JPH02244135A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve shelf stability as well as to obtain high sensitivity and a reduced residual color by color-sensitizing a silver halide emulsion using silver chlorobromide or silver chloroiodobromide contg. >=50mol% silver chloride prepd. in the presence of water soluble rhodium and iridium salts with a specified sensitizing dyestuff. CONSTITUTION:A silver halide emulsion using silver chlorobromide or silver chloroiodobromide contg. >=50mol% silver chloride prepd. in the presence of water soluble rhodium and iridium salts is color-sensitized with at least one of sensitizing dyestuffs represented by formulae I, II. In the formula I, each of R1 and R5 is H, alkyl, alkoxy, etc., and each of R2-R4 is alkyl, etc. In the formula II, each of R8 and R10 is alkoxy or halogen, R7 and R9 are R2 and R4 in the formula I, respectively, and R8 is R3 in the formula I. High sensitivity and a reduced residual color are obtd. and shelf stability is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a light-sensitive material for facsimile.

[Background of the invention]

In recent years, He--Ne lasers, LEDs, and semiconductor lasers have generally been used as light sources for facsimile machines. In the case of a facsimile machine using such a light source, various characteristics are required of the photosensitive material used. For example, in the case of an LED (emission wavelength: 660 nm), it is preferable that the silver halide photographic material has sufficient photosensitivity and that the sensitivity is as high as possible. In particular, as the running speed of facsimile machines has increased in recent years, higher sensitivity has been required, especially at high illuminance at 10"-' seconds.

Generally, in order to increase the spectral sensitivity in the red wavelength region, US Pat.
Pigments described in No. 710, No. 2454629, No. 2776280, etc. are known. Also, JP-A-62
Supersensitization is known, as described in Japanese Patent Laid-open No. 62355, JP-A-63-109436, and the like. However, in any case, silver chlorobromide or silver chloroiodobromide emulsions containing 50 mol% or more of silver chloride may suffer from dye discoloration or storage stability under high temperatures or high temperatures and high humidity, especially in emulsions with high illumination characteristics. The problem was that it was inferior.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide a silver genide photographic material which has high sensitivity, little residual color, and excellent storage stability.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, in which the silver halide emulsion is formed in the presence of a water-soluble rhodium salt and a water-soluble iridium salt. silver chloride 5, prepared with
It consists of 0 mol% or more of silver chlorobromide or silver chloroiodobromide, and is colored by at least one sensitizing dye of the following formula [I] and at least one of the sensitizing dyes of the following formula (U). This was achieved using a silver halide photographic material that is characterized by being sensitized.

The following is a blank general formula (1) [In the formula, R8 and R may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkoxy group,
Represents a halogen atom, sulfamoyl group, or carboxyl group. R2 and R1 may be the same or different and represent an alkyl group. R3 represents an alkyl group.

Xl represents a counter anion. m is 0 or I; is 1 and is 0 when an inner salt is formed. ] General formula II) [In the formula, R6 and RIG may be the same or different and represent an alkoxy group and a halogen atom, respectively.

R7 and R9 have the same meaning as R2 and R4, respectively, and R has the same meaning as R1. n is synonymous with m. Also, X, e is X
It is synonymous with 10. ] The present invention will be specifically explained below.

First, regarding formula [I].

In the formula, R1 and Rs may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted alkyl group having 2 or more carbon atoms (for example, a methyl group, an ethyl group, an ethoxy group, etc.), or a carbon number 1 It represents the above alkoxy groups (eg, methoxy group, ethoxy group, etc.), halogen atoms (eg, chlorine, bromine, etc.), sulfamoyl group, and carboxyl group.

R8 and R4 may be the same or different and represent a substituted or unsubstituted alkyl group having 2 or more carbon atoms. R
8 represents an alkyl group having 2 or more carbon atoms.

xel represents a counteranion (eg Bre, Ie, etc.). m is O or l and 0 when forming an inner salt
It is.

Specific compounds represented by the formula CI) are illustrated below, but the present invention is not limited thereto.

I-4 Concrete example ■ So, to Next, regarding general formula (If).

In the formula, R8 and R10 may be the same or different, and each represents an alkoxy group having 1 or more carbon atoms (e.g., methoxy group, ethoxy group, etc.), /10 gen atom (e.g., nasal, bromine, etc.) . R7 and R6 are R2 and R, respectively
4 is synonymous, and n is synonymous with m.

Hereinafter, specific compounds represented by the formula (U) will be exemplified, but the present invention is not limited thereto.

(CHz)z CtHs■ so,e The above compound CI), (I[) may be added to the silver halide emulsion during or after chemical ripening, and the amount added is 1 silver halide. A range of 10 to 1000 mg each per mole is suitable, more preferably 50 to 300+ ng each.

Moreover, the ratio of compound CI) and [II] is preferably 1:3 to 3:1.

Further, it is preferable to add at least one compound having an absorption wavelength range of 400 to 600 nm to the silver halide emulsion layer of the present invention and/or the protective layer provided on the layer.

Examples of compounds that can be advantageously used as such compounds include compounds represented by the following formulas (III) to (I).

C, Hs C,H.

Br' - Formula (III) General formula [■] General formula (IV) General formula [■] General formula (V) General formula (Vl) O-C...' General formula CIzx In the formula, Z is Benz Represents a group of nonmetallic atoms necessary to form the heterocyclic nucleus of thiazole, naphthothiazole, or benzoxazole. Q represents an atomic group necessary to form pyrazolone, barbylic acid, thiobarbylic acid, or 3-oxythionaphthene.

R is substituted or unsubstituted alkyl; JL R1+ R,,
R1 and R4 each represent a hydrogen atom, an alkoxy group, a dialkylamino group or a sulfone group, and Rs represents a hydrogen atom or a halogen atom. R,,R,,R,,R,.

R+o+ R111R1! l R131R141R
ISI Rlm and R17 each represent a hydrogen atom, a chlorine atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, a carboxyl group, or a sulfone group. However, Rlm and R13 may be combined with each other to form a benzene ring. R18 is a hydrogen atom, an acyl group or an alkoxycarbonyl group, R8 is a hydrogen atom or an alkyl group, R3゜+R11 and R22 are each a hydrogen atom,
Represents an alkyl group or a sulfone group. M is a hydrogen atom, sodium atom or potassium atom, X is an anion, m, n
+ and n represent l or 2, respectively. However, when m is 1, an inner salt is formed. Y represents an alkyl group or a carboxyl group.

Generally, these compounds can be added to the emulsion after chemical ripening, and if added to the protective layer, they can be added at any time before coating.
What is necessary is just to make it contain loOmg - 3.0g per m2. Next, specific examples of compounds represented by general formula [■] to general formula C (hereinafter referred to as compound (III) to compound (II)) will be shown.

However, the present invention is not limited to these specific examples.

Specific example of compound (I[) (I[[) -(1) (■) Specific example of compound (IV) (rV) -(l) (IV) NaO,5 (V) (Vl) -(l) (VI) SO, 03K (VI) Specific example of compound [■] [■] [■] [■] Specific example of compound [■] [■] -(l) SO,Na [■] [■] [■] 0■ [■ ] [■] [■] H 5O,Na Specific example of compound (ff) (II)-(1) (ff)-(4) (Iri-(2) (II)-(5) (ff)- (3) Additives selected from compounds (III) to (I) reduce the sensitivity in unnecessary photosensitive wavelength ranges (400 to 600 nm), and greatly contribute to the use of bright safe light. The silver halide emulsion used in the light-sensitive material contains silver chloride bromide or silver chloroiodobromide containing 50 mol or more of silver chloride, more preferably 60 mol % or more of silver chloride. The silver particles may be obtained by any of the acid method, neutral method, and ammonia method, and the particle size is preferably 0.2 μm or more and 0.5 μm or less.

A water-soluble rhodium salt and a water-soluble iridium salt are added to the silver halide grains used in the emulsion of the present invention during the grain formation process, and are included inside the grains and/or on the grain surfaces. The amount added is lo-1 per mole of silver halide.
The silver halide grains, which are preferably 10-9 mol, may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain. It may be a particle in which a latent image is mainly formed on the surface, or it may be a particle in which a latent image is mainly formed inside the particle.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.

Also, U.S. Patent Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-A-55-42
737, etc., and The Journal of Photographic Science (J, Photgr, S
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literatures such as Ci), 21.39 (1973), and used. Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention 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 emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. They may be used alone or in combination. or,
A polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

In the present invention, monodisperse emulsions are preferred. As monodisperse silver halide grains in a monodisperse emulsion, the weight of silver halide contained within a grain size range of ±20% around the average grain size r is 60% or more of the weight of all silver halide grains. A certain amount is preferable, particularly preferably 70% or more, and still more preferably 80% or more.

Here, the average particle size T is the frequency ni of particles having particle size ri
The particle size r when the product n1Xri'' of and ril is maximum
Define i.

(3 significant digits, round off the smallest digit.) The grain size here refers to the diameter in the case of spherical silver halide grains, and the projected image in the case of grains with shapes other than spherical. This is the diameter when the circumferential area is converted into a circular image.

The particle size can be obtained, 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 grains to be measured is indiscriminately 1,000 or more.) Particularly preferred highly monodispersed emulsions of the present invention are those with a degree of monodispersity of 20 or less, more preferably 15 or less. It is something.

Here, the average particle diameter and particle diameter standard deviation shall be determined from ri defined above. The monodispersed emulsion is disclosed in JP-A-54-41S5.
No. 21, No. 5B-49938 and No. 60-12293
It can be obtained by referring to Publication No. 5 and the like.

Although the photosensitive silver halide emulsion can be used as a so-called post-thermal (Pr1mltive) emulsion without chemical sensitization, it is usually chemically sensitized.

For chemical sensitization, the Glafkides or Z
a 1 ik■an et al.'s book, or H, Fr1ese
rJil de Grundrakensha Chill-7 Otographisien Prozesse Mid Zilpelhalogenideen (
Die Gruadlagen der Photog
raphischen Prozesse wit S
ilberhalogeniden, Akade+w
icche Verlagsgesellschaft
, 1968) can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, and gold or other noble metal compounds can be used.

As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof are described in U.S. Pat. No. 1,574,944.
No. 2,410.689 1. 2,278.947
No. 2,728.668 and No. 3,656.955. As reduction sensitizers, stannous salts,
Amines, hydrazine derivatives, formamidisulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat. Nos. 2,487,850 and 2,419.9.
No. 8, No. 2,518.698, No. 2,983.609
No. 2,983,610, and No. 2,694,637. For noble metal sensitization, in addition to total complex salts, complex salts of metals in group II of the periodic table, such as platinum, iridium, and palladium, can be used.
, No. 399,083, No. 2.448.060, British Patent No. 618.061, etc.

In addition, there are no particular limitations on the conditions such as pH, pAg, a degree, etc. during chemical sensitization, but the pH value is preferably 4 to 9, especially 5 to 8, and the pAg value is 5 to 11, especially 7 to 9. It is preferable to keep it at Further, the temperature is preferably 40 to 90°C, particularly 45 to 75°C.

In addition to the aforementioned sulfur sensitization and gold/sulfur sensitization, the photographic emulsion used in the present invention can also be subjected to reduction sensitization using a reducing substance, noble metal sensitization using a noble metal compound, or the like.

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

When carrying out the present invention, for example, 4-hydroxy-6-methyl-1,3,
Various stabilizers can also be used, including 3a,7-titrazaindene, 5-mercapto.l-phenyltetrazole, 2.mercaptobenzothiazole, and the like.

Furthermore, if necessary, a silver halide solvent such as a thioether, or a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the completion of the growth of silver halide grains, or they may be left in the emulsion. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage, or storage of the silver halide photographic light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles,
benzimidazoles (especially nitro- or halogen-substituted), peterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially l
-7enyl-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 tetraazaindenes (especially Many compounds known as stabilizers can be added, such as 4-hydroxy substituted (1,3,3a,7)tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, etc.

An example of a compound that can be used is in The Theory of the Photographic Process, by K. Mees.
Theory of the Photography
ic Process, 3rd edition, 1966), citing the original literature.

For more detailed examples and other methods of use, see, for example, U.S. Pat.
No. 82.947, No. 4,021.248 or Tokuko Sho 5
The description in No. 2-28660 can be referred to.

Further, the silver halide photographic light-sensitive material of the present invention has U.S. Pat. No. 3,411.911 and U.S. Pat.
12, Japanese Patent Publication No. 45-5331, etc., may be included.

The silver halide photographic material of the present invention may contain the following various additives. As thickeners or plasticizers, for example, U.S. Pat.
No. 15, Belgian Patent No. 762.833, now US Patent No. 3
, 767.410 and Belgian Patent No. 58L143, such as styrene-sodium maleate copolymer, dextran sulfate, etc.
Hardening agents include aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinyl sulfone-based, isocyanate-based, sulfonic acid ester-based, carbodiimide-based, mucochloric acid-based, acyloyl-based hardening agents, and ultraviolet absorbers. As the agent, for example, US Pat. No. 3,253,921
Compounds described in the specifications of British Patent No. 1.3 (No. 19,349), especially 2-(2'-hydroxy-5
-tertiary butylphenyl)benzotriazole, 2-(2
'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3
', tertiary butyl, 5'-/tylphenyl)-5-chlorobenzotriazole, 2-(2', hydroxy-3',
Examples include 5'-di-tertiary butylphenyl)-5-chlorobenzotriazole. Furthermore, coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials are described in British Patent No. 548.5.
No. 32, No. 1,216,389, U.S. Patent No. 2,026
．． No. 202, No. 3,514.293, Special Publication No. 1974/2
No. 6580, No. 43-17922, No. 43-1792
No. 6, No. 43-3166, No. 48-20785, French Patent No. 202.588, Belgian Patent No. 773.45
Anionic, cationic, nonionic or amphoteric compounds described in No. 9, JP-A-48-101118, etc. can be used, and among these, anionic surfactants having a sulfone group, For example, sulfuric acid ester sulfonates, alkylbenzene sulfonates, and the like are preferred. In addition, as an antistatic agent, Japanese Patent Publication No. 46-241
No. 59, JP-A-48-89979, U.S. Patent No. 2,88
No. 2.157, No. 2,972,535, Japanese Unexamined Patent Publication No. 1972-
No. 20785, No. 48-43130, No. 48.903
No. 91, Special Publication No. 46-24159, No. 46-3931
No. 2, No. 48-43809, JP-A-47-33627
There are compounds described in each publication.

In the manufacturing method of the present invention, 98 of the coating liquid is 5.3 to 7
．． It is preferable that it is in the range of 5. For multi-layer coating,
It is preferable that the pH of the coating liquid obtained by mixing the coating liquids for each layer in the ratio of coating amounts is within the above range of 5.3 to 7.5. When po is less than 5.3, the progress of hardening is undesirable, and when pH is greater than 7.5, it is undesirable because it adversely affects photographic performance.

In the light-sensitive material of the present invention, the constituent layers include matting agents, such as silica described in Swiss Patent No. 330.158, glass powder described in French Patent No. 1,296.995, and British Patent No. 1.
, 173.181; inorganic particles such as alkaline earth metals or carbonates such as cadmium, zinc, etc.; starch as described in U.S. Pat. No. 2,322.037, Belgian Patent No. 62
Starch derivatives described in No. 5.451 or British Patent No. 981.198, polyvinyl alcohol described in Japanese Patent Publication No. 44-3643, polystyrene or polymethyl methacrylate described in Swiss Patent No. 330.158, and US Pat. No. 330.158. , 079,257, and polycarbonate described in US Pat. No. 3,022,169.

In the light-sensitive material of the present invention, the constituent layers include slipping agents, such as U.S. Pat.
Higher aliphatic higher alcohol esters described in US Patent No. 3,295,979, higher aliphatic calcium salts described in UK Patent No. 1.263.722, UK Patent No. 1,313.32 No. 4, U.S. Patent No. 3,04
2,522, fB13.489.567, etc. may be included.

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

The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176, 1 tem.
17643 (December 1978) and volume 187■t
em18716 (November 1979), and the relevant parts are summarized in the table below.

Additive type RD 17643 RD 187
161, chemical sensitizer page 23 6
Page 48, right column 2, Sensitivity enhancer
Same as above 4, brightener 7, stain inhibitor 8, dye image stabilizer 9, hardener 10, binder 11, plasticizer/lubricant 12.1! [Fabric aid/surfactant 13, static prevention agent 24 pages 25 pages right column 650 pages left to right column 25 pages 26 pages 651 pages left column 26 pages same as above 27 pages 650 right column pages 26-27 same as above page 27 same as above book The photographic principle of the silver halide photographic material according to the invention is as follows:
Various methods can be used without particular limitations.

The Asahi temperature is usually selected between 18℃ and 50℃,
The temperature may be lower than 18"C or higher than 50C.

The developing agents used in the black and white developer used in the present invention are dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. l-
7enyl-3-pyrazolidone), aminophenols (
For example, N-methyl-p-aminophenonyl) can be used alone or in combination.

The silver halide photographic material of the present invention may be photographically processed using a developer containing imidazoles as a silver halide solvent. It is also possible to process with a developer containing a silver halide solvent and an additive such as indazole or triazole. The developing solution generally contains various other preservatives, alkaline agents, pH buffering agents, antifoggants, etc., and, if necessary, solubilizing agents, color toning agents, development accelerators, surfactants, antifoaming agents, etc. It may contain a water softener, a hardening agent, a viscosity imparting agent, etc.

It is also possible to perform a so-called "squirrel base" development process. As a special type of development processing, a method may be used in which a developing agent is contained in the light-sensitive material, for example, in an emulsion layer, and the light-sensitive material is treated with an aqueous alkaline solution to perform development. Among the developing agents, hydrophobic ones can be incorporated into the emulsion layer by the method described in Research, Disclosure 16 (19) and others. May be combined with salt stabilization geography.

As the fixer, one having a commonly used composition can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The exposure for the photographic emulsion used in the present invention varies depending on the state of chemical sensitization, the purpose of use, etc.
Various light sources such as fluorescent lamps, arc lamps, mercury lamps, xenon sunlight, xenon flashes, cathode ray tube flying spots, laser beams, electron beams, X-rays, and fluorescent screens for X-ray photography can be used as appropriate.

In addition to normal exposure of 1/1000-100 seconds, exposure time is 1/1000-100 seconds for xenon flash, cathode ray tube, and laser light.
Short exposures of /10-' to l/10-1 seconds can be applied.

[Examples] Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited thereto.

Example 1 (Preparation of coating solution for emulsion layer) Solution A Sodium chloride gelatin solution B 9.712 0g Sodium chloride gelatin Potassium bromide 3.8Q 80g 4g 20g O, oi% aqueous solution of potassium hexachloroiridate salt 28ra
Q 0.01% aqueous solution of potassium hexabromorodate salt 5.0mm
solution water
3.8a Silver nitrate 1
, 700g of the above solution A kept at 38°C has a pH of 3.
, 5. While maintaining the pAg at 8.0, the above solution B and solution C were added functionally at the same time over 90 minutes, and further 10
After stirring for a minute, the pH was adjusted to 5 with an aqueous sodium carbonate solution.
．． 8 and 20% magnesium sulfate aqueous solution 1.7
g and 5% aqueous solution of polynaphthalene sulfonic acid 2.55
Q is added and the emulsion is flocculated at 35°C, decanted and washed with water to remove excess aqueous salt. Next, 3.7Q of water is added to disperse the mixture, and 0.9ffi of a 20% magnesium sulfate aqueous solution is added again to remove the excess salt in the aqueous solution. And 3.7
Add water from a and gelatin from 1419 and disperse at 55°C for 30 minutes. As a result, particles of 35 mol % of silver bromide, 65 mol % of silver chloride, and an average monodispersity of 0.35 μm 1 are obtained. Further, 12 mL of 1% citric acid aqueous solution and 60 mff of 5% potassium bromide aqueous solution were added to adjust the pH to 5-5 and pA.
After adjusting to g7, 120ml of an aqueous solution of 0.1% sodium thiosulfate (1) was added, and 80+of of 0.2% aqueous chloroauric acid was added and aged at 60°C to achieve the highest sensitivity.

The above emulsion was divided into 10 equal parts, each containing 1-phenyl-5-mercaptotetrazo as an antifoggant.

- 25 ml of 0.5% solution of 12. As a stabilizer, 180 mL of a 1% solution of 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene in a 10% aqueous solution of gelatin was
After stopping the aging by adding 00mQ, the compound CI in Table 1 was added.
) and (1), and further added 5011+2 of a 10% solution of hydroquinone as an antifoggant, 50mQ of a 5% solution of potassium bromide, and 20mQ of a 5% solution of potassium bromide as a spreading agent.
% saponin aqueous solution as a 19mQ thickener.
50ml of 4% aqueous solution of maleic acid polymer121 30g of ethyl acrylate polymer latex, hard f
Formalin and 1-hydroxy-3,5-dichlorotriazine sodium salt were added as fling agents, and the above emulsion was deposited on a subbed polyethylene terephthalate support coated with an antihalation layer at 4.0 g/m of silver.
, the amount of gelatin is 1.79/in”!:: ft 6
J: Sea urchin.

Furthermore, as a protective film, a 10% potassium bromide aqueous solution 1ooIIIQ was added to an aqueous solution of 500 g of gelatin, a surfactant shown in Table 1 was added, and 125 g of amorphous silica with an average particle size of 3.5 μm was added and dispersed. is 0.8g
The emulsion layer and the protective layer were coated at the same time in such a manner that the coating layer had a coating thickness of 100 mm/m''.

The sample obtained in this way was exposed through a facsimile machine (PT-503) manufactured by Matsushita Denso Co., Ltd. equipped with an LED light source, and then processed using a regular roller type automatic developing machine using a developer and fixer having the following composition. The samples were processed under the following conditions and evaluated for sensitivity and residual color. In addition, the above sample was left at 50° C. and 70% RH for 48 hours, and the sensitivity was compared with a non-geographic sample.

Note that the residual color is evaluated in five levels, with 5 being the best, 1 to 2 being unusable, and 3 or more being usable.

The results are shown in Table 1.

From Table 1, it can be seen that the products of the present invention have high sensitivity, good residual color, and also good storage stability.

Processing conditions Development time 35℃ 13 seconds Fixing time 34℃ 13 seconds Washing time Regular IL 10 seconds Drying time 10 seconds at 50 Developer formulation Pure water (ion exchange water) 800 + i1
2 Disodium ethylenediaminetetraacetate 2g Diethylene glycol 25g Potassium sulfite (55% A/V aqueous solution) 60mff Potassium carbonate 159 Hydroquinone 2095-Methylbenzotriazole 300IIIgl-Phenyl-5-mercaptotetrazole 60a+g Potassium hydroxide IO, 5g Potassium bromide 3.5g 1 When using the -phenyl-4,4-dimethyl-3-pyrazolidone developer, pure water was added to finish it to IQ. pH is 1O
It was 08.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 24
0mg sodium sulfite 179
Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (90%
W/W aqueous solution) 13, 6m4 (composition) Pure water (ion exchange water) 17m (1
Sulfuric acid (50% W/W aqueous solution) 4.
7y aluminum sulfate (ha*os equivalent content 8.1% W/W (7) aqueous solution)
When using a 26.5 g fixer, it was dissolved in 500 mQ of water in the order of the above composition A1 and finished to 1Q. The pH of this fixer was about 4.6.

[Effects of the Invention] According to the present invention, it was possible to provide a silver halide photographic material that has high sensitivity, little residual color, and good storage stability.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, wherein the silver halide emulsion is formed in the presence of a water-soluble rhodium salt and a water-soluble iridium salt. Prepared, consisting of silver chloride bromide or silver chloroiodobromide containing 50 mol% or more of silver chloride, and having the following general formula [I]
A silver halide photographic light-sensitive material characterized in that it has been color sensitized with at least one sensitizing dye represented by the formula [II] below. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a carboxyl group. R_2 and R_4 may be the same or different and represent an alkyl group. R_3 represents an alkyl group. X_1^■ represents a counter anion. m is 0 or 1, and is 0 when forming an inner salt. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_6 and R_1_0 may be the same or different and represent an alkoxy group and a halogen atom, respectively. R_7 and R_9 are synonymous with R_2 and R_4, respectively, and R_8 is synonymous with R_3. n is synonymous with m. Also, X_2^■ is synonymous with X_1^■. ]