JPH0476532A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a high-contrast image rapidly and stably by incorporating an iridium compound and a hydrazine compound in at least one of emulsion layers and regulating the pAg of silver halide emulsion to <=10.0 at the time of finishing feed of an emulsion, addition of a mixture, and desalting. CONSTITUTION:The silver halide photographic sensitive material is provided on a support at least one of the emulsion layers containing the iridium compound, and the hydrazine compound. The pAg of the emulsion is regulated to <=10.0 at the time of ending the feed of the emulsion, the addition of the mixture, and the desalting, the permitting the obtained silver halide photographic sensitive material to form an image small in occurrence of black spots and good in finished quality.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material, and in detail,
The present invention relates to a silver halide photographic material that provides high-contrast images, has high sensitivity, has no illuminance failure, and is free from black spots.

[Conventional technology]

In general, high-contrast photographic images are used in the photolithography process to form characters and halftone-resolved photographic images, and in the ultra-precision photolithography process to form fine line images. It is known that silver halide photographic materials for this purpose can form photographic images with extremely high contrast.

Conventionally, for example, a photosensitive material made of a silver chlorobromide emulsion with an average grain size of 0.2 gm, a narrow grain distribution, a uniform grain shape, and a high silver chloride content (at least 50 mol% or more) has been processed using sulfite ions. A method of obtaining an image with high contrast, high sharpness, and high resolution, such as a halftone dot image or a fine line image, is carried out by processing with an alkaline hydroquinone developer having a low concentration.

This type of silver halide photosensitive material is known as a lithium-type photosensitive material.

The photolithography process involves converting a continuous-tone original into a halftone image, that is, converting the continuous-tone density changes of the original into a set of halftone dots with an area proportional to the density. There is.

For this purpose, a halftone dot image is formed by using the above-mentioned lithium-type photosensitive material and photographing an original through an intersection screen or contact screen, followed by development processing.

For this purpose, a silver halide photographic light-sensitive material containing a silver halide emulsion with fine grains and uniform grain size and grain shape is used. When processed with a commercially available developer, the halftone image formation, etc., is inferior to when developed with a Lith type developer.

Therefore, it is processed with a developer called a Lith type developer, which has an extremely low sulfite ion concentration and uses hydroquinone as a single developing agent. However, Lith-type developer is susceptible to auto-oxidation and has extremely poor storage stability.
There is a strong demand for a control method that keeps development quality constant even during continuous use, and great efforts have been made to improve the retention of this developer.

A replenisher that compensates for the deterioration in activity due to development processing in order to maintain the stability of the above Lith type developer (processing fatigue replenishment)
and a replenisher that compensates for oxidative deterioration over time (time-related fatigue replenishment).
A liquid separation and replenishment system is generally widely adopted in automatic development m for photolithography and the like. However, the above method has the disadvantage that it is necessary to control the replenishment balance of the two liquids, which complicates the equipment and operation.

In addition, in the Lith type development, it takes a long time (induction period) until an image appears due to development, and therefore an image cannot be obtained quickly.

On the other hand, quickly without using the above-mentioned Lith type developer.

There are known methods to obtain high-contrast images.
For example, U.S. Patent No. 2,419,975,
16t623 and! As seen in #Kokai No. 51-20921, etc., a hydrazine compound is contained in a silver halide photosensitive material. Image forming methods using these hydrazine compounds can obtain very high-contrast images; however, when photographing unexposed areas, such as black sesame seeds between halftone dots using a contact screen in photosensitive materials for printing. The appearance of dots (herein referred to as "black spots") is observed. There was also a phenomenon of illumination failure, which had a major impact on work efficiency. On the other hand,
JP-A No. 81-29837 discloses a method of adding a hydrazide compound and an iridium compound to an emulsion containing emulsion grains with a controlled content, but this method lacks sensitivity and contrast; Furthermore, there is a problem in that the finish quality deteriorates due to the occurrence of black spots.

[Problem to be solved by the invention]

Therefore, a first object of the present invention is to provide a silver halide photographic material that can rapidly and stably obtain high-contrast images.

A second object of the present invention is to provide a silver halide photographic material that can stably obtain high-contrast images with little sensitivity loss and high sensitivity.

A third object of the present invention is to provide a silver halide photographic material that is free from black spots and has a good finishing quality.

A fourth object of the present invention is to provide a silver halide photographic material with high contrast and no illuminance failure.

[Means to solve the problem]

The above object is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support.
At least one of the emulsion layers contains an iridium compound and a hydrazine compound.

This is achieved by a silver halide photographic light-sensitive material characterized in that the silver halide grains have a pAg of 1O10 or less when emulsion preparation, mixing and addition and desalting are completed.

The present invention will be explained in detail below.

Examples of the hydrazine compound used in the present invention include compounds represented by the following general formula (1), CI) or CDI).

General formula CI) [In the formula, R1 and R2 represent an aryl group or a heterocyclic group, R represents a divalent organic group, n represents O to 6, and m represents 0 or 1.] General formula ( II) [wherein R21 represents an aliphatic group, aromatic group or heterocyclic group, R22 represents a hydrogen atom, an optionally substituted alkoxy group, a heterocyclic oxy group, an amino group, or an aryloxy group, Pl and R2 represent a hydrogen atom, an acyl group, or a sulfinic acid group] General formula (III) 閤Ar-NHNH-C-R31 [In the formula, Ar represents a diffusion-resistant group or /\silver chloride adsorption-promoting group. represents an aryl group containing at least one, and R31 represents a substituted alkyl group.] The compound represented by the general formula [■] will be described below.

In general formula CI), examples of the aryl group represented by R1 and R2 include phenyl group, naphthyl group, etc., and examples of the heterocyclic group include pyridyl group, penzothiazolyl group, quinolyl group, thienyl group, etc. and R2
Preferred is an aryl group. Various substituents can be introduced into the aryl group or heterocyclic group represented by RI and R2. Examples of substituents include halogen atoms (for example, chlorine, fluorine, etc.), alkyl groups (for example, methyl, ethyl, dodecyl, etc.), alkoxy groups (for example, methoxy, ethoxy, impropoxy, butoxy, octyloxy, dodecyloxy, etc.), acylamino groups ( For example, acetylamino, pyherylamino, benzoylamino, tetradecanoylamino, α-(2,4-di-t-amylphenoxy)butyrylamino, etc.), sulfonylamino groups (e.g. methanesulfonylamino), butanesulfonylamino, dodecane sulfonylamino, benzenesulfonylamino, etc.), urea groups (e.g., phenylurea, ethylurea, etc.), thiourea groups (e.g., phenylthiourea, ethylthiourea, etc.), hydroxy groups, amide groups, alkylamino groups (e.g., methylamine, dimethylamino, etc.), a carboxy group, an alkoxycarbonyl group (eg, ethoxycarbonyl), a carbamoyl group, a sulfo group, and the like.

Examples of the divalent organic group represented by R include alkylene groups (e.g., methylene, ethylene, trimethylene, tetramethylene, etc.), arylene groups (e.g., phenylene, naphthylene, etc.), aralkylene groups, etc. Regarding the group represented by R, the group may contain an oxy group, thio group, seleno group, carbonyl group, -N- group (R3 represents a hydrogen atom, an alkyl group, an aryl group), a sulfonyl group, etc. in the bond. Various substitutions can be introduced. As a substituent, for example, -C0NHNHR5(R4
has the same meaning as R1 and R2 described above), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a carboxy group, an acyl group, an aryl group, and the like. R is preferably an alkylene group.

Among the compounds represented by the general formula (I), preferably R1 and R2 are substituted or unsubstituted phenyl groups, n=m
=1 and R represents an alkylene group.

Representative compounds represented by the above general formula CI) are shown below.

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ =33 ■ ■ ■ ■ ■ ■ LCdl,.

■ ■ ■ ■ ■ LCJ++ LC,H ■ -53 ■ -50 ■ ■ -55 Next, the compound represented by the general formula (II) will be explained.

In the general formula (II), the aliphatic group represented by R21 preferably has 6 or more carbon atoms, particularly a linear, branched or cyclic alkyl group having 8 to 50 carbon atoms. The branched alkyl group may contain one or more heteroatoms therein and may be cyclized to form a saturated heterocycle, and the alkyl group may be an aryl group, an alkoxy group, a sulfoxy It may have substituents such as group 1.

Is the aromatic group represented by R21 monocyclic or ? It is a ring 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.

Examples include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazomyl ring, a virolazole ring, a quinoline ring, an inquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R21 is an aryl group.

The aryl group or unsaturated heterocyclic group of R21 may be substituted. Typical substituents include a linear, branched or cyclic alkyl group (preferably a monocyclic alkyl group having 1 to 20 carbon atoms). or two rings), alkoxy groups (
(preferably those having 1 to 20 carbon atoms), W-substituted amino groups (preferably amino groups substituted with alkyl groups having 1 to 20 carbon atoms), acylamino groups (preferably those having 2 to 30 carbon atoms), sulfones. Amide group (preferably one or more carbon atoms)
30), a ureido group (preferably a carbon number of 1 to
30).

Among the groups represented by R22 in the general formula [■], the optionally substituted alkoxy group has 1 to 20 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

Among the groups represented by R22 in general formula (II), the optionally substituted aryloxy group or heterocyclic oxy group is preferably a monocyclic group, and examples of the substituent include a halogen atom, an alkyl group, and an alkoxy group. group, cyano group, etc.

Among the groups represented by R22, preferred are an optionally substituted alkoxy group or an amine group, and A2 is an optionally substituted alkyl group, an alkoxy group, or a 10-,
- It may be a cyclic structure containing a 5-5-N- group bond,
However, R22 is never a hydrazino group.

R21 or R22 in general formula (n) may have a ballast group incorporated therein which is commonly used in immobile photographic additives such as couplers.The ballast group is 8
It is a relatively inert group with respect to photography having the above carbon number, and can be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, and the like.

R21 or R22 in general formula (II) may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Examples of such adsorption groups include a thiourea group, a heterocyclic thioamide group, and a mercapto group. Examples include groups described in US Pat. No. 4,355,105, such as a heterocyclic group and a triazole group. Among the compounds represented by the general formula [■], the compounds represented by the following general formula [■-a) are particularly preferred.

General formula (II-a) In the above general formula (II-a), R23 and R24 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, butyl group, dodecyl group, 2-hydroxypropyl group) , 2-cyanoethyl group, 2-chloroethyl group)
, an optionally substituted phenyl group (e.g. phenyl group, p
-methylbenzyl group) 5M optionally substituted naphthyl group (
For example, naphthyl group, α-hydroxynaphthyl group), li
cyclohexyl group that may be substituted (e.g., cyclohexyl group, P-methylcyclohexyl group), pyridyl group that may be substituted (e.g., pyridyl group, 4-propyl-2-
pyridyl group), a pyrrolidyl group that may be substituted (for example, a pyrrolidyl group, a 4-methyl-2-pyrrolidyl group).

R25 is a hydrogen atom or a benzyl group which may be substituted with W (
For example, benzyl group, p-methylbenzyl group), alkoxy group (e.g. methoxy group, ethoxy group), alkyl group (
For example, ethyl group, butyl group).

R24 and R27 represent a divalent aromatic group (e.g. phenylene group or naphthylene group), Y represents a sulfur atom or an oxygen atom, and L represents a divalent bonding group (e.g. -'1(h
cH2cIhNH-'; Q2NH1-0GHzSOzN
H, -D-1-CH-N-), R2B represents -R"R" or -0R29, R',
R'' and R29 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, dodecyl group), phenyl groups (e.g. phenyl group, p-methylphenyl group, P~
methoxyphenyl group), naphthyl group (e.g. α-naphthyl group, β-naphthyl group) or heterocyclic group (e.g. unsaturated heterocyclic group such as pyridine, thiophene, furan, or saturated such as tetrahydrofuran, sulfolane). R' and R'' represent a ring (e.g., a heterocyclic group) together with a nitrogen atom.
piperidine, piperazine, morpholine, etc.).

m and n represent 0 or 1, and when R26 represents 0R29, Y preferably represents a sulfur atom.

Representative compounds represented by the above general formulas (II) and (II-a) are shown below.

■ l ■ ■ ■ ■ ■ l-11 ■ ■ ■ ■ ■ ■ ■ ■ ■ CM.

O ■ *→I(NHCCOCH, CH, SO, CH, CHjO
H■ ※-INNHCCOCIl*C)I*SCH*CI(*O
H■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ H3 C1oHz+n O O ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ =47 H3 ■ ■ ■ ■ ■ ■ ■ * η −NHNHCCNHC, f H,.

■ ■ ■ ■ ■ ■ ■3 ■-58 ■-59 next, Among the above specific compounds, compound II -45゜■ Taking 47 as an example, The synthesis method is shown below.

Synthesis of compound ■-45 Synthesis scheme (E) Compound 4-nitrophenylhydrazine 153g and 500g
A layer of diethyl oxalate is mixed, refluxed for 1 hour to remove ethanol, and finally cooled to precipitate crystals. 50 of the crystals (A) obtained after filtration, washing several times with petroleum ether, and recrystallization.
Pd/
Compound (B) is obtained by reduction in a H2 atmosphere pressurized to 50 Psi under a C (palladium/carbon) catalyst.

22 g of this compound (B) was dissolved in a solution of 200 acetonitrile and 16 g of pyridine, and the compound (G) 24 was dissolved at room temperature.
g of acetonitrile solution was added dropwise. After filtering out insoluble matter,
The filtrate was concentrated and purified by recrystallization to obtain 31 g of Compound (D).

30 g of compound (D) was hydrogenated in the same manner as above to obtain compound (
E) 20g was obtained.

Compound (E) IOg was dissolved in 10h4 of acetonitrile, ethyl inthiocyanate LOg was added, and the mixture was refluxed for 1 hour. After distilling off the solvent, the compound (F) is purified by crystallization.7.
Obtained 0g. Compound (F) 5.0g methanol 50g
Methylamine (40% aqueous solution 81I text) dissolved in intestinal tract
was added and stirred. After slightly concentrating methanol, the precipitated solid was taken out and purified by recrystallization to obtain Compound 1-45.

Synthesis of compound 11-47 (B) (C) (D) (E) Compound 1-47 Dissolve 22 g of compound (B) in 200 g of pyridine and add p-nitrobenzenesulfonyl chloride 2 to a stirring vessel.
After adding 2 g of the reaction mixture to water, the precipitated solid was taken out to obtain Compound (C). Compound (G) was subjected to the same reaction as compound (1)-45 according to the synthesis scheme to obtain compound (1)-47.

Next, the compound represented by general formula (m) will be explained.

In the general formula (m), At represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and the diffusion-resistant group is commonly used in immobile photographic additives such as couplers. A ballast group is preferred, and the ballast group is a group having 8 or more carbon atoms and relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. You can choose from.

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385,108, such as a thiourea group, a thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.

R31 represents a substituted alkyl group, and the alkyl group represents a linear, branched, or cyclic alkyl group.

Examples include groups such as methyl, ethyl, propyl, butyl, inpropyl, pentyl, and cyclohexyl.

Substituents introduced into these alkyl groups include alkoxy (e.g. methoxy, ethoxy, etc.), aryloxy (e.g. phenoxy, P-chlorophenoxy, etc.), heterocyclic oxy (e.g. pyridyloxy, etc.), mercapto, alkylthio (e.g. methylthio, ethylthio, etc.),
Arylthio (e.g., phecolthio, p-chlorophenylthio, etc.), heterocyclic thio (e.g., pyridylthio, pyrimidylthio, thiadiazolylthio, etc.), alkylsulfonyl (e.g., methanesulfonyl, butanesulfonyl, etc.)
, arylsulfonyl (e.g. benzenesulfonyl, etc.)
, heterocyclic sulfonyl (e.g. pyridylsulfonyl, morpholinosulfonyl, etc.), acyl (e.g. acetyl, benzoyl, etc.), cyano, chloro, bromine, alkoxycarbonyl (e.g. ethoxycarbonyl, methoxycarbonyl, etc.), aryloxycarbonyl (e.g. phenoxycarbonyl) etc.), carboxy, carbamoyl, alkylcarbamoyl (eg tomethylcarbamoyl, N, tomethylcarbamoyl, etc.).

Arylcaroctamoyl (e.g. N-phenylcaroctamoyl, etc.), amines, alkylaminos (e.g. methylamino, N,N-dimethylamino, etc.), arylaminos (e.g. phenylamino, naphthylamino, etc.), acylaminos (e.g. acetylamino, henshylamino, etc.), alkoxycarbonylamino (e.g., ethoxycarbonylamino, etc.), aryloxycarbonylamino (e.g., phenoxycarbonylamino, etc.), acyloxy (e.g., acetyloxy, benzoyloxy, etc.), alkylaminocarbonyloxy (e.g., methylaminocarbonyloxy) etc.), arylaminocarbonyloxy (e.g., phenylaminocarbonyloxy, etc.), sulfo, sulfamoyl, alkylsulfamoyl (e.g., methylsulfamoyl, etc.), arylsulfamoyl (e.g., phenylsulfamoyl, etc.), etc. Can be mentioned.

The hydrogen atom of hydrazine is a sulfonyl group (e.g., methanesulfonyl, toluenesulfonyl, etc.), an acyl group (e.g., acetyl, trifluoroacetyl, etc.), an oxalyl group (
Typical compounds represented by the above general formula (m) include those shown below.

III-8! 11-9 1 [[-5 III - 10 ■ -11 ■ Ill -13 III -14 ■ -15 ■ -16 ■-22 ■ ■ -24 ■-25 ■-26 ff-17 I[[-18 ■- 20 ■-21 ■ ■ ■ -29 ■ -30 1[[-31 *-NHN)lccH,OcH,cH,0cI(,CH
, OH■-32 ■-33 ■ -34 ■-35 ■ -40 ■ ■-42 ■-43 ■ ■ -37 ■ -38 ■ ■ -44 ■ ■-46 ■ ■ ■-49 ■ Next, compound m- A synthesis example of No. 5 will be described.

Synthesis of Compound m-5 Compound m-5 was obtained according to the synthesis scheme of compound 11-45.

The amount of the compound of general formula CI), (II), or (m) contained in the emulsion layer of the silver halide photographic light-sensitive material of the present invention is 5 x 10-7 to 5 x IQ per mole of silver halide. A molar range is preferred, more preferably 5 x 10-
5 to I X 10-2 mo/I/(7) range -c.

Next, as specific examples of water-soluble iridium salts used in the present invention, iridium chloride (IrC or 3 and IrC14)
, potassium hexachloroiridate, ammonium hexachloroiridate, and the like. These compounds are preferably added as an aqueous solution during or after grain formation, physical ripening, chemical ripening of the silver halide emulsion, and particularly preferably during grain formation. The amount added is I x 10-2 per mole of silver halide.
It is preferable to add up to 1×IQ−10 mol, and particularly preferably 10 −5 to 1 O −8 mol.

In silver halide emulsions, /＼logen conversion is performed by a water-soluble compound at 80% or more before the completion of grain formation.
In the present invention, halogen conversion is preferably carried out at 90% or more, more preferably at 85% or more, before grain formation. Furthermore, it is possible to carry out the process after particle formation, after desalination, before chemical ripening, or after completion of chemical ripening. Preferably, before desalting.

The amount added is preferably 0.3 to 0.8 g/Ag 1 mol, particularly preferably 0.5 to 0.7 g/Ag 1 mol, within 0.1''lOg/Ag 1 mol.

The silver halide grains used in the present invention have a pAg of 10.0 or less, preferably 9.0 or less, upon completion of emulsion preparation, mixing, addition, and desalting.

The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method.

Any shape of silver halide grains can be used. One preferred example is a cube having a (100) plane as a crystal surface. Also, U.S. Patent No. 4,183
, No. 758, same! No. 4,225,888, Japanese Unexamined Patent Publication No. 1983
-28589, Special Publication No. 55-42737, etc., The Journal of Φ Photographic Science (J, Photogr, 5ci), 21.39 (
Octahedron,
Particles having shapes such as tetradecahedrons and dodecahedrons can also be prepared and used. Furthermore, particles having twin planes may be used.

The silver halide grains t± may be of a single shape or may be a mixture of grains of various shapes.

Also, any grain size distribution may be used, and it may be an emulsion with a wide grain size distribution (polydisperse emulsion) or an emulsion with a narrow grain size distribution (monodisperse emulsion) alone or in combination of several types. Alternatively, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

In the present invention, a monodisperse emulsion is preferable.The silver halide grains in the monodisperse emulsion have an average grain size of 12
It is preferable that the weight of silver halide contained within the grain size range of 0% is 60% or more of the weight of all silver halide grains,
Particularly preferably 70% or more, more preferably 80% or more.

Here, the average particle size r is the frequency n of particles having particle size r1.
It means the particle size when fini·Xri3 between i and ri3 becomes maximum.

(3 significant digits, round off the smallest digit) The grain size here refers to the diameter in the case of spherical silver halogenide grains, or the projection of the grain in the case of grains with shapes other than cubic or spherical. It represents the diameter when the image is compared to a circular image with the same area.

The particle size can be determined, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print.
(# The number of fixed particles is assumed to be 1000 or more indiscriminately.) In the present invention, preferably a highly monodispersed emulsion, with a coefficient of variation (monodispersity) defined by the following formula of 20 or less. Preferably, it is more preferably 15 or less.

Here, the average particle diameter and particle diameter standard deviation shall be determined from ri defined above. Monodisperse emulsion is disclosed in Japanese Patent Application Laid-Open No. 54-4852.
No. 1, No. 58-49938 and No. 60-122935
You can obtain it by referring to the number etc.

Although the photosensitive silver halide emulsion can be used as a so-called ptigitive emulsion without chemical sensitization, it is usually chemically sensitized. For chemical sensitization, the C1afkides or Zelikma
The book by H.
Lagen der Photography
n Prazesse with Silbarhalo
geniden, Akademische Verl
agggege! 1schaft.

19811) can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with # ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. may be used alone or in combination. Can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat. No. 1,574,944,
It is described in No. 2,410.689, No. 2,278,947, No. 2.728,688, and No. 3.858,955. Examples of reduction sensitizers include stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid,
Silane compounds etc. can be used, and specific examples thereof include U.S. Pat.
No. 2,518,898, reJ2,983,809, reJ2,983,610, jiIQ 2,894
, No. 637. For noble metal sensitization, in addition to gold complex salts, complex salts of metals in group I of the periodic table, such as platinum, iridium, and palladium, can be used. Specific examples thereof include U.S. Pat. 448,080
No. 618,061, British Patent No. 618,061, etc.

In addition, there are no particular restrictions on the conditions such as p)I, pAg, temperature, etc. during chemical sensitization, but pHm is preferably 4 to 9;
In particular, the pAg value is preferably 5 to 8, preferably 5 to 11, and particularly preferably maintained at 8 to 10.

Also, the temperature is preferably 40 to 90°C, particularly 45 to 90°C.
75°C is preferred.

As the photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed.

After completion of chemical sensitization as described above, a stabilizer such as 4-hydroxy-6-methyl-1,3,3a, 7-chitrazaindene can be used. Furthermore, if necessary, a silver halide solvent such as a thioether may be used, and a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound, or a sensitizing dye may be used during the formation of silver halide grains or during grain formation. It may be added and used after the completion of the treatment.

In the silver halide photographic material according to the present invention, the photographic emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. , cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc. Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei, and nuclei in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, pentthiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus,
Quinoline nuclei etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl forge welding, and other 5- to 6-membered heteroartic ring nuclei.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used in ordinary negative-working silver halide emulsions. In particular, it is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion. sensitizing dye per mole of silver halide. OX 10-5 to about 5 X 10-
It is preferably used in a concentration of 4.times.10@-4 mol, particularly 4.times.10@-4 to 2.times.10@-4 mol as a sensitizing dye per mole of silver halide.

In the present invention, one or more of the above sensitizing dyes are used! More specific examples of sensitizing dyes that can be used in combination with the above and which can be advantageously used in the present invention include the following.

That is, examples of sensitizing dyes used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929.080, US Pat. No. 2,231,858, US Pat. No. 2,5113.001, No. 2,912,329, No. 3,858,958, No. 3
, No. 672,897, No. 3,894.2] No. 7, No. 4,
No. 025,439, No. 4,048,572, 5 British Patent No. 1,242,588, Japanese Patent Publication No. 14030/1970, No. 52-24844, Japanese Patent Publication No. 73137/1973, No. 8
1-172140 and the like can be mentioned. Further, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, US Pat. No. 1,939,201;
No. 2,072,908, No. 2.738. No. I49, 2. Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in FJ45,7B3, British Patent No. 505.1179, Japanese Patent Publication No. 48-42172, and the like. Furthermore,
Sensitizing dyes used in red-sensitive and infrared-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 2,270,378, No. 2,442,71Q, rf712,454,829, No. 2,778,28
No. 0, Japanese Patent Publication No. 17725/1972, Japanese Patent Publication No. 824/1973
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 25, No. 6129838, No. 80-80841, and the like.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Typical examples are U.S. Pat. No. 2,888,545;
No. 877.229, No. 3,397,080, No. 3,5
No. 22,052, No. 3.527,841, No. 3.61
No. 7,293, No. 1, No. 3,628.1164.

Same 3. f6t6t, t80, 3,872,8138
No. 3.67fl, No. 428, rail 3,70
No. 3,377, No. 3,789,301, l'2f7
No. 3,814,609, No. 3,837,882, No. 4
, No. 028,707, British Patent No. 1,344,281,
It is described in Japanese Patent Publication No. 1,507,803, Japanese Patent Publication No. 43-4938, Japanese Patent Publication No. 53-12375, Japanese Patent Publication No. 110818-1981, Japanese Patent Publication No. 52-10111125, etc.

The silver halide photographic material according to the present invention may contain a water-soluble dye in the wood-philic colloid layer as a filter dye or for various purposes such as preventing irradiation, preventing halation, etc. Dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

In the silver halide photographic light-sensitive material according to the present invention, when dyes, ultraviolet absorbers, etc. are included in the wood-philic colloid layer, they may be mordanted with a cationic polymer or the like.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Or, during chemical ripening or at the end of chemical ripening, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance.
and/or after chemical ripening and before coating the silver halide emulsion, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted ), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole)
, mercaptopyridines, the above-mentioned heterocycles having a water-soluble group such as a carboxyl group or a sulfone group, mercapto compounds, thioketo compounds such as oxazolinthione, azaindenes such as tetrazaindenes (especially 4-hydroxy substituted (1,3 , 3a, 7) Tetrazaindenes),
Adding anti-capri agents or stabilizers such as benzenethiosulfonic acids, benzenesulfinic acids, etc.

An example of a compound that can be used is K. Mies (K.

Mess), The Theory of the Photograph 4
-/Reprocess (The Theor7 of th
e Photograpbi (Hprocess, 3rd
Edition, 1!168), citing the original literature.

For more detailed examples and other methods of use, see, for example, U.S. Pat.
The descriptions in No. 82.1347, No. 4,021,248, or Japanese Patent Publication No. 52-28880 can be referred to.

In addition, U.S. Patent No. 3,411,4111,
3.411.1112, Japanese Patent Publication No. 45-5331, etc., may be included.

The photosensitive material may contain the following various additives, namely:
As thickeners or plasticizers, e.g. U.S. Pat.
No. 04, Special Publication No. 43-4939, West-German Application Publication 1,
No. 104,804, Japanese Patent Publication No. 48-63715, Belgian Special Fraud No. 782,833, U.S. Patent No. 3,787,41
0, Belgian Patent No. 588,143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde, epoxy, and ethyleneimine hardeners. ,
Various hardeners such as active halogen type, vinyl sulfone type, incyanate type, sulfonic acid ester type, carbodiimide type, mucochloric acid type, acyloyl type, etc. Ultraviolet absorbers include 1, for example, U.S. Pat. No. 3,253,921, UK Compounds described in the specifications of Patent No. 1,309,349, especially 2-(2'-hydroxy-5-tertiary butylphenyl)benzotriazole, 2-(2''-hydroxy-3', 5'-di-tertiary butylphenyl)benzotriazole, 2-(2-hydroxy-3'-3
butyl-5'-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'
-di-tertiary butylphenyl)-5-chlorobenzotriazole and the like. Further, coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials include British Patent No. 548,532;
No. 1,2113.389, U.S. Patent No. 2,028,20
No. 2, same, No. 3,514.2E13, Special Publication No. 44-28
No. 580, No. 43-17922, No. 43-17928
No. 43-3186, No. 4θ-20785, Inter-French Patent No. 202,588, Belgian Patent No. 773,459
Anionic, cationic, nonionic or amphoteric compounds described in JP-A-48-101118 and the like can be used, and among these, anionic surfactants having a sulfone group, e.g. Succinic acid ester sulfonated compounds, alkylbenzene sulfonated compounds, etc. are preferable, and as an antistatic agent, Japanese Patent Publication No. 4G-2415
No. 9, JP-A-48-89878, U.S. Patent No. 2,882
, No. 157, No. 2,972,535, Japanese Patent Publication No. 1972-20
No. 785, No. 48-43130, No. 48-80391
No., Special Publication No. 4B-24159, No. 4B-3!1131
No. 2, No. 4B-43809, JP-A No. 47-33627
There are compounds described in each publication.

The constituent layers of the photosensitive material include matting agents, such as Swiss Patent No. 33.
Silica as described in No. 0,158, Buddhist Patent No. 1,296.9
Glass powder described in No. 85, British Patent No. 1,173,181
Inorganic particles such as alkaline earth metals or carbonates of cadmium, zinc, etc.; US Pat. No. 2,322.03
7, the starch derivatives described in Belly Patent No. 625,451 or British Patent No. 881,198;
Polyvinyl alcohol described in Japanese Patent Publication No. 44-3643, polystyrene or polymethyl methacrylate described in Swiss Patent No. 330, 158, U.S. Patent No. 3,
Organic particles such as the polyacrylochotriles described in US Pat. No. 078,257 and the polycarbonates described in US Pat.

The average particle size of the matting agent is preferably 2 to 81 L.

A slippery agent is added to the constituent layers of the photosensitive material, such as U.S. Pat.
Higher aliphatic higher alcohol esters described in No. 88,756 and No. 3,121,080, U.S. Patent No. 3,285
．． Casein described in No. 878, British Patent No. 1,263,7
Higher aliphatic calcium salts described in No. 22, British Patent No. 1,
313.384, US Pat. No. 3,042,522, and US Pat. No. 3,489,567.

Dispersions of liquid paraffin and the like can also be used for this purpose.

The photosensitive material may further contain various additives depending on the purpose. These additives, including those mentioned above, can be found in more detail in Research Disclosure Vol. 178 T.
tem 17843 (December 1978) and 18
It is described in Volume 7, Item 1871B (November 1979), and the relevant sections are summarized in the table below.

l, chemical sensitizer 2. Sensitivity enhancer 3. Spectral sensitizer supersensitizer 4. Brightener 5. Antifogging agent and stabilizers 6, light absorber, filter dye.

Ultraviolet absorber 7, anti-stain agent 25 right column 8, dye image stabilizer 25 page 9, hardener 2B page io, binder 26 page If, plasticizer/lubricant 27 page 12, coating aid 2B-27 page Surfactant 13, Sudachi Fuku Inhibitor Page 23 Page 27 Same as above Page 23-24 Page 24 Page 24-25 Page 25-26 Page 648 Right column Same as above Page 648 Right column ~ Page 849 Right column Page 649 Right column Page 649 Right column ~ Page 649, left column [Page 150, left to right column, page 651, left column, same as above, page 850, right column, same as above Gelatin is usually used as a binder for silver halide emulsions, but if necessary, gelatin derivatives, gelatin and Hydrophilic colloids such as graft polymers of other polymers, other proteins, sugar derivatives, cellulose conductors, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

Gelatin includes lime-processed gelatin, acid-processed gelatin, bulletin Φon ◆Society on Japan (Bull, Soc, Sci, Phot, Japan)
No.

Oxygen-treated gelatin as described on page 16.30 (198B) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. As gelatin derivatives, various compounds such as acid halides, acid anhydrides, incyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkyleonoxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. Specific examples thereof include U.S. Pat. No. 2,814,928 and U.S. Pat. I32,845,
3,186,848, 43,312,553, British Patent No. 8E11,414, same! , (133,1119
No. 1,005,784, Special Publication No. 42-26845
It is written in the number etc.

Examples of proteins include albumin and casein; examples of cellulose derivatives include hydroxyethylcellulose, carboxymethylcellulose, and sulfur esters of cellulose; and examples of sugar derivatives include alginated soda and starch derivatives, which may be used in combination with the gelatin.

Examples of the graft polymer of gelatin and other polymers include gelatin and derivatives such as acrylic acid, methacrylic acid, their esters and amides, and single (homo) or copolymer of vinyl yarns such as acrylonitrile and styrene. A grafted graft can be used. Particularly preferred are graft polymers of gelatin with polymers which are compatible to some extent, such as acrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates, examples of which are described in U.S. Pat.
No. 83,625, No. 2,831.7E17, No. 2.9
No. 58,884, etc.

In the light-sensitive material, for example, the silver halide emulsion layer and other layers can be constructed by coating on one or both sides of a flexible support commonly used in photographic light-sensitive materials.

In the present invention, the amount of gelatin on the silver halide emulsion layer side of the light-sensitive material is preferably 10 g or less per rrr'.

For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used. The pt+ of the coating liquid is preferably in the range of 5.3 to 7.5. In the case of multilayer coating, the pH of the coating liquid obtained by mixing the coating liquids of each layer in the ratio of coating amounts is 5.3 as above. It is preferable that it is in the range of ~7.5.

If pl+ is less than 5.3, the progress of dura mater is undesirable, and if the pH is greater than 7.5, it is undesirable because it adversely affects photographic performance.

Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta paper or α - Paper coated or laminated with olefin polymers (eg, polyethylene, polypropylene, ethylene/butene copolymers), etc.

The support may be colored using a dye or pigment,
The surface of these supports, which may be colored blue for the purpose of blocking light, is generally subjected to an undercoat treatment to improve adhesion with silver halide emulsion layers and the like.

The undercoating treatment is as per JP-A-52-104'113 and JP-A-58-113.
No. 18949, No. 59-191340, No. 58-18
The treatments described in each publication No. 949 are suitable.

The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

Furthermore, when carrying out the present invention, Japanese Patent Application Laid-Open No. 81-28041
It is also possible to use an organic desensitizer in which the sum of the anode potential and the picture electrode potential of a polarograph is positive, as described in the above.

The light-sensitive material of the present invention can be exposed to electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material has sensitivity. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, quartz lamps, mercury lamps, microwave UV lamps, xenonark lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, It is possible to use any known light source, such as light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, etc.
-210458 and other UV light sources may be equipped with an absorption filter that absorbs wavelengths of 370 nm or less, or the emission wavelength may be reduced to 3
Preferable results can also be obtained by using a UV light source having a main wavelength of 70 to 420 n-.

The exposure time is not only the 1 millisecond to 1 second exposure time normally used in cameras, but also the exposure time shorter than 1 microsecond (100 nanoseconds to 1 microsecond exposure using a cathode ray tube or xenon flash tube). It is also possible to provide exposures longer than 1 second. These exposures may be performed continuously or intermittently.

Next, a method for processing a photosensitive material according to the present invention will be explained.

The method for processing a photosensitive material of the present invention preferably includes the steps of development, fixing, washing, and/or stabilization, and is preferably employed in processing using an automatic processor. The automatic developing machine has a developing tank, a fixing tank, a washing tank, and/or a stabilizing tank, and has a transition section between each tank.

A combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones is preferred as a developing agent used in a developer used in development processing, especially a black and white developer, since it is easy to obtain good performance. It may also contain a phenolic developing agent.

Examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, bromohydroquinone,
Isopropyl hydroquinone, methyl hydroquinone,
2,3-dichlorohydroquinone, 2.5-); chlorohydroquinone, 2,3-dibromohydroquinone,
Examples include 2,5-dimethylhydroquinone, and hydroquinone is particularly preferred.

The developing agent for the above l-phenyl-3-pyrazolidone or its derivative is 1-phenyl-4,4-dimethyl 3-
Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl 4.4-
Examples include dihydroxymethyl-3-pyrazolidone.

The above-mentioned p-aminephenol-based developing agents include N-methyl-p-aminophenol, p-aminephenol, N-
(β-hydroxyethyl)-p-7 minophenol, N
-(4-hydroxyphenyl)glycine 2-methyl-P
-aminephenol, p-benzylaminophenol, etc. Among them, tomethyl-p-aminophenol is preferred.

The developing agent is usually 0. It is preferable to use O in an amount of 1 mol/cross to 1.2 mol/vert.

Sulfites are preferably used as preservatives in the developer, and examples of such sulfites include sodium sulfite, potassium sulfite, potassium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. . Sulfites are 0.
More than 2 moles/statement, especially 0.4 moles/! ;L or more is preferable, and the upper limit is preferably up to 2.5 mol/l.

The pH of the developer is preferably in the range of 9 to 13, more preferably in the range of 110 to 12. Alkaline agents used for pH adjustment include pH adjusters such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate, 4iH1] No. 1987-28708. (Borate)
, JP-A-80-8343θ (e.g., sucrose,
acetoxime, 5-sulfosalicylic acid), phosphate,
Buffers such as carbonates may also be used.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide, 22-ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, Organic solvents such as methanol = 1-phenyl-5-mercaptotetrazole, mercapto compounds such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, penztriazole such as 5-methylbenztriazole It may contain an antifoggant such as a type compound, and if necessary, a color toning agent, a surfactant, an antifoaming agent, a water softener, and JP-A-58-1.
It may also contain the amino compounds described in No. 06244.

In the present invention, a silver stain preventive agent, for example, a compound described in JP-A No. 56-24347, a compound described in JP-A-58-1
Amino compounds such as the alkanolamines described in No. 06244 can be used.

In addition, "Chemistry in Photographic Processing" by F. A. Meson, published by Focal Man Press (1
988), pp. 226-228, U.S. Patent No. 2.1!9
No. 3,015, No. 2,592,384, JP-A-488
Those described in No. 4831 may also be used.

The development temperature is preferably about 25°C to 50°C,
More preferably it is 30°C to 40°C. Development time is 19
The time is preferably less than 1 second, more preferably 17 seconds or less.

The fixing solution used in the next fixing step is an aqueous solution containing thiosulfate, and has a pH of preferably 3.8 or more, and more preferably a pH of 4.2 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium periosulfate, but ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed.The amount of the fixing agent used can be changed as appropriate, and is generally about 0.1 to about 6 mol/liter. It is.

The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, ammonium sulfate, potassium alum, and the like.

The fixing solution includes tartaric acid, citric acid, or their salts alone, or 2.1! The above can be used together. Those containing 0.005 mol or more of these compounds per fixer 11 are effective, particularly 0.005 mol or more per fixer 11. O1 mole/or ~0.03 mole/view is effective.

The fixing solution optionally contains a preservative (for example, sulfite monobisulfite), a pH 1 buffer (for example, acetic acid, nitric acid),
It can contain a pH adjuster (for example, sulfuric acid), a chelating agent with water softening ability, and a compound described in Japanese Patent Application No. 80-213582.

The fixing temperature is preferably from about 0°C to about 50°C, but from 30°C to
40°C is more preferable, and even more preferably 30°C to 40°C
It is.

In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being developed and fixed.

Any method known in the art can be applied to the washing or stabilization treatment, and water containing various additives known in the art can also be used as the washing water or stabilizing liquid. By using anti-mold water as the washing water or stabilizing liquid, not only is low replenishment possible, but the piping for installing the automatic processing machine becomes unnecessary, and the number of stock tanks can be reduced.

Furthermore, in addition to the silver image stabilizer, various surfactants can be added to the washing water for the purpose of preventing uneven water droplets. As the surfactant, any of the cationic, highly ionic, nonionic, and amphoteric types may be used.Specific examples of surfactants are listed in the "Surfactant Handbook" published by Kogaku Tosho ■. There are compounds listed.

Various compounds are added to the above stabilizing bath for the purpose of stabilizing the image. For example, adjusting the membrane pH (for example, P)1
Typical examples include various buffering agents for 3 to 8) and aldehydes such as formalin. In addition, various additives such as chelating agents, bactericidal agents, optical brighteners, and hardening agents may be used, and two or more compounds for the same or different purposes may be used in combination.

The water washing or stabilizing bath temperature according to the above method is O”0 to 50.
The temperature is preferably 15°C to 4Q''C, more preferably 15°C to 40°C.

The developed, fixed, and washed photosensitive material is dried by squeezing out the washing water, that is, by using a squeeze roller method. Preferably, drying is carried out at a temperature of about 0°C to about 100°C.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of silver halide emulsion A) A silver iodobromide emulsion (I iodide per mole of silver) was prepared using the simultaneous mixing method.
R2 mol%) was prepared. 95% of particle formation during this mixing
At the time of #2bC sentence 6! 8 x 10 per mole
-7 mol was added. Furthermore, after grain formation was completed, potassium iodide solution was added to this emulsion in the amount shown in Table 1, and the resulting emulsion had an average grain size of 0.20. It was a cubic crystal of g and m.

Thereafter, modified gelatin (exemplified compound G-8 of Japanese Patent Application No. 1-180787) was added, and the mixture was washed with water and desalted in the same manner as in the Example of Japanese Patent Application No. 1-180787. 40 after desalting
The pAg at °C was as shown in Table 1.

Further, during redispersion, a mixture of the following compounds (A), CB), and (C) was added.

Compound (A) CB) + (C) (manufactured by vJ, a silver halide photographic material) Thickness: 0.0 mm on both sides.
Thickness: 100 mm with a 1 μm undercoat layer (see Example 1 of JP-A-59-1111941). Apply the following formulation (1
) silver halide emulsion layer with a gelatin amount of 2.0 g/ln
', Coating so that the flJ amount is 3.2g/rn',
Furthermore, on top of that, a protective layer of the following formulation (2) is applied with a gelatin amount of 1. On the other undercoat layer on the opposite side, apply a backing layer according to the following recipe (3) so that the amount of gelatin is 2.4g/ln'. , and on top of that, a protective layer of the following formulation (4) is applied with a gelatin amount of Ig.
/rn' to obtain samples Nos. 1 to 17.

Treatment 1) (Halogen silver emulsion layer composition) Gelatin
2.0 g/silver iodobromide emulsion silver amount Antifoggant: adenine stabilizer: 4-methyl-6-hydroxy 1.3.3a, 7-chitrazaindene surfactant: sabonin tt: S -1 3, 2g/rn'25mg/rrr' 30s+g/go 0.1g/m'8mg/m' Polyethylene glycol molecular weight 4000 latex polymer: 1g/rn' Hydrazine compound Amount sensitizing dye shown in Table 1: Hardener H-1 69Bg /rn' Gelatin 0.8g/rrIJ Matting agent: Average particle size 3.5L Otori silica 3mg10T
'Surfactant: S-2 10+*g/m' CH2G00CH2(C2)1s)G4■90H000
CH2C)l(Cz)I5)C4H90xNa Hardening agent: Formalin 30 girrr (a) Gelatin 2.7g/rn'
Surfactant: sabonin O, 1g/rn'
tt; S-I BI1g/
mJ (4) (Backing protective layer composition) Gelatin Ig/m' Matting agent; Polymethyl methacrylate with average particle size of 30-5.0 μm 50 mg/rn' Surfactant: S-2
10 g/rn' Hardening agent: Glyoxal 25 g/rn' //: H-135
mg/rn' The obtained sample was exposed to 3200 tungsten light for 5 seconds with a step wedge in close contact with it, and then rapidly processed under the following conditions in an automatic developing machine using a developer and a fixing wave having the composition shown below. Regarding the obtained sample, 1i by the following method
I did fli.

(#1 quality) Step wedge with halftone dot surface fi50% 1)
- a part of the tube (150 iJl 7 inches) was attached, the sample was brought into close contact with this, and exposed to a xenon light source for 5 seconds.
This sample was developed under the following conditions using an automatic development machine for quick processing using the following developer and fixer, and the halftone dot quality of the sample was observed with a 100x magnifying glass. The highest rank is "5" and the following are r4J, "3", "2"
, 5 ranks up to "1". Note that ranks "l" and "2" are levels that are not preferred in practice.

(Black spots) Black spots in the halftone dots are also evaluated in the same manner as the quality of the halftone dots, and those with no black spots at all are ranked the highest R5J.
According to the degree of occurrence of black spots in the halftone dots, the rankings are ``4'', ``3'', and ``2'' rlJ, and the ranks are lowered in order. In addition, in ranks "1" and "2", the black spots are also large and are at a level that is not desirable for practical use.

(Sensitivity and gamma) The obtained sample was also measured using a Konica digital densitometer PDA-65.
The sensitivity at a concentration of 3.0 for sample No. 1 was set to 1.
The relative sensitivity is shown as 00, and the concentrations are 0.3 and 3.0.
Gamma is expressed as the tangent of .

(Method for evaluating illuminance failure) The obtained sample was placed in close contact with a step wedge and exposed to 3200 tungsten light for 50 seconds. At this time, the exposure amount E when tungsten is exposed for 5 seconds to 3200 as described above.
I attached a filter and exposed the images so that they were the same. After that, it is processed with the above-mentioned developer and fixer, exposed for 5 seconds and 50
The difference in exposure amount giving optical densities of 2 and 5 for second exposure is shown in logarithmic value.

mass! Disodium ethylenediaminetetraacetate 1g Titrium sulfite 60g Trisodium phosphate (decahydrate) 75g Hyde a-quinone
22.5g N,N-diethylethanolamine 15g Sodium Bromide
3g5-methylbenzotriazole 0
．． 25g] -Phenyl-5-mercaptotetrazole 0
．． 08g Metol 0.25
g Add water to make one sentence, and adjust the pH to 1 with sodium hydroxide.
tl on 1.7! Arrange.

Fixer formulation (composition A) Sodium sulfite sodium acetate trihydrate Boric acid Sodium citrate dihydrate (composition) Pure water (ion exchange water) Sulfuric acid (50% W/W aqueous solution) 4.7 g When using a fixer, the above composition A was dissolved in 500 layers of water in the order of composition A, and the fixer was finished into one layer. P of this fixer
H was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development
40'0 15 seconds fixing 35°C 15 seconds washing with water 30°C 10 seconds drying 50''CtO seconds Note that the following (a) was used as a comparative compound for the hydrazine compound added to the silver halide emulsion layer in formulation (1).
The compounds of ~(c) were used.

In addition, for comparison samples 1o, 1B, and No. 17, emulsions that were not subjected to temperature conversion and were not doped with It were used.

(a) (c) The results of the above examples are shown in Table 1.

As is clear from Table 1, sample No. according to the present invention.

It can be seen that samples No. 6 to No. 15 have high sensitivity, high contrast, and good halftone dot quality, black porosity, and illuminance failure compared to the comparison.

In addition, in sample No. 6, hydrazine compound ■-38
I-9, l-13, l-21, l-24, knee 31,
Similar evaluations were made using l-37, l-38, l-41, and l-45, and the effects of the present invention were confirmed.

Example 2 (Preparation of silver halide emulsion B) An emulsion was prepared in the same manner as emulsion A in Example 1 except that potassium iodide was added at 88% of completion of grain formation. B was prepared.

The same evaluation as in Example 1 was performed and the results are shown in Table 2.

However, as in Example 1, the emulsions used in Comparison No. 18 and No. 17 in Table 2 were emulsions that were not subjected to temperature conversion and were not doped with Ir.

The results in Table 2 show that the sample of the present invention, like Example 1, has higher sensitivity and higher contrast than the comparison, and also has better halftone dot quality, poor illuminance, and black spots.

In addition, in sample No. 6, hydrazine compound ■39 was added to I-9, Ni 13, Ni 21, Ni 24, Ni 31,
When the same evaluation was performed in place of l-17, ■-38, ■-41, and ■-45, the effect of the present invention was confirmed.

KBr
2.38g N,N-diethylethanolamine
21g5-methylbenzotriazole 0
．． Add 375g of water to make 1M, and add sodium hydroxide.
Adjust the pH to 11.7.

Example 3 Example 1 and all I did the trick.

Tue t L Toman Metol DTA NaH9O: + 45% KOH Q K 3POs KC Dan〈Similar samples were treated with the following processing agent 0.7 g 2.0 g 128.5 g 145.5 set 38.5 g 33.2 g 4. Add 22.5g of ■liquid to 75g ■liquid 1 to make 3.8 sentences.

As a result of Table 3, the sample of the present invention, similar to Example 2.3,
In comparison, it can be seen that the sensitivity is high, the contrast is high, and the quality of halftone dots, poor illuminance, and black spots are also good.

In addition, in sample No. 6, hydrazine compound ■-39
I-9, l-13, knee 21, knee 24, knee 31,
(2) Similar evaluations were made in place of 1-37, 1-38, 1-41, and 1-45, and the effects of the present invention were confirmed.

〔Effect of the invention〕

According to the present invention, it was possible to provide a silver halide photographic material with high sensitivity, high contrast, and less black spots and illuminance failure.

Claims (1)

[Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the emulsion layers contains an iridium compound and a hydrazine compound, and silver halide grains are mixed in the emulsion. A silver halide photographic light-sensitive material, characterized in that the grains have a pAg of 10.0 or less when addition and desalting are completed.