JPH03217837A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To render high sensitivity to a sensitive material and to reduce a residual color and fog due to light from an IR sensor by incorporating a specified sensitizing dye and a specified dye. CONSTITUTION:This sensitive material contains one or more kinds of sensitizing dyes represented by formula I in a desired layer, e.g., an emulsion layer and one or more kinds of dyes represented by formula III in a desired colored layer, e.g., the backing layer. In the formula I, each of Y1 and Y2 is a group of atoms required to form a prescribed ring, each of R1 and R2 is alkyl having a prescribed substituent, R3 is methyl, ethyl, etc., X1 is an anion, each of n1 and n2 is 1 or 2 and m1 is 1 or 0. In the formula III, each of Z1 and Z2 is a group of atoms required to form a prescribed ring, each of R1-R6 is (un)substd. alkyl, L is (un)substd. methine, X is an anion and n is 1 or 2. Concrete examples of the compds. represented by the formulae I, III are compds. represented by formulae I, IV, respectively.

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 performance.

[Background of the invention]

In recent years, an increasing number of newspaper 7 axis plotters are equipped with infrared sensors for detecting photosensitive materials. He-Ne as a light source for facsimile printers
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 [I ], and at least one layer of the silver halide photographic material contains at least one compound represented by the following general formula [■]? This was achieved by a silver halide photographic material characterized by containing:

General formula [I) (XIe)m1 [wherein, Y1 and Y2 are each a penzothiazole ring,
Represents a nonmetallic atomic group necessary to form a penzoselenazole ring, a tothiazole ring, a toselenazole ring, or a quinoline ring, and these heterocycles include lower alkyl groups, alkoxy groups, aryl groups, and hydroxyl groups. It may be substituted with a group, an alkoxycarbonyl group, or a halogen atom.

R1 and R2 each represent a lower alkyl group, an alkyl group having a sulfo group, or an alkyl group having a carpoxyl group. R represents a methyl group, an ethyl group, or a proyl group. X1 represents an anion.

n1 and n2 represent ■ or 2. m represents 1 or 0, and when it is an inner salt, m=0. ] General formula ([) RI R4 (X)en
-1 [wherein R +, R x. Rs. R4,R
s and R6 may be the same or different from each other and represent a substituted or unsubstituted alkyl group, and z1 and z2 are nonmetallic atomic groups necessary to form a substituted or unsubstituted benz fused ring or naphtho fused ring, respectively. shows. however,
R+, Rx, Rs, R4, Rs. Rs. Z I and z2
indicates a group that allows the dye molecule to have at least 4 acid groups. L represents a substituted or unsubstituted methine group, and X0 represents an anion.

n is l or 2, and when the dye forms an inner salt, l
It is. ] The details of the present invention will be explained below.

General formula [I] will be explained.

In the above general formula (I), Y1 and Y2 are each a penzothiazole ring, a penzoselenazole ring, a naphthothiazole ring,
Represents a group of nonmetallic atoms necessary to form a natetoselenazole ring or a quinoline ring, and these heterocycles are lower alkyl groups (e.g., methyl group, ethyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, etc.) , a hydroxyl group, an aryl group (for example, a phenyl group), an alkoxyl group (for example, a tomexycarponyl group), a halogen atom (for example, a chlorine atom, a bromine atom, etc.), or the like. R. , R, represents a lower alkyl group (e.g., methyl group, ethyl group, probyl group, butyl group, etc.), an alkyl group having a sulfo group, e.g., β-sulfoethyl group, γ-sulfovir group, γ-sulfobutyl group, δ -sulfobutyl group, sulfoalcoquinalkyl group (e.g. sulfoethoxyethyl group, sulfopropoxyethyl group)}, alkyl group having a carpoxyl group (e.g. β-carpoxylethyl group, γ-carpoxyprobyl group, γ-carpoxybutyl group) , δ-carpoxybutyl group, etc.). R represents a methyl group, an ethyl group, or a proyl group. X1 represents an anion commonly used in cyanine dyes (eg, halogen ion, benzenesulfonate ion, p-toluenesulfonate ion, etc.). m represents ■ or 0, and represents m-0 when it is an inner salt.

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 [I] used in the present invention will be shown. However, the compounds used in the present invention are not limited to these.

■ ■ ■ - 6 E1 7 ■ 8 I - 9 ■ l0 ■ -11 ■ -12 CH. CH, ■ l4 CH. ■ -15 ■ -16 ■ -17 ■ 18 ■ l9 I -20 ■ -21 ■ 22 ■ 23 ■ -24 ■ 25 (CHJsSOsθ C.H. (CHt)sS(h' ■ 26 ■ =27 ■ -28 ■ -29 ■ 30 ■ -31 ■ -32 ■ -33 I -34 ■ 35 ■ 36 ■ 37 Blur 3 CH3 The sensitizing dye of the present invention is preferably 1 mg to 2 g per mole of silver halide, more preferably 5 ■ It is contained in the silver halide photographic emulsion in the range of g - 1 g.

The sensitizing dyes of the present invention can be directly dispersed into emulsions. Alternatively, they can be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl alcohol, acetone, water, pyridine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution.

The sensitizing dyes of the present invention may be used alone or in combination of two or more. Furthermore, sensitizing dyes other than those of the present invention may be used in combination. When a sensitizing dye is used in combination, it is preferable that the total amount is the above content.

The sensitizing dye of the present invention can be easily synthesized with reference to US Pat. No. 2,503,776, British Patent No. 742,112, French Patent No. 2,065,662, and Japanese Patent Publication No. 40-2346.

Next, general formula (If) will be explained.

General formula [■] In the formula, R ,,R 2+R 3. R4. R5. R
a may be the same or different from each other and represent a substituted or unsubstituted alkyl group, and z1 and z2 each represent a group of nonmetallic atoms necessary to form a substituted or unsubstituted benzo-fused ring or naphtho-fused ring; .

However, R l+R 2, R 3, R 4+R s. R
s. 2 1.2 At least 4 of the groups represented by 2"C' have acid substituents (e.g. sulfonic acid groups or carboxyl acid groups), particularly preferably when the dye molecule has 4 sulfonic acid groups. represents a group that allows for

In the present invention, a sulfonic acid group means a sulfo group or a salt thereof, and a carboxylic acid group means a carpoxyl group or a salt thereof.

Examples of salts include alkali metal salts such as Na and K, ammonium salts, and organic ammonium salts such as triethylamine, tributynoleamine, and pyridine.

L represents a substituted or unsubstituted methine group, and X represents an anion. Specific examples of the anion represented by X0 include halogen ions (C4, Br), p-toluenesulfonic acid ions, and ethyl sulfate ions.

n represents 1 or 2, and is 1 when the dye forms an intramolecular salt.

R l + R . ', R3, R 4. Rs. The alkyl group represented by R & is preferably a lower alkyl group having 1 to 5 carbon atoms (e.g. methyl group, ethyl group, n-propyl group,
n-butyl group, isoprobyl group, n-pentyl group, etc.)
represents a substituent (e.g. sulfonic acid group, carboxyl group,
hydroxyl group, etc.).

More preferably, R and R represent a lower alkyl group having 1 to 5 carbon atoms (eg, 2-sulfoethyl group, 3-sulfoprobyl group, 4-sulfobutyl group, etc.) having a sulfonic acid group.

2. As substituents of the benzo-fused ring or the na-7-fused ring formed by the nonmetallic atom group represented by ,2, sulfonic acid group, carboxylic acid group, hydroxyl group, halogen atom (for example, F, CQ, Br, etc.) , a cyano group, a substituted amine group {e.g., dimethylamino group, jetylamino group, ethyl-4-sulfobutyl group, di(3-sulfopyl)amino group, etc.}, or bonded to the ring directly or via a divalent linking group. Substituted or unsubstituted alkyl group having 1 to 5 carbon atoms {for example, methyl group, ethyl group, probyl group, butyl group, etc. (substituents include sulfonic acid group, carboxyl group,
Hydroxyl group etc. are preferred)}, and divalent linking groups are, for example, 10-, -NHCO-, -NHSO2-, =NH
COO-, -NHCONH-, -Coo-, -Co-
,-SO! - etc. are preferred.

The substituent of the methine group represented by L has 1 to 5 carbon atoms.
Substituted or unsubstituted lower alkyl groups (e.g., methyl group, ethyl group, 3-hydroxypropyl group, benzyl group, 2-sulfoethyl group, etc.), halogen atoms (e.g., F
, CQ, Br, etc.), substituted or unsubstituted aryl groups (e.g., 7enyl M, 4-chlorophenyl group, etc.),
A lower alkoxy group (for example, a methquine group, an ethquine group, etc.) is preferred.

Also, the substituents of the methine group represented by L are bonded together to form a 6-membered ring (for example, a 4,4-dimethylcyclohexene ring) containing three methine groups.

Specific examples of the dye compound represented by the general formula [3] used in the present invention are shown below, but the scope of the present invention is not limited thereto.

(I 1) (■ 2) (n-3) (■ 4) (II-5) (■ 6) (II-7) (n-8) (I[-9) (■ 10) (■ 11) (If -12) (I [ -13) (■ 14) (■ 15) (■ 16) (■ 17) (■ 18) (■ 19) (■ 20) (■ 21) (IF -23) (■ 24) (■ 25) The dye represented by the general formula [II] has an absorption maximum at wavelength 73.
In the range of 0 to 850 nm, the Journal of the
Chemical Society (J.Che+s.Soc.
189 (1933)) and U.S. Patent No. 2,895.955.
It can be synthesized by referring to the synthesis example in No.

The above dye is dissolved in a suitable solvent (for example, water, alcohols such as methanol and ethanol, methyl cellosolve, etc., or a mixed solvent thereof) to form a hydrophilic colloid layer to form a desired colored layer of the photosensitive material. It can be used by adding it to a coating solution.

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

The specific amount of dye used varies depending on the purpose and is difficult to set uniformly, but it is generally between 10-3g/m" and 0.5g/m".
m21 special! : 10-”g/m”-0.2g/+
1”+7) can be found in the range YF t L.

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 0.2
It is preferable that the amount is .mu.■ or more and 0.5 .mu.l 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 IO-'' per mole of silver halide.
~IO-9 moles are preferred.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/null grains in which the silver halide composition differs between the interior and surface layer of the grain, in which 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
Specifications such as No. 737, The Journal of Photographic Science x (J.Photogr.
Sci). 21. Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in documents such as 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 when the product niXri' of and rl3 is maximum
Define l.

(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. The monodisperse emulsion is JP-A-54-411L.
No. 521, No. 5 4'IQ No. 38 and No. 6G-1229
It can be obtained by referring to Publication No. 35 and the like.

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

For chemical sensitization, the Glafkides or Z
The book by elika+an et al., or the book by H. Frieser
Edition De Grundlagen der Fotographisien Fist Flotsese Mito ● Sino Level Halogen Nieden (D
ie Grundlagen der Photogr
aphischen Prozesse sit Si
lberhalogeniden, Akade*ic
che 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, thiosulfate, thio atoms, 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, formamidisulptaic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat. Nos. 2,487.850 and 2,419. .97
No. 4, No. 2,518.698, No. 2.91i3,60
No. 9, No. 2.983,610, No. 2,694,637
listed in the number. 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. No. 448.060, British Patent No. 618.061, etc.

In addition, there are no particular restrictions on the conditions such as pH, pAg, temperature, etc. 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 8. It is preferable to keep it at 9. 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,
3a. 7-tetrazaindene, 5-mercapto-1-7
Various stabilizers can also be used, including henynoretetrazole, 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 bezothiazolium salts, nitroindazoles, triazoles, penzotriazoles,
Penzimidazoles (especially nitro- or halogen-substituted), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially l
-phenyl-5-merkabutotetrazole), mercagutoviridines, the above-mentioned heterocycles having a water-soluble group such as a carpoxyl group or a sulfone group, merkabut compounds, thioketo compounds such as oxazolinthione, azaindenes such as tetraazaindenes ( In particular, 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 K. Mees, The Theory of the Photographic Process
Theory of the Photography
ic Process, 3rd edition, 1966), with reference to 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, Peruvian Patent No. 762.833, US Patent No. 3
, No. 767.410 and Belgian Patent No. 588.143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardening agents include aldehyde-based and eboxy-based , ethyleneimine type, active halogen type, vinyl sulfone type, isocyanate type, sulfonic acid ester type, carposiimide type, mucochloric acid type, acyloyl type, etc., and UV absorbers include, for example, U.S. Pat. ,253,92
No. 1, British Patent No. 1,309,349, particularly 2-(2'-hydroquine-
5-tertiary butylphenyl)penzotriazole, 2-(2
'-hydroxy-3',5'-di-tertiary butylphenyl)penzotriazole, 2-(2-hydroxy-
3'-tertiary butyl-5'-butyl 7enyl l5-chlorobenzotriazole, 2-(2'-hydroxy-3
',5'-di-tertiary butylphenyl) 5-chlorobenzotriazole, and the like. Furthermore, coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials are described in British Patent No. 548.
No. 532, No. 1,216,389, U.S. Patent No. 2,02
No. 6,202, No. 3.51.4.293, Special Publication No. 1972
-26580, 43-17922, 43-17
No. 926, No. 43-3166, No. 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, and among these, anionic surfactants having a sulfone group, For example, amber ugly ester sulfonates, alkylbenzene sulfonates, and the like are preferred. In addition, as an antistatic agent,
No. 4159, JP-A-48-89979, U.S. Patent No. 2,
No. 882.157, No. 2,972.535, JP-A-4
No. 8-20785, No. 48-43130, No. 48-9
No. 0391, Special Publication No. 46-24159, No. 46-39
No. 312, No. 48-43809, JP-A No. 47-336
There are compounds described in each publication of No. 27.

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 solution obtained by mixing the coating solutions for each layer in the ratio of coating amounts is within the above range of 5.3 to 7.5. If the pH value is greater than 7.5, it may adversely affect 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. Organic particles such as polyacrylonitrile described in US Pat. No. 3,022,169 and polycarbonate described in U.S. Pat.

In the photosensitive material of the present invention, the constituent layers include slipping agents, such as those described in US Pat. No. 2,588,756 and US Pat. l21.060
Higher aliphatic higher alcohol esters described in No. 2, casein described in U.S. Pat. No. 3,295.979, British patent I. 263. Higher aliphatic calcium salts described in US Pat. No. 722, UK Pat. No. 1,313,384, US Pat. No. 3,0
42,522 and 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.
17643 (December 1978) and Volume 187 I
teml8716 (November 1979), and the additive type I. Chemical sensitizer 2. Sensitivity enhancer RD 17643 page 23 RD 18716 page 648 right column same as above 4, brightener page 24 7. Stain inhibitor Page 25, right column 8. Dye image stabilizer page 259. Hardener
Page 26 Page 651 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 6
Page 50, left to right column: The photographic process 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 treatment temperature is usually chosen between 18°C and 50°C, but it may also be below 18°C or above 50°C.

The developing agents used in the black and white developer used in the present invention are dihydroxybenzenes (e.g. hydroquinone), 3-virazolidones (e.g. l-
7enyl-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, 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. Research on hydrophobic developing agents. It can be included in the emulsion layer by the method described in 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 a fluorescent lamp, an arc lamp, a mercury lamp, a xenon sunlight, a xenon flash, a cathode ray tube 7-line duplex, a laser beam, an electron beam, an X-ray, and a fluorescent screen for X-ray photography can be used as appropriate.

Exposure times include normal exposure of 1/1000 to 100 seconds, xenon flash, cathode ray tube, laser beam ray tube,
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
9.7Q Sodium Chloride 2
0g gelatin 105g solution B water
3.8a Sodium chloride 3
80g Gelatin 94g Potassium Bromide 420g Hexacroiridate Potassium Salt 0. Ol% aqueous solution 28a+1
0.2 of potassium salt of hexapromorodate. Ol% aqueous solution 5.0m solution C water
3.8Q silver nitrate 1
, 700g of the above solution A kept at 38°C with a pH of 3.
．． 5.I) While maintaining Ag8.0, add the above solution B and solution C functionally at the same time over 90 minutes, and then add 1
After stirring for 0 minutes, the pH was adjusted to 5.8 with an aqueous sodium carbonate solution, and 1.0% aqueous magnesium sulfate solution was added.
74 and 5% aqueous solution of polynaphthalenesulfonic acid 2.5
5Q was added and the emulsion was cured for 7 portions at 35°C, decanted and washed with water to remove excess salts from the aqueous solution. Next, add 3.70% water to it and disperse it,
0.9Q of 20% magnesium sulfate aqueous solution is added again to remove excess salt in the aqueous solution. And 3.7Q
of water and 141 g of gelatin are added and dispersed at 55°C for 30 minutes. This yields grains of 35 mol % silver bromide, 65 mol % silver chloride, and an average monodispersity of 0.35 μI 1 and 9. Furthermore, an aqueous solution of 1% citric acid was added to 12111+1,
Add 60ml2 of 5% potassium bromide aqueous solution to pH 5.
．． 5. After adjusting pAg to 7, sodium thiosulfate 0
．． 120 ml of 1% aqueous solution, and 0.2 ml of chloroauric acid
% water solubility by adding 3Qml and aging at 60°C to achieve maximum sensitivity.

The above emulsion was divided into IO equal parts, each containing 0 and 5 ml of l-722-5-mercaptotetrazole as an antifoggant.
% solution in 25+ml2, 4-hydroquine 6 as stabilizer
-Methyl-1.3.3a. 1% of 7-tetrazaindene
Solution 18012, lθ% aqueous solution of gelatin was added with 400 tungsten a to stop ripening, and then General Formula [I] and Compounds A, B, and C were added in the amounts shown in Table 1, respectively, and coarsely mixed. As an antifoggant, 50 m4 of a 1O% solution of hydroquinone and 50oQ of a 5% solution of potassium bromide were added.
20% saponin aqueous solution as a spreading agent 19@Q 4% aqueous solution of styrene-maleic acid polymer as a thickener
Ill2, 30g of high molecular weight polymer latex of ethyl acrylate was added with formalin and 1-hydroquine-3.5-dichlorotriazine sodium salt as a hardening agent,
The above emulsion was deposited on a subbed polyethylene terephthalate support with 4.0 g of silver/II12 and an amount of gelatin of 1.
7 g/II12, and as a protective film, add 1 lo% potassium bromide aqueous solution to an aqueous solution of 500 g of gelatin.
00i was added, bis(2-ethylhexyl) sulfosuccinate was added as a surfactant, 125 g of amorphous silicone with an average particle size of 3.5 gm was added and dispersed, and gelatin was reduced to 0.8 g/■2. The emulsion layer and protective layer were coated at the same time.

Compound A (CH 2 ) 3 So 3 Na (cow)xsoxe Compound B Compound C (Preparation of packing layer coating solution) Swell 71.3 g of gelatin in 1150 cc of water, add 0.7 g of Compound D, 5 g of Compound E, and 5 g of Compound F. 2.5g of was added. Additionally, 4.2g of Merck's sabonin, 0 citric acid.
．． 5g and 4 of styrene-maleic acid polymer as a thickener.
% aqueous solution was added. Add the general formula (I) to the above solution.
Add compound N and compounds G and H in the amounts shown in Table 1, add 18 cc of 4% glyoxal solution as a hardening agent, and add water to make the gelatin concentration 4%. It was made into a liquid.

Compound D Compound E CH 2 SO. ■ Compound F Compound G Compound H (Preparation of Baking Protective Solution) Swell 40 g of gelatin in 900 ml of water, and add 2.5 g of polymethyl methacrylate with an average particle size of 3.5 μm. 1g,
55 mQ of a 1% bis(2-ethylhexyl) sulfosuccinate solution and 5 g of NaCQ were added, 7 cc of a 4% glyoxal solution was added as a hardening agent, and water was added to give a gelatin concentration of 5% to prepare a coating solution. Packing layer gelatin 2.3g/m on polyester base coated with packing protective liquid.
2 and packing protective layer LO+a/+2.

<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 packing layer facing toward the sensor, and irradiated for 30 minutes. At this time, the light intensity of the sensor is 2
The volume was adjusted to 0x. Next, the irradiated sample was processed using Konica GR-26SR using a developer and fixer with the following composition.
It was processed using an automatic processor under the following conditions. Further, the residual color sample was also subjected to the same treatment.

The value of the infrared sensor force was determined as the difference between the values measured using a DT-101 dot meter manufactured by Dainippon Screen Co., Ltd. for samples irradiated for 0 minutes and 30 minutes. In addition, residual color evaluation is performed visually.
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. IO to PT-50
The value when exposed at step 3 is assumed to be 100, and the relative value is η.
child .

Processing conditions 38℃　　　　12 seconds 36℃　　　　12 seconds Room temperature 10 seconds 50°0 10 seconds Development time Fixation time Washing time Drying time developer prescription Pure water (ion exchange water) Ethylenediaminetetraacetic acid dibasic acid to Rium 800ml2 2g diethylene glycol 25g potassium sulfite (55% W/V aqueous solution) 60+oR potassium carbonate 15g hydroquinone 20g 5~Methylbenzoto Riazole ■-Phenyl-5-menolecaptote potassium hydroxide potassium bromide 1-phenyl-4.4 dimethyl 3 to 300+mg lazor 60mg 10.5g 3.5g Don 300mg Pyrazoli Finished in 1Q When using developer, add pure water I used it. The pH is lO. It was 8.

Fixer composition (composition A) Ammonium sulfate (72.5% W/V aqueous solution) 240+aα Sodium sulfite 17g Sodium acetate trihydrate 6.5g Nitric acid
6g Sodium citrate/acetic acid dihydrate (90% W/W aqueous solution) (Composition B) Pure water (ion exchange water) Sulfuric acid (50% W/II+ aqueous solution) Aluminum sulfate (Al220. equivalent content is 8.1%) w/w aqueous solution)
2g 13.6+oQ 17tQ 4.7g 26.5g When using a fixer, the above Composition 1 Composition B was dissolved in Water 501112 in the order of IQ and used. 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 capri 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 compound represented by the following general formula [II]. 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. ] General formula [I
I] ▲ Numerical formulas, chemical formulas, tables, etc. represents a group of nonmetallic atoms necessary to form a substituted or unsubstituted benz fused ring or naphtho fused ring, respectively. however,
R_1, R_2, R_3, R_4, R_5, R_6, Z
_1 and Z_2 indicate groups that allow the dye molecule to have at least 4 acid groups. L represents a substituted or unsubstituted methine group, and X^■ represents an anion. n is 1 or 2, and 1 when the dye forms an inner salt.
It is. ]