JPH0325432A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a sensitive material having high sensitivity, a slight residual color and satisfactory shelf life stability by incorporating specified compds. CONSTITUTION:Compds. represented by formulae I-III are incorporated. In the formulae I, II, each of R1 and R5 is H, alkyl, etc., each of R2 and R4 is alkyl, R3 is alkyl, each of X1<e> and X2<e> is a counter anion, each of (m) and (n) is 0 or 1, when inner salts are formed, (m) and (n) are 0, each of R6 and R10 is alkoxy or halogen and R7-R9 are R2-R4, respectively. In formula III, at least two of R1-R6 are hydroxyl and the others are H, halogen, etc. A sensitive material having high sensitivity, improved shelf life stability at high temp. and humidity and superior suitability to safelight is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION In recent years, demands on silver halide photographic light-sensitive materials have become more and more severe, and in particular, there is a strong demand for the development of light-sensitive materials with high sensitivity and excellent image characteristics.

Techniques for spectral sensitization by adding photosensitive dyes to silver halide photographic light-sensitive materials for the purpose of high sensitivity have been well known for a long time. Research on so-called supersensitization, which allows even higher sensitivity to be obtained through combinations, has been actively carried out in the industry.

For example, Special Publications No. 54-34535, No. 48-42501
56-38936, etc., there is a description regarding supersensitization.

However, although these combinations improve spectral sensitivity, many of them degrade storage stability under high temperature and high humidity conditions, safety against seilite properties, and coating solution stagnation properties, resulting in high sensitivity, Further research is required to improve performance.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide a silver halide photographic material which has high sensitivity, improved storage stability under high temperature and high humidity conditions, and has excellent safelight properties.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, at least one compound represented by the following general formula [I]; This was achieved by a silver halide photographic material containing at least one compound represented by the general formula CIO) and a compound represented by the general formula Clll).

General formula [I] [wherein, R. 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 carpoxyl group. R and R may be the same or different and represent an alkyl group. R3 represents an alkyl group.

Xi represents a counter anion. m is 0 or! and when forming an inner salt, it is 0. ] General formula (II) [In the formula, R. and R. may be the same or different, and represent an alkoxy group and a halogen atom, respectively. R
7 and R are synonymous with R2 and R4, respectively, and R is R.
, is synonymous with . n is synonymous with m. Also, X2e is Xl
It is synonymous with e. ] General formula (II[) R. κ4 (At least two sites of Rl, R!, R3, R, R, are hydroxyl groups, and the remaining sites are hydrogen atoms, halogen atoms, sulfonic acid groups or alkyl groups,
represents an aryl group, an aralkyl group, a carbonyl group, a heterocyclic group, or 10-R, or =S-R, or R1, R,, R,, R, R. A 5- or 6-membered carbocyclic ring formed by two adjacent moieties;
may form a heterocycle. R represents an alkyl group, an aryl group, an aralkyl group, or a hetyl2J] group. ] The present invention will be specifically explained below.

First, regarding general formula (1).

In the formula, R. and R 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 an alkoxy group having 1 or more carbon atoms. It represents a group (eg, methoxy group, ethoxy group, etc.), a halogen atom (eg, chlorine, bromine, etc.), a sulfamoyl group, and a carboxyl group.

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

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

Specific compounds represented by the general formula (I) will be illustrated below, but the present invention is not limited thereto, as shown in Specific Example I-1! -2 1-3 SOsK SOs0I-4 I-5 SO3” Next, regarding the general formula (I[).

In the formula, R6 and RIO may be the same or different, and each represents an alkoxy group having 1 or more carbon atoms (eg, methoxy group, ethoxy group, etc.) or a halogen group (eg, base, bromine, etc.). R, and R. are respectively R. ,R,
are synonymous, and n is synonymous with m.

Specific compounds represented by the general formula [■] will be illustrated below, but the present invention is not limited thereto.

n-1 I-6 - 2 It-3 General formula (t[I) p C,H. C. Hs Br0 1[-4 (CH2)3 CzH. SO30 The above compound (I). (I[) may be added to the silver halide emulsion during or after chemical ripening, and the appropriate amount is 10" 1000 mg per mol of silver halide. , more preferably 50 to 300 g each.

Further, the ratio of the compound [C] to [■] is preferably 1:3 to 3:1.

At least two sites among κ4 R1, R,, R,, R4, R, and R are hydroxyl groups, and the remaining sites each have a hydrogen atom, a halogen atom, a sulfonic acid group, or a substituent. When a good alkyl group, aryl group, aralkyl group, heterocyclic group, or carponyl group has a substituent, for example, the substituent for the alkyl group includes a hydroxyl group, an alkoxyl group, a sulfone group, etc. Substituents for aralkyl groups such as alkyl groups, hydroxyl groups, nitro groups, etc. are alkyl groups, hydroxyl groups, etc. Substituents for 1M ring include carbonyl groups such as alkyl groups, hydroxyl groups, alkoxyl groups, amino groups, etc. The group is an alkyl group, a hydroxyl group, an alkoxyl group, etc., or represents 10-R, or -S-R, and R R,
, R3, R, R5, R, two adjacent to each other
The two moieties may form a 5- or 6-membered carbocyclic ring or a heterocyclic ring. R is an alkyl group, aryl group, aralkyl group, or heterocyclic group that may have a substituent,
When having a substituent, for example, as a substituent for an alkyl group, a hydroxyl group, an alkoxyl group, a sulfone group, etc.
Substituents of the aryl group include an alkyl group, a hydroxyl group,
Substituents for aralkyl groups such as nitro groups include alkyl groups and hydroxyl groups, and examples of heterocyclic groups include alkyl groups, hydroxyl groups, alkoxyl groups, and amide groups.

Next, specific examples of the compound represented by the above general formula (In) used in the present invention will be shown. However, as a matter of course, the compounds used in the present invention are not limited to these.

Examples of the compounds represented by the above general formula (I [ l) No. 32, same No. 2.008.33
No. 7, No. 2,732.300, No. 3.379.5
No. 29, JP-A-49-129536, JP-A-50-9
No. 39671 and E.C. Armstrong et al.
E. C. Ar++strong at al) Journal of the American Chemical Society (J.A.
m. Che+s. Soc. ) 82.1928
1935 (1960), D.E. Core Lens (
D. E. Koalens) Journal●American●Chemical Society 56,247&-2481
(. 1934), Pharmaceutical Journal 56.814-828 (
1936) and others.
The amount of the chemical represented by general formula (III) used in the present invention is arbitrary, but it is used in an amount of up to 10g per mol of silver halide contained in the silver halide photographic material of the present invention. is preferable.

The compound represented by the general formula (II[) can be dissolved in a suitable solvent such as water, methanol, ethanol, etc., and added to the constituent elements of the silver halide photographic light-sensitive material according to the present invention. The compound represented by the general formula (III) is preferably added to the silver halide emulsion layer. However, if necessary, it can also be added to layers adjacent to the silver halide emulsion layer, such as a protective layer and an intermediate layer, to the extent that it does not affect photographic performance. Further, the compound represented by the general formula (I[I) can be added to a constituent element of the silver halide photographic material at any time during the manufacturing process of the silver halide photographic material.

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.

Compounds represented by the following general formulas (IV) to [X] can be mentioned as compounds that can be advantageously used as such compounds.

General formula (IV) General formula [v] General formula [■] General formula (Vl) O-C-- General formula [■] General formula [X] O Rl5 R+7 General formula [■] Complex of ru or benzoxazole Represents a group of nonmetallic atoms necessary to form a ring nucleus. Q represents an atomic group necessary to form vilazolone, barbituric acid, thiobarbituric acid or 3-oxythionaphthene.

R is a substituted or unsubstituted alkyl group, Rl, R2. R. ．．
and R4 each represent a hydrogen atom, an alkoxy group, a dialkylamino group or a sulfonate group, and Ra represents a hydrogen atom or a halogen atom. R *. R y, R a. R s,
RIO+ Rllll Rl21 R131 R
l41 Rls+ Rts and RIF each represent a hydrogen atom, a chlorine atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, a carpoxyl group, or a sulfonate group. However, R12 and R. and may be combined with each other to form a benzene ring. R. is a hydrogen atom,
An acyl group or an alkoxyl group, R1 represents a hydrogen atom or an alkyl group, R 10+ R 21 and R2m each represent a hydrogen atom, an alkyl group or a sulfonyl group. M
is a hydrogen atom, a sodium atom or a potassium atom, X is an anion, m. b and n2 each represent l or 2.

However, when l is 1, an inner salt is formed. Y represents an alkyl group or a carpoxyl 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 1. Next, specific examples of compounds represented by general formulas (IV) to general formulas [X] (hereinafter referred to as compounds [, [V] to compounds (X)) will be shown.

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

Specific example of compound (IV) (IV)-(1) (hereinafter referred to as the meeting) Specific example of compound (V) (V) -(l) (V) -(2) NaO,S (V) = (3 ) So,K Specific example of compound [■] [■] One (l) [■] -(2) [■] -(3) CQ Specific example of compound (Vl) (Ml) -(1) (Vl) 1 (2) (Vl) -(3) [■] -(4) Specific example of SO3H compound [■] [■] -(l) [■] -(2) [■] -(3) (II) -(4) 0H CI! ) -(5) (III) -(6) [E] -(7) 0H Compound CI! ) Specific example CI! ) −(l) CI! ) -(2) H (II) -(3) Specific example of compound (X) (X) -(l) 0 So , Na [x] -(2) 0 SO. Na(X)-(3)0 SO. Na (X)-(4) 0 (X)-(5) 0 The additive selected from compounds (IV) to (X) lowers the sensitivity in the unnecessary photosensitive wavelength range (400 to 600 nm) and increases brightness. The silver halide emulsion used in the light-sensitive material of the present invention, which greatly contributes to the use of safe light, preferably contains silver chlorobromide or silver chloroiodobromide containing 50 moles or more of silver chloride as silver halide. has a silver chloride content of 60 mol % or more.

The silver halide grains may be obtained by any of the acidic method, neutral method and ammonia method, and preferably have a grain diameter of 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 process of shaping the grains, and the salts are incorporated inside the grains and/or on the grain surfaces. The amount added is 101 to 1 mole of silver halide.
10-' moles are preferred.

Silver halide grains may have a uniform silver halide composition or distribution within the grain, or they may be core/shell grains in which the silver halide composition differs between the interior and surface layer of the grain, and the latent image is The particles may be formed mainly on the surface or may be formed mainly inside the particles.

Any shape of the silver halide grains according to the present invention can be used. One preferable example is a cube having a crystal surface having a tioo} plane.

Also, U.S. Patent Nos. 4,183.756 and 4,225.6
No. 66, JP-A-55-26589, JP-A-55-42
737, and The Journal of Photographic Science (J.Photgr.
sci). Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literature such as 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 silver halide emulsions formed separately.

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 grain size ri when the product niX ri'' of and rK3 is maximum is defined.

(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 shall be 1000 or more indiscriminately.) Particularly preferred highly monodisperse emulsions of the present invention have a degree of monodispersity of 20 or less, more preferably 15 or less. be.

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
This information can be obtained by referring to the Publication No.

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

For chemical sensitization, the Glafkides or Z
11 of Elikman et al. or H. Frieser ed.
Grund1agen der PhoLograph
ischen Prozesse sit Sifbe
rhalogeniden, Akademicche
Verlagsgesellschaft, 196
The method described in 8) 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, specific examples of which are described in U.S. Pat. No. 1,574.944.
No. 2,410.689, No. 2,278.947, No. 2,728.663, No. 3,656. 9
It is described in No. 55. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidisulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat. No. 2,487,850 and U.S. Pat. , No. 419.974, No. 2,518.698, No. 2
, No. 983,609, No. 2,983,610, No. 2,
No. 694,637. 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.
No. 060, British Patent No. 618.061, etc.

In addition, there are no particular restrictions on the conditions such as pHN pAgs temperature during chemical sensitization, but the pH value is preferably 4 to 9, particularly preferably 5 to 8<, and the PAg value is preferably 5 to 11, particularly 7 to 9. It is preferable to keep it. The temperature is preferably 40 to 900C, particularly 45 to 75C.

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-tetrazaindene, 5-mercapto-l-phenyltetrazole, 2-mercaptobenzothiazole, and the like.

Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, 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 elongation of the silver halide grains is completed, 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 photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material. Namely, azoles such as penzothiazolium salts, rhindazoles, lyazoles, penzotriazoles, penzimidazoles (particularly nitro- or halogen-substituted), heterocyclic mercapto compounds such as mercabutothiazole. mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially 1-7enyl-5-mercaptotetrazole), mercaptoviridines, the above-mentioned heterologous compounds having a water-soluble group such as a carboxyl group or a sulfone group. rings, mercapto compounds,
Thioketo compounds such as oxazolinthione, azaindenes such as tetraazaindenes (particularly 4-hydroxy substituted (1.3.3a,7)te1-raazaindenes),
Many compounds known as stabilizers can be added, such as benzenethiosulfonic acids, benzenesulfinic acids, and the like.

An example of a compound that can be used is K. Mees, The Theory of the Photographic Process
Theory of the Photography
ic Process, 3rd edition, 1966), with extensive references.

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
You can refer to the description in No. 2.28660.

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.
-63715, Belgian Patent No. 762.833, US Patent No. 3,767.410, Belgian Patent No. 588.
Substances described in each specification of No. 143, such as styrene-sodium maleate copolymer, dextransal 7
Various hardeners such as aldehyde, eboxy, ethyleneimine, active halogen, vinyl sulfone, incyanate, sulfonic acid ester, carbodiimide, mucochloric acid, acyloyl, etc. As UV absorbers, for example, U.S. Patent No. 3,25
3.921, British Patent No. 1,309,349, etc., especially 2-(2'-hydroxy-5-tertiary butylphenyl)penzotriazole, 2-(2'- hydroxy-3',5'-di3
butylphenyl)penzotriazole, 2-(2-hydroxy-3'-tertiary butyl-5'-phthyl7enyl)
-5-chlorobenzotriazole, 2-(2'-hydroxy-3'.5'-di-tertiary butylphenyl)-
Examples include 5-chlorobenzotriazole. Further, as coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials, British Patent No. 548,532, No. 1,216.389, US Pat. No. 2,026.202, US Pat.
43.17926, 43-3166, 48-
20785, French Patent No. 202.588, Belgian Patent No. 773,459, JP-A-48-101118, etc., anionic, cationic, nonionic or amphoteric compounds can be used. Among these, anionic surfactants having a sulfone group, such as succinic acid esterenolephonate, anolequinolebenzene sulfonate, and the like are particularly preferred. In addition, as an antistatic agent, Japanese Patent Publication No. 46-24159 and Japanese Patent Publication No. 48-899
No. 79, U.S. Patent No. 2,882.157, U.S. Patent No. 2,972
．． No. 535, JP-A-48-20785, JP-A No. 48-43
No. 130, No. 48-90391, Special Publication No. 46/241
There are compounds described in each of the following publications: No. 59, No. 46-39312, No. 48-43809, and JP-A-47-33627.

In the manufacturing method of the present invention, the pH 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, some layers may contain 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.
．． Inorganic particles such as alkaline earth metals or carbonates such as cadmium, zinc, etc. as described in US Pat. No. 173.181; starch as described in US Pat. No. 2,322.037;
Starch derivatives described in No. 5.451 or British Patent No. 981.198, polyvinyl alcohol described in Japanese Patent Publication No. 44-3643, Swiss Patent No. 330. 158, polyacrylonitrile as described in U.S. Pat. No. 3,079.257, U.S. Pat. No. 3,022. Organic particles such as the polycarbonate described in No. 169 may be included.

In the photosensitive material of the present invention, the structural layer contains a slipping agent, for example, U.S. Pat.
higher alcohol esters of higher aliphatics as described in US Pat. No. 3,295,979; higher aliphatic calcium salts as described in British Patent No. 1,263,722; , U.S. Patent No. 3,042
, No. 522, and No. 3,489.567.

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 I
tem18716 (November 1979), and the additive type RD 17643 RDl8716 1. Chemical sensitizers page 23, page 648, right column 2. Sensitivity increasing agent 4. Brightener page 247. Stain inhibitor page 25 right column 650
Page left to right column 8. Dye image stabilizer page 259.
Hardener Page 26 Page 651 Left column 10. Binder 26 pages
Same as above 11. Plasticizer/Lubricant page 27
650 Right column 12. ! IL fabric aid/surfactant
Pages 26-27 Same as above 13. Static inhibitor
Page 27 Same as above The photographic processing of the silver halide photographic light-sensitive material according to the present invention is not particularly limited, and various methods can be used.

The processing temperature is usually chosen between 18°C and 50°C,
The temperature may be lower than 18°C or higher than 50°C.

The developing agents used in the black and white developer used in the present invention are dihydroxybenzenes (e.g. hydroquinone), 3-virazolidone M (e.g. 1-
7-phenyl-3-virazolidone), aminophenols (
For example, N-methyl-p-aminophenol) 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 further contains dissolving aids, color toners, development accelerators, surfactants, antifoaming agents, etc. as necessary. , a water softener, a hardening agent, a viscosity imparting agent, and the like.

It is also possible to perform a so-called "squirrel type" 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. Research on hydrophobic developing agents. It can be included in the emulsion layer by the method described in Disclosure No. 169 and others. Such development treatment may be combined with silver salt stabilization treatment using thiocyanate.

As the fixer, a commonly used fixer 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 1/10-' seconds can be applied.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 (Preparation of emulsion) Solution A Water
9.70 Sodium chloride 2
0 g gelatin 105 g
Solution B water
3.8 Theory a Sodium chloride
380g gelatin 94
g Potassium bromide 420 g 0.10% aqueous solution of hexachloroiridate potassium salt 28 + sl
0.001% aqueous solution of potassium 2-hexabromorodate salt 5.0ml
2 solution C water
3.8mff silver nitrate
1700 g in the above solution A kept at 40°C,
pH 3. The above solutions B and C were added functionally simultaneously over 90 minutes while maintaining the pAg at 7.7, and after continued stirring for an additional 10 minutes, p
Adjust H to 6.0 and add 20% magnesium sulfate aqueous solution 2.
Q and 5% water of polyna 7 talenesulfonic acid? I liquid 2.
55Qt- is added and the emulsion is flocculated at 40°C, decanted and washed with water to remove excess aqueous salt. Next, 3.7Q of water is added to disperse it, and 0.9Q of a 20% aqueous magnesium sulfate solution is added again to remove the excess salt in the aqueous solution.

Add 3.712 g of water and 141 g of gelatin to it and disperse at 55° C. for 30 minutes. As a result, cubic silver bromide 35 mol%, silver chloride 65 mol%, average grain size 0.35
Grains having a μ theory monodispersity of 9 were obtained, and this emulsion was designated as EmA. Ea+B was obtained by gradually removing potassium hexabumolodate from EmA.

Add 120 mQ1 of 1% citric acid aqueous solution to each of these emulsions.
Add a 5% aqueous solution of potassium bromide to pu
5.5. To the emulsion adjusted to pAg 7, sodium thiosulfate O. A 1% aqueous solution was aged at 60°C with the addition of 120 mQ and 0.2% chloroauric acid aqueous solution to obtain the highest sensitivity.

The above emulsion was divided into IO equal parts, each containing 100% of the compound 1-phenyl-5-mercaptotetrazole as an antifoggant.
．． 25 mL of 5% solution 4-hydroxy-6 as stabilizer
-Methyl 1.3.3a, 7-tetrazaindene 180ml+2 10% aqueous solution and gelatin 10% aqueous solution were added to stop ripening, and the general formulas (I), (II), (I [
) were added as shown in Table 1, (a) was added as a sensitizing dye, and 5% solution of potassium bromide was added as an antifoggant. +12 added, 20% as spreading agent
Using saponin aqueous solution as 19IIQ1 thickener, 50 g/1 4% aqueous solution of styrene-maleic acid polymer, and polymeric polymer latex of ethyl acrylate, 0.8 g/1
l-hydroxy-3 as a hardening agent.
, 5.dichlorotriazine sodium salt and formalin were added, and the above emulsion was deposited on a subbed polyethylene terephthalate support with 1.7 g/m of gelatin and 4.5 g/m of silver.
2 g/m", and as a protective film, add 100 g of a 10% potassium bromide aqueous solution to an aqueous solution of 500 g of gelatin.
mff was added, and 1-decyl 2-(3-
400a+12 of a 1% aqueous solution of sodium impentyl succinate-2-sulfonate was added, and the average particle size was 3.
A matting agent of silica with a μ layer and a polymethyl methacrylate layer with an average particle size of 5μ is each used at 200a+g/l”%5.
The gelatin in the protective layer was added and dispersed at a concentration of 0 g/rm2 and coated simultaneously with the emulsion layer and the protective layer.

The sample obtained in this way was equipped with an LED light source;
It was exposed using a facsimile machine (PT503) manufactured by Matsushita Electric Transmission Co., Ltd., and processed under the following conditions in an ordinary roller-type automatic developing machine using the following set of developer and fixer, and the sensitivity and SE7 light were determined. An evaluation was made.

In addition, the above sample was left at 50°070%RH for 48 hours,
Sensitivity comparisons were made with untreated samples. Safelight test was conducted using Konica Safelight Glass No. The saillight time under 5clm was determined.

Development processing conditions (process) (temperature) (time) Development 38℃ 1
Fixation for 3 seconds and 2 seconds Landing on water Washing and drying Dry developer assembly (assemble A) Pure water (ion-exchanged water) Ethylenediaminetetraacetic acid disodium salt 2g Diethylene glycol 25g Potassium sulfite (55% V/V aqueous solution) 60g Potassium carbonate
15 g hydroquinone
20 g5-methylbenzotriazole
300 mQl-Phenyl-5-merkabutotetrazole 60 mg 9 seconds Room temperature 36°C taQ 9 seconds 800 Approx. 50°C l-Phenyl-4,4-dimethyl-3-birazolidinone 300 mg Potassium bromide 3.5g Potassium hydroxide 10.5g Add pure water and
Finish to Q. The pH was 10.8.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 2
40 ta (1 17 g trihydrate 6.58 6 g 2 g 13.6 ml2 Sodium sulfite Sodium acetate/Boric acid Sodium citrate/Dihydrate acetic acid (90% W/V aqueous solution) (Composition B) Pure water (ion exchange water ) Sulfur ra (90% W/V aqueous solution) Aluminum sulfate (Aqueous solution with AI2201 conversion content of 8.1% W/W) 1
7 raQ 3.5g 26.5g When using the fixer, add the above set A1 or B in water 500+Q.
It was dissolved in the following order and finished to 1Q and used.

The results in Table 1 show that the samples of the present invention have high sensitivity, little residual color, and good storage stability.

〔Effect of the invention〕

ADVANTAGE OF THE INVENTION According to the present invention, it was possible to provide a silver halide photographic material with 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, at least one compound represented by the following general formula [I] and the general formula A silver halide photographic material comprising at least one compound represented by [II] and a compound represented by general formula [III]. 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_2 is synonymous with R_3. n is synonymous with m. Also, X_2^■ is synonymous with X_1^■. ] General formula [III] ▲ Contains mathematical formulas, chemical formulas, tables, etc. represents a sulfonic acid group or an alkyl group, an aryl group, an aralkyl group, a carbonyl group, a heterocyclic group, or -O-R_7 or -S-R_7, or R_1, R_2, R_3, R_4, R_
Two adjacent sites of 5 and R_6 may form a 5- or 6-membered carbocycle or heterocycle. R_7 is an alkyl group, an aryl group, an aralkyl group,
Represents a heterocyclic group. ]