxide / 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml Add water to make up to 1.0 liter, and adjust to pH 8.5 using ammonia water or 50% sulfuric acid.

[0228]

[Table 4]

[0229]

[Table 5]

The silver halide photographic light-sensitive material of the present invention gave good photographic performance with high sensitivity over the same day and over time (substitute thermo) and reduced fog and sensitivity fluctuation, as compared with the comparative sample. In addition, it was excellent in comparison of residual color contamination.

Example 6 (Preparation of silver halide photographic emulsion A) Silver chloroiodobromide (62 mol% of silver chloride, 0.5 mol% of silver iodide and the others were bromide) Silver) emulsion was prepared.

During the mixing step from the formation of 5% of the final average particle size to the final average particle size, K ₂ IrC
₁₆ × 8 ^-7 mol per mol of silver was added. Then
After desalting by flocculation using denatured gelatin treated with phenyl isocyanate, the resultant is dispersed in gelatin, and the above compound HS-5 is added as a deodorant, and a cubic monodisperse having an average particle diameter of 0.3 μm is added. Particles (coefficient of variation 10
%).

The emulsion was mixed with citric acid and sodium chloride.
After adjusting H to 5.8 and pAg to 7.0, it was optimally chemically aged at 60 ° C. using sodium thiosulfate pentahydrate and chloroauric acid, and then 1-phenyl-5-mercaptotetrazole was added. 4-hydroxy-6-methyl-1,3,3
a, 7-tetrazaindene was added in an amount of 60 m
The ripening was stopped by adding g and 600 mg.

Then, the following additives SA-1 and NU
An appropriate amount of -1, NA-1, LX-1 and HD-1 was added to prepare an emulsion coating solution.

[0235]

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(Preparation of silver halide photographic emulsion B) A silver chloroiodobromide (62 mol% of silver chloride, 0.5 mol% of silver iodide and silver bromide in other moles) was prepared by a double jet method. Was prepared.

Desalting was performed by flocculation using denatured gelatin treated with phenyl isocyanate, then dispersed in gelatin, and the above compound HS-5 was used as a deodorant.
Was added to obtain an emulsion composed of cubic monodisperse particles having an average particle diameter of 0.3 μm (coefficient of variation: 10%). The emulsion was adjusted to pH 5.8 and pAg to 7.0 with citric acid and sodium chloride, and then optimally chemically ripened at 60 ° C. using sodium thiosulfate pentahydrate and chloroauric acid. 1-phenyl-5-mercaptotetrazole and 4-hydroxy-6
The ripening was stopped by adding 60 mg and 600 mg of -methyl-1,3,3a, 7-tetrazaindene, respectively, per mol of silver.

(Preparation of Silver Halide Photographic Emulsion C) A silver chloroiodobromide emulsion (40 mol% of silver chloride, 0.5 mol% of silver iodide, and silver bromide in each other) was prepared by a double jet method. Was prepared.

In the mixing step from the formation of 5% of the final average particle size to the final average particle size, K ₂ IrC
₁₆ × 8 ^-7 mol per mol of silver was added. After desalting by a flocculation method using denatured gelatin treated with phenyl isocyanate, the resultant was dispersed in gelatin, and the above-mentioned compound HS-5 was added as a deodorant.
An emulsion composed of μm cubic monodisperse grains (coefficient of variation: 10%) was obtained.

The emulsion was mixed with citric acid and sodium chloride.
After adjusting H to 5.8 and pAg to 7.0, it was optimally chemically aged at 60 ° C. using sodium thiosulfate pentahydrate and chloroauric acid, and then 1-phenyl-5-mercaptotetrazole was added. 4-hydroxy-6-methyl-1,3,3
a, 7-tetrazaindene was added in an amount of 60 m
The ripening was stopped by adding g and 600 mg.

The emulsions B and C thus obtained were chemically sensitized in the same manner as the emulsion A described above, and the same additives were added to prepare emulsion coating solutions.

(Preparation of silver halide photographic light-sensitive material) One side of a 100 μm-thick polyethylene terephthalate film having a 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19994) On the undercoat layer, a silver halide emulsion layer having the following formulation (1) was
/ M ² and a silver amount of 3.2 g / m ^2, and an emulsion protective layer of the following formula (2) is further coated thereon with a gelatin amount of 1.0 g / m ^2.
g / m ^2, and a backing layer on the other undercoat layer on the opposite side according to the following formula (3) so that the gelatin amount becomes 2.4 g / m ^2. Further, a backing protective layer of the following formula (4) was further applied thereon so that the amount of gelatin became 1.0 g / m ² , and samples III-1 to III-
31 was obtained.

Formulation (1) [Silver halide emulsion layer composition] Gelatin 2.0 g / m ² silver halide emulsion: Emulsions A, B, C 3.2 g / m ² Photosensitive dye: Compound of the present invention and comparative compound ( (Described in Table 6) 1.5 × 10 ⁻⁴ mol / mol silver Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: adenine 10 mg / m ² : 1-phenyl-5-mercaptotetrazole 5 mg / m ² Surfactant: saponin 0.1 g / m ² : SA-1 8 mg / m ² Hydrazine derivative: NU-1 35 mg / m ² Nucleation promoter: NA- 170 mg / m ² latex polymer: LX-1 1.0 g / m ² polyethylene glycol (molecular weight 4000) 0.1 g / m ² Hardener: HD-1 60 mg / m ²

[0244]

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Formulation (2) [Emulsion protective layer composition] Gelatin 0.9 g / m ² Surfactant: SA-21 10 mg / m ² : SA-31 10 mg / m ² Matting agent: Single particle having an average particle size of 3.5 μm Dispersed silica 3 mg / m ² Hardener: 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Formulation (3) [Backing layer composition] Gelatin 2.4 g / m ² Surfactant: saponin 0.1 g / m ² : SA-1 6 mg / m ² Colloidal silica 100 mg / m ² Coloring dye: F-1 30 mg / m ² : F-2 75 mg / m ² : F-3 30 mg / m ²

[0246]

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Formulation (4) [Backing protective layer composition] Gelatin 1.0 g / m ² Surfactant: SA-21 10 mg / m ² Matting agent: Monodispersed polymethyl methacrylate having an average particle size of 5.0 μm 50 mg / m ² Hardener: glyoxal 35 mg / m ² Each of the obtained samples was divided into two parts, one of which was kept as it was and the other was subjected to 20% R for evaluation of stability under high temperature.
H, left in an environment of 50 ° C. for 3 days for forced deterioration.

(Evaluation of photographic performance) A wedge was tightly attached to the obtained sample, and a Wratten filter no. 1 through 21
0 gives ^-5 sec exposure were treated under the following conditions with a developer and fixer poured the rapid processing automatic processor GR-26S having the following composition (produced by Konica Corporation).

The obtained sample was subjected to an optical densitometer PDA-65.
(Manufactured by Konica Corporation), and the sensitivity was calculated by taking the reciprocal of the exposure at the fog density +0.3 as in the usual method.
o. The sensitivity was shown as a relative value with the sensitivity of the sample immediately after coating and drying of III-1 taken as 100.

The residual color contamination rank was evaluated by developing and fixing an unexposed film and visually evaluating the residual color when five sheets were superimposed.

A sample having no residual color is designated as the highest rank "5". Hereinafter, "4", "3", "3"
"2", "1" and the rank were sequentially reduced and evaluated.

The ranks “2” and “1” represent levels that are not preferred for practical use.

[Developer Composition] Potassium sulfite 60.0 g Hydroquinone 15.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 1.0 g Disodium ethylenediaminetetraacetate 0.5 g Potassium carbonate 50.0 g Potassium bromide 5.0 g 2-mercaptobenzimidazole 0.25 g 5-methylbenzotriazole 0.4 g Water was added to 1 liter, and the pH was adjusted to 10.5 with potassium hydroxide.

[Composition of Fixing Solution] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17.0 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g (aqueous solution in terms of Al ₂ O ₃ content of 8.1% W / V) (composition B) pure water (ion exchange water) (aqueous solution of 50% W / V) 17ml sulfate 4.7g aluminum sulfate 8. 5 g of the above composition A and composition B in 500 ml of water when using a fixing solution.
, And finished to 1.0 liter. The pH of the fixing solution was adjusted to 4.8 with acetic acid.

[Development Conditions] (Step) (Temperature) (Time) Development 38 ° C. for 20 seconds Fixing 35 ° C. for 20 seconds Washing 30 ° C. for 15 seconds Drying 50 ° C. for 15 seconds The results obtained are shown in Table 6.

[0256]

[Table 6]

As is clear from Table 6, the silver halide photographic light-sensitive material of the present invention was excellent in that fog and sensitivity fluctuation were suppressed on the same day and over time (thermo substitution) as compared with the comparative sample using a conventionally known dye. Photographic performance. This effect was remarkably observed in a silver halide photographic emulsion containing an iridium compound and having a high silver chloride composition concentration.

Further, it can be seen that the benzimidazole derivative of the present invention is superior to the comparative compound (I) also in terms of residual color contamination.

[0259]

According to the present invention, firstly, there is provided a novel benzimidazole derivative and a silver halide photosensitive material which is spectrally sensitized by using it as a photosensitive dye and has improved photographic characteristics. The second is to provide a silver halide photographic material having improved photographic characteristics such as residual color contamination with high sensitivity by using a novel photosensitive dye, and thirdly, sensitized by a novel photosensitive dye. Thus, a silver halide light-sensitive material having a silver halide photographic emulsion layer having improved photographic characteristics could be provided.

Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C07D 403/06 231 C07D 403/06 231 233 233 235 235 403/08209 403403 209 403/14 233 403/14 233 405/14 235 405 / 14 235 413/04 235 413/04 235 413/06 235 413/06 235 413/14 213 413/14 213 235 235 417/04 235 417/04 235 417/06 235 417/06 235 417/08 235 417 / 08 235 417/14 235 417/14 235 421/06 421/06 C09B 23/00 C09B 23/00 L G03C 1/10 G03C 1/10 1/12 1/12

Claims (8)

[Claims] 1. A benzimidazole derivative represented by the following general formula (1) or (2). Embedded image [Wherein, R ¹ and R ² each represent an aliphatic group, and V ^{1 to} V ⁴ each represent a hydrogen atom, a halogen atom or a substituent;
^A fused ring may be formed between ² and V ³ . A ¹ represents an atom group necessary for forming a methine dye by bonding through a conjugated chain. X represents an ion required to neutralize the intramolecular charge, and n represents a number required to neutralize the intramolecular charge.
However, V ¹ and V ⁴ are not simultaneously hydrogen atoms,
V ¹ and V ⁴ do not form a ring with other substituents. [Chemical formula 2] [Wherein, R ¹ and R ² each represent an aliphatic group, and V ^{1 to} V ⁴ each represent a hydrogen atom, a halogen atom or a substituent;
^A fused ring may be formed between ² and V ³ . A ² represents an atom group necessary for forming a methine dye by bonding through a conjugated chain. However, V ¹ and V ⁴ do not simultaneously become hydrogen atoms, and V ¹ and V ⁴ do not form a ring with other substituents. ] 2. The general formula (1) is a benzimidazole derivative represented by the following general formula (3), and the general formula (2) is a benzimidazole derivative represented by the following general formula (4). The benzimidazole derivative according to claim 1, wherein Embedded image Wherein each R ^1, R ² and R ³ represents an aliphatic group, V ¹
To V ⁴ each represent a hydrogen atom, a halogen atom or a substituent, and each of V ² and V ³ may form a condensed ring. L
^{1 to} L ³ each represent a nitrogen atom or a methine group, n ¹ represents an integer of 0 to 3, and n ² represents 0 or 1. Z
Represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic group, and may be condensed with a saturated carbon ring, a benzene ring, a naphthalene ring or a heterocyclic ring. X represents an ion necessary for neutralizing an intramolecular charge, and n represents a number required for neutralizing an intramolecular charge. However, V ¹ and V ⁴ do not simultaneously become hydrogen atoms, and V ¹ and V ⁴ do not form a ring with other substituents. [Formula 4] [Wherein, R ¹ and R ² each represent an aliphatic group, and V ^{1 to} V ⁴ each represent a hydrogen atom, a halogen atom, or a substituent;
L ^4, L ⁵ each represent a nitrogen atom or a methine group, n ³
Represents an integer from 0 to 3. Q represents an atomic group necessary for forming a 5- or 6-membered carbocyclic or heterocyclic ring, and may be condensed with a saturated carbocyclic ring, a benzene ring, a naphthalene ring or a heterocyclic ring. However, V ¹ and V ⁴ do not simultaneously become hydrogen atoms, and V ¹ and V ⁴ do not form a ring with other substituents. ] 3. The substituent V ^{1 of the} general formulas (1) to (4)
Represents a halogen atom or a substituent, and V ⁴ represents a hydrogen atom. The benzimidazole derivative according to claim 1 or 2, wherein 4. The substituent V ^{3 of the} general formulas (1) to (4)
Is a substituent selected from the group consisting of a halogen atom, a cyano group, a trifluoromethyl group, an aryl group, a sulfamoyl group, a carbamoyl group, and an alkoxy group. Imidazole derivatives. 5. The benz according to claim 1, wherein the substituent R ^{2 in the} general formulas (1) to (4) is an aliphatic group having 3 or less carbon atoms. Imidazole derivatives. 6. A silver halide emulsion comprising at least one of the benzimidazole derivatives represented by formulas (1) to (4). 7. A support having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers contains the silver halide emulsion according to claim 6. A silver halide photographic light-sensitive material comprising: 8. A support having at least one photosensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers contains the silver halide emulsion according to claim 6. A silver halide color photographic light-sensitive material comprising: