JPH06161011A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material good in fogging pressure resistance and black spot. CONSTITUTION:In a silver halide photographic sensitive material having at least a photosensitive silver halide emulsion layer on a substrate, the silver halide photographic sensitive material contains an iridium compd. and a hydrazine derivative in at least one layer of emulsion layers, the silver halide particles are laminated structual particles, iodine is contained inside particles before completion of particles formation and iodine is not contained at all outside particles.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having less fog, excellent pressure resistance, and no black spots and high contrast.

[0002]

BACKGROUND OF THE INVENTION Generally, in a photolithography process, a high-contrast image forming method is used to convert a continuous tone original into a halftone dot image, that is, a change in the continuous tone density of the original is converted into the density. The process of converting to a set of halftone dots having a proportional area is included. For this purpose, a lith-type photosensitive material is used, and the original is photographed through an intersecting screen or a contact screen, and then the concentration of sulfurous acid is very low, and a developer called a lith-type developer containing only a hydroquinone developing agent is used. Is processed in. However, since the squirrel-type developer is apt to undergo auto-oxidation and has extremely poor stability, a control method for keeping the development quality constant even during continuous use is required as much as possible. Great efforts have been made to improve sex. Further, in the lith development, it takes a long time (induction period) until an image appears by development, so that an image cannot be obtained quickly.

On the other hand, there is known a method of rapidly obtaining a high-contrast image without using the lith developer. For example, as disclosed in U.S. Pat. Nos. 2,419,975, 4224401, JP-A-51-16623 and JP-A-51-20921, a hydrazine compound is contained in a silver halide light-sensitive material. According to these methods, the sulfite ion concentration in the developing solution can be kept high, and the processing can be performed in a state where the preservative property is enhanced. However, in the development process of printing plate making, an automatic developing machine is usually used to continuously work while replenishing a development replenisher according to the area of the processed film, and in such a working mode, a hydrazine derivative is used. When used, there was a problem that so-called black spots were likely to occur. The black spots mean that the developed silver image appears in spots even in the unexposed area. Moreover, the phenomenon of reciprocity failure is also observed, and both are serious problems in work.
On the other hand, JP-A-61-29837 discloses a method of adding a hydrazine derivative and an iridium compound to an emulsion containing emulsion grains having an adjusted iodide content. There is a problem that the contrast is insufficient, and the quality of the finished product is deteriorated due to the generation of black spots and pressure. On the other hand, Japanese Patent Application Laid-Open No.
No. 70647 discloses a method of solving by silver halide grains having a laminated structure, characterized in that the iodide content inside the grains is higher than that outside the grains. Fog tends to occur, and further improvements in black spots and pressure resistance are desired.

[0004]

SUMMARY OF THE INVENTION With respect to the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material having no black spots, good pressure resistance and high contrast.

[0005]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one of the emulsion layers contains an iridium compound and a hydrazine derivative. Characterized in that the silver halide grain is a laminated structure grain, which contains iodine inside the grain before the completion of grain formation and does not contain any iodine outside the grain. This is achieved by using a silver halide photographic light-sensitive material. Hereinafter, the present invention will be specifically described.

Examples of the hydrazine derivative used in the present invention include compounds represented by the following general formula [1], [2] or [3].

[0007]

[Chemical 1]

(Wherein R ₁ and R ₂ represent an aryl group or a heterocyclic group, R represents an organic bonding group, n is 0 to 6,
m represents 0 or 1, and when n is 2 or more, each R may be the same or different. )

[0009]

[Chemical 2]

(In the formula, R ₂₁ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₂₂ represents a hydrogen atom, an optionally substituted alkoxy group, a heterocyclic oxy group, an amino group or an aryloxy group. Where P ₁ and P ₂ are a hydrogen atom, an acyl group,
Alternatively, it represents a sulfonic acid group. )

[0011]

[Chemical 3]

(In the formula, Ar represents an anti-diffusion group or an aryl group containing at least one silver halide adsorption promoting group,
R ₃₁ represents a substituted alkyl group. In the general formula [1], R ₁ and R ₂ represent an aryl group or a heterocyclic group, R represents a divalent organic group, n represents 0 to 6, m represents 0 or 1.

Examples of the aryl group represented by R ₁ and R ₂ include a phenyl group and a naphthyl group, and examples of the heterocyclic group include a pyridyl group, a benzothiazolyl group, a quinolyl group and a thienyl group. R ₁ and R ₂ are preferably aryl groups. Various substituents can be introduced into the aryl group or heterocyclic group represented by R ₁ and R ₂ . Examples of the substituent include a halogen atom (eg chlorine, fluorine etc.), an alkyl group (eg methyl, ethyl, dodecyl etc.), an alkoxy group (eg tomexyl,
Ethoxy, isopropoxy, butoxy, octyloxy, dodecyloxy etc.), an acylamino group (eg acetylamino, pivalylamino, benzoylamino, tetradecanoylamino, α- (2,4-di-t-amylphenoxy) butyrylamino etc.), Sulfonylamino group (eg, methanesulfonylamino, butanesulfonylamino, dodecanesulfonylamino, benzenesulfonylamino, etc.), urea group (eg, phenylurea, ethylurea, etc.), thiourea group (eg, phenylthiourea, ethylthiourea, etc.), hydroxy group , An amino group, an alkylamino group (eg, methylamino, dimethylamino, etc.), a carboxy group, an alkoxycarbonyl group (eg, ethoxycarbonyl), a carbamoyl group,
Examples thereof include a sulfo group. Examples of the divalent organic group represented by R include an alkylene group (eg, methylene,
Ethylene, tolylethylene, tetramethylene, etc.), arylene group (eg, phenylene, naphthylene, etc.), aralkylene group, and the like.
A (R ₃ )-group (R ₃ represents a hydrogen atom, an alkyl group or an aryl group) may contain a sulfonyl group or the like. Various substitutions can be introduced for the group represented by R. Examples of the substituent include -CONHNHR ₄ (R ₄ is the above R ₁ and R ₂
The same meaning as), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a carboxy group, an acyl group,
An aryl group and the like can be mentioned.

R is preferably an alkylene group.

Of the compounds represented by the general formula [1], R ₁ and R ₂ are preferably substituted or unsubstituted phenyl groups, and n = m = 1 and R is an alkylene group.

Representative compounds represented by the above general formula [1] are shown below.

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[0019]

[Chemical 6]

The aliphatic group represented by R ₂₁ for the general formula [2] is preferably one having 6 or more carbon atoms, particularly a straight chain, branched or cyclic group having 8 to 50 carbon atoms. It is an alkyl group. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heraro atoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group and the like.

The aromatic group represented by R ₂₁ 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, pyrrolazole ring, quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, etc. preferable. Particularly preferred as R ₂₁ is an aryl group.

The aryl group or unsaturated heterocyclic group of R ₂₁ may be substituted, and a typical substituent is a linear, branched or cyclic alkyl group (preferably having an alkyl moiety having 1 to 20 carbon atoms). Monocyclic or bicyclic), 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 Has 2 to 30 carbon atoms), sulfonamide group (preferably 1 to 30 carbon atoms)
), Ureido group (preferably having 1 to 30 carbon atoms), and the like.

The alkoxy group which may be substituted among the groups represented by R ₂₂ has 1 to 20 carbon atoms and may be substituted with a halogen atom, an aryl group or the like.
Of the groups represented by R ₂₂ , the optionally substituted aryloxy group or heterocyclic oxy group is preferably a monocyclic group, and examples of the substituent include a halogen atom alkyl group, an alkoxy group and a cyano group. Preferred among the groups represented by R ₂₂ is an optionally substituted alkoxy group or amino group.

In the case of an amino group, N (A ₁ ) (A ₂ ) is a group in which A ₁ and A ₂ may be substituted, an alkyl group, an alkoxy group or a —O—, —S—, —N— group bond. It may be a cyclic structure containing. However, R ₂₂ is not a hydrazino group.

R ₂₁ or R ₂₂ 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 is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a funinoxy group, and an alkylphenoxy group. You can

R ₂₁ or R ₂₂ may have a group incorporated therein to enhance adsorption to the surface of the silver halide grain. Examples of the adsorptive group include groups described in US Pat. No. 4,355,105 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group and triazole group.

Among the compounds represented by the general formula [2], the compound represented by the following general formula [2a] is particularly preferable.

[0029]

[Chemical 7]

In the above general formula [2a], R ₂₃ and R ₂₄ are a hydrogen atom or an optionally substituted alkyl group (eg, methyl group, ethyl group, butyl group, dodecyl group, 2-hydroxypropyl group, 2-cyanoethyl group). Group, 2-chloroethyl group), optionally substituted phenyl group, naphthyl group, cyclohexyl group, pyridyl group, pyrrolidyl group (eg, phenyl group, p-methylphenyl group, naphthyl group, α-hydroxynaphthyl group, cyclohexyl group, p-methylcyclohexyl group, pyridyl group, 4-propyl-2-pyridyl group,
Pyrrolidyl group, 4-methyl-2-pyrrolidyl group), R
₂₅ represents a hydrogen atom or a benzyl group, an alkoxy group and an alkyl group which may be substituted (eg, benzyl group, p-methylbenzyl group, methoxy group, ethoxy group, ethyl group, butyl group).

R ₂₆ and R ₂₇ represent a divalent aromatic group (for example, a phenylene group or a naphthylene group), Y represents a sulfur atom or an oxygen atom, and L represents a divalent linking group (eg -S.
O ₂ CH ₂ CH ₂ NH-SO ₂ NH, -OCH ₂ SO ₂ NH, -O-, -CH = N-)
R ₂₈ represents —NR′R ″ or —OR ₂₉ ,
R ′, R ″ and R ₂₉ are hydrogen atoms, optionally substituted alkyl groups (eg methyl group, ethyl group, dodecyl group), phenyl groups (eg phenyl group, p-methylphenyl group, p-methoxyphenyl group) A naphthyl group (for example, an α-naphthyl group,
β-naphthyl group) or a heterocyclic group (for example, an unsaturated heterocyclic group such as pyridine, thiophene, furan, or a saturated heterocyclic group such as tetrahydrofuran or sulfolane), and R ′ and R ″ are nitrogen. A ring (eg, piperidine, piperazine, morpholine, etc.) may be formed with the atom.

M and n represent 0 or 1. When R ₂₈ represents OR ₂₉ , Y preferably represents a sulfur atom.

Representative compounds represented by the above general formulas [2] and [2a] are shown below.

[0034]

[Chemical 8]

Next, the general formula [3] will be described.

In the general formula [3], Ar represents an anti-diffusion group or an aryl group containing at least one silver halide adsorption promoting group, and the anti-diffusion group is commonly used in immobile photographic additives such as couplers. Preferred are ballast groups. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can

Examples of the silver halide adsorption-promoting group include thiourea group, thiourethane group, heterocyclic thioamide group, mercaptoheterocyclic group, triazole group and the like, US Pat. No. 4,385,108
The groups described in No. R ₃₁ represents a substituted alkyl group, and the alkyl group represents a linear, branched or cyclic alkyl group, and examples thereof include methyl, ethyl, propyl, butyl, isopropyl, pentyl and cyclohexyl groups.

Substituents introduced into these alkyl groups include alkoxy (eg, methoxy, ethoxy, etc.),
Aryloxy (such as phenoxy, p-chlorophenoxy and the like), heterocyclic oxy (such as pyridyloxy and the like), mercapto, alkylthio (methylthio, ethylthio and the like),
Arylthio (for example, phenylthio, p-chlorophenylthio, etc.), heterocyclic thio (for example, pyridylthio, pyrimidylthio, thiadiazolylthio, etc.), alkylsulfonyl (for example, methanesulfonyl, butanesulfonyl, etc.),
Arylsulfonyl (eg benzenesulfonyl etc.), Heterocycle sulfonyl (eg pyridylsulfonyl, morpholinosulfonyl etc.), Acyl (eg acetyl, benzoyl etc.), cyano, chloro, bromine, alkoxycarbonyl (eg ethoxycarbonyl, methoxycarbonyl etc.), aryl Oxycarbonyl (eg, phenoxycarbonyl), carboxy, carbamoyl, alkylcarbamoyl (eg, N-methylcarbamoyl, N, N-dimethylcarbamoyl, etc.), arylcarbamoyl (eg, N-phenylcarbamoyl, etc.), amino, alkylamino (eg, , Methylamino, N, N-dimethylamino etc.), arylamino (eg phenylamino, naphthylamino etc.), acylamino (eg acetylamino, benzoylamino etc.), alkoxy Carbonylamino (eg, ethoxycarbonylamino, etc.), aryloxycarbonylamino (eg, phenoxycarbonylamino, etc.), acyloxy (eg, acetyloxy, benzoyloxy, etc.), alkylaminocarbonyloxy (eg, methylaminocarbonyloxy, etc.), aryl Examples include groups such as aminocarbonyloxy (eg, phenylaminocarbonyloxy), sulfo, sulfamoyl, alkylsulfamoyl (eg, methylsulfamoyl), arylsulfamoyl (eg, phenylsulfamoyl), etc. To be The hydrogen atom of hydrazine may be substituted with a substituent such as a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl, etc.), an acyl group (eg, acetyl, trifluoroacetyl, etc.), an oxalyl group (eg, ethoxalyl, etc.), etc. Good.

Of the compounds represented by the above general formula [3], the compound represented by the following general formula [3a] is particularly preferable.

[0040]

[Chemical 9]

In the above general formula [3a], R ₁ , R ₂ and R ₃
Is a hydrogen atom, an optionally substituted alkyl group (for example, a methyl group, an ethyl group, a butyl group, a 3-aryloxypropyl group), an optionally substituted phenyl group, a naphthyl group, a cyclohexyl group, a pyridyl group, a pyrrolidyl group, An optionally substituted alkoxy group (eg, methoxy group, ethoxy group,
Butoxy group) and an optionally substituted aryloxy group (eg, phenoxy group, 4-methylphenoxy group).

R ₁ and R ₂ are preferably substituted alkyl groups (substituents are alkoxy groups and aryl groups).

R ₃ is preferably a hydrogen atom or an alkyl group.

R ₄ represents a divalent aromatic group (eg phenylene group, naphthylene group), and Y represents a sulfur atom or an oxygen atom.

R ₅ represents an alkyl group, an alkoxy group or an amino group which may be substituted, and examples of the substituent include an alkoxy group, a cyano group and an aryl group.

Typical compounds represented by the above general formulas [3] and [3a] are shown below.

[0047]

[Chemical 10]

The compounds represented by the above-mentioned general formulas [1], [2] and [3] and the synthesis examples are described in JP-A-4-70647.
The materials described in the lower right column of page (2) to the upper right column of page (17) can be used, but the present invention is not limited thereto. The amount of the compounds of the general formulas [1], [2] and [3] contained in the silver halide photographic light-sensitive material of the present invention is 1 mol of silver halide contained in the silver halide photographic light-sensitive material of the present invention. The amount is preferably 5 × 10 ^-7 to 5 × 10 ^-1 mol, and more preferably 5 × 10 ^-6 to 1 × 10 ^-2 mol.

Next, specific examples of the water-soluble iridium salt used in the present invention include iridium chloride (IrCl ₃ and IrC).
l ₄ ), potassium hexachloroiridate, ammonium hexachloroiridate, and the like.
These compounds are preferably added as an aqueous solution during grain formation of the silver halide emulsion, during physical ripening, during chemical ripening, or thereafter, but particularly preferably during grain formation. The addition amount is 1 × 10 ^-2 to 1 × per mol of silver halide.
It is 10 ^-10 mol.

The silver halide emulsion is subjected to halogenation conversion with a water-soluble iodine compound at the completion of grain formation of 90% or more. In the present invention, halogen conversion is preferably carried out at the time of completion of grain formation of 90% or more, more preferably at the location of 95% or more completion. Furthermore, after particle formation and desalting,
It is possible before and after chemical aging. It is preferably before desalting.

The amount of the water-soluble iodine compound added is 0.1
~ 10g / AgI mol, preferably 0.2 ~ 0.8g / AgI mol,
Particularly preferred is 0.5 to 0.7 g / AgI mol. The silver halide grain used in the present invention is a grain having a laminated structure. Here, the laminated structure includes a case where it is a layered structure such as a core / shell type in which the inner layer and the outer layer are not clearly distinguished except the layered structure which is clearly distinguished.

The silver halide emulsion used in the light-sensitive material of the present invention may be one obtained by any of the acidic method, the neutral method and the ammonia method. Any shape can be used. One preferable example is a cube having a {100} plane as a crystal surface. Also, U.S. Pat.
4,225,666, JP-A-55-26589, JP-B-55-42737 and the like, and The Journal of Photographic Science (J. Photgr. Sci). 21.39 (197
By the method described in the literature such as 3), particles having a shape such as an octahedron, a tetrahedron and a dodecahedron can be prepared and used. Further, grains having twin planes may be used. The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes.

Any grain size distribution may be used, an emulsion having a wide grain size distribution (referred to as polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as monodisperse emulsion). .) May be used alone or in combination of several kinds. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used. In the present invention, a monodisperse emulsion is preferred. As the monodisperse silver halide grains in the monodisperse emulsion, the weight of silver halide contained within the grain size range of ± 20% centering on the average grain size r is 60% or more of the total weight of silver halide grains. Some are preferable, particularly preferably 70% or more, more preferably 80%
That is all.

Monodisperse emulsions are disclosed in JP-A-54-48521 and JP-A-58-4.
It can be obtained by referring to 9938 and 60-122935.

Various known sensitizing methods, additives and the like can be used in the silver halide emulsion of the present invention depending on the purpose.
For more details on these additives, Research Disclosure Vol. 176, Item 17643 (December 1978) and Id.
Volume 87, Item 18716 (November, 1979), and the relevant parts are summarized below.

Additives RD17643 RD18716 1. Chemical sensitizer, page 23, page 648, right column 2. Sensitivity enhancer, same as above 3. Spectral sensitizer, page 648, right column to pages 23 to 24 Supersensitizer, page 649 Right column 4. Whitening agent page 24 5. Antifoggant page 24 to 25 page 649 right column and stabilizer 6. Light absorber, filter page 25 to 26 649 Right column to 650 left column Dye, UV absorber 7. Anti-staining agent Page 25 Right column Page 650 Left-right column 8. Dye image stabilizer Page 25 9. Hardening agent Page 26 651 Page left column 10. Binder page 26 Same as above 11. Plasticizer / lubricant Page 27 650 Right column 12. Coating Aids / Surfactants, pages 26 to 27, same as above 13. Antistatic Agent, pages 27, same as above The binder used in the light-sensitive material of the present invention is preferably gelatin, but other known binders generally used in light-sensitive materials. Can be used. In the practice of the silver halide photographic light-sensitive material of the present invention, for example, an emulsion layer and other layers can be formed by coating one side or both sides of a flexible support which is usually used for photographic light-sensitive materials. As the flexible support, various supports known in the photographic material industry can be used.

In the silver halide photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method or the like can be used.

As the developing solution and other processing solutions used in the light-sensitive material of the present invention, various developing solutions, processing solutions, additives and the like known for light-sensitive materials, especially for printing plate making can be used.

[0059]

EXAMPLES Hereinafter, the effects of the present invention will be specifically illustrated by examples.

(Preparation of Silver Halide Emulsion A) The pAg was kept at 8.3 for the initial 20 minutes by using the double jet method, and then the pAg was adjusted to 8.
A silver iodobromide emulsion was prepared so that the iodine content in each layer of the laminated structure (core / shell) was set to 7 in Table 1. During this mixing, K ₂ IrCl ₆ was added at 8 × 10 ^-7 mol per mol of silver.
Further, at the time of 95% completion of grain formation, 56.6 ml of 1% potassium iodide solution per mol of silver was added to this emulsion, and the obtained emulsion was cubic crystal having an average grain size of 0.20 μm.

After that, modified gelatin (exemplified compound G-8 of Japanese Patent Application No. 1-180787) was added and washed with water and desalted by the method of Example of Japanese Patent Application No. 1-180787. The pAg at 40 ℃ after desalting is 7.60
Met.

Further, at the time of redispersion, the following compound (A),
The mixture of (B) and (C) was added.

[0063]

[Chemical 11]

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate film having 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) On the undercoat layer, a silver halide emulsion layer of the following formulation (1) was applied so that the amount of gelatin was 2.0 g / m ² and the amount of silver was 3.5 g / m ² , and then the following formulation The protective layer of (2) was coated so that the amount of gelatin would be 1.5g / m ^2, and the backing layer on the other side of the other side had 2.4g of gelatin according to the following prescription (3). / m ^{2 so} that the amount of gelatin is 1g on the protective layer of the following formulation (4).
Each sample No. 1 to 17 was obtained by coating so as to be / m ² .

Formulation (1) (Silver halide emulsion layer composition) Gelatin 2.0 g / m ² Silver halide emulsion A Silver amount 3.2 g / m ² Antifoggant: Adenine 25 mg / m ² Stabilizer: 4-methyl-6 -Hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Surfactant: saponin 0.1 g / m ² 〃: S-1 8.0 mg / m ² polyethylene glycol molecular weight 4000 0.1 g / m ² latex polymer L 1.0 g / m ² hydrazine derivative Amount shown in Table 1 Sensitizing dye D 8.0 g / m ² Hardener H-1 60 mg / m ² Formulation (2) [Emulsion protective layer composition] Gelatin 0.9 g / m ² Matting agent: Polymethylmethacrylate having an average particle diameter of 3.5 μm 3 mg / m ² Surfactant: S-2 10 mg / m ² Hardener: Formalin 30 mg / m ²

[0066]

[Chemical 12]

Prescription (3) (Backing layer composition)

[0068]

[Chemical 13]

Gelatin 2.7 g / m ² Surfactant: Saponin 0.1 g / m ² 〃: S-1 6.0 mg / m ² formulation (4) [Backing protective layer composition] Gelatin 1 g / m ² Matting agent: Average particle size 3.0 to 5.0 μm polymethylmethacrylate 50 mg / m ² Surfactant S-2: 10 mg / m ² Hardener: Glyoxal 25 mg / m ² 〃: H-1 35 mg / m ^{2 The} obtained sample was step wedge. After closely adhering and exposing for 5 seconds with 3200K tungsten light, rapid processing was performed under the following conditions. The obtained sample was evaluated by the following methods.

(Evaluation of Black Spots) Regarding the black spots in the halftone dots, the highest rank “5” is given to the spots where no black spots occur in the halftone dots, and the degree of occurrence of black spots in the halftone dots is determined. Accordingly, the ranks are evaluated by sequentially lowering the rank to “4”, “3”, “2”, “1”. In addition, rank "1" and
With "2", black spots are large and are at a level not preferable for practical use. (Evaluation of pressure resistance) Next, the pressure resistance was evaluated. For evaluation, the sample was dried before development, the load was applied to a sapphire needle having a spherical tip, and the sample was moved on the emulsion surface. No evaluation was made to rank "5", and those having strong fog due to pressure were ranked "1", and 5 grades of 1 to 5 were performed.

Developer Formulation 1 Ethylenediaminetetraacetic acid disodium salt 1g Sodium sulfite 60g Trisodium phosphate (12-hydrate) 75g Hydroquinone 22.5g N, N-diethylethanolamine 15g Sodium bromide 3.0g 5-Methylbenzotriazole 0.25g 1-Phenyl-5-mercaptotetrazole 0.08g Metol 0.25g Add water to make 1 liter and adjust pH to 11 with sodium hydroxide.
Adjust to 7.

Fixer Formulation 1 (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g (Composition B) Pure Water (ion-exchanged water) 17 ml Sulfuric acid (50% w / w aqueous solution) 4.7 g Aluminum sulphate (Al ₂ O ₃ equivalent content is 8.1% w / w aqueous solution) 26.5 g When the fixer is used, the above composition is added to 500 ml of water. A and composition B were melted in this order and finished to 1 liter for use. PH of this fixer
Was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Image 40 ℃ 15 seconds Settlement 35 ℃ 15 seconds Water wash 30 ℃ 10 seconds Dry 50 ℃ 10 seconds Note that the formulation (1) The following compounds (a) to (c) were used as comparative compounds added to the silver halide emulsion layer.

[0074]

[Chemical 14]

The results of the above examples are shown in Table 1.

[0076]

[Table 1]

As is clear from Table 1, the samples according to the present invention
It can be seen that Nos. 6 to 15 have good black spots, fog, and pressure resistance in comparison.

When the hydrazine derivative 3-5 in Sample No. 6 was replaced with 1-1 to 1-9 and evaluated in the same manner, the effect of the present invention was confirmed.

Example 2 (Preparation of silver halide emulsion B) Emulsion B was prepared in the same manner as emulsion A except that potassium iodide was added after the grain formation was completed in preparation of silver halide emulsion A in Example 1. Prepared.

The same evaluations as in Example 1 were carried out and the results are shown in Table 2. However, the emulsions used for comparison No. 16 and No. 17 in Table 2 were the same as in Example 1 except that the iodine conversion and the iridium doping were not performed.

[0081]

[Table 2]

As shown in Table 2, the samples of the present invention were also good in fog, pressure resistance and black spots, as in Example 1, in comparison. In addition, in sample No. 6, hydrazine derivative 3-5
Was evaluated in the same manner by substituting 1-1 to 1-9, the effect of the present invention was confirmed.

Example 3 The same procedure as in Example 1 was carried out except that the sample used in Example 1 was treated with the treating solution having the following formulation. The results are shown in Table 3.

Developer Formulation 2 Hydroquinone 38.5 g Metol 0.7 g Ethylenediaminetetraacetic acid disodium salt 2.0 g NaHSO ₃ 2.0 g 45% KOH 126.5 g Potassium hydroxide 55.0 g K ₃ PO ₄ 33.2 g KCl 4.75 g Potassium bromide 2.3 g N , N-Diethylethanolamine 21g 5-Methylbenzotriazole 0.37g Add water to make 1 liter, pH with sodium hydroxide
Was adjusted to 11.7.

Fixer formulation 2 (Composition C) Ammonium thiosulfate (59.5% w / v aqueous solution) 850 ml EDTA 0.527 g Sodium sulfite 64.71 g Acetic acid 83.88 g Boric acid 23.01 g Sodium citrate 16.06 g Gluconic acid (50% w / v aqueous solution) 8.75g (Composition D) Sulfuric acid (36N) 749.9g Aluminum sulphate (48% w / w aqueous solution) 50.9g Liquid D 22.5g was added to liquid C 1L to make 3.8L.

The results of the above examples are shown in Table 3.

[0087]

[Table 3]

Results in Table 3 The samples of the present invention were also good in fog, pressure resistance and black spots, as in Examples 1 and 2, for comparison. In addition, in sample No. 6, the hydrazine derivative 3-
When 5 was replaced with 1-1 to 1-9 and evaluated in the same manner, the effect of the present invention was confirmed.

[0089]

According to the present invention, a silver halide photographic light-sensitive material having good fog, pressure resistance and black spots can be provided.

Front page continuation (72) Inventor Mariko Kato 1 Konica Stock Company, Sakura Town, Hino City, Tokyo In-house (72) Inventor Yuji Aritomi 1 Konica Stock Company, Sakura Town, Hino City, Tokyo In-house

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein at least one emulsion layer contains an iridium compound and a hydrazine derivative and halogenated. A silver halide photographic light-sensitive material characterized in that the silver particles are laminated structure grains, and the grains have iodine inside the grains before the completion of grain formation and no iodine outside the grains. .