JPH01233439A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photosensitive material having a less residual color and an excellent shelf-life with age by comprising a silver halide emulsion layer spectrally sensitized by a cationic tricarbocyanine dye and/or a cationic dicarbocyanine dye, and a hydrophilic colloid layer contg. a specified dyestuff in the sensitive material. CONSTITUTION:The sensitive material comprises at least one layer of the silver halide emulsion layers spectrally sensitized by at least one kind of the cationic tricarbocyanine dye and/or the cationic dicarbocyanine dye and the hydrophilic colloid layer contg. at least one kind of the dyes shown by formula I. In formula I, R1-R6 are each alkyl group, Z1 and Z2 are each a nonmetal atomic group necessary for forming a benzocondensed ring or a naphthocondensed ring, L is methine group, X<-> is an anion, (n) is an integer of 1 or 2. Thus, the photosensitive material having the less residual color at the time of development processing, the high sensitivity against infra-red rays and the excellent shelf-life with age is obtd.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive 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 scanning an original image and exposing the silver halide photographic light-sensitive material based on the image signal to form a negative or positive image corresponding to the image on the original image. 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 ++e-Ne lasers, argon lasers, etc., and emits light in the infrared region.
The use of a photosensitive material that is sensitive to the infrared region has the advantage of improving handling efficiency because 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 or 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 tricarbocyanine 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 good storage stability over time. It was found that it 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.

[Structure of the invention]

The above object of the present invention is to provide at least one silver halide emulsion layer spectrally sensitized with at least one of a cationic tricarbocyanine dye and/or a cationic dicarbocyanine; This was achieved by a silver halide photographic material having a hydrophilic colloid layer containing at least one of the dyes shown.

General formula (1) In the formula, R, , R2 + R3 + R4, R5 and R6 each represent an alkyl group, and Z1 and Z2 each represent a nonmetallic atomic group necessary to form a benzo-fused ring or a 7-fused ring. represent. However, Rl, R2, R3, Ra.

R, , R, , Z and z2 allow the dye molecule to have at least two acid groups and -CH.

It represents a group that allows at least two ° substituents to have one or more CHzORy groups. R represents a hydrogen atom or an alkyl group. L represents a methine group, and Xe represents an anion. n represents an integer of 1 or 2. When the dye forms an inner salt, n is l.

The present invention will be explained in more detail below.

In the general formula [I], at least two of the groups represented by R, , R, , R, , R4゜R, , Rs, Z r and Z are acid substituents (e.g. sulfo group, carboxy )
9 groups), particularly preferably the dye molecules have at least 2
represents a group that allows it to have sulfo groups. A sulfo group and a carboxyl group each include their salts. Examples of the salt include alkali metal salts such as sodium and potassium salts, and organic ammonium salts such as ammonium, triethylamine, and pyridine.

Furthermore, at least two of the groups represented by Rl, R2, Rs, R4+RS+Rs, Zr and Z2 are -co
z c Hz Contains a substituent having one or more OR7 groups. The alkyl group represented by R7 may be substituted, and examples include groups such as methyl, ethyl, methoxymethyl, and cyanoethyl.

The alkyl groups represented by R, , R, , R, , R4+Rs and R6 are preferably lower alkyl groups having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, i-propyl,
butyl group, etc.), and may have a substituent other than the acid group (for example, a hydroxyl group).

Particularly preferably, R1 and R1 are a lower alkyl group having 1 to 5 carbon atoms having a sulfo group (for example, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl group, etc.) or -CI(2C)1. OR, a lower alkyl group having 1 to 8 carbon atoms (e.g., hydroxyethyl, hydroxyethoxyethyl, methoxyethoxyethyl, hydroxyethylcarbamoylmethyl, hydroxyethoxyethylcarbamoylmethyl, N.

N-dihydroxyethylcarbamoylmethyl, hydroxyethylsulfamoylethyl, methoxyethoxyethoxycarbonylmethyl group, etc.).

The substituents on the benzene ring or naphthalene ring represented by 21 and Z include a sulfo group, a carboxyl group, a hydroxyl group, a halogen In, a cyan group, or a -CHzCHxORt group directly or via a divalent linking group. Examples include substituents.

Divalent linking groups include O, NHCO, NH30*-
, -NHCOO-, -NHCONt(-, -coo-,
-CO-, -so□-1-N-, etc., CH*
As the substituent containing the CHxORy group, the same ones as explained for R and R4 above can be mentioned.

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-hydroxypropyl, a-loethyl group, etc.), halogen atom (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 (e.g., 4,4-
dimethylcyclohexene ring).

The anion represented by xo is not particularly limited, but specific examples include a halogen ion, p-toluenesulfonate ion, and ethylsulfate ion.

The dye represented by the general formula CI) used in the present invention (
Specific examples of dyes (hereinafter referred to as the dyes of the present invention) are shown below.
The present invention is limited to these (2)! bυs”
(CHt) zu 5 (13K shin, shi UN
tRJl, LaI3sui bh=shiυN1
IL, tlxshi12su■(shitlzLH2U), H(C
8, CH, 0JffiH and H, LH, OH to H, to H,
OH The dye represented by the general formula [I] is the gloss of the Chemical Society (J, Chem, Soc,)
189 pages (1933), U.S. Patent 2,895,955
Synthesis can be carried out by referring to the following No. and the following synthesis examples.

Synthesis Example 1 (Synthesis of dye (1)) ■-(2-sulfoethyl)-2,3,3-1-limethyl-5-(2,-hydroxyethoxy)indolenine6.
6.0 g of triethylamine and 2.8 g of glutaconaldehyde cyanyl hydrochloride were added to a mixed solution of 5 g of methanol and 100 o4 of methanol, and acetic anhydride 2IIQ was added dropwise. 3 at room temperature
After stirring for an hour, the mixture was filtered, and a solution of 3.9 g of potassium acetate dissolved in 50++12 methanol was added to the filtrate, followed by further stirring at room temperature for 2 hours. The generated precipitate was collected by filtration and recrystallized with methanol to obtain 3.0 g of crystals of dye (1).

Synthesis Example 2 (Synthesis of dye (8)) 1-(2-hydroxyethylcarbamoylmethyl)-2
, 6.8 g of 3,3-trimethyl-5-(or 4-1 or 6, - or 7-) sulfoindolenine and 10 g of methanol.
6.0 g of triethylamine and 2.8 g of glutaconaldehyde cyanyl hydrochloride were added to the mixed solution of 0IIQ, and 2 mQ of acetic anhydride was added dropwise. After stirring at room temperature for 3 hours, the mixture was filtered, a solution of 3.9 g of potassium acetate dissolved in 50 mff of methanol was added to the solution, and the mixture was further stirred at room temperature for 2 hours. The formed precipitate was collected by filtration and recrystallized with methanol to obtain dye (8).
2.6 g of crystals were obtained.

λtBax (methanol) = 750 nm 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 in general:
10-' to 1 g/II+", preferably L< is used in the range 10-0,5 g/m".

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 redundant 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 barrier 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.

As the infrared sensitizing dye used in the present invention, compounds represented by the following general formulas (II-a) and (II-b) are preferred.

General formula (ff -a) General 2 B-b) In the formula, Y11+, □, Y2. and Y2□ 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, and a benzoxazole ring. ring, naphthoxazole ring,
Examples include a quinoline ring, a 3,3-dialkylindolenine ring, a benzimidazole nucleus, and a pyridine ring.

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

1? ,,,R,□+ R21 and R2□ each represent a substituted or unsubstituted alkyl group, aryl group, or aralkyl group.

R13+ R1,, RI51 R13+ R24+ R
2S and R2& each represent a hydrogen atom, a substituted or unsubstituted atom (1 to 18, preferably 1 to 4), and an aryl group, and W and W2 are connected to each other to form a 5- or 6-membered atom. A nitrogen-containing heterocycle can also be formed.

Further, R13 and RIs and R23 and R1 can be linked to each other to form a 5-membered ring or a 6-membered ring. X
1 and X2+ represent anions. n, l+ n12
+n21 and n! □ represents 0 or l.

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)-I to 13 are the compounds represented by the above-mentioned general 2B-b), and 11-14 to 21 are compounds represented by the general formula [11-a).

He I-4 He Czl(s C!H
ae He Summer e ■-8 CaHs C5) (s Cff0aeC
zHsCJs n-i.

He l-11 He l-12 Summer e I[-13 CH,CH,0HCHICI(,OH ■-14 He ■-15 CJs Ie C2H5Io C28S Ie ■-18 C2H4Ie l-19 CJs C2H61e
-20 CHICI, OHre l-21 The sensitizing dye of the present invention is preferably contained in the silver halide photographic emulsion in an amount of lrag to 2 g, more preferably 1 g of 5B'' per mole of silver halide.

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 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 pAg in the mixing pot. 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 silver halide grains.

Silver halide grains contain cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (jl
! Metal ions can be added using at least one selected from iron salts (including salts) and iron salts (including #salts) to contain these metal elements inside the particles and/or on the surface of the particles. By placing the particles in a reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

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 (111) 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 with 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). A particle with a value of 0.20 or less when divided by the average grain size.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with a shape other than spherical. This indicates the diameter when the 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.

Furthermore, there are no particular limitations on the exposure and development conditions for the photosensitive material of the present invention. For example, the photographic emulsion layer and other hydrophilic colloid layers of the photosensitive material using the RD17643 silver halide emulsion may have improved dimensional stability. For purposes such as this, a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer can be included.

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.

〔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
980m12 Sodium chloride
2.0g gelatin 20g 0.10% aqueous solution of hexachloroiridate potassium salt 2.8trr
Q o, oot% aqueous solution of potassium hexabromorodate salt 2.5 + Q solution B water
380IIIQ Sodium Chloride
38g potassium bromide 4
2g solution solution
380Ilff Silver Nitrate
170g of the above solution kept at 40°C, pH
3, the above solution B and solution C were added functionally to each other simultaneously for 80 minutes while keeping the pAg at 7.7, and
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 12 water and 30g gelatin and disperse at 50°C for 30 minutes. As a result, cubic grains containing 35 mol % of silver bromide, 65 mol % of silver chloride, and an average grain size of 0.27 μI are obtained.

Add 10 ml of 1% citric acid aqueous solution and 10 mQ of 5% sodium chloride aqueous solution to adjust the pH to 5.5 and pAg 7. To the emulsion, add 10 ml of 0.1% sodium thiosulfate aqueous solution.
Add 0+sQ and 0.2% chloroauric acid aqueous solution 7taQ and ripen at 57°C to achieve maximum sensitivity.

The above emulsion was divided and 50 IIIQ of 0.1% medanol solutions of the inventive and comparative infrared sensitizing dyes shown in Table 4 were added per mole of silver halide to each. -25 mL of 0.5% solution of 5-mercaptotetrazole 4-hydroxy-6-methyl 1.3.3a, 1% solution of 7-chitrazaindene 180a+12. A 10% aqueous gelatin solution 300I112 was added to stop the ripening.

As a coating aid, add 10% aqueous solution of sodium salt of treatypropylnaphthalene sulfonate to 15μa1 of these.
50g of a 4% aqueous solution of styrene-maleic acid copolymer as a thickener, 30g of butyl acrylate polymer latex, and 20% of hydroquinone as a stabilizer.
20mL of aqueous solution 20mL of 10% aqueous solution of potassium bromide
Add Q and stir, and add tetrakis (vinylsulfonylmethyl)methane and taurine potassium salt as a hardening agent: 1:0.
50 μg of 25 mol reaction product was added per Ig of gelatin, and the emulsified dispersion shown in Table 1 was added as an optical brightener loading amount of 15 μg.
mg/w+” and adjust pH= with citric acid.
5.6 to prepare a coating solution for emulsion layer.

(Preparation of coating solution for antihalation layer) 40 g of gelatin
To the aqueous solution, add the dye listed in Table 4 so that the loading amount is 200 mg/Ilz, and further add the emulsified dispersion shown in Table 1 so that the optical brightener loading amount is 15+mg/Ilz. A coating solution for an antihalation layer was prepared by adding 15+i12 of a 4% aqueous solution of styrene-maleic anhydride copolymer as a thickener.

(Preparation of coating solution for protective layer) Add 3Qrag/to'' of 2-sulfosuccinic acid his(2-ethylhexyl) ester sodium salt as a coating aid to a gelatin aqueous solution, and add 3Qrag/to'' of 2-sulfosuccinic acid his(2-ethylhexyl) ester sodium salt as a coating aid and an average particle size of 4 μm as a matting agent.
40mg/m'' of polymethyl methacrylate, and 30a+g/m of the following compound (S) as a fluorine-containing surfactant.
II 2. A coating solution for a protective layer was prepared by adding 10 mg of formalin per Ig of gelatin as a hardening agent.

Fluorine-containing surfactant (S) C1(zcOOcHz(CFz)sH Na03S C[(COOCHz(CFt)sH (Sample preparation and evaluation) Antihalation layer coating solution and emulsion layer coating solution prepared in this way , and a coating solution for a protective layer, which has a hydrophilic colloid backing layer and an undercoat layer, and contains 15% titanium dioxide.
Three layers were simultaneously coated on a polyethylene coated paper having a thickness of 110 μι containing vt%. The coated silver amount of the obtained sample was 1.
4g/n”, gelatin coating amount is 1 for antihalation layer
．． 4g/+w”, emulsion layer 1.4g/m2, protective layer 0
．． It was 9g/m2.

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. - Same-day and aged samples were passed through an optical wedge and Kodak Wratten filter No. 88A with a xenon flash for 10-'
After a second flash exposure, Sakura Automatic Processor GR-14 (manufactured by Konica Corporation) was used as an automatic developing machine.
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 were: development at 38°020 seconds, fixing at about 38°020 seconds, washing at room temperature for 20 seconds, and drying temperature at about 40°C.

The results obtained are shown in Table 4. 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 4, Samples 2.6.9 and IO belonging to the present invention have good sensitivity and residual color, and show little deterioration in performance over time.

Table 1 Preparation of oil-soluble optical brightener emulsion dispersion Table 2 Developer formulation Table 3 Comparison of fixer formulation Infrared sensitizing dye (C1,), SO, eC, H.

Comparative Dye A (CH2)ZSO3e(CHz)zsOJ Example 2 60g of gelatin was dissolved in water, and 2.0g of each of the dyes shown in Table 5 was added thereto. Furthermore, as a spreading agent, I-
Decyl-2-(3-isopentyl)succinate-2-
40 mQ of a 1% aqueous solution of sulfonic acid sodium salt and 45+Q of a 4% aqueous solution of glyoxal as a hardening agent were added to give a total IQ. This gelatin-containing aqueous solution was coated on a polyethylene terephthalate film support with a gelatin loading of 3.2
On the other hand, a silver chlorobromide emulsion (silver bromide content 38 mol%, cubic crystals with an average grain size of 0.26 μm) chemically sensitized with gold and sulfur compounds was coated so that Add 50a+ff of 0.1% methanol solution of the infrared sensitizing dye shown in Table 5 per mole of silver halide, and add 50mL of 10% methanol solution of hydroquinone as an antifoggant. l(
J+d.

Added 50 mL of a 4% aqueous solution of styrene-maleic acid copolymer as a thickener, and 30 g of ethyl acrylate polymer latex, and added t-hydroxy-3 as a hardening agent.
,5-di°chlorotriazine sodium salt 1% aqueous solution 2
0+IQ and 4% formalin aqueous solution 10-Q were added, stirred, and coated on the opposite side of the film from the gelatin coated side. Furthermore, an aqueous solution containing gelatin and 1-decyl-2-(3-inpentyl)succinate-2-sulfonic acid sodium salt was applied thereon as a protective layer.

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 48% relative humidity, it was sealed and packaged with a moisture-proof material laminated with polyIt vinyl (thickness: 100 μm), and heat-treated in a thermostat at 55°C and 50% relative humidity for 72 hours. The results are shown in Table 5.

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 5, the samples of the present invention have good sensitivity and residual color, and have little deterioration in performance over time. [Effects of the Invention] As explained in detail in the above examples, the present invention provides
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] At least one silver halide emulsion layer spectrally sensitized with at least one of a cationic tricarbocyanine dye and/or a cationic dicarbocyanine;
A silver halide photographic material comprising a hydrophilic colloid layer containing at least one dye represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, R_3, R_4, R_5, and R_6 each represent an alkyl group, and Z_1 and Z
Each of _3 represents a group of nonmetallic atoms necessary to form a benzo-fused ring or a naphtho-fused ring. However, R_1, R_
2, R_3, R_4, R_5, R_6, Z_1 and Z
_2 allows the dye molecule to have at least two acid groups and -CH_2CH_2OR_7 groups to one
represents a group capable of having at least two substituents. R_7 represents a hydrogen atom or an alkyl group. L represents a methine group, and X^■ represents an anion. n represents an integer of 1 or 2. n is 1 if the dye forms an inner salt. ]