JPH03209458A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity, and to restrain dye stains due to residual dyes and fog due to infrared sensor light by incorporating a specified compound in one layer of the silver halide photographic sensitive material and a water-soluble dye having an absorption maximum in a wavelength region of >=700nm in one layer of the material. CONSTITUTION:One layer of this photographic sensitive material contains the compound represented by formulae I, and one layer of the material contains the water-soluble dye having the absorption maximum in the wavelength region of >=700nm. In formula I, each of Y1 and Y2 is a nonmetallic atomic group necessary to form a benzothiazole, benzoselenazole, naphthothiazole, naphthoselenazole ring, or the like; each of R1 and R2 is lower alkyl, alkyl optionally substituted by sulfo or carboxy; R3 is methyl, ethyl, or propyl; X1 is an anion; each of n1 and n2 is 1 or 2; and m1 is 0 or 1, and in the case of forming an intramolecular salt, m1 is 0, thus permitting sensitivity to be enhanced and dye stains due to residual dyes and fog due to infrared sensor light to be restrained.

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 photosensitive material with little residual color and improved infrared sensor fog.

[Background of the invention]

In recent years, an increasing number of newspaper facsimile plotters are equipped with infrared sensors for detecting photosensitive materials. He-Ne as a light source for facsimile plotters
There are lasers, LEDs, and semiconductor lasers. Although the silver halide photographic materials used in these materials have virtually no color sensitivity in the infrared region, fogging occurs when irradiated with even weak infrared light for a long period of time.

Generally, in order to solve the above problems in silver halide photographic materials with increased spectral sensitivity in the infrared wavelength region, attempts have been made to use large amounts of dyes to prevent halation or improve safelight properties. There is. However, increasing the amount of the dye causes a new problem of deterioration of residual color.

[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 is highly sensitive and has improved residual color and fog caused by infrared sensor light.

[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 at least one layer in the silver halide photographic material has the following general formula CI). A silver halide photographic light-sensitive material containing at least one compound represented by the following, and a water-soluble dye having an absorption maximum at 700 nm or more in at least one layer of the silver halide photographic light-sensitive material. achieved by the material.

General formula CI) (x+')■1 In the formula, Yll and Y are each a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring, or a nonmetal necessary to form quinoline 1. Represents an atomic group, and these heterocycles are lower alkyl groups,
It may be substituted with an alkoxy group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, or a halogen atom.

R+ and Rz each represent a lower alkyl group, an alkyl group having a sulfo group, or an alkyl group having a carboxyl group. R1 represents a methyl group, an ethyl group, or a propyl group. xl represents an anion.

nl and nl represent 1 or 2. m represents l or 0, and in the case of an inner salt, m=0.

Next, the configuration of the present invention will be explained in more detail.

First, specific examples of the compound represented by the above general formula CI) used in the present invention will be shown. However, the compounds used in the present invention are not limited to these.

Examples of compounds represented by the above general formula CI).

-1 ■ 2 -3 ■ 4 -5 ■ -6 ■ ■ 8 ■ ■ 10 ! 11 ■ 13 ■ 14 CH.

■ =15 16 ■ 7 ■ 18 ■ 19 ■ 20 ■ 21 (shiH2)4Sυ3- Shi1i ■ -22 ■ 23 ■ 24 ■ 25 ■ 26 ■ =27 ■ 28 ■ 29 SO, θ ■ 0 ■ 31 ■ 32 ■ 33 ■ 34 ■ 35 ■ 36 ■ 37 C.B.

f13 In the present invention, a water-soluble dye having an absorption maximum of 700 nm+m or more is used, preferably a dye of the following general formula (II a)
, (11b), and (IIc).

General formula (II a) General formula 1: I[b) (X)n-+ General formula (I[c) [In the formula, Rl+Rz, R3, R4, RS and R6 each represent an alkyl group, and Yl and Yl represents a nonmetallic atom group necessary to form a pyrrolopyridine ring, and is included in the ring of Y.

R in general formula (I[a),,R,,R,,R,,
R,,R,.

Y , ,Y , ,R , ,R in general formula (nb)
,R,,R4゜R,,R,,Y,,Y,and R8゜R,,Rs,R,,R,,R in the general formula [1[c]
,,Y l+Y! are each a group that allows the dye molecule to have at least two acid groups or -〇〇, CH,
Represents a group capable of having at least two substituents having one or more OR groups.

R represents a hydrogen atom or an alkyl group.

L represents a methine group, and Xe represents an anion.

m represents an integer of 4 to 5, and n represents an integer of 1 or 2.

When the dye forms an inner salt, n is l. ] Examples of the acid groups in the general formulas (IIa), [:l1b) and [I[c] include sulfonic acid groups, carboxylic acid groups, phosphonic acid groups, etc., and these acid groups each have their salts. include. Examples of the salt include alkali metal salts such as sodium and potassium salts, and organic ammonium salts such as ammonium, triethylamine, and pyridine.

The alkyl group represented by R(, R!, Rs, R4, Rs and R6 is preferably a lower alkyl group having 1 to 8 carbon atoms (
For example, methyl, ethyl, propyl, i-propyl, butyl group, etc.), and represents the above-mentioned acid substituent or -CH, CH!
It may have a substituent other than the OR group.

The alkyl group represented by R is preferably a lower alkyl group having 4 or less carbon atoms.

Examples of substituents containing -CHICtl and OR groups include hydroxyethyl group, hydroxyethoxyethyl group, methoxyethoxyethyl group, hydroxyethylcarbamoylmethylthylcarbamoylmethyl group, N,N-dihydroxyethylcarbamoylmethyl group, hydroxyethylsul7 Examples include an amoylethyl group and a methoxyethoxyethoxycarbonylmethyl group.

Y. Other substituents that Yl may have include sulfo groups (including salts), carboxyl groups (including salts)
, hydroxyl group, cyano group, halogen atom (e.g.
fluorine, chlorine, bromine atoms, etc.).

The methine group represented by L may also have a substituent, and examples of the substituent include substituted or unsubstituted lower alkyl groups having 1 to 5 carbon atoms (for example, methyl, ethyl, 3-hydroxypropyl, 2-sulfoethyl groups), halogen atoms (e.g.
Examples include fluorine, chlorine, bromine atoms, etc.), aryl groups (eg, phenyl groups), and alkoxy groups (eg, methoxy, ethoxy groups, etc.). In addition, the substituents of the methine group are bonded to each other to form a 6-membered ring containing three methine groups (for example, 4,4-
dimethylcyclohexene ring).

) (The anion represented by e is not particularly limited, but specific examples include a halogen ion, p-toluenesulfonic acid ion, and ethyl sulfate ion.

The general formulas (I[a), ('Ilb
) and (Ilc) (hereinafter referred to as the dye of the present invention) are shown below, but the present invention is not limited thereto.

specific compound (■ -2) (u-3) (n-4) (II-5) (IF-6) (It-7) (I[-8) (■ -9) (■ -10) (II-11) (n-12) (■ -13) (11 -14) (■ -15) (■ -16) (I[-17) (II-18) (n-19) (II-20) (n 21) (■ -24) (■ 25) (CHz)xPOsHx (CHx)xPOsT.

(If-26) (■ -27) (n-28) (II -29) (n-30) (n -31) (■ -32) (■ -33) The dye of the present invention is The Chemical Society 4 (J, Chem-5oc,) 189 pages (1
933), US Pat. No. 2,895,955, and Japanese Patent Application Laid-Open No. 123454/1983.

Examples of the mother nucleus of the dye of the present invention include the following compounds.

Compound (A) is J, Chew, Soc, ,
3202 (1,959) and British Patent 8
It can be synthesized by the method described in No. 70.753.

Compound (B) has been described in J. Chem. Soc., 584 (19
It can be synthesized by the method described in 61).

Compound (C) can be synthesized by the method described in British Patent No. 841.588.

Using these cores, quaternization, sulfonation, etc. can be performed as necessary. Or J, Cbem.

Soc, 3202 (1959) and J. Chem.
, Soc, 584 (1961) to synthesize N-alkyl-N-pyridylhydrazine, perform a cyclization reaction via hydrazone, and if necessary, treat with acid to form l-alkyl-substituted -3H -pyrrolopyridine derivatives can also be obtained and used as starting materials.

The above dye is dissolved in a suitable solvent (eg, water, alcohol, methyl cellosolve (eg, methanol, ethanol, etc.), or a mixed solvent thereof) and added to the coating solution for the hydrophilic colloid layer of the present invention.

The dyes of the present invention can also be used in combination of two or more.

In the present invention, it is sufficient that at least one of the compounds represented by the general formula (I[a), (I[b), or (nc)] is contained in the light-sensitive material to be subjected to the Asahi photosensitive material; Furthermore, two or more types can be used in any combination (for example, compounds represented by the same general formula or compounds represented by different formulas).

The specific amount of dye used varies depending on the purpose, and is uniformly fixed at 10 - "g/m" - 1,0 g 7 m.
In particular, a preferable amount can be found in the range of 1G-g/m=0.5g/m.

The silver halide emulsion used in the light-sensitive material of the present invention contains silver chlorobromide or silver chloroiodobromide containing 50 mol or more of silver chloride, more preferably 60 mol % or more of silver chloride. . The silver halide grains may be obtained by any of the acidic method, neutral method, and ammonia method, and have a particle size of 0 to 2.
It is preferably H theory or more and 0.5 μl 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 10-1 mole of silver halide.
' to 10-' moles are preferred.

Silver halide grains 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, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that 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 P hotgr, S
It is also possible to prepare particles having shapes such as octahedron, tetradecahedron, dodecahedron 1, etc. by the method described in literature such as Ci), 21.39 (1973), and use them. 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 particle size ri when the product n1
Define.

(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. It is the diameter when converted into a circular image with a circumferential area of t;

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 without chemical sensitization as a so-called primitive emulsion, it is usually chemically sensitized.

For chemical sensitization, the Glafkides or Z
elikman et al. or H. Frleser, ed.
Die
Grundlagen der Photogra
phischen Prozesse wit
Silberhalogeniden, Akademi
cche 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, No. 2,278,947, No. 2,728.668, and No. 3,656.955. 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. .97
No. 4, No. 2,518.698, No. 2,983.609
No. 2,983.610, No. 2, 694, 63
It is stated in No. 7. For noble metal sensitization, in addition to total 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. No. 448.060, British Patent No. 618.061, etc.

In addition, there are no particular restrictions on the conditions such as pH and pAgs temperature during chemical sensitization, but the pH value is preferably maintained at 4 to 9, particularly 5 to 8, and the pH value is preferably maintained at 5 to 11, particularly 7 to 9. is preferred. Also, the temperature is 40 to 90°C, especially 4
5-75°C is preferred.

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-1-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 growth of silver halide grains is completed, or they may be left contained. 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. That is, 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 tetraazaindene J [( In particular, many compounds known as stabilizers can be added, such as 4-hydroxy substituted (1,3,3a,7)tetraazaindenes), benzenethiosulfone sew, benzenesulfinic acid, 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 contains 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. 2,960,404, Japanese Patent Publication No. 43-4939,
West German Application Publication No. 1,904.604, Japanese Unexamined Patent Publication No. 1983-6
No. 3715, Belgian Patent No. 762.833, U.S. Patent No. 3,767.410, Belgian Patent No. 588.1
Substances described in each specification of No. 43, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde-based, epoxy-based,
Various hardeners and ultraviolet absorbers such as ethyleneimine, active halogen, vinyl sulfone, incyanate, sulfonic acid ester, carbodiimide, mucochloric acid, and acyloyl-based agents include, for example, U.S. Pat. No. 3,253.
, 921 and British Patent No. 1,309.349, particularly 2-(2'-hydroxy-5-tertiary butylphenyl)benzotriazole, 2
-(2'-hydroxy-3',5'-di-tert-butyl-7enyl)benzotriazole, 2-(2-hydroxy-3'-tert-butyl-5'-butylphenyl)-5-
Examples include chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tertiary butylphenyl)-5-chlorobenzotriazole, and the like. Furthermore,
Coating aids, emulsifiers, permeability improvers for processing liquids, etc.
As a surfactant used as an antifoaming agent or to control various physical properties of photosensitive materials, British Patent No. 5
No. 48.532, No. 1,216.389, U.S. Patent 2
, No. 026.202, No. 3,514,293, Special Publication No. 44-26580, No. 43-17922, No. 43-
No. 17926, No. 43-3166, No. 48-2078
No. 5, Buddhist Patent No. 202,588, Belgian Patent No. 77
Anionic, cationic, nonionic or amphoteric compounds described in No. 3.459, JP-A-48-101118, etc. can be used, but among these, anionic surface active compounds having a sulfonic group are particularly suitable. Agents such as succinic acid ester sulfonates, alkylbenzene sulfonates, and the like are preferred. In addition, as an antistatic agent,
-24159, JP 48-89979, JP 2,882.157, JP 2,972.535, JP 48-20785, JP 48-43130, JP 48
-90391, Special Publication No. 46-24159, 46-
No. 39312, No. 4g-43809, JP-A-47-3
There are compounds described in each publication of No. 3627.

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. If the pH is less than 5.3, the progress of hardening is undesirable, and if the 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.
．． 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. 3643/1983, polystyrene or polymethyl methacrylate described in Swiss Patent No. 330,158, and U.S. Pat. , 079.257, and polycarbonate described in U.S. 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 No. 2, casein described in U.S. Patent No. 3,295.979, higher aliphatic calcium salts described in British Patent No. 1 and No. 263.722, British Patent No. 1,313,384 , U.S. Patent No. 3,042
．． 522 and 3,489.567, etc., may also 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 187@I
tem18716 (November 1979), additive type 1, chemical sensitizer 2, sensitivity enhancer RD 17643 page 23 RD 18716 page 648 right column same as above 4, brightener 24 page 5, fog prevention Agents and stabilizers p. 24-25 p. 649 right column 6, light absorbers, filter dyes, ultraviolet absorbers p. 25-26 7, stain inhibitors p. 25 right column 8, dye image stabilizers
25 page 9, hardening agent page 26
651 page left column 10, binder
Page 26 Same as above 11, Plasticizer/Lubricant
Page 27 650 Right column 12, Coating aid/Surfactant Pages 26-27 Same as above 13, Static inhibitor Page 27 Same as above 649 Right column - 6
50 Left Column Page 650 Left to Right Columns The photographic processing of the silver halide photographic light-sensitive material according to the present invention is as follows:
Various methods can be used without particular limitations.

The processing temperature is usually chosen between 18°C and 5o°C,
The temperature may be lower than 18°C or higher than 50'O.

The developing chemicals 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-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, 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.

Furthermore, so-called "squirrel-type" development processing can be performed. 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 No. 169 and others. You can also use Such development treatment may be combined with silver salt stabilization treatment using thiocyanate.

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

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 (Preparation of coating solution for emulsion layer) Solution A Water
9.7a Sodium chloride 2
0g gelatin 105g Solution B Solution sodium gelatin Potassium bromide 0.01% aqueous solution of potassium hexachloroiridate salt Solution C Water 3.8Q 80g 4g 20g 8mQ 5.0 Intestine 3.8g silver nitrate 1, 700g3
pH 3.5, pAg 8 in the above solution A kept at 8°C.
．． While maintaining the pH at 0, the above solution B and solution C were added functionally at the same time over 90 minutes, and after continuing to stir for an additional 10 minutes, the pH was adjusted to 5.8 with an aqueous sodium carbonate solution,
1.74 ml of a 20% aqueous magnesium sulfate solution and 2.5512 ml of a 5% aqueous polynaphthalene sulfonic acid solution are added to flocculate the emulsion at 35° C., decanted and washed with water to remove excess salts from the aqueous solution. Then,
3.7a of water is added thereto for dispersion, and 0.90% of a 20% aqueous magnesium sulfate solution is added again to remove excess salt in the aqueous solution. Plus 3.7Q of water and 141g
gelatin and disperse at 55°C for 30 minutes. As a result, particles of 35 mol % of silver bromide, 65 mol % of silver chloride, an average of 0.35 μm, and a monodispersity of 9 are obtained. Further, 12s of 1% citric acid aqueous solution + 60-a of 5% hydrium bromide aqueous solution was added to adjust the pH to 5.5 and pAg 7, and then 120ml of 0.1% sodium thiosulfate aqueous solution was added.
2. Furthermore, 0.2% water-soluble chloroauric acid 801a was added and aged at 60°C to obtain the highest sensitivity.

The above emulsion was divided into 10 equal parts, and 0.5% of l-phenyl-5-mercaptotetrazole was added to each as an antifoggant.
1% solution of 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene as stabilizer 25mL 1% solution 1
After adding 400s12 of a 10% aqueous solution of gelatin to stop the ripening, general formula [I] and compounds A, B, and C were added in the amounts shown in Table 1, respectively, and further antifogging was performed. Add 50g of a 10% solution of hydroquinone as an agent; 50g of a 5% solution of potassium bromide;
A 20% aqueous solution of saponin was used as a spreading agent.
■Q1 Ethyl acrylate polymer latex 30g1 hardening agent with formalin and l-hydroxy-3
, 5-dichlorotriazine sodium salt and the emulsion was coated onto a subbed polyethylene terephthalate support. Og/m", -t' latin amount is 1,
7 g/■2, and as a protective film, add 100 g of a 10% potassium bromide aqueous solution to an aqueous solution of 500 g of gelatin.
11I2 was added, bis(2-ethylhexyl) sulfosuccinate was added as a surfactant, and 125g of amorphous silica with an average particle size of 3.5μ■ was added and dispersed.
The emulsion layer and the protective layer were coated at the same time at a gelatin concentration of 0.8 g/2.

Compound A Compound B Compound C (Preparation of backing layer coating solution) 71.3 g of gelatin was swollen in 1150 cc of water, and 0.7 g of Compound D, 5 g of Compound E, and 2.5 g of Compound F were added. In addition, 4.2 g of saponin manufactured by Merck and Quen 1
5 g of O, and 45 μa of a 4% aqueous solution of styrene-maleic acid polymer as a thickener were added. Add the general formula (I) to the above solution.
[a) CI[b), compound of (I[c) and compound G,
H was added in the amounts shown in Table 1, 18 cc of 4% glyoxal solution was added as a hardening agent, and water was added to give a gelatin concentration of 4% to prepare a coating solution.

compound Compound E Compound F Compound G Compound H All of the above D-H absorption maxima are below 700 nm.

(Preparation of backing protective liquid) Swell 40 g of gelatin in 900 mQ of water, and prepare an average particle size of 3.
．． 5 μ intestinal polymethyl methacrylate 2.1 gs Bis-(2-ethylhexyl) sulfosuccinate 1
55 mQ of % solution and 5 g of NaCff were added, 7 cc of 4% glyoxal solution was added as a hardening agent, and water was added so that the gelatin concentration was 5% to prepare a coating solution. Backing layer coating liquid is applied to polyester paste with backing protection liquid undercoated, backing layer gelatin 2.3g/ra”
and a backing protective layer were simultaneously coated at a concentration of 1.0 g/m''.

<Evaluation Method> The sample thus obtained was placed on the part of a facsimile machine (PT-503) manufactured by Matsushita Electric Transmission Co., Ltd. that was exposed to infrared sensor light, with the backing layer facing the sensor side, and irradiated for 30 minutes. At this time, the light intensity of the sensor is 20% during normal use.
Prepared to double in size. Next, the irradiated sample was processed using a developing solution and a fixing solution having the following composition in a GR-26SR automatic processor manufactured by Konica Corporation under the following conditions. Further, the residual color sample was also subjected to the same treatment.

The value of infrared sensor fog was determined as the difference between the values measured using a DT-101 dotmeter manufactured by Dainippon Screen Co., Ltd. for samples irradiated for 0 minutes and 30 minutes. In addition, residual color evaluation is done visually and is 1 to 3.
Out of the two samples, the worst one was 11 and the best one was 5, and the evaluation was made on a five-point scale. Sensitivity is sample no.

The value when 10 was exposed with PT-503 was set as 100, and the relative value was shown.

Processing conditions Development time Fixing time Washing time Drying time Developer prescription Pure water (ion-exchanged water) Ethylenediaminetetraacetic acid dichloride 38°C 12 seconds 36°C 12 seconds Room temperature 10 seconds 50°0 10 seconds Thorium 800+sff g Diethylene glycol 5g Potassium sulfite (55 %W/V aqueous solution) 60■a Potassium carbonate 15gHydroquinone 20g5-methylbenzotriazole 300■g1-phenyl~5-mercaptotetrazole0mg Potassium hydroxide IO,5gPotassium bromide 3.5g1-phenyl-
001 g of 4,4-dimethyl-3-pyrazolidone When using the developer, pure water was added to make it Iff. The pH was 1O68.

Fixer composition (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 24
0■a Sodium sulfite 7g Sodium acetate trihydrate 6.5g Nitric acid 1m
6g Sodium citrate dihydrate 2g Acetic acid (90% W/W aqueous solution) 13-6
mj2 (composition) Pure water (ion exchange water) 17■Q Sulfuric acid (50% wiw aqueous solution) 4.7g
26.5 g of aluminum sulfate (AffiffiO, aqueous solution with a converted content of 8.1% w/v) When used as a fixer, the above compositions were dissolved in 500 μa of water in the order of the above composition A1 and used after finishing to 1β. As is clear from Table 1, the inventive product has high sensitivity and improved residual color and fog caused by infrared sensor light.

〔Effect of the invention〕

ADVANTAGE OF THE INVENTION According to the present invention, it was possible to provide a silver halide which is highly sensitive and has improved residual color and fog caused by an infrared sensor.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, at least one layer of the silver halide photographic material has the following general formula [I ] Contains at least one compound represented by
A silver halide photographic light-sensitive material characterized in that at least one layer of the silver halide photographic light-sensitive material contains at least one water-soluble dye having an absorption maximum at 700 nm or more. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. These heterocycles may be substituted with a lower alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, or a halogen atom. R_1 and R_2 each represent a lower alkyl group, an alkyl group having a sulfo group, or an alkyl group having a carboxyl group. R_3 represents a methyl group, an ethyl group, or a propyl group. X_1 represents an anion. n_1 and n_2 represent 1 or 2. m represents 1 or 0, and when it is an inner salt, m=0. ]