JPH023037A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To lessen the residual color of the title material after development processing, and to improve the sensitivity of the sensitive material against an infra-red ray by spectrally sensitizing an emulsion layer contd. in the sensitive material with a pigment selected from the group comprising cationic di- and tri-carbocyanine pigments, and by providing a hydrophilic colloid layer contg. a specified dye on the sensitive material. CONSTITUTION:The emulsion layer is spectrally sensitized with at least one of the pigments selected from the group comprising the cationic di- and tri- carbocyanine pigments and the hydrophilic colloid layer contg. at least one of the compds. shown by formula I as the dye, is provided on the sensitive material. In formula I, Q is a group capable of forming a carbon ring or a heterocyclic ring, L is methine group, R is aryl group, (l) is an integer of 1 or 2. Thus, the high sensitivity and the less residual color of the sensitive material are obtd., and the sensitive material which has very less deterioration of the performance of the sensitive material during preservation and is capable of sensitizing with the infra-red ray, is obtd.

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 materials is scanning the original image.

A so-called scanner-based image forming method is known in which a silver halide photographic light-sensitive material is exposed to light based on the image signal to form a negative image or a positive image corresponding to the image of 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 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, the photographic emulsion layer or one other layer is often colored for the purpose of absorbing light in a specific wavelength region.

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.

When these layers to be colored are composed of hydrophilic colloids,
Therefore, for coloring, a water-soluble dye is usually included in the layer. This dye must satisfy the following conditions.

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

(2) It must be photochemically inert. In other words, it has an adverse effect on the performance of the silver halide photographic emulsion layer in a chemical sense.
For example, it should not reduce sensitivity or cause 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 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. This is achieved by a photosensitive material characterized by having a hydrophilic colloid layer which is spectrally sensitized by one of the following compounds and which contains at least one compound represented by the following general formula (I) as a dye.

General Formula (I) In the formula, Q represents a carbocyclic or heterocyclic ring forming group, L represents a methine group, and R represents an aryl group. a represents an integer of 1 or 2.

The dye represented by general formula (I) used in the present invention will be described.

Q is a carbocyclic ring such as 1.3=cyclopentanedione, l,3-indanedione, and pyrazolone, isoxacilone, barbylic acid, thiobarbylic acid, 3-oxydithionaphthene, rhodanine, 2-thiohydantoin, 2
-Represents the atomic group necessary to form a heterocycle such as thioxazolidinedione, pyrazolopyridine, or quinolone.

L represents a methine group, an alkyl group having 1 to 3 carbon atoms (for example, methyl, ethyl, etc.), a phenyl group, a benzyl group,
It may be substituted with a phenethyl group, a hydroxyl group, an acyloxy group, a halogen atom, or the like. Further, the substituents of the methine group may form a ring (for example, 5°5-dimethyl-1-cyclohexen-1-yl-3-ylidene, etc.).

The dye represented by general formula (I) preferably has an acid group (sulfo group, carboxyl group, phosphonic acid group, phosphinic acid group, phosphoric ester group, phosphoric acid amide group, etc.) in the molecule.

Each of these acid groups includes its salts. As salt,
Examples include alkali metal salts such as sodium and potassium salts, and organic ammonium salts such as ammonium, triethylamine, and pyridine.

Examples of the dye represented by the general formula (I) include dye compounds represented by the following general formula (I)-1.

General formula (I)-1 L and Q are as described above, but Q is preferably 2, which gives particularly good results in the present invention.

R1 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group.

Examples of the alkyl group represented by R include methyl, 1
Examples include straight chain, branched, and cyclic groups such as thyl, propyl, isopropyl, butyl, and nclohekynyl; examples of aralkyl groups include benzyl and 7-enethyl; examples of aryl groups include phenyl and naphthyl; Examples of the heterocyclic group include benzothiazolyl, pyridyl, pyrimidyl, and sulfolanyl, but alkyl groups, aralkyl groups, and aryl groups are preferable.

The alkyl group, aralkyl group, aryl group, and heterocyclic group represented by R8 can have various substituents, such as sulfo, carboxy group, hydroquine, /ano, halogen (e.g., fluorine, chlorine, etc.), Alkyl (e.g. methyl, isopropyl, trifluoromethyl, t-butyl, ethoxycarbonylmethyl, sulfomethyl, etc.), amino (e.g. amino, dimethylamino, sulfoethylamino, piperidino, morpholino, etc.), alcoquine (e.g.
(e.g. methoxy, ethquin, sulfopropoxy),
Sulfonyl (e.g. methanesulfonyl, ethanesulfonyl, etc.), sulfamoyl (e.g. sulfamoyl,
dimethylsulfamoyl, etc.), acylamino (e.g. acetamide, benzamide, sulfobenzamide, etc.), carbamoyl (e.g. carbamoyl, phenylcarbamoyl, sulfophenylcarbamoyl, etc.), sulfonamide (e.g. methanesulfonamide, benzenesulfonamide, etc.), alkoxycarbonyl (e.g. ethoxycarbonyl, hydroxyethoxycarbonyl,
Examples include groups such as pendyloxycarbonyl, aryloxycarbonyl (eg, phenoxycarbonyl, nitrophenoxycarbonyl, etc.), and the like.

The aralkyl group and aryl group represented by R3 preferably have at least one acid group, more preferably at least one sulfo group, on their aromatic nucleus.

In the formula, R2 is an alkyl group, an aryl group, an aralkyl group,
Heterocyclic group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, ureido group, thioureido group, r//ruamino group, acyl group, imido group, cyano group 1. Represents a hydroquine group, an alkoxy group, and an amino group.

an alkyl group, an alkoxycarbonyl group represented by R2,
Specific examples of the aryloxycarbonyl group, carbamoyl group, acylamino group, alkoxy group, and ami7 group are the specific examples of the substituents introduced into the alkyl group, aralkyl group, aryl group, and heterocyclic group represented by R3 mentioned above. The same thing can be mentioned. Furthermore, the aryl group represented by R3 includes, for example, phenyl, sulfopropoxyphenyl, cyanophenyl, carboxyphenyl, nitrophenyl,
Examples of aralkyl groups such as sulfophenyl include benzyl, 7enethyl, and sulfobenzyl; examples of heterocyclic groups include furyl and thienyl; examples of ureido groups include methylureido and phenylureido; and examples of thiourido groups include, for example. Examples of the imide group include succinimide and 7-talimide, and examples of the acyl group include acetyl and pivalyl.

The group represented by R2 is preferably an alkyl group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, a ureido group, an acylamino group, an acyl group, an imide group, a cyano group, a hydroxyl group, an alkoxy group, or an amino group, but further Preferred are an alkyl group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, a cyano group, an alkoxy group, and an amino group.

2! / R1 represents -02, group or -N group, where \ Z.

Zl, Z2 and Z each represent a hydrogen atom or an alkyl group, and Z and Z may be the same or different, or may be bonded to each other to form a ring.

2. 2. ．． 2. Examples of the alkyl group represented by include methyl, ethyl, butyl, hydroxyalkyl (e.g. hydroxyethyl), alkoxyalkyl (e.g.
β-dihydroxyethyl, etc.), carboxyalkyl (e.g., β-carboxyethyl, etc.), alkoxycarbonylalkyl (e.g., β-ethoxycarbonylethyl, etc.), cyanoalkyl (e.g., β-cyanoethyl, etc.), sulfoalkyl (e.g., β-cyanoethyl, etc.), -sulfoethyl, γsulfopropyl, etc.).

Z2 and Z may be bonded to each other to form a 5- to 6-membered ring, and specific examples include morpholino, piperidino, and pyrrolidino groups.

z / R1 is preferably a -N group.

＼ 2゜R1 represents a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a sulfo group, or a carboxyl group. Examples of the alkyl group include methyl and ethyl, and examples of the halogen atom include chlorine. Examples of the alkoxy group include methoxy and ethoxy. Furthermore, R1 and R4 may form a methylenedioxy ring. m represents an integer of 1 to 4.

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 not limited to these.

SO, Na 5O,Na to 5o3 CH.

)υ3NM SO, Na SQ,)[ C,H.

(CH*)2sO3Na (CHJzSOJ (C11□), So, K CH, C) 1.50. Na Next, a method for synthesizing the compound of the present invention will be described.

- The compound of the present invention can be obtained by reacting 1 mol of an aldehyde compound with 1 mol of an acidic core compound such as pyrazolone in the shell.

Regarding these condensation reactions, please refer to JP-A-51-362.
No. 3, No. 51-10927, No. 48-68623,
The synthesis method described in Japanese Patent Publication No. 5,649,953, etc. can be referred to.

To synthesize the dye of the present invention containing a cyclic group such as a cyclohexene ring in the methine chain, for example, for compound (I1), first, an acidic core and isophorone are reacted to synthesize a cyclohexenylidene substituted core. do.

Compound (I1) can be obtained by reacting this with p-dimethylaminobenzaldehyde in the presence of a base according to a conventional method.

The aldehyde compound used in the present invention (C
he+s, Ber,) Volume 91, pages 850-61 (I9
58) and Journal of Organic Chemistry (J, Org, Chem,) Volume 40 (Issue I5)
, pp. 2243-2245 (I975).

It can be synthesized by the method described in . Other compounds can be synthesized in a similar manner.

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 an organic or inorganic alkali salt of the dye can be dissolved in water to form an aqueous dye solution of an appropriate concentration, and the solution can be 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 per meter of area on the photographic material:
It is applied and used in an amount of 1 to 800 m9 per coat.

Next, as the cationic di- or tricarbocyanine infrared sensitizing dye used in the present invention, compounds represented by the following general formulas [1] and (II-b) are preferred.

General formula (na) Iz General formula (II-b) In the formula, Y , , Y , Y , and Y22
each represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, such as a benzothiazole ring,
Examples include a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, a benzoxazole ring, a naphthoxazole ring, a quinoline ring, a 3,3-dialkylindolenine ring, a benzimidazole nucleus, and a hyridine ring.

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

RIl+ RI! + RII and R1! each represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

R131R141R16+ Rz++ R24+ Rx
i and Rza are each a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a phenyl group, a benzyl group, C, H.

C, Hs 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.

Further, R13 and R16, R2, and R2% can be linked to each other to form a 5-membered ring or a 6-membered ring. X
, and X! 1 represents an anion. nll+ nl! +
n21 and n represent 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 to 13 are the above-mentioned general formula [■-b], and ■-14 to 21 are C, H.

c, o, Ie Tsukuda・ \5-/ 1θ I-7 ■ Ie Number 0 too C@H.

QO4e I[-9 C,)I.

C,H.

Ie C2) 1゜tHs n-11 ■-12 l-13 CH2Cl, OH ■-20 CHyoC)1. OH tHs CHiCH*OH l-14 Ie C2H@Ie f-16 Js Ie t-17 C,H,Ie The sensitizing dye of the present invention is preferably lg to 2g per mole of silver halide, more preferably is contained in the silver halide photographic emulsion in the range of 5+mg-1g.

The sensitizing dyes of the present invention can be directly dispersed into emulsions. They can also be first dissolved in a suitable solvent, such as evaporative 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. It is also possible to use a combination of sensitizing dyes other than those of the present invention. 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.

The silver halide emulsion of the present invention can use any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver chloroiodobromide, and silver chloride. .

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. Alternatively, it may be generated by sequentially and simultaneously adding halide ions and silver ions while controlling the pH and/or l)Ag in the mixing pot, taking into consideration the critical growth rate of silver halide crystals. . 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.

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 (I00) plane to the +1111 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). 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 (I97
(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, 28 of R017643,
You can refer to the description on pages 30 to 30.

A dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer may be contained in the photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using a silver halide emulsion for the purpose of improving dimensional stability. can.

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.

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
980 Sodium Chloride
2.0g gelatin
20g 0.1% aqueous solution of potassium hexachloroiridate salt 2.8+Q 0.001% aqueous solution of potassium hexabromorodate salt 2.5 a
Solution B water
380mff sodium chloride
38g potassium bromide 4
2g solution solution
380mff silver nitrate
Add 170g of the above solution B to the above solution kept at 40°C while keeping the pAg at 3.pAg at 7.7.
and Solution C were added simultaneously functionally over a period of 80 minutes, stirring was continued for an additional 5 minutes, and then the pH was adjusted with an aqueous sodium carbonate solution.
After adjusting to 5.6 and going through normal desalination and water washing process,
Add 0mff of water and 30g of gelatin and boil at 50℃ for 3 minutes.
Disperse for 0 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 μm are obtained.

1% citric acid aqueous solution 1Q + sQ, sodium chloride 5
% aqueous solution was added to IO+ff, pH 5.5, pAg7
10 mg of a 0.1% sodium thiosulfate aqueous solution and 7 mQ of a 0.2% chloroauric acid aqueous solution were added to the prepared emulsion.
and ripened at 57°C to achieve maximum sensitivity.

The above emulsion was divided, and 50 ml of 0.1% methanol solutions of infrared sensitizing dyes of the present invention 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-titrazaindene 180 mff1. Then, 300 ml of an lθ% aqueous solution of gelatin was added to stop the ripening.

As a coating aid, add 15ml of 10% aqueous solution of sodium salt of streamy propylnaphthalene sulfonate to these.
．． 4% of styrene-maleic acid copolymer as thickener
The aqueous solution was 59n12. Add 30g of butyl acrylate polymer latex as a stabilizer, add 20+sQ of a 20% aqueous solution of hydroquinone, and 20II (2) of a 10% aqueous solution of potassium bromide, stir, and add tetrakis(vinylsulfonylmethyl)methane and potassium taurine as a hardening agent. 50 mg of the 25 mole reaction product per Ig of gelatin was added, the emulsified dispersion shown in Table 1 was added to give an optical brightener loading of 15 n+g/s+, and the pF+ was added with citric acid. -5 and -6 to prepare a coating solution for emulsion layer.

(Preparation of coating solution for antihalation layer) 40 g of gelatin
The amount of the dye listed in Table 4 added to the aqueous solution was 200 mg/
Furthermore, the emulsified dispersion shown in Table 1 was added at a concentration of 15 g/m2 as a fluorescent brightener, and styrene-maleic anhydride copolymer was added as a thickener. A coating solution for an antihalation layer was prepared by adding 15+sff of a 4% aqueous solution.

(Preparation of coating solution for protective layer) In an aqueous gelatin solution, 30a+g/a'' of 2-sulfosuccinic acid bis(2-ethylhexyl) ester sodium salt was added as a coating aid, and polymethyl methacrylate with an average particle size of 4μ was added as a matting agent. 40IIg/II+2, 30mg/of the following compound (S) as a fluorine-containing surfactant
112, formalin as a hardening agent per 1 g of gelatin
0 mg was added to prepare a protective layer coating solution.

Fluorine-containing surfactant (S) CHzCOOCl(*(CFz)sH NaOIS C1(COOCHt(CFz)aH (sample preparation and evaluation) Antihalation layer coating liquid, emulsion layer coating liquid 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 110 μm thick polyethylene coated paper containing vt%. The coated silver amount of the obtained sample was 1.
4g/s+", gelatin coating amount is 1.4g/m" for antihalation layer, 1.4g/haze 2 for emulsion layer, 0 for protective layer.
．． 9g/fi".

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 exposed to a 10-' second flash of xenon through an optical wedge and a Kodak Wratten filter No. 88A, using a Sakura Automatic Processor GR-14 (manufactured by Konica Corporation) as an automatic processor and a developer. Development processing was carried out using the developer and fixer prescribed in Tables 2 and 3, and evaluation was made. Also,
For evaluation of residual color, unexposed samples were also processed in the same manner. The processing conditions are: development at 38°C for 20 seconds, and fixing at approximately 38°C.
020 seconds, washing with water at room temperature for 20 seconds, drying temperature about 40°C
Met.

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.

For samples processed without exposure, residual color was visually evaluated and evaluated on a five-point scale, with "5" being colorless and "l" being colorless.
showed a strong blue residual color. Residual color below “3” is
-It is at a level that cannot be used inside the shell.

As is clear from the results in Table 4, samples No. 1.2.3.4.5.6 and 7 belonging to the present invention have good sensitivity and residual color, and have little deterioration in performance over time. I understand.

Table 1 Preparation of oil-soluble optical brightener emulsion dispersion Table 2 developer prescription Comparative infrared sensitizing dye (CTo)tsOs.

comparison dye C,H.

Table 3 Fixer Prescription 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. Furthermore, as a spreading agent, l-
Decyl-2-(3-isopentyl)zak/nate-2-
40 mQ of a 1% aqueous solution of sulfonic acid sodium salt and 45 mQ of a 4% aqueous solution of glyoxal as a hardening agent were added to make the total amount IQ. 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 (5 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.
, 7tetrazaindene was divided by adding 0.29 of 1.591-phenyl-5-mercaptotetrazole, and a 0.1% methanol solution of the infrared sensitizing dye shown in Table 5 was added to 50a+Q per mole of silver halide. In addition, a 10% methanol solution of hydroquinone was added to 50++Q as an antifoggant.
9mQ of 20% saponin aqueous solution as a spreading agent.

A 4% aqueous solution of styrene-maleic acid copolymer 50111I2 was added as a thickening agent, 30 g of a polymer latex of ethyl acrylate was added, and a 1% aqueous solution of 1 hydroxy-3,5-dichlorotriazine sodium salt 20+ was added as a hardening agent. *(2 and 4% formalin aqueous solution 10a+12 were added, stirred, and coated on the opposite side of the film from the gelatin-coated side. Furthermore, gelatin and 1-decyl-2-(3 -inpentyl) succinate-2-sulfonic acid sodium salt was applied.

The thus produced film was subjected to the same geography as in Example 1 to evaluate its photographic properties. 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 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, it can be seen that the samples of the present invention have good sensitivity and residual color, and little deterioration in performance over time.

Example 3 In Example 2, silver iodobromide (silver iodide 2
A sample was prepared and evaluated in the same manner as in Example 2 with silver bromide (98 mol%, silver bromide 98 mol%, average particle size 0.9 μm, 1 cubic crystal grain) and evaluated. As a result, the sensitivity and residual color were similarly good, and the aging properties were excellent. I got something.

〔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 is selected from the group consisting of cationic di- and tricarbocyanine dyes. 1. A silver halide photographic material comprising a hydrophilic colloid layer spectrally sensitized by at least one dye and containing at least one dye represented by the following general formula (I). General Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, Q represents a carbocyclic or heterocyclic ring-forming group, L represents a methine group, and R represents an aryl group. l is 1 or 2
represents an integer. ]