JPH02201352A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the photographic sensitive material having high sensitivity to IR ray with which the after colors after a development processing are less by incorporating hydrophilic colloidal layers which are spectrally sensitized by at least one selected from a group consisting of cationic di- and tricarbocyanine dyestuff and contain the dye of specific condition into emulsion layers. CONSTITUTION:The emulsion layers contain at least one layer of the hydrophilic colloidal layers which are spectrally sensitized by at least one selected from the group consisting of the di- and tricarbocyanine dyestuff and contain at least one kind of the dye expressed by the formula I. In the formula, X and Y denote a cyano group, carbamoyl group, carboxylate group, etc.; R1 and R2 denotes a group which can be substd.; R3 and R4 denote a hydrogen atom, alkyl group, aryl group, etc.; R3 and R4 may form a ring; l denotes 0 to 6 integer; m denotes 0 to 4 integer. The photosensitive material which has the high sensitivity and decreases the after colors is obtd. in this way.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silver halide photographic material that is spectrally sensitized in the infrared region, and more specifically, it relates to a silver halide photographic material that has little residual color and has excellent storage stability over time. This invention relates to silver halide photographic materials.

[Background of the invention]

One of the exposure methods for photographic light-sensitive materials is to scan an original image and expose the silver halide photographic light-sensitive material based on the image signal to form a negative, image, or positive image corresponding to the image on the original image. An image forming method using a single scanner is known. A semiconductor laser is most preferably used as the recording light source in this method. This semiconductor laser is small, inexpensive, easy to modulate, has a longer lifespan than other He-Ne lasers, argon lasers, etc., and emits light in the infrared region, so it uses a photosensitive material that is sensitive to the infrared region. It has the advantage of improving handling workability because a bright safelight can be used.

In silver halide photographic materials, photographic emulsion layers or other layers are often colored for the purpose of absorbing light in a specific wavelength range.

When it is necessary to control the spectral composition of light incident on the photographic emulsion layer, a colored layer is provided on the photographic light-sensitive material on the side farther from the support than the photographic emulsion layer.

Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers, such as in a multilayer color light-sensitive material, a filter layer may be located between them.

It is based on the fact that the light scattered during or after passing through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support, or the surface of the light-sensitive material on the opposite side of the emulsion layer, and enters the photographic emulsion layer again. For the purpose of preventing image blurring, that is, halation, a colored layer is provided between the photographic emulsion layer and the support, or on the opposite side of the support from the photographic emulsion layer. Such a colored layer is called an antihalation layer. In the case of a multilayer color photosensitive material, an antihalation layer may be placed between each layer.

Decreased image sharpness due to light scattering in the photographic emulsion layer (
In order to prevent this phenomenon (generally called irradiation), the photographic emulsion layer is also colored.

These layers to be colored often consist of hydrophilic colloids, and therefore, for coloring them, water-soluble dyes are usually incorporated into the layers. This dye must satisfy the following conditions.

(1) Must have appropriate spectral absorption according to the purpose of use.

(2) Photochemically inert. In other words, it should not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense, such as a decrease in sensitivity or fog.

(3) No harmful coloration remains on the photographic material after processing by being bleached or dissolved and removed during the photographic processing process.

As an infrared absorbing dye that satisfies these conditions,
For example, there is a tricarbodianine dye having at least three acid groups in the molecule described in JP-A No. 62-123454, but when this is applied to a silver halide photographic light-sensitive material, it does not necessarily have a long shelf life. It was found that the film was not sufficiently stable and caused a decrease in sensitivity or deterioration of residual color.

[Purpose of the invention]

Therefore, a first object of the present invention is to provide a silver halide photographic material that is highly sensitive to infrared light and has little residual color after processing. A second object of the present invention is to provide a silver halide photographic material that forms good images and has excellent stability over time.

Means for Solving Problem C] The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which the emulsion layer contains cationic di- and tricarbohydrates. It is characterized by containing at least one hydrophilic colloid layer that is spectrally sensitized with at least one selected from the group consisting of dianine dyes and contains at least one dye represented by the following general formula [I]. This was achieved using a silver halide photographic material.

General formula [I] In the formula, X and Y represent a cyano group, a carbamoyl group, a carboxylic acid ester group, and a carboxyl group, and R1 and R2
represents a substitutable group, R1 and R4 represent a hydrogen atom, an alcohol group, an aryl group, or a heterocyclic group, and R1 and R4 may form a ring. α represents an integer of 0 to 6, and m represents an integer of θ to 4.

The present invention will be explained in more detail below.

Among the groups represented by Examples include groups such as

Examples of substitutable groups represented by R and R2 include halogen atoms, alkyl, aryl, heterocycle, aralkyl, aryloxy, hydroquine, acyloxy, carboxy, alkoxycarbonyl, aryloxycarbonyl, mercapto, alkylthio, arylthio, Alkylsulfonyl, arylsulfonyl, acyl,
Examples include multiple groups such as acylamino, sulfonamide, carbamoyl, sulfamoyl, sulfo or a salt thereof, cyano, nitro, incyanato, and ureido. When α and m are each 2 or more, each of the plurality of R1 and R2 may be the same or different.

Examples of the alkyl group represented by R1 and R include groups such as methyl, ethyl, propyl, cyclo-\xyl, benzyl, and 7enethyl; examples of the aryl group include groups such as phenyl and naphthyl; Examples of the group include groups such as pyridyl, tetrahydrofuryl, and sulfolanyl.

These groups may have a substituent, and examples of the substituent include a halogen atom and a number of compounds such as hydroxy, alkoxy, carboxy, alkoxycarbonyl, alkylsulfonyl, sulfonamide, cyano, sulfo, acylamino, carbamoyl, and sulfamoyl. The following groups can be mentioned.

Furthermore, R1 and R1 may be combined to form a ring (for example, a morpholine ring).

At least one of R, R, R, and R4 may itself be a water-soluble group such as a sulfo group or a carboxy group, or a group having a sulfo group or a carboxy group as a substituent. preferable.

The dye represented by the general formula (I) used in the present invention (
Specific examples of dyes (hereinafter referred to as dyes of the present invention) are shown below.
The present invention is limited to these specific compounds (lO) :) U3K Next, a method for synthesizing the compound of the present invention will be described.

The compound of the present invention can be easily obtained by the following steps.

Oxidizing agent This synthetic method is described in, for example, Chemistry Letters (1987).
No, 9. pL76L-1762 can also be referred to.

In the light-sensitive material of the present invention, the dye represented by the general formula (I) can be incorporated into a silver halide emulsion and used as an irradiation-preventing dye, or can be used as a non-photosensitive hydrophilic colloid. It can also be incorporated into a layer and used as a filter dye or an antihalation dye. Furthermore, depending on the purpose of use, two or more types of dyes may be used in combination, or in combination with other dyes. The dye of the present invention is contained in a silver halide emulsion layer or
Incorporation into other hydrophilic colloid layers can be easily carried out by conventional methods. In general,
The dye or the organic/inorganic alkali salt of the dye is dissolved in water to form an aqueous dye solution of an appropriate concentration, which is added to a coating solution and coated by a known method to incorporate the dye into the photosensitive material. The content of these dyes varies depending on the purpose of use, but in general, the content of these dyes is
It is applied and used in an amount of 1 to 800+*g per coat.

The light-sensitive materials to which the present invention is applied include not only black-and-white photographic materials but also color photographic materials. Examples of the former include photosensitive materials for printing.

The above dye is dissolved in a suitable solvent (eg, water, alcohol, methyl cellosolve, etc.) and added to the coating solution for the hydrophilic colloid layer. These dyes can also be used in combination of two or more.

The amount of dye added varies depending on the purpose, but generally 10
-' ~ l g/m", preferably 10-' ~ 0.5
g/m” range.

The dye of the present invention is particularly effective for the purpose of preventing irradiation, and when used for this purpose, it is mainly added to the emulsion layer.

The dyes of this invention are also particularly useful as antihalation dyes, in which case they are added to the back of the support or between the support and the emulsion layer.

The dyes of the invention can also be used as dyes to impart safelight safety, in which case they are placed on top of the emulsion layer, optionally in combination with dyes that absorb light at other wavelengths. Added to layers (protective layers, etc.).

Additionally, the dyes of the present invention can be advantageously used as filter dyes.

The dye of the present invention can be introduced into the desired photographic constituent layer by a conventional method. That is, a solution of a dye at an appropriate concentration may be added to an aqueous solution of a hydrophilic colloid, which is a binder for a photographic constituent layer, and this solution may be coated on the support or other constituent layers.

In the present invention, the dye may be added to any of the hydrophilic colloid layers constituting the silver halide photographic material, such as the protective layer, silver halide emulsion layer, antihalation layer, and pack layer.

In the present invention, when the dye is contained substantially only in the non-photosensitive hydrophilic colloid layer, it is sufficient to prevent the dye from diffusing from the non-photosensitive hydrophilic colloid layer to the emulsion layer. For example, a method is used in which a silver halide emulsion layer is coated and completely set, and then a non-photosensitive hydrophilic colloid layer containing a non-diffusible dye is coated on this emulsion layer. In addition, when coating an emulsion layer and a non-photosensitive hydrophilic colloid layer at the same time using a multilayer simultaneous coating method, it is necessary to add a non-diffusible dye or a polymer mordant together with the dye to the non-photosensitive hydrophilic colloid layer. is most preferred.

Next, the cationic di- or tricarbodianine infrared sensitizing dye used in the present invention has the following general formula (II-a
) and CI[-b) are preferred.

General formula (II-a) R1l R+ 4 General formula (
n-b) In the formula, Y1□, Y, 2. Y2. and Y22 each represents a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, such as a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, a benzoxazole ring. , a na7toxazole ring, a quinoline ring, a 3,3-dialkylindolenine ring, a benzimidazole nucleus, a pyridine ring, and the like.

These heterocycles include lower alkyl groups, alkoxy groups, hydroxyl groups, aryl groups, alkoxycarbonyl groups,
It may be substituted with a halogen atom.

RIl+RI□, R21 and R22 each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

RI3+ R141RI! 1 R1m1 R241R
2S and R3 can each be a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a phenyl group, a benzyl group, or can be linked to form a 5- or 6-membered ring. X++ and X21 represent anions. nll+
n12+nz+ and n. represents 0 or 1.

Next, specific examples of the sensitizing dye used in the present invention (hereinafter referred to as the sensitizing dye of the present invention) will be shown, but the present invention is not limited thereto. In addition, ■-1 to -13 is the above general formula CII-b) and ■-14 to 21 are general formula C1r-a
) is a compound represented by

■-1 or represents an unsubstituted alkyl group (alkyl moiety has 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms), or an aryl group,
Wl and W2 can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle.

Also, RI3 and R+s and R2, and RZ& are mutually connected CJs C! H.

G ■e e +1-5 CJs　CsHs CQO,e C,H.

C! Hs n-11 n-12 CI, CH, OH ■-18 +1-19 ■-20 CI, CH, O)! C,H.

the law of nature CH, CH, 0 ■ ■ le "-15 2Hs le C2H.

(e I[-17 - C2H5le) The sensitizing dye of the present invention is preferably contained in the silver halide photographic emulsion in an amount of 1 mg to 2 g, more preferably 5 mg to 1 g, per mole of silver halide.

The sensitizing dyes of this invention can be fractionated directly into emulsions. Alternatively, they can be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, 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.

In the silver halide emulsion of the present invention, silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, silver chloride, etc. are used as silver halide in ordinary silver halide emulsions. Any one that can be used can be used.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling the pH and/or I)Ag in the mixing tank. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After growth, a conversion method may be used to change the halogen composition of the particles.

When producing a silver halide emulsion, a silver halide solvent can be used as necessary to control the grain size, grain shape, grain size distribution, and grain growth rate of the silver halide grains. .

During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( (including complex salts) to add metal ions to the inside of the particles and/or
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure (Research D 1s
Closure (hereinafter abbreviated as RD)) No. 17643, Section (2) may be used.

The 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 of the grain and the surface layer.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (100) plane to the (ill) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The average grain size of the silver halide grains (grain size represents the diameter of a circle having an area equal to the projected area) is preferably 2 μm or less, and particularly preferably 0.7 μm or less.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). When divided by the average grain size, the value is 0.20 or less.The grain size is the diameter in the case of spherical silver halide, and the diameter in the case of grains with a shape other than spherical. It shows the diameter when the projected image is converted into a circular image with the same area. ) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

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

Various additives can be used in the photosensitive material of the present invention depending on the purpose.

These additives are detailed in RD17643 (197
(December 1979) and No. 18716 (November 1979), and the relevant sections are summarized in the table below.

There are no particular limitations on the exposure and development conditions for the light-sensitive material of the present invention. For example, the photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the RD17643 silver halide emulsion have stability stability. For the purpose of improving
A dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer can be contained.

Examples of the support for the photosensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate,
For example, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, polystyrene films, etc. are used depending on the purpose of use.

Further, various inorganic white pigments, inorganic coloring pigments, dispersants, optical brighteners, antistatic agents, antioxidants, stabilizers, etc. can be added to the photographic paper support of the present invention. Further, the surface of the support may be subjected to a surface activation treatment such as a corona discharge treatment or a flame treatment, and an undercoat layer may be provided as necessary.

〔Example〕

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

Example-1 (Preparation of coating solution for emulsion layer) Solution A Water
980tQ Sodium Chloride
2.0g gelatin 20g
0.10% aqueous solution of potassium hexachloroiridate salt 2.8 m4 0.001% aqueous solution of potassium hexabromorodate salt 2.5 mQ Solution B Water
380m+2 sodium chloride
38g potassium bromide 42
g solution solution
380+nQ silver nitrate
70g of the above solution kept at 40°C, pH
Add solution B and solution C simultaneously over 80 minutes while maintaining pAg at 7.7, and add 5
After stirring for a minute, the pH was adjusted to 5 with an aqueous sodium carbonate solution.
．． 6, after normal desalination and water washing process, 500m
Add water from Q and 30g of gelatin and disperse at 50°C for 30 minutes. This resulted in 35 mol% silver bromide and 6 mol% silver chloride.
Cubic particles of 5 mol % and an average particle size of 0.27 μm are obtained.

10 ml of 1% citric acid aqueous solution. sodium chloride 5
% aqueous solution was added to the emulsion to adjust the pH to 5.5 and pAg to 7. To the emulsion was added 10 ml of a 0.1% sodium thiosulfate aqueous solution and 7 ml of a 0.2% chloroauric acid aqueous solution, and the emulsion was aged at 57°C. to the highest sensitivity.

The above emulsion was divided and 0.1% methanol solutions of infrared sensitizing dyes of the present invention and comparative infrared sensitizing dyes shown in Table 1 were added to each of them at 50 m<2 per mole of silver halide, and l- 25 mL of 0.5% solution of 7 enyl-5-mercaptotetrazole 4-hydroxy-6-methyl 1,3.3a, 1 of 7 tetrazaindene as stabilizer
% solution 180m+2. and 10% aqueous solution of gelatin 30
Aging was stopped by adding 0n++2.

As a coating aid, 15 mQ of 10% aqueous solution of sodium salt of tremie propylnaphthalene sulfonate was added to these as a coating aid.
50ml of a 4% aqueous solution of styrene-maleic acid copolymer as a thickener, 30g of butyl acrylate polymer latex, and 20ml of hydroquinone as a stabilizer.
% aqueous solution to 20ml12. 20ml of a 10% aqueous solution of potassium bromide was added and stirred, and a 0.25 mol reaction product of tetrakis(vinylsulfonylmethyl)methane and taurine potassium salt as a hardening agent was added per Ig of gelatin. The emulsified dispersion shown was added to give a fluorescent brightener loading of 15 mg/m', and the pH was adjusted to -5, 6 with citric acid to prepare a coating solution for an emulsion layer.

(Preparation of coating solution for antihalation layer) 40 g of gelatin
The dyes listed in Table 1 were applied in an amount of 200 mg/m' to an aqueous solution of
Furthermore, the emulsified dispersion shown in Table 1 was added so that the amount of optical brightener added was 15 mg/m'',
A 4% aqueous solution of styrene-maleic acid copolymer was added as a thickener to prepare a coating solution for an antihalation layer.

(Preparation of coating solution for protective layer) In an aqueous gelatin solution, 30 mg/m2 of 2-sulfosuccinic acid bis(2-ethylhexyl) ester sodium salt was added as a coating aid, and 40 mg/m2 of polymethyl methacrylate with an average particle size of 4 μm was added as a matting agent. A coating solution for a protective layer was prepared by adding 30 mg/m2 of the compound (S) below as a fluorine-containing surfactant and 10 mg of formalin per Ig of gelatin as a hardening agent.

Fluorine-containing surfactant (S) C) I2COOCHz (CFz)iH Na0sS CHCOOCHz (CFz)eH (Sample preparation and evaluation) Coating solution for antihalation layer, coating solution for emulsion layer, and protection thus prepared The layer coating solution has a hydrophilic colloid backing layer and a subbing layer, and contains 15% titanium dioxide.
Three layers were simultaneously coated on a polyethylene coated paper having a thickness of 110 μm and containing % wt. The coated silver amount of the obtained sample was 1.
4g/l112, gelatin coating amount is /%
7 prevention layer: 1.4 g/m", emulsion layer: 4 g/m"
2. The protective layer is 0.9g/m" and ivy.

Each of the obtained samples was divided into two parts, one half was left as is, and the other half was placed in a polyethylene bag and then wrapped in a paper bag to check its stability over time.
Heat treatment was performed in a 0% constant temperature oven for 72 hours.

After exposing the same-day and aged samples to a xenon flash for 10 seconds through an optical wedge and Kodak Roughten Film No. 88A, Sakura Automatic Processor GR-14 (manufactured by Konica Corporation) was used as an automatic processor. Development was carried out using the developer and fixer prescribed in Tables 2 and 3 and evaluated. In addition, unexposed samples were also processed in the same manner for evaluation of residual color. The processing conditions are: development at 38°C for 20 seconds, and fixing at about 38°C.
8℃ 20 seconds, washing with water at room temperature for 20 seconds, drying temperature about 40℃
It was C.

The results obtained are shown in Table 84. Note that the sensitivity is at a concentration of 1.0.
It is the reciprocal of the exposure amount required to give , and is a relative value with sample 1 being 100.

In addition, for samples processed without exposure to light, residual color was visually evaluated and evaluated on a five-point scale, with "5" being colorless and "1" being colorless.
” showed a strong blue residual color. Residual color below "3" is at a level that cannot withstand general use.

As is clear from the results in Table 1, sample 2 belonging to the present invention
．． 6.9 and 1O, both sensitivity and residual color are good, and it can be seen that there is little deterioration in performance over time.

(Preparation of emulsified dispersion of oil-soluble optical brightener) Dissolve 5.0 g of the following oil-soluble optical brightener (F) in a mixed solution of 100 mQ of talesyl phenyl phosphate and 100 mQ of ethyl acetate. 12% gelatin aqueous solution containing 3g of sulfonic acid sodium salt 150
After mixing with 0 mff and emulsifying and dispersing by ultrasonic fraction,
Butyl acrylate polymer latex as solid content 1
0 g was added to prepare an emulsified dispersion of an oil-soluble optical brightener.

Fluorescent brightener (F) developer prescription Pure water (ion exchange water) potassium sulfite Ethylenediaminetetraacetic acid disodium potassium hydroxide 5-methylbenzotriazole diethylene glycol l-phenyl-4,4-dimethyl- 3-pyrazolidinone l-phenyl-5-purkabutoti sol potassium bromide hydroquinone potassium carbonate Pure water (ion exchange water) increase.

The pH of the developer was approximately 10.8.

Fixer formulation (composition A) Add ammonium periosulfate 0mg 3.5g 0g 5g to OOOmQ (72.5% w/v aqueous solution) Approximately 800+++Q 0g Lium salt 2g 10.5g 00mg 5g 00mg Sodium trisulfite acetic acid Sodium trihydrate boronic acid Sodium citrate dihydrate acetic acid (90% w/w aqueous solution) (Composition) Pure water (ion-exchanged water) Acetic acid (50% w/w aqueous solution) Aluminum sulfate (AQ20. Aqueous solution with a converted content of 8.1% w/w) 40
mQ 7g 6.5g g g 13.6m (2 17m (2 4.7g 26.5g) When using, dissolve the above composition in the order of A1 in 500ml of water,
It was finished to lQ and used.

The pH of the solution was approximately 4.3.

Comparative Fixed Comparative Dye Example 2 of Comparative Infrared Sensitizing Dye Composition 60 g of gelatin was dissolved in water, and 2.0 g of each of the dyes shown in Table 2 was added thereto. Further, 40 mQ of a 1% aqueous solution of l-decyl-2-(3-isopentyl)succinate-2-sulfonic acid sodium salt as a spreading agent and 45 mC of a 4% aqueous solution of glyoxal as a hardening agent were added to give a total volume of 1.
It was set to f2. This gelatin-containing aqueous solution was coated on a polyethylene terephthalate film support with a gelatin loading of 3.2
g/m''.Meanwhile, silver chlorobromide (silver chloride 62 mol%, silver bromide 38 mol%) was coated in the same manner as in Example 1.
An emulsion (1 cubic grains with an average grain size of 0.26 μm) was obtained. After gold sensitization and sulfur sensitization of this emulsion, 4-hydroxy-6-methyl-1,3,3a was added per mole of silver halide.
, 7-chitrazaindene to 1.591-phenyl-5-
Add 0.2g of mercaptotetrazole and divide, Table 2
50 m+2 of a 0.1% methanol solution of the infrared sensitizing dye shown in Figure 1 was added per mole of silver halide, a 10% methanol solution of hydroquinone [-50 mQ] was added as an antifoggant, and 19 mff of a 20% saponin aqueous solution was added as a spreading agent.

Added 50ml of a 4% aqueous solution of styrene-maleic acid (i-form) as a thickener (!, 30g of ethyl acrylate polymer latex, and added 1 hydroxyl as a hardener).
3,5-dichlorotriazine sodium salt 1% aqueous solution 2
0m(2) and 10ml of a 4% formalin aqueous solution were added, stirred, and coated on the opposite side of the film from the gelatin-coated side.Furthermore, gelatin and 1-
Decyl-2-(3-impentyl)succinate-2-
An aqueous solution containing sulfonic acid sodium salt was applied.

The film thus produced was subjected to the same processing as in Example 1, and its photographic properties were evaluated. However, the evaluation of stability over time was performed using the following method. In other words, divide one and a half into two
After controlling the humidity at 3°C and relative humidity of 48%, it was sealed and packaged with a moisture-proof material laminated with polyvinyl acetate (thickness: 100 μm), and heat-treated in a thermostat at 55°C and relative humidity of 50% for 72 hours. The results are shown in Table 2.

However, as in Example 1, the photographic sensitivity is expressed as a relative sensitivity when sample 1 is taken as 100.

As shown in Table 2, it can be seen that the samples of the present invention had good sensitivity and residual color, and had little deterioration in performance over time.

Example 3 A solution IQ containing 130 g of KBr, 2.5 g of Kl, 30 mg of l-phenyl-5-mercaptotetrazole and 15 g of gelatin was stirred at 40° C.
．． 500 m4 of a solution containing 5 moles of ammoniacal silver nitrate
2 minutes after addition, acetic acid was added to adjust the pH to 6.
I set it to 0. After another minute, solution 5 containing 0.5 mol of silver nitrate
After stirring for 15 minutes, the emulsion was condensed by adding formalin condensate of t-lium naphthalene sulfonate and an aqueous solution of magnesium sulfate. After removing the supernatant, 40°C warm water 2I2 was added, and after stirring for 10 minutes, an aqueous solution of magnesium sulfate was added again to coagulate the emulsion. After removing the supernatant, 5% gelatin solution 300IIIQ was added and the mixture was heated to 55°C. The mixture was stirred for 30 minutes to form an emulsion.

This emulsion has an average grain size of 0.40 μm, 0.2 to 0.67 μm.
90% of the total number of particles was contained in μm.

Next, ammonium thiocyanate, chloroauric acid and sodium thiosulfate were added to this emulsion to perform gold-sulfur sensitization.

The following sensitizing dyes were added to the resulting emulsion, and 4-
Hydroxy-6-methyl-1-3-3a=7-thitrazaindene at 1.0% per mole of silver halide. Added Og.

As a sensitizing dye backing layer, 400 g of gelatin, 2 g of polymethyl methacrylate, 6 g of sodium dodecylbenzenesulfonate, 20 g of the following anti-nolation dye, and N, N'-ethylene bis-(vinylsulfonylacetamide), sodium polyethylene sulfonate, Glycidyl methacrylate 501%, methyl acrylate 10W%,
One side of a polyethylene terephthalate base was coated with an aqueous copolymer dispersion obtained by diluting a copolymer consisting of three monomers containing 40W% butyl methacrylate to a concentration of IOW%. Gelatin on the side,
A mixture of a matting agent (polymethyl methacrylate: average particle size 3.5 μm) and the following structural formula.

CsF+zSOzN(CxHy)CHzCOOK mixture C,lF+ 7501N(C3H7)(CH*C
)IzO)IsH A drag-backed support was prepared by coating with a protective layer solution consisting of a mixture of IsH. The coating amount is 2 for the backing layer and the protective layer, each with gelatin.
．． 5 g/m' and 2.0 g/m2.

(Antihalation dye) H
0g1 Nitrophenyl-triphenylphosphonium chloride 50mg, 1,3-dihydroxybenzene-4
-Ammonium sulfonate Igq2-mercaptobenzimidazole-5-sodium sulfonate 10 and the like were added to form an emulsion layer.

The protective layer solution was prepared as follows.

(Protective layer liquid) The amount added is expressed per coating liquid IQ.

Lime-treated inert gelatin 68g Acid-treated gelatin 2gNau3>-1,
itl lyυUu@n++ Polymethyl methacrylate Matting agent with area average particle size of 3.5 μm Silicon dioxide particles Matting agent with area average particle size of 1.2 μm Ludox AM (manufactured by DuPont) (Colloidal silica) 2-4-dichloro-6-hydroxy- 2% aqueous solution of 1,3,5-tosodium salt (hardener) Formalin 35% (hardener) 40% glyoxal aqueous solution (hardener) CH2COO (
CHz)sCHs 1.1g 0.5g 0g Lyazine 0m12 2m(2 1,5mQ NaOxS CH-COOCHzCCJa)sHCH
2COOCH2(CJs)J
0.5gF+*C*-0CCH2CH2Of'WCH
2CH2-OH3mgCJsSOsK
2mg Each layer was coated on the above backed base using the slide hopper method, and the silver halide emulsion layer and protective layer were sequentially coated from the support at a coating speed of 60m.
A sample was obtained by coating two layers at the same time at a speed of /min. The amount of silver was 2.59/m'', the amount of gelatin was 3 g/m'' in the emulsion layer, and 1.3 g/m'' in the protective layer.

When the above sample was evaluated in the same manner as in Example 2, it was found that both the sensitivity and residual color were good, and the aging properties were excellent.

〔Effect of the invention〕

As explained in detail in the above embodiments, according to the present invention,
It was possible to provide an infrared sensitized silver halide photographic material with high sensitivity, little residual color, and extremely little deterioration in performance during storage.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the emulsion layer contains at least one selected from the group consisting of cationic di- and tricarbodianine dyes. 1. A silver halide photographic material comprising at least one hydrophilic colloid layer which is spectrally sensitized by a hydrophilic colloid layer and which contains at least one dye represented by the following general formula [I]. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc. R_3 and R_4 represent a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group, and R
_3 and R_4 may form a ring. l is an integer from 0 to 6,
m represents an integer of 0 to 4. ]