JPH0736075B2 - Silver halide photographic light-sensitive material and ultrahigh contrast negative image forming method using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material and a superhigh contrast negative image forming method using the same, and particularly to a silver halide used in a photomechanical process. The present invention relates to a photographic light-sensitive material and a super-high contrast negative image forming method using the same.

(Prior Art) In the field of graphic arts, image formation showing photographic characteristics of ultra-high contrast (especially gamma of 10 or more) in order to improve reproduction of continuous gradation images or halftone images by halftone dot images. System required.

Conventionally, a special developer called a lith developer has been used for this purpose. The lith developer contains only hydroquinone as a developing agent, and a sulfite salt as a preservative is used in the form of an adduct with formaldehyde so as not to impair the infectious developability thereof, and the concentration of free sulfite ion is extremely low (usually 0.1 Mol / l or less). Therefore, the lith developer has a serious drawback that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.

As a method of obtaining a high-contrast photographic property using a stable developing solution, U.S. Patent Nos. 4,224,401 and 4,168,977.
No. 4, No. 4,166,742, No. 4,317,781, No. 4,272,60
There is a method using a hydrazine derivative described in No. 6, No. 4,211,857, No. 4,243,739 and the like. According to this method, photographic characteristics with high contrast and high sensitivity can be obtained, and since it is permissible to add a high concentration of sulfite to the developing solution, the stability of the developing solution against air oxidation is not improved in the lith developer. Greatly improved compared to.

On the other hand, various light sources (for example, LE
D, He-Ne laser, Ar laser, etc.) have been developed and put into practical use, and it is necessary to select a spectral sensitizing dye in order to have optimum spectral sensitivity to the spectral energy distribution of these light sources. It has also been performed in systems using conventional lith developer. That is, in the above-mentioned image forming system using a hydrazine derivative to obtain a photographic characteristic of high contrast using a stable developing solution, a cation compound (Japanese Patent Application No. 58-24891, No. (No. 9347) promotes high feeling and high contrast, resulting in higher practical skill D _max (described later).

Even with spectral sensitizing dyes, by using cation dyes, higher performance than using anion dyes and betaine dyes
D _max is realized.

(Problems to be Solved by the Invention) However, at the same time, it causes an undesired phenomenon of an increase in black spots (also referred to as blacks and peppers), which causes a serious problem in the photomechanical process.

Therefore, great efforts have been made to improve black spots by using a cationic dye as a spectral sensitizing dye and maintaining its high practical skill D _max .

As a conventional means for improving black spots, for example, there is a means for reducing the amount of a hydrazine derivative used, but this means also causes high sensitivity / inhibition of contrast enhancement, and often the sensitivity, γ (gamma) and practical D _max With a drop.

Therefore, a system for improving black spots while maintaining high practical D _max and sensitivity by using cationic dyes has been strongly desired.

(Object of the invention) Therefore, the object of the present invention is to use a stable developer, γ is extremely high sensitive tone of more than 10, practical D _max and high photographic characteristics with a few black spots, various photographic characteristics, It is an object of the present invention to provide a silver halide photographic light-sensitive material having an optimum spectral sensitivity with respect to the spectral energy distribution of a light source and an image forming method using the same.

(Means for Solving Problems) An object of the present invention is to provide a photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein hydrazine is contained in the silver halide emulsion layer or other hydrophilic colloid layer. A silver halide photographic light-sensitive material characterized by containing 1 to 500 mg / m ^{2 of a} derivative and at least one cationic dye selected from cyanine, hemicyanine and rhodacyanine and ascorbic acid; After containing 0.15 mol / l or more sulfite ions,
It was achieved by a method of forming a super-high contrast negative image by processing with a developer having a pH of 10.5-12.3.

Hereinafter, the present invention will be described in detail.

The hydrazine derivative used in the present invention is preferably a compound represented by the following general formula (1). General formula (1) In the formula, A represents an aliphatic group or an aromatic group, B represents a formin group, an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, an alkoxy or aryloxycarbonyl group, a sulfinamoyl group. Represents an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, or a heterocyclic group, and R ₀ and R ₁ are both hydrogen atoms or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted Represents an arylsulfonyl group or a substituted or unsubstituted acyl group.

However, B, R ₁ and the nitrogen atom to which it is bonded may form a partial structure —N═C of hydrazone.

In the general formula (1), the aliphatic group represented by A preferably has 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms.
Is a linear, branched or cyclic alkyl group. The branched alkyl groups herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, an alkyl or arylsulfinyl group, a sulfonamide group, a carbonamido group.

Examples thereof include t-butyl group, n-octyl group, t-octyl group, cyclohexyl group, pyrrolidyl group, imidazolyl group, tetrahydrofuryl group and morpholino group.

The aromatic group represented by A in the general formula (1) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.
Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Among the isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring and the like, those containing a benzene ring are preferable.

Particularly preferred as A is an aryl group.

The aryl group or unsaturated heterocyclic group of A may have a substituent. Typical substituents include linear, branched or cyclic alkyl groups (preferably having 1 to 20 carbon atoms) and aralkyl groups (preferably having 1 to 3 carbon atoms in the alkyl moiety). Group), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably having 2 to 30 carbon atoms) Group), a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms), and the like.

A in the general formula (1) may have a ballast group incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and includes, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can choose from.

A in the general formula (1) may be one in which a group that enhances adsorption to the surface of the silver halide grain is incorporated.
Examples of the adsorptive group include thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group, US Patent Nos. 4,385,108, 4,459,347, and JP-A-59-195,233.
Issue 59-200,231 Issue 59-201,045 Issue 59-201,046
No. 59-201,047, 59-201,048, 59-201,049
And Japanese Patent Application Nos. 59-36,788, 60-11459 and 60-19739.

B is specifically a formyl group, an acyl group (acetyl group,
Propionyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, 4-chlorobenzoyl group, pyruvoyl group, methoxalyl group, methyloxamoyl group, etc., alkylsulfonyl group (methanesulfonyl group, 2
-Chloroethanesulfonyl group, etc.), arylsulfonor group (benzenesulfonyl group, etc.), alkylsulfinyl group (methanesulfinyl group, etc.), arylsulfinyl group (benzenesulfinyl group, etc.), carbamoyl group (methyl Carbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (dimethylsulfamoyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, methoxyethoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), sulfinamoyl Group (methylsulfinamoyl group etc.), alkoxysulfonyl (methoxyfurfonyl group, ethoxysulfonyl group etc.), thioacyl group (methylthiocarbonyl group etc.), thiocarbamoyl group (methylthiocarbamoyl group etc.) or heterocyclic group (pyridine Representing the etc.).

A formyl group or an acyl group is particularly preferable as B.

B in the general formula (1) is a partial structure of hydrazone together with R ₁ and the nitrogen atom to which they are bonded. May be formed.

In the above, R ₂ represents an alkyl group, an aryl group or a heterocyclic group. R ₃ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

R ₀ and R ₁ are a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of the substituent constants of the hamet is −0.5 or more). Group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of the substituent constants of Hamet is −0.5 or more, or a straight-chain, branched or cyclic unsubstituted or Substituted aliphatic acyl group (the substituent includes, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group). R ₀ and R ₁ are most preferably a hydrogen atom. preferable.

Specific examples of the hydrazine derivative are shown below. However, the present invention is not limited to the following compounds.

When the hydrazine derivative is contained in the photographic light-sensitive material, it is preferably contained in the silver halide emulsion layer, but other non-photosensitive hydrophilic colloid layers (eg protective layer,
Intermediate layer, filter layer, anti-halation layer, etc.). Specifically, when the compound to be used is water-soluble, as a water solution, and when it is poorly water-soluble, as a solution of water-miscible organic solvent such as alcohols, esters, and ketones, a hydrophilic colloid solution. Can be added to. When it is added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added after the completion of chemical ripening and before coating. Particularly, it is preferable to add it to the coating solution prepared for coating.

The content of the hydrazine derivative is optimal depending on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion layer, the type of antifoggant compound, etc. It is desirable to select the amount of and the method of testing for that selection is well known to those skilled in the art. Usually preferably 10 ^-6 to 1 × 10 ^-1 mol, especially 10 ^-5 to 4 ×, per mol of silver halide.
Used in the range of 10 ^-2 mol.

Further, the hydrazine derivative can be used by being mixed in the developing solution. In that case, the addition amount is 5 mg per liter of developer.
-5 g, especially 10 mg-1 g are preferred.

Next, the cationic dye used in the present invention will be described. The cyanine dye is represented by the following general formula (II).

General formula (II)Where Z¹And Z²Is required to form a 5- or 6-membered heterocycle.
Represents a group of essential atoms, whether they are the same or different
Good. Where R¹And R²Can be the same or different,
Represents a alkyl group or a substituted alkyl group. L¹, L²And
And L³Represents a methine group or a substituted methine group. p and
And q represents 0 or 1. m is 0, 1, 2 or 3
Represent. X₁ Represents an anion. k represents 1. F
The mycyanine dye is represented by the following general formula (III).

General formula (III)Where Z³Is Z¹And Z²Is synonymous with R³Is R¹And R²
Is synonymous with. L^Four, L^Five, L⁶And L⁷Is L¹, L²And L³
And r are synonymous with p and q. X₂ Is X₁
Is synonymous with and j is 1 or 2. n is 0 or 1
Or 2 for G¹And G²Can be the same or different
A hydrogen atom, an alkyl group or a substituted alkyl group,
Represents a reel group or a substituted aryl group, and G¹And G²When
May form a ring derived from a cyclic secondary amine.

The rhodacyanine dye is represented by the following general formula (IV).

General formula (VI) In the formula, Z ⁴ and Z ⁵ have the same meanings as Z ¹ and Z ² . R ⁴ and R ⁵ are synonymous with R ¹ and R ² . R ⁶ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or a heterocyclic group.

L⁸, L⁹, L^Ten, L¹²Is L¹, L², L³Is synonymous with. W¹Is 5
Represents the atomic group necessary to form a 6-membered heterocycle.
h and l have the same meaning as m. s and t are synonymous with p and q. X
₂ Is X₁ Is synonymous with. i is synonymous with k.

Examples of the 5- to 6-membered heterocycle formed by Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ include the following.

Thiazole nucleus (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, etc.), benzothiazole nucleus (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4
-Methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-
Methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiar, 5-chloro-6- Methylbenzothiazole, 5,6-methylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, etc., naphthothiazole nucleus (for example, naphtho [2,1-d] thiazole) , Naphtho [1,2-d] thiazole, naphtho [2,3-
d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole,
8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] thiazole, etc.), thiazoline nucleus (eg, thiazoline, 4-methylthiazoline, 4-
Nitrothiazoline, etc.), oxazole nucleus (eg, oxazole, 4-methyloxazole, 4-nitroxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, etc.), benzoxazole Nuclear (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole,
5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole,
6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6
-Dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, etc.), naphthoxazole nucleus (for example, naphtho [2,1-
d] oxazole, naphtho [1,2-d] oxazole,
Naphtho [2,3-d] oxazole, 5-nitronaphtho [2,1-d] oxazole etc.), isoxazole nucleus (eg 5-methylisoxazole, benzisoxazole etc.), oxazoline nucleus (eg 4,4- Dimethyloxazoline, etc.), selenazole nucleus (eg,
4-methylselenazole, 4-nitroselenazole, 4
-Phenylselenazole, etc.), benzoselenazole nucleus (eg, benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitro) Benzoselenazole, 5-chloro-6
-Nitrobenzoselenazole etc.), naphthoselenazole nucleus (eg naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole etc., tellurazole nucleus (eg benzoterrazole, 5-methylbenzoterrazole) , 5,6-dimethylterrazole, 5-methoxybenzoterrazole, 5-hydroxybenzoterrazole,
5-methylthiobenzoterrazole, 5,6-dimethoxybenzoterrazole, naphtho [1,2-d] tetrazole, 8-methylnaphtho [1,2-d] telrazole, 6-
Methoxynaphtho [1,2-d] terrazole etc.), 3,3-
Dialkyl indolenine nucleus (eg, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-6-nitroindolenine, 3,3 -Dimethyl-5-nitroloindolenine, 3,3-dimethyl-5-methoxyindolenine,
3,3,5-Trimethylindolenin, 3,3-dimethyl-5-
Chloroindolenin, etc.), imidazole nucleus {eg,
1-alkylimidazole, 1-alkyl-4-phenylimidazole, 1-alkylbenzimidazole, 1
-Alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-
5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl-6-
Chloro-5-cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-alkylnaphtho [1,2-d] imidazole,
1-allyl-5,6-dichlorobenzimidazole, 1-
Allyl-5-chlorobenzimidazole, 1-arylimidazole, 1-arylbenzimidazole, 1-
Aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1-aryl-5
-Cyanobenzimidazole, 1-arylnaphtho [1,
2-d] imidazole, the aforementioned alkyl group having 1 carbon atom
~ 8 things, such as methyl, ethyl, propyl,
An unsubstituted alkyl group such as isopropyl and butyl, a hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl, etc.) and the like are preferable. Particularly preferred are methyl group and ethyl group. The aforementioned aryl represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl and the like. }, A pyridine nucleus (eg, 2-pyridine, 4-pyridine, 5-methyl-
2-pyridine, 3-methyl-4-pyridine, etc., quinoline nucleus (for example, 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro -2-quinoline, 8-fluoro-2
-Quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-
Quinoline, 6-ethoxy-4-quinoline, 6-nitro-
4-quinoline, 8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 8-methoxy-4-quinoline, isoquinoline, 6-nitro-1
-Isoquinoline, 3,4-dihydro-1-isoquinoline,
6-nitro-3-isoquinoline), imidazo [4,5
-B] quinoxaline nucleus (for example, 1,3-diethylimidazo [4,5-b] quinoxaline, 6-chloro-1,3-diallylimidazo [4,5-b] quinoxaline, etc.), oxadiazole nucleus, thiadiazole A nucleus, a tetrazole nucleus, a pyrimidine nucleus and the like can be mentioned.

W ¹ forms a 5- to 6-membered nitrogen-containing heterocycle, and preferable examples of W ¹ include the following. For example, -S-, -O-, (R ₇ has the same meaning as R _{6 in} formula [IV]), -CH _2- , -CH = CH- and the like.

L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ ,
Among the methine groups and substituted methine groups represented by L ¹² , the substituents include, for example, an alkyl group (eg, methyl, ethyl, etc.), an aryl group (eg, phenyl, etc.), an aralkyl group (eg, benzyl group), a halogen ( For example, chloro, bromo, etc.), an alkoxy group (eg, methoxy, ethoxy, etc.) and the like, and the substituents of the methine chain may form a 4- to 6-membered ring.

Examples of the optionally substituted alkyl group represented by R ¹ , R ² , R ³ , R ⁴ , and R ⁵ include, for example, 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 alkyl groups { Unsubstituted alkyl groups (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl, etc.), substituted alkyl groups such as aralkyl groups (eg, benzyl, 2-phenylethyl, etc.), hydroxyalkyl groups ( For example, 2-hydroxyethyl, 3-hydroxypropyl, etc., an alkoxyalkyl group (eg, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl, etc.), a heterocyclic-substituted alkyl group (eg, 2- (pyrrolidine-2). -On-1-yl) ethyl, tetrahydrofurfuryl, etc.), 2-acetoxyethyl, carbome Toxymethyl, 2-methanesulfonylaminoethyl, allyl group, etc.}.

Examples of the alkyl group, substituted alkyl group, aryl group, substituted aryl group and heterocyclic group represented by R ⁶ include, for example, an alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms (for example, Methyl group, ethyl group, propyl group,
Isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, dodecyl group, octadecyl group, etc.),
Substituted alkyl group (for example, aralkyl group (for example, benzyl group, 2-phenylethyl group, etc.), hydroxyalkyl group (for example, 2-hydroxyethyl group, 3-hydroxypropyl group, etc.), alkoxyalkyl group (for example, 2
-Methoxyethyl group, 2- (2-methoxyethoxy) ethyl group, etc.), heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1-yl) ethyl group, tetrahydrofurfuryl group, 2-morpholinoethyl Group), 2-
Acetoxyethyl group, carbomethoxymethyl group, 2-methanesulfonylaminoethyl group, allyl group, etc.}, aryl group (eg, phenyl group, 2-naphthyl group, etc.), substituted aryl group (eg, 3-chlorophenyl group, 3-methylphenyl group) Groups, etc.), heterocyclic groups (eg, 2-pyridyl groups, 2-thiazolyl groups, etc.) and the like.

p, q, r, s, and t represent 0 or 1. m, l, h
Represents 0, 1, 2, or 3. k and i are 1,
j represents 1 or 2. n represents 0, 1 or 2.

Specific examples are shown below, but the scope of the present invention is not limited thereto.

These may be used alone or in combination of two or more. The amount of these dyes used is not particularly limited, but it is 1 × 10 ^-7 to 1 × 10 ^-2 , and particularly 1 × 10 ^-6 to 1 mol per mol of silver halide.
It is preferably 1 × 10 ⁻³ mol.

The ascorbic acid used in the present invention may be added to any layer such as an undercoat layer, an emulsion layer and a protective layer. The addition amount is 1 mg to 500 mg / m ² , preferably 10 mg to 200 mg / m ² , and more preferably 20 mg to 100 mg / m ² .

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide and silver iodochlorobromide, but 70 mol% or more, particularly 90 mol% or more is silver bromide. The silver halide consisting of The content of silver iodide is preferably 10 mol% or less, more preferably 0.1 to 5 mol%.

The average grain size of the silver halide used in the present invention is preferably fine grains (for example, 0.7 μ or less), and particularly preferably 0.5 μ or less. The particle size distribution is basically not limited, but it is preferably monodisperse. The monodispersion as used herein means that at least 95% by weight or the number of particles is composed of a particle group having a size within ± 40% of the average particle size.

The silver halide grains in the photographic emulsion may have a regular crystal such as a cube or octahedron,
Further, it may have irregular crystals such as spheres and plates, or may have a composite form of these crystal forms.

The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases. Two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof, etc. are allowed to coexist in the process of formation or physical ripening of silver halide grains. Good.

The silver halide particularly suitable for use in the present invention is prepared in the presence of 10 ⁻⁸ to 10 ⁻⁵ mol of iridium salt or its complex salt per mol of silver, and the silver iodide content on the surface of the grain is the average grain size. The silver haloiodide has a higher silver iodide content.
When an emulsion containing such a silver haloiodide is used, higher sensitivity and high gamma photographic characteristics can be obtained.

In the above, it is preferable to add the above-mentioned amount of iridium salt before the completion of physical ripening in the production process of the silver halide emulsion, particularly during grain formation.

The iridium salt used here is a water-soluble iridium salt or iridium complex salt, for example, iridium trichloride, iridium tetrachloride, potassium hexachloroiridium (III), potassium hexachloroiridium (IV), potassium hexachloroiridium (III), Examples include ammonium hexachloroiridium (III).

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate,
Sugar derivatives such as starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Synthetic hydrophilic polymeric substances can be used.

The silver halide emulsion used in the present invention may not be chemically sensitized, but may be chemically sensitized. As a method of chemically sensitizing a silver halide emulsion, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination. Good.

Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts of platinum, palladium, rhodium, etc. may be contained. Specific examples thereof are described in US Pat. No. 2,448,060 and British Patent 618,061.

As the sulfur sensitizer, in addition to the sulfur compound contained in gelatin, various sulfur compounds such as thiosulfate, thiouric acid compounds, thiazoles, rhodanines and the like can be used.

As the reduction sensitizer, a primary tin salt, amines, formamidine sulfinic acid, a silane compound or the like can be used.

The compounds described in Japanese Patent Application Nos. 58-248913 and 60-9347 can be added to the photographic light-sensitive material of the present invention for the purpose of promoting high sensitivity and high contrast. These may be used alone or in combination of two or more.

In the present invention, a cationic dye may be used in combination with one or all of anionic dyes, betaine dyes and uncharged dyes.

Examples of dyes which may be used in combination are JP-A-55-52050, Nos. 45 to 53.
The sensitizing dyes described in the page (for example, cyanine dye, methocyanine dye, etc.) can be mentioned.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, existing or during photographic processing, or stabilizing photographic performance. That is, azoles, for example, benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles. , Etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaine Dens), pentaazaindenes, etc .; many compounds known as antifoggants or stabilizers such as benzenethiosulphonic acid, benzenesulphonic acid, benzenesulphonic acid amide, etc. It can be obtained. Among these, preferred are benzotriazoles (eg, 5-methyl-benzotriazole) and nitroindazoles (eg, 5-nitroindazole).
Is. Further, these compounds may be contained in the treatment liquid.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers.
For example, chromium salts (chromium vanadium, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane) Etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s). -Triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid, etc.), and the like can be used alone or in combination.

For the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention, a coating aid, antistatic, slip property improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, contrast enhancement, sensitization). Various surfactants may be included for various purposes such as.

For example, saponin (steroidal), alkylene oxide derivative (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate,
Polyethylene glycol alcohol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid) Nonionic surfactants such as acid polyglycerides, alkylphenol polyglycerides, fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkylcarboxylic acid salts, alkylsulphonic acid salts, alkylbenzenesulphonic acid salts, alkyls Naphthalene sulfonate, alkyl sulfates,
Carboxyl groups, sulfo groups such as alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. , Anionic surfactants containing acidic groups such as phospho group, sulfate group, phosphate group; amphoteric groups such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides Surfactants; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and cationic surface active agents such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings. Using agents It can be.

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

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

The light-sensitive material of the present invention, for the purpose of improving dimensional stability,
It may contain a dispersion of a water-soluble or sparingly soluble synthetic polymer. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, and Acrylic acid, methacrylic acid, α, β
-Unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate,
A polymer having a monomer component of a combination of styrene sulfonic acid and the like can be used.

As the support of the light-sensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate and the like can be used, but polyethylene terephthalate film is most preferable.

In order to obtain super-high contrast and high-sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, the conventional infectious developer or US Pat.
It is not necessary to use the highly alkaline developing solution close to pH 13 described in 2,419,975, and a stable developing solution can be used.

That is, the silver halide light-sensitive material of the present invention contains sulfite ion as a preservative in an amount of 0.15 mol / l or more and has a pH of 10.5-1.
With a developer having a pH of 2.3, particularly pH 11.0 to 12.3, a sufficiently super negative tone image can be obtained.

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

In the silver halide light-sensitive material of the present invention, dihydroxybenzenes are particularly used as the main developing agent and 3-hydroxy compounds are used as the auxiliary developing agent.
It is suitable to be processed with a developing solution containing pyrazolidones or aminophenols. Preferably, dihydroxybenzenes in this developer are 0.05 to 0.5 mol / l, 3
-0.06 mol of pyrazolidones or aminophenols
Used together in the range of / l or less.

Further, as described in U.S. Pat. No. 4,269,929, addition of amines to a developing solution can increase the developing rate and shorten the developing time.

Other developers include alkali metal sulfites, carbonates,
A development inhibitor such as a pH buffer such as borate and phosphate, bromide, iodide, and an organic antifoggant (particularly preferably nitroindazoles or benzotriazoles) or an antifoggant You can Further, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant (particularly preferably the above-mentioned polyalkylene oxides), an antifoaming agent, a film hardener, and a film silver stain preventive agent. (For example, 2-mercaptobenzimidazole sulfonic acids, etc.) may be included.

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

The processing temperature in the process of the invention is usually chosen between 18 ° C and 50 ° C.

Although it is preferable to use an automatic processor for photographic processing, even if the total processing time from putting the light-sensitive material in the automatic developing machine until it comes out is set to 90 seconds to 120 seconds by the method of the present invention. , Photographic characteristics of negative gradation of ultra-high contrast can be obtained.

〔Example〕

 The present invention is described in detail below with reference to examples.

In the examples of the present invention, the developing solutions having the following formulations were used.

Developer Basic Formula Hydroquinone 35.0g N-methyl-p-aminophenol 1/2 sulfate 0.8g Sodium hydroxide 13.0g Potassium triphosphate 74.0g Potassium sulfite 90.0g Ethylenediaminetetraacetic acid tetrasodium salt 1.0g Potassium bromide 4.0 g 5-methylbenzotriazole 0.6 g 3-diethylamino-1,2-propanediol 15.0 g Water was added to 1 (pH = 11.5) pH = 11.5 was used to prepare developer (I) and 11.6 was used. (II).

Example 1 4 × 10 ⁻⁷ per 1 mol of Ag in an aqueous gelatin solution kept at 50 ° C.
An aqueous solution of nitrate and an aqueous solution of potassium iodide and potassium bromide were simultaneously added in the presence of 1 mol of iridium (III) hexachloride and ammonia for 60 minutes, and the pAg was kept at 7.8 during that period to obtain an average particle size of 0.25μ and an average iodine content. A cubic monodisperse emulsion having a silver halide content of 1 mol% was prepared. To these silver iodobromide emulsions, compounds as shown in Table 1 were added as sensitizing dyes, and further 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, poly Dispersion of ethyl acrylate, polyethylene glycol, 1,3-vinylsulfonyl-2-propanol, 1-phenyl-5-mercaptotetrazole, 1,4-bis [3- (4-acetylamino-pyridinio) propionyloxy] -tetra Methylene dibromide, compound I-3 and ascorbic acid were added in the amounts shown in Table 1 and coated on a polyethylene terephthalate film so that the amount of silver was 3.4 g / m ² . At the same time, a gelatin layer was coated on the emulsion layer so that the coating amount of gelatin was 1.0 g / m ² . Each sample was exposed and developed and photographic properties were measured. The results are shown in Table 1. As is clear from Table 1, the samples 2 to 7 of the present invention have a remarkable effect of improving the black spots without lowering the sensitivity, γ and the practical skill D _max as compared with the comparative sample. Photographic performance in Table 1,
The black spots were evaluated as follows.

The relative sensitivity was the relative value of the reciprocal of the exposure amount giving a density of 1.5 at 38 ° C. for 30 seconds development, and the value of Sample 1 was set to 100.

The black spots are evaluated on a scale of 5 by microscopic observation. "5" is the best and "1" is the worst quality.
"5" or "4" is practical, "3" is poor but practically practical, and "2" or "1" is not practical.
The one between "1" and "2" was evaluated as "1.5".

The evaluation of black spots is the result of developing solution II at 38 ° C. for 40 seconds.

Practical skill D _max evaluation method Manual typesetting paper PL-100WP (Fuji Photo Film Co., Ltd.)
The long horizontal line part of the character "shi" of the 7th grade of Mincho type printed by using the product was vertically scanned with a microdensitometer, and the line width (black part) of the optical density of the reflected light was 0.8.
Was confirmed to be 40μ. Using this as a manuscript, a reflection type plate-making camera DSC-351 (manufactured by Dainippon Screen Co., Ltd.) was used to take an image of the sample. The same part of the film is similarly scanned with a microdensitometer and the line width of the transmitted light at an optical density of 0.8 (white part)
The sample that has been exposed to light of 40 μ is called 1: 1 return condition. Under this 1: 1 return condition, the optical density of the transmitted light in the portion on the negative film (black solid portion) corresponding to the white background portion of the original is measured with the Macbeth densitometer TD-504 and evaluated as D _max . . Generally, the practical skill D _max is 3.5, which is close to the practical limit, and is preferably 4.0 or more.

Example 2 In the same manner as in Example 1, a sample containing a hydrazine compound and a sensitizing dye as shown in Table 2 and containing additives was prepared.

Each sample thus obtained was evaluated in the same manner as in Example 1 and the results shown in Table 2 were obtained.

As is clear from Table 2, it can be seen that Samples 17 to 22 of the present invention have improved black spots without deterioration in photographic properties.

(Effects of the Invention) As described above, according to the present invention, an image with few black spots can be obtained without deteriorating photographic characteristics such as sensitivity, γ (gamma), and practical skill D _max .

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ozomi Sasaoka 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd. (56) References JP-A-53-66731 (JP, A) JP-A-57-129436 (JP, A) JP-A-50-136381 (JP, A)

Claims (2)

[Claims] 1. A photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer or other hydrophilic colloid layer is selected from a hydrazine derivative and cyanine, hemicyanine and rhodacyanine. A silver halide photographic light-sensitive material containing at least one cationic dye and 1 to 500 mg / m ^{2 of} ascorbic acid. 2. A photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer or other hydrophilic colloid layer is selected from a hydrazine derivative and cyanine, hemicyanine and rhodacyanine. The silver halide photographic light-sensitive material containing 1 to 500 mg / m ^{2 of} at least one cationic dye and ascorbic acid is exposed to light, and then contains 0.15 mol / l or more of sulfite ion and has a pH of 10.5-12.3. A method for forming an ultrahigh contrast negative image, which is characterized in that development processing is carried out with the above developing solution.