JP2660421B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material spectrally sensitized in the infrared region, and more specifically, it has little residual color and excellent storage stability over time. It relates to a silver halide photographic material.

[Background of the Invention]

A so-called scanner that scans an original drawing as one of the exposure methods of a photographic photosensitive material and performs exposure on a silver halide photographic photosensitive material based on the image signal to form a negative image or a positive image corresponding to the image of the original drawing. 2. Description of the Related Art There is known an image forming method by a method. A semiconductor laser is most preferably used as a recording light source in this method. This semiconductor laser is small, inexpensive, easy to modulate, has a longer life than other He-Ne lasers, argon lasers, etc., and emits light in the infrared region. When used, a bright safelight can be used, which has an advantage that handling workability is improved.

In a silver halide photographic light-sensitive material, a photographic emulsion layer or another layer is often colored in order to absorb light in a specific wavelength range.

When it is necessary to control the spectral composition of light to be incident on the photographic emulsion layer, a colored layer is provided on the photographic light-sensitive material on a 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 a multilayer color light-sensitive material, a filter layer may be located between them.

Light scattered when passing through or after transmission through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support or at the surface of the photosensitive material on the side opposite to the emulsion layer and reenters the photographic emulsion layer. 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 surface of the support opposite to the photographic emulsion layer. Thus, the coloring layer is called an antihalation layer. In the case of a multilayer color light-sensitive material, an antihalation layer may be provided between the layers.

Decrease in image sharpness due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation)
The photographic emulsion layer is also colored to prevent the occurrence of the photographic emulsion.

These layers to be colored often consist of hydrophilic colloids, so that for their coloring a water-soluble dye is usually included in the layers. This dye must satisfy the following conditions.

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

(2) Photochemically inert. In other words, the performance of the silver halide photographic emulsion layer must not be adversely affected in a chemical sense, for example, a decrease in sensitivity or fogging.

(3) No harmful coloring is left on the processed photographic light-sensitive material by being decolorized or dissolved and removed in the photographic processing.

Examples of the infrared absorbing dye satisfying such conditions include a tricarbocyanine dye having at least three acid groups in a molecule described in JP-A-62-123454. It has been found that when applied to photographic light-sensitive materials, they are not always sufficiently stable in terms of storage stability with time, causing a reduction in sensitivity or deterioration of residual colors.

[Object of the invention]

Accordingly, a first object of the present invention is to provide a silver halide photographic material having high sensitivity to infrared light with little residual color after the phenomenon processing. A second object of the present invention is to provide a silver halide photographic light-sensitive material which forms a good image and has excellent stability over time.

[Means for solving the problem]

The object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the emulsion layer is at least one selected from the group consisting of cationic di- and tricarbocyanine dyes. At least two acid groups or at least one substituent having one or more formula —CH ₂ CH ₂ OR (where R is a hydrogen atom or an alkyl group) in the dye molecule. Achieved by a silver halide photographic material having a hydrophilic colloid layer containing at least one selected from the group consisting of hepta having two pyrropyridine rings, thienopyrrole rings and flopyrrole rings, and a nanomethine cyanine dye. Is done.

The dye compound of the present invention is represented by the following general formulas [Ia], [Ib] and [Ic].

General formula (Ia) General formula (Ib) General formula (Ic) 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 ₂ each represent a non-metal atom required to form a pyrrolopyridine, thienopyrrole, and floppyrrole ring. Represents a group.

Y ₁ and Y ₂ represents a non-metallic atomic group necessary for forming a pyrrolopyridine ring, and, in the Y ₁ ring Including a bond, within the ring of Y ₂ It shall include a bond.

R ₁ in the general formula _{(Ia), R 2, R 3, R} 4, R 5, R 6, Z 1, Z 2, R in the general formula [Ib] _{1, R 2, R 3,} R 4, R 5 , R ₆ , Y ₁ , Y ₂ and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , Y ₁ , Z ₂ in the general formula (Ic) each have a dye molecule of at least two acids. Represents a group capable of having a group or a group capable of having at least two substituents having one or more —CH ₂ CH ₂ OR groups. R represents a hydrogen atom or an alkyl group.

 L represents a methine group; Represents an anion. m is 4
Represents an integer of 1 to 5, and n represents an integer of 1 or 2. Dye
N is 1 when forming an intramolecular salt.

Examples of the acid group in the general formulas [Ia], [Ib] and [Ic] include a sulfonic acid group, a carboxylic acid group and a phosphonic acid group, and each of these acid groups includes a salt thereof.
Examples of the salt include alkali metal salts such as sodium and potassium, and organic ammonium salts such as ammonium, triethylamine and pyridine.

The alkyl group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is preferably a lower alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, i-propyl, butyl And the like, and may have a substituent other than the aforementioned acid substituent or —CH ₂ CH ₂ OR group.

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

As the substituent containing a -CH ₂ CH ₂ OR group, such as hydroxyethyl group, hydroxyethoxy ethyl group, methoxyethoxyethyl group, hydroxymethyl diethylcarbamoylmethyl group, hydroxyethoxy diethylcarbamoylmethyl group,
N, N-dihydroxyethylcarbamoylmethyl group, hydroxyethylsulfamoylethyl group, methoxyethoxyethoxycarbonylmethyl group and the like can be mentioned.

Z ₁ , Z ₂ , Y ₁ and Y ₂ may have. Examples of the other substituent include a sulfo group (including a salt), a carboxyl group (including a salt), a hydroxyl group, a cyano group, and a halogen atom (for example, a fluorine, chlorine, bromine atom, and the like).

The methine group represented by L may also have a substituent, and the substituent may be a substituted or unsubstituted lower alkyl group having 1 to 5 carbon atoms (eg, methyl, ethyl, 3-hydroxypropyl, 2-sulfoethyl Groups, etc.), halogen atoms (eg, fluorine, chlorine, bromine atoms, etc.), aryl groups (eg, phenyl groups), and alkoxy groups (eg, methoxy, ethoxy groups, etc.). Further, a 6-membered ring containing three methine groups (eg, 4,4
-Dimethylcyclohexene ring).

 X The anion represented by is not particularly limited,
Physically, a halogen ion, p-toluenesulfonic acid
ON, ethyl sulfate ion and the like.

Specific examples of the dyes represented by the general formulas [Ia], [Ib] and [Ic] (hereinafter, referred to as the dyes of the present invention) used in the present invention are shown below, but the present invention is not limited thereto. It is not something to be done.

Specific compounds The dyes of the present invention are available from Journal of the Chemical
The compound can be synthesized with reference to J. Chem. Soc., Page 189 (1933), U.S. Pat. No. 2,895,955, JP-A-62-123454, and the like.

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

Compound (A) can be synthesized by the method described in J. Chem. Soc., 3202 (1959) and the method described in British Patent 870,753.

Compound (B) can be synthesized by the method described in J. Chem. Soc., 584 (1961).

Compound (C) can be synthesized by the method described in British Patent No. 841,588.

Compound (D) Chemical Abstracts (CA) 62, 104
38c and CA 71 , 22045m.

Compound (E) can be synthesized by the method described in CA 71 , 22045m.

Compounds (F) and (G) can be synthesized in a similar manner.

Using these mother nuclei, quaternization, sulfonation, and the like can be performed as necessary. Or J. Chem. Soc., 3202 (19
N-alkyl-N-pyridylhydrazine is synthesized according to the synthesis method described in 59) and J. Chem. Soc., 584 (1961), a cyclization reaction is carried out via hydrazine, and if necessary, an acid treatment. 1-alkyl-substituted-3H-pyrrolopyridine derivatives are obtained, which can also be used as starting materials.

Synthesis of Compound (39) Compound (B) synthesized according to the above-mentioned literature was quaternized with propane sultone according to a conventional method.
After heating and dissolving 5 g in 40 ml of acetic acid, 1.0 g of glutaconaldehyde cyanyl hydrochloride, 9 ml of acetic anhydride and 13 ml of pyridine were added, and the mixture was heated and stirred at a bath temperature of 80 to 85 ° C. for 30 minutes. After cooling, isopropyl ether was added and the mixture was purified by decantation to obtain a compound (39).

Synthesis of Compound (40) Compound (A) synthesized according to the above-mentioned literature was quaternized with propane sultone according to a conventional method, reacted under the same reaction conditions as compound (39), and purified to obtain compound (40). ) Got.

Synthesis of Compound (41) 2,3,3-Trimethyl-5-chloro-1,4-diazaindene was synthesized according to the aforementioned literature. After quaternizing this compound with propane sultone according to a conventional method, 0.41 g of this quaternized product was dissolved in 3 ml of acetic acid, and 0.19 g of glutaconaldehyde dianyl hydrochloride, 0.7 ml of acetic anhydride, and 1 ml of pyridine were added. The mixture was heated and stirred at 90 to 105 ° C for 1 hour.

After cooling, 40 ml of ethyl acetate was added to the reaction solution, and the mixture was stirred and filtered to obtain 0.36 g of compound (41) as a yellow-green solid.

Synthesis of Compound (42) 2,3,3-Trimethyl-5-methoxy-1,4-diazaindene was synthesized according to the aforementioned literature. This compound was quaternized in the same manner as in the synthesis of the compound (41), and then condensed to obtain a compound (42).

Synthesis of Compound (44) In the synthesis of Compound (39) described above, after purification by decantation, this was further stirred with 100 ml of saturated saline for 2 hours, and then filtered to obtain a yellow-green solid.

Synthesis of Compound (49) After purification by decantation in the synthesis of Compound (42) described above, Compound (49) was obtained by treating with saturated saline in the same manner as Compound (44).

Synthesis of Compound (20) Compound (A) was quaternized with propane sultone, and then sulfonated with concentrated sulfuric acid and fuming sulfuric acid.

Dissolved in 2.6 ml of N, N- ヂ methylsulfamide 10 ml, and added 1.0 g of glutaconaldehyde dianyl hydrochloride,
2 ml of pyridine and 2 ml of acetic anhydride were added, and the mixture was heated and stirred at a bath temperature of 100 ° C. for 20 minutes.

Isopropyl ether was added to the reaction mixture, followed by decantation and purification to obtain a compound (20).

The dyes represented by the general formulas (Ia), (Ib) and (Ic) of the present invention can be contained in a silver halide emulsion and used as an anti-irradiation dye. In a hydrophilic colloid layer, and used as a filter dye or an antihalation dye. Further, two or more dyes may be used in combination depending on the purpose of use, or may be used in combination with another dye. The dye of the present invention can be easily contained in a silver halide emulsion layer or another hydrophilic colloid layer by an ordinary method. In general, a dye or an organic / inorganic alkali salt of a dye is dissolved in water to form an aqueous solution of a dye having an appropriate concentration, which is then added to a coating solution, and coating is performed by a known method so that the photosensitive material contains the dye. Can be. As the content of these dyes,
Depends on the intended use, but generally the area on the photographic material
It is used by applying so as to be 1 to 800 mg per 1 m ² .

Next, as the cationic di- or tricarbocyanine infrared sensitizing dye used in the present invention, compounds represented by the following general formulas [II-a] and [II-b] are preferable.

General formula [II-a] General formula [II-b] In the formula, Y ₁₁ , Y ₁₂ , Y ₂₁ and Y ₂₂ each represent a non-metallic atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring, for example, a benzothiazole ring, a naphthothiazole ring,
Benzoselenazole ring, naphthoselenazole ring, benzoxazole ring, naphthoxazole ring, quinoline ring,
3,3-dialkylindolenin sensation, benzimidazole nucleus, pyridine ring and the like can be mentioned.

These heterocycles are a lower alkyl group, an alkoxy group,
It may be substituted with a hydroxyl group, an aryl group, an alkoxycarbonyl group, or a halogen atom.

R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

R ₁₃ , R ₁₄ , R ₁₅ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group,
Phenyl group, benzyl group, Represents Here, W ₁ and W ₂ each represent a substituted or unsubstituted alkyl group (having 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms in the alkyl portion) and an aryl group, and W ₁ and W ₂ are linked to each other. To form a 5- or 6-membered nitrogen-containing heterocycle.

R ₁₃ and R ₁₅ and R ₂₃ and R ₂₅ can be linked to each other to form a 5- or 6-membered ring. X ₁₁ and X ₂₁
Represents an anion. n ₁₁ , n ₁₂ , n ₂₁ and n ₂₂ are 0 or 1
Represents

Next, specific examples of the sensitizing dye used in the present invention (hereinafter, referred to as the sensitizing dye of the present invention) are shown, but the present invention is not limited thereto. In addition, II-1 to 13 are compounds represented by the general formula [II-b], and II-14 to 21 are compounds represented by the general formula [II-a].

The sensitizing dye of the present invention is contained in a silver halide photographic emulsion in an amount of preferably from 1 mg to 2 g, more preferably from 5 mg to 1 g, per mol of silver halide.

The sensitizing dye of the present invention can be directly dispersed in an emulsion. These can be first dissolved in a suitable solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and 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. Further, sensitizing dyes other than the present invention can be used in combination. When a sensitizing dye is used in combination, it is preferable that the total content is the above content.

The sensitizing dyes of the present invention are described in U.S. Patent No. 2503776, British Patent No. 742112, French Patent No. 2065662, Japanese Patent Publication No. 40-2346.
Can be easily synthesized with reference to the reference numbers.

In the silver halide emulsion of the present invention, silver halides used in common silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride are used. Any of the above can be used.

The silver halide grains used in the silver halide emulsion are:
Any of the acidic method, neutral method and ammonia method may be used. The particles may be grown at a time, or may be grown after the seed particles have been made. The method of producing the seed particles and the method of growing may be the same or different.

In the silver halide emulsion, a halide ion and a silver ion may be mixed at the same time, or one of them may be mixed in a liquid in which one is present. Alternatively, it may be formed by sequentially and simultaneously adding halide ions and silver ions while controlling the pH and / or pAg in the mixing vessel, while taking into account the critical growth rate of silver halide crystals. According to this method, silver halide grains having a regular crystal form and a nearly uniform grain size can be obtained. After the growth, the halogen composition of the grains may be changed using a conversion method.

In the production of the silver halide emulsion, a silver halide solvent can be used, if necessary, to control the grain size, grain shape, grain size distribution, and grain growth rate of the silver halide grains.

In the course of forming and / or growing the silver halide grains, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt) and iron salt ( Metal ions by using at least one member selected from the group consisting of a complex salt and a metal ion, and these metal elements can be contained inside the particles and / or on the surface of the particles. A reduction sensitization nucleus can be provided inside the grains and / or on the grain surface.

In the silver halide emulsion, unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or may be kept contained. When removing the salts, use Research Disclosure (hereinafter referred to as R).
(Abbreviated as D) 17643 No. II.

The silver halide grains may have a uniform silver halide composition distribution within the grains, or may be core / shell grains having different silver halide compositions between the inside of the grains and the surface layer.

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

The silver halide grains may have a regular crystal form such as cubic, octahedral, or tetradecahedral, or may have an irregular crystal form such as spherical or plate-like. In these particles, any ratio between {100} plane and {111} plane can be used. Further, those having a composite form of these crystal forms may be used, and particles of various crystal forms may be mixed.

The average grain size of the silver halide grains (the 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.

The silver halide emulsion having any grain size distribution may be used. Emulsions having a wide grain size distribution (referred to as polydisperse emulsions) may be used, and emulsions having a narrow grain size distribution (referred to as monodisperse emulsions). When the value is divided by the average grain size, it means that the value is 0.20 or less, where the grain size is the diameter in the case of spherical silver halide, and the projected image in the case of grains other than spherical. The diameter when converted to a circular image of the same area is shown.) Or a mixture of several types. Further, a polydisperse emulsion and a monodisperse emulsion may be used in combination.

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

Various additives can be used in the light-sensitive material of the present invention depending on the purpose.

These additives are described in detail in RD17643 (December 1978
) And No. 18716 (November 1979), and the relevant locations are summarized in the table below.

The exposure and development conditions of the light-sensitive material of the present invention are not particularly limited, and for example, reference can be made to the description on pages 28 to 30 of RD17643.

A photographic emulsion layer of a light-sensitive material using a silver halide emulsion and other hydrophilic colloids may contain a water-insoluble or sparingly soluble synthetic polymer dispersion (latex) for the purpose of improving dimensional stability and the like. .

As the support of the photosensitive material of the present invention, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, for example, a polyester film such as polyethylene terephthalate, a polyamide film, a polypropylene film, a polycarbonate film, A polystyrene film or the like is used depending on the purpose of use.

In the photographic paper support of the present invention, various inorganic white pigments, inorganic color pigments, dispersants, fluorescent whitening agents, antistatic agents,
Antioxidants, stabilizers and the like can be added. Also,
The surface of the support is subjected to a surface activation treatment such as a corona discharge treatment or a flame treatment, and an undercoat layer can be provided as necessary.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

Example 1 (Preparation of coating solution for emulsion layer) Solution A 980 ml of water 2.0 g of sodium chloride gelatin 20 g 0.10% aqueous solution of potassium hexachloroiridate 2.8 ml 2.5 ml of 0.001% aqueous solution of potassium hexabromorhodate acid Solution B water 380 ml 38 g of sodium chloride, 42 g of potassium bromide, solution C, 380 ml of water, 170 g of silver nitrate, 170 g of silver nitrate. After further stirring for 5 minutes, the pH was adjusted to 5.6 with an aqueous sodium carbonate solution, and through ordinary desalting and washing steps, 500 ml of water and 30 g of gelatin were added.
Disperse for a minute. This gives 35 mol% of silver bromide, silver chloride
Cubic particles having 65 mol% and an average particle size of 0.27 μm are obtained.

10 ml of a 1% aqueous solution of citric acid and 10 ml of an aqueous solution of 5% sodium chloride were added to the emulsion, which was adjusted to pH 5.5 and pAg7. 10 ml of an aqueous solution of 0.1% sodium thiosulfate and 7 ml of an aqueous solution of 0.2% chloroauric acid were added. In addition, aged at 57 ° C for maximum sensitivity.

The emulsions were divided, and 50 ml of a 0.1% methanol solution of each of the present and comparative infrared sensitizing dyes shown in Table 4 per mol of silver halide was added thereto, and 1-phenyl-5 was used as an antifoggant. -Of mercaptotetrazole
25 ml of a 0.5% solution, 4-hydroxy-6 as a stabilizer
180 ml of a 1% solution of methyl 1,3,3a, 7-tetrazaindene,
Then, ripening was stopped by adding 300 ml of a 10% aqueous solution of gelatin. 15 ml of a 10% aqueous solution of sodium tri-i-propylnaphthalenesulfonate as a coating aid, 50 ml of a 4% aqueous solution of a styrene-maleic acid copolymer as a thickener, and a polymer latex of butyl acrylate. 30g, 20% aqueous solution of hydroquinone as a stabilizer 20m
l, 20 ml of a 10% aqueous solution of potassium bromide was added and stirred. As a hardening agent, a reaction product of tetrakis (vinylsulfonylmethyl) methane and taurine potassium salt of 1: 0.25 mol was added in an amount of 50 mg per 1 g of gelatin. The emulsified dispersion shown was added so that the amount of the fluorescent whitening agent became 15 mg / m ² , 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) The dye shown in Table 4 was added to an aqueous solution of 40 g of gelatin in an amount of 2 g.
00 mg / m ^2, and the emulsified dispersion shown in Table 1 was further added so that the amount of the fluorescent whitening agent became 15 mg / m ^2, and a styrene-maleic anhydride copolymer was used as a thickener. Of a 4% aqueous solution was added to prepare a coating solution for an antihalation layer.

(Preparation of Coating Solution for Protective Layer) In a gelatin aqueous solution, 2-sulfosuccinic acid bis (2-ethylhexyl) ester sodium salt was 30 mg / m ² as a coating aid, and polymethyl methacrylate having an average particle size of 4 μm as a matting agent. , 40 mg / m ² , 30 mg / m ² of the following compound (S) as a fluorine-containing surfactant, and 10 mg of formalin as a hardening agent per 1 g of gelatin to prepare a coating solution for a protective layer.

Fluorine-containing surfactant (S) (Preparation and Evaluation of Sample) The coating solution for the antihalation layer, the coating solution for the emulsion layer, and the coating solution for the protective layer thus prepared were prepared by using a titanium dioxide having a hydrophilic colloid backing layer and an undercoat layer. 15
Three layers were simultaneously coated on a 110 μm thick polyethylene coated paper containing wt%. The coated silver amount of the obtained sample was 1.4 g /
m ² , gelatin coating amount is 1.4 g / m ^{2 for} the antihalation layer,
The emulsion layer was 1.4 g / m ² and the protective layer was 0.9 g / m ² .

The obtained sample is divided into two, and one half remains as it is.
The other half is placed in a polyethylene bag and then wrapped in a paper bag to check the stability over time.
Was heated for 72 hours.

Same-day and aged samples are xenon flashed through optical wedge and Kodak Wratten filter No.88A
After the flash exposure of 10 ⁵ seconds, cherry automatic processor GR-14 as an automatic developing machine (manufactured by Konica Co., Ltd.),
A developing treatment was performed using a developing solution and a fixing solution prescribed in Tables 2 and 3 as the developing solution, and the evaluation was made. Unexposed samples were similarly treated for residual color evaluation. Processing conditions were: development at 38 ° C for 20 seconds, fixing at 38 ° C for 20 seconds, and water washing at room temperature.
The drying temperature was about 40 ° C. for 20 seconds.

Table 4 shows the obtained results. The sensitivity is 1.0
Is the reciprocal of the amount of exposure required to give

For the sample processed without exposure, the residual color was visually evaluated and evaluated on a scale of 1 to 5. "5" was colorless.
“1” indicated a strong blue-colored residual color. The residual color below “3” is a level that does not endure general use.

As is clear from the results in Table 4, the samples belonging to the present invention
It can be seen that Nos. 1, 2, 3, 4, 5, 6, and 7 have good sensitivity and residual color and have little deterioration in performance over time.

Example 2 60 g of gelatin was dissolved in water, and 2.0 g of each of the dyes shown in Table 5 was added thereto. Further, 40 ml of a 1% aqueous solution of 1-decyl-2- (3-isopentyl) succinate-2-sulfonate sodium salt as a spreading agent and 45 ml of a 4% aqueous solution of glyoxal as a hardening agent were added to make a total amount of 1.
This gelatin-containing aqueous solution was coated on a polyethylene terephthalate film support so that the gelatin coverage was 3.2 g / m ² . On the other hand, a silver chlorobromide (62 mol% of silver chloride, 38 mol% of silver bromide, average grain size of 0.26 μm, cubic grains) emulsion was obtained in the same manner as in Example 1. This emulsion was subjected to gold sensitization and sulfur sensitization, followed by 4-hydroxy-sensitization per mole of silver halide.
6-methyl-1,3,3a, 7-tetrazaindene was added to 1.5 g of phenyl-5-mercaptotetrazole in an amount of 0.2 g, and the mixture was divided. A 0.1% methanol solution of an infrared sensitizing dye shown in Table 5 was halogenated. 50 ml per mole of silver halide, 50 ml of a 10% methanol solution of hydroquinone as an antifoggant, 19 ml of a 20% aqueous saponin solution as a spreading agent, 50 ml of a 4% aqueous solution of a styrene-maleic acid copolymer as a thickener, acrylic 30 g of a polymer latex of ethyl acid is added, and 20 ml of 1% aqueous solution of 1-hydroxy-3,5-dichlorotriazine sodium salt and 10% of 4% formalin aqueous solution are used as hardeners.
Then, the mixture was added to the above-mentioned film, stirred, and coated on the surface of the film opposite to the surface coated with gelatin. An aqueous solution containing gelatin and 1-decyl-2- (3-isopentyl) succinate-2-sulfonic acid sodium salt was further applied thereon as a protective layer.

The film thus produced was processed in the same manner as in Example 1 to evaluate photographic characteristics. However, the evaluation of the stability over time was performed by the following method. In other words, half of the half
After humidity control at 23 ° C and 48% relative humidity, polyvinyl acetate (thickness 100
μm) and sealed with a moisture-proof material laminated at 55 ° C
Heat treatment was performed for 72 hours in a thermostat at a relative humidity of 50%. The results are shown in Table 5. However, the photographic sensitivity of Sample 1 was the same as in Example 1.
Is shown as a relative sensitivity when the value is set to 100.

As shown in Table 5, it is understood that the sample of the present invention had good sensitivity and residual color, and showed little deterioration of performance with time.

Example 3 In the same manner as in Example 2 except that silver iodobromide (2 mol% of silver iodide, 98% of silver bromide, average grain size of 0.9 μm, cubic grains) was used instead of silver chlorobromide. A sample was prepared and evaluated. As a result, a sample having good sensitivity and residual color and excellent in aging was obtained.

[Effects of the Invention] As described in detail in the above examples, according to the present invention, an infrared-sensitized silver halide photographic light-sensitive material having high sensitivity, little residual color, and extremely little deterioration in performance during the storage period Could be provided.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-55544 (JP, A) JP-A-62-123454 (JP, A) JP-A-60-80841 (JP, A) JP-A-1- 280750 (JP, A) JP-A-1-303433 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein said emulsion layer is formed by at least one selected from the group consisting of cationic di- and tricarbocyanine dyes. At least two substituents which are spectrally sensitized and have at least two acid groups or one or more formula -CH ₂ CH ₂ OR (where R is a hydrogen atom or an alkyl group) in the dye molecule. Having a hydrophilic colloid layer containing at least one selected from the group consisting of a hepta having a pyrrolopyridine ring, a thienopyrrole ring and a flopyrrole ring as a nucleus and a nanomethine cyanine dye material.