JPS5977435A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material high in sensitivity, prevented from fog, and improved in fluctuation of sensitivity due to temp. change at the time of exposure, by incorporating a specified asymmetric cyanine dye as a sensitizing dye as a red sensitive emulsion layer. CONSTITUTION:A red sensitive emulsion layer contains as a red sensitive sensitizing a dye represented by the shown formula in which A<1>, B<1>, C<1>, D<1>, A<2>, B<2>, C<2>, and D<2> are each H, lower alkyl, lower alkoxy, aryl, COOH, halogen, NO2, OH, CN, NH2, SO2NH2, CONH2, acyl, heterocyclic, or the like, and A<1> and B<1>, B<1> and C<1>, C<1> and D<1>, A<2> and B<2>, B<2> and C<2>, and C<2> and D<2> each may link together to form a ring; Y<1> is O, S, or Se; Y<2> is O, S, Se, or N-R<3>, and R<3> is alkyl or aryl; Z is an atomic group needed to form a 5- - 7-membered ring together with -N-C=C-; R<1> is H, halogen, lower alkyl, heterocyclic, or the like; R<2> is alkyl; X<-> is an anion; and (m) is 0 or 1. As a result, a superior image free from fog is obtained with high sensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material sensitized with a novel sensitizing dye and having improved photographic properties.

It is generally known that when a sensitizing dye is added to a photosensitive silver halide emulsion, the sensitive wavelength range of the silver halide emulsion is expanded and the emulsion is optically sensitized.

A large number of compounds have been known as optical sensitizing dyes used for such purposes, such as those described in "The Theory of the Photographic Process" 4th edition (1977) , Macmillan Publishing,
Cyanine dyes, merocyanine dyes, xanthine dyes, etc. described on pages 194 to 234 are poorly known.

These sensitizing dyes must normally be added to the silver halide emulsion.

(1) The spectral sensitization range due to dye sensitization is appropriate.

(2) The sensitization efficiency is good and sufficiently high sensitivity can be obtained.

(3) There is no adverse interaction with other types of additives, such as stabilizers, antifoggants, coating aids, color formers, etc.

(4) Variation in sensitivity due to temperature changes during II forward light is small.

(5) No fogging should occur.

The above thermal conditions have an important meaning especially in the preparation of red-sensitive silver halide emulsions for silver halide color photographic light-sensitive materials.

That is, as sensitizing dyes conventionally used in red-sensitive silver halide emulsions, for example, rhodacyanine dyes and pentamethine dyes are known, but these dyes do not necessarily have sufficient sensitizing efficiency and cannot achieve the desired sensitivity. Not only is it not possible to obtain Km, but when used in combination with other types of additives, the Km degree may decrease during storage of the photosensitive material, and the sensitivity may vary greatly due to temperature changes during exposure. is often accompanied by the occurrence of fog, and no satisfactory sensitizing dye has been found.

Therefore, the object of the present invention is, firstly, to provide a silver halide photographic material with improved photographic properties using a sensitizing dye that is highly sensitive and does not cause fog;
Another object of the present invention is to provide a silver halide photographic material with improved sensitivity variations due to temperature changes during exposure.
A third object of the present invention is to provide a red-sensitive silver halide photographic material which is sensitized using a novel sensitizing dye and has improved photographic properties.

As a result of various studies, the present inventors have found that the above object is achieved in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support. The silver decagenide grains have the following general formula (
It has been found that this can be achieved using a silver halide photographic material color-sensitized with the compound represented by I).

General formula (I) where A", B", C', D', A",
B2. C2 and P each represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, an aryol group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a haloken atom,
Represents a nitro group, hydroxy group, cyano group, amine group, acylamino group, sulfonylamino group, acyloxy group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group or heterocyclic group, A' and Bl, Bl and C ', cl, A2 and B2, B2 and C2, or C2 and B2 may be linked to each other to form a ring.

Y′ represents an oxygen atom, a sulfur atom or a selenium atom,
Y2 is an oxygen atom, a sulfur atom, a selenium atom or N-R”
represents a group (here, R3 represents an alkyl group or an aryl group). Z represents an atomic group necessary to form a 5- to 7-membered ring with -N-C=C-.

Moreover, R1 is a hydrogen atom, a halogen atom, a lower alkyl group,
It represents an aryl group, a lower alkoxy group or a heterocyclic group, and R2 represents an alkyl group. X- represents an anion, and m represents O or an integer of 1.

The present invention will be explained in more detail below.

61 In the present invention, AI to Dl of the general formula (I)
The lower alkyl group represented by A2 to 1'112 preferably has 1 to 6 carbon atoms, and may be linear, branched, or cyclic, and may be saturated or unsaturated.

Furthermore, it may have a substituent, and examples thereof include ehamedyl, ethyl, 180-propyl, cyclohexyl, allyl, trifluoromethyl, hydroxyethyl, acetoxyethyl, carboxymethyl, and ethoxycarbonylmethyl.

The lower alkoxy group preferably has 1 to 6 carbon atoms, and may further have a substituent, such as methoxy, 180-propoxy, chloroethoxy, and the like.

Furthermore, examples of aryl groups include phenyl, naphthyl, p-tolyl, etc.; examples of alkyl carbonyl groups include ethoxycarbonyl and butoxycarbonyl; and examples of aryl groups include phenoxycarbonyl. .

Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of the amine 7 group include amine, alkylamino 7, arylami/, di-substituted amino, and specific examples include methylamine, diethylamino, anilino, and the like. Further, examples of the acylamino group include acetamide and benzamide, and examples of the sulfonylamino group include alkylsulfonylamino and arylsulfonylamino, and specific examples include methanesulfonamide and benzenesulfonamide. Next, examples of acyloxy groups include acetoxy, benzoyloxy, etc., and examples of carbamoyl groups include carbamoyl, alkylcarbamoyl, arylcarbamoyl, diR-substituted carbamoyl, etc. Specifically, examples include methylcarbamoyl, phenylcarbamoyl, etc. It will be done.

In addition, examples of the sulfa-7yl group include sulfamoyl, alkylsulfamoyl, arylsulfamoyl, di-substituted sulfamoyl, etc. Specifically, examples include ethylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc. Keralel.

Examples of the sulfonyl group include alkylsulfonyl, arylsulfonyl, heterocyclic sulfonyl, etc., such as methanesulfonyl, cyclohexanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, pyridinesulfonyl, 1-piperidinesulfonyl, N-morpholinosulfonyl, etc. be able to. Next, examples of the acyl group include acetyl, benzoyl, 1-piperidinocarbonyl, N-morpholinocarbonyl, etc., and examples of the heterocyclic group include benzoxacylyl, benzothiazolyl, piperidino, morpholinocarbonyl, etc. Examples include succinimide, frill, chenyl, and the like.

Next, as mentioned above, A' and B', B' and C1, C' and D
l, A2 and B2, B2 and C2, Pitopi can be connected to each other to form a ring, but the rings that can be formed include the above A
For example, a naphthalene ring, a quinoline ring, a benzothiophene ring, an isobenzofuran ring, an indole ring, a 9-chroman ring, a tetrahydroquinoline ring, etc. formed together with a benzene ring substituted with 1 to B2 can be mentioned. Furthermore, these rings have substituents such as alkyl, halogen atom, aryl, carboxy, ester, nitro, hydroxy, cyano, amino, acylamino, sulfonylamino, acyloxy, carbamoyl, sulfamoyl, sulfonyl, acyl, heterocycle, etc. The group may be substituted.

Furthermore, R of the -N-R3 group represented by Y2 in the general formula (I)
3 represents an alkyl group, and the alkyl group may be linear, branched, or cyclic, and may be saturated or unsaturated. Specifically, for example, methyl, ethyl,
Examples include cyclohexyl, n-heptyl, benzyl, hydroxylethyl, acetoxyethyl, acetoxypropyl, ethoxyethyl, hydroxyethoxyethyl, sulfopropyl, and the like.

Examples of the aryl group represented by R3 include phenyl and p-tolyl.

Next, the 5- to 7-membered ring 10 represented by Z in the general formula (I)
The atomic group capable of forming - is preferably R4 -+C, where R4 and R5 are an alkyl group spanning a hydrogen atom (for example, a lower alkyl group such as methyl or ethyl), and n is 2 to It is an integer of 4.

Further, the lower alkyl group represented by R1 in the general formula (I) is preferably one having 1 to 6 carbon atoms, and is straight chain, branched,
It may be cyclic, and may be saturated or unsaturated.

Furthermore, it may have a substituent, such as methyl, ethyl, IBO-propyl, cyclohexyl, etc. Furthermore, aryl groups include phenyl, p-)lyl, etc., and halogen atoms include fluorine, chlorine, bromine,
There is iodine.

The lower alkoxy group preferably has 1 to 6 carbon atoms, and may have a substituent, such as methoxy, ethoxy, RI0/I/ethoxy, and the like. Furthermore, examples of the heterocyclic group include furyl, chenyl, imidazolyl, and the like.

Among the above, alkyl groups and aryl groups are particularly preferred.

Next, the alkyl group represented by R2 in the general formula CI) includes substituted alkyl groups normally used in cyanine dyes, such as alkyl groups without substituents (methyl, ethyl, butyl, etc.), hydroxyalkyl groups ( 2-hydroxyethyl, 4-hydroxybutyl, etc.), acetoxyalkyl groups (2-acetoxyethyl, 3-acetoxyethyl, etc.), alkoxyalkyl groups (2-methoxyethyl, 2-hydroxyethyl, etc.),
-ethoxyethyl, etc.), carboxyalkyl groups (2-carboxyethyl, 3-carboxypropyl, p-carboxybenzyl, etc.), sulfoalkyl groups (2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- Hydroxy-3-sulfopropyl, p-
sulfobenzyl, etc.), aralkyl group (hensyl, phenylethyl, etc.).

The anion represented by
Thiocyanate ion, sulfate ion, perchlorate ion, p
-Toluenesulfonate ion.

These include boron tetrafluoride ion, methyl sulfate ion, and ethyl sulfate ion. And m represents an integer of O or 1, and m is 0 when the compound forms an inner salt.

The compound represented by the general formula (I) of the present invention is an aromatic bicyclic ring (for example, pyrido C2,1-b ]Benzothiazole, naphtho[2',
1. ': 4. 5) It is a pentamethine dye having a structural feature of having thiazolo f3゜2-a]pyridine, etc.) on one side.

Symmetrical trimethine, pentamethine, heptamethine cyanine dye u having a heterocyclic nucleus as described above, British Patent No. 615
, No. 205, No. 1,153,342, Special Publication No. 1973
-5493, 57-25331, zh.

Qbshch, Khim, 33(9)3016(1
963), 34(7), 2441 (1964), and the like. however,
The descriptions in these publications do not suggest anything about the temperature dependence at the time of exposure, which has a great influence on the color balance of sensitizing dyes, and the known pentamethine cyanine dyes mentioned above Poor temperature dependence.

Therefore, no one could have predicted that the asymmetric cyanine dye represented by the general formula (I) derived from the symmetric cyanine dye according to the present invention would have excellent temperature dependence properties as shown in the Examples below. That's what happened. Furthermore, the pentamethine cyanine dye according to the present invention has an excellent spectral sensitizing effect compared to known cyanine dyes, and also suppresses the generation of capri, but it also improves sensitivity variations due to temperature changes during exposure. I have to say that this point is a particularly important feature.

Hereinafter, K represents a typical example of the sensitizing dye represented by the general formula (I).

(Exemplary compound) 14-5Or (5) c, H
50,2) 17- 18- Next, typical synthesis examples of the above compounds will be described.

Synthesis Example 1 (Synthesis of Exemplary Compound (1)) f [I) [ID Chemical Abstracts, Vol. 70 (1969) 115047
2,3-dihydro-IH-
Pyrido[2,1-+]benzothiazole (the above compound [■]) was synthesized.

Next, according to the reaction scheme, the above compound [1) 14.11 was added little by little to 360 mL of acetic anhydride containing 23.311 of β-ethylglobendianil hydrochloride and stirred.
9- Added. After reacting for 2 hours at room temperature, most of the reaction solution was concentrated and ethyl acetate was added to precipitate a solid to obtain DO'&. The yield was 37%, and the melting point was 146°C (decomposed).

Next, the above-obtained 4-[2-(N-acetylanilinomethylidene)butylidene:]-1,2゜3.4-
Tetrahydropyrido [2,], -b]benzothiazolium chloride (above compound [II:)) It, □g and 5.7 g of anhydro-2-methyl-3-sulfobutylbenzothiazolium hydroxide were dissolved in triethyl The mixture was heated to reflux with stirring for 40 minutes in 70 d of ethanol together with amino 6, II. Solid '? which precipitated when the reaction mixture was left to cool? : F was taken and recrystallized from a mixed solvent of fluorinated alcohol and ethanol to give 1.5 p of crystals (yield 14%).
) was obtained. This crystal is an exemplary compound (1) with a melting point of 210°C (decomposed).

Synthesis Example 2 According to the reaction scheme, β-ethylprobendianil 1
3.9 g of acetic anhydride 801111j K was dissolved and the above compound (I) 7. was added to the mixture while stirring at room temperature. Og was added little by little. After stirring for 30 minutes at room temperature, the reaction mixture ICp-toluenesulfonic acid monohydrate 10.5. li+ was added and the reaction was further allowed to proceed for 4 hours at room temperature. Ether was added to the reaction mixture, the washing was repeated several times, and the mixture was concentrated and dried to obtain the above compound (III) with red caramel 20.79 (yield 100%)
)was gotten.

4-(2-(N-acetyl 21-anilinomethylidene)butylidene)-1,2,3゜4- obtained above
Tetrahydropyrido[2,1-b]benzothiazolium I)-)luenesulfonate (above compound IJIr)
) 13. sg and 2-methyl-3-hydroxyethylbenzothiazolium p-toluenesulfonate 6.8
The mixture was heated to reflux with stirring in 100 Ml of ethanol together with 5.6 g of triethylamine and li+.

The reaction mixture was allowed to cool, and the precipitated solid P was collected and recrystallized from methanol to obtain 1.8 g of crystals (yield: 16%) of the above compound [■]. Melting point: 230°C (decomposition) Above, typical synthesis examples of the sensitizing dye according to the present invention have been described. Cyanine soybean and
It can be synthesized with reference to "Related Fund Pound" (Interscience Publishers, New York, 1964).

The pentamethine cyanine sensitizing dye according to the invention is used in a concentration of about 1.times.10@-5 mole to 2.times.10@-3 mole per mole of silver halide 22@2 used in the silver halide emulsion. When adding the above-mentioned sensitizing dye to the silver halide emulsion, the dye may be directly dispersed in the above-mentioned emulsion, or it may be dissolved in an appropriate solvent such as methanol, ethanol, dimethylformamide, etc. alone or in combination. It may then be added to the emulsion. Although it can be added at any time during the manufacturing process of the light-sensitive material, it is generally preferable to add it to the silver halide emulsion during the second ripening or immediately after the second ripening.

Of course, the merocyanine dyes according to the present invention may be used alone or in combination with each other, or may be used in combination with other cyanine dyes, styryl dyes, etc., for spectral sensitization or supersensitization. can be provided.

The silver halide emulsion used in the present invention is usually prepared by mixing a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. able to make. The silver halides include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide,
Any halide used in conventional silver halide photographic materials, such as silver chloroiodobromide, can be used.

These silver halide emulsions are produced according to known and conventional methods (for example, single or double jet method, controlled double jet method, etc.). Furthermore, two or more types of silver halide photographic emulsions formed separately may be mixed.

Furthermore, even if the crystal structure of silver halide grains is uniform throughout the interior, there are also grains with a layered structure with different interior and exterior structures, conversion emulsions, Lippmann emulsions, covered grain emulsions, and other grains that have been optically pre-treated. The target may also be chemically fogged.

Further, either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particle may be used. These photographic emulsions are produced using the generally accepted ammonia method,
It can be prepared by various methods such as a neutral method and an acidic method.8The type of silver halide, content and mixing ratio of silver halide, average grain size, size distribution, etc. will depend on the type and use of the photographic material. be selected as appropriate.

These methods are described in Cbim by P. Glafkides.
ie otPhyslque Photography
que (published by Paul Morite1, 1967), Photograph by G. F. Duffin
,ic EmulsionChemlstry (Th
e Focal Press, 1966), V.
Making by L. Zelikman et al.
and Coating Ph,oto-graph
ic Emulsion (The Focal Pr.
ess, 1964).

In order to form a photographic light-sensitive material, silver halide is dispersed in a suitable protective colloid to constitute a light-sensitive layer, and the light-sensitive layer and other auxiliary layers such as an intermediate layer, a protective layer, a filter layer, etc. The protective colloid used for this is generally alkali-treated gelatin;
Derivative gelatin, colloidal albumin, cellulose [
There are synthetic resins such as polyvinyl alcohol, polyvinylpyrrolidone, etc., and these can be used alone or in combination.

The above silver halide emulsion can be 25-sensitized with a chemical sensitizer. Chemical sensitizers include noble metal sensitizers (potassium aurithiocyanate, ammonium chloroparadate, potassium chloroplatinate, etc.), sulfur sensitizers (allylthiocarbamide, thiourea, cystine, etc.), and selenium sensitizers (active and inactive). They are broadly classified into four types: active selenium compounds, etc.) and reduction sensitizers (stannic salts, polyamines, etc.). Silver halide emulsions can be chemically sensitized using these sensitizers alone or in combination as appropriate.

Kowara's chemical sensitization method is described, for example, in US Pat. No. 1,574.
No. 944, No. 1,623,499, No. 2,410゜689, No. 2,448,060, No. 2,399,0
No. 83, No. 2,642,361, No. 2,487,85
No. 0, No. 2.518.698, No. 1.623.499
No. 1゜602.592, etc.

Moreover, polyalkylene oxide thread compounds and the like can also be used as other sensitizers.

Furthermore, various other additives can be added to the silver halide emulsion. For example, aldehydes such as formaldehyde, halogen-substituted 26-substituted fatty acids such as mucobromic acid, epoxy compounds, active halogen compounds,
Active vinyl compounds, hardening agents such as ethyleneimine compounds, saponins, surfactants such as nonionic surfactants, cationic surfactants, anionic surfactants, double-sided active agents, azoles, 1-phenyl- 5-merkabutotet 5"l-ru'Jo) heterocyclic mercapto compound, 4-
Azaindenes such as hydroxy-6-methyl-1,3,3a, 7-titrazaindene, antifoggants or stabilizers such as benzenethiosulfonic acid and benzenesulfinic acid, physical properties such as glycerin polymer aqueous dispersion (latex) Improving agents, dye image-forming couplers and colored couplers such as 5-pyrazolone magenta couplers, acylacetanilide yellow couplers or phenol and naphthol cyan couplers, for improving image sharpness and graininess and adjusting gradation. Couplers such as beating couplers, development inhibitor-releasing couplers (DIR Dollar), dibutyl phthalate, triphenyl phosphate, tricresyl phosphate, N, N
-diethyl laurylamide, ethyl acetate, butyl acetate,
Dispersants which are also used as coupler solvents such as chloroform and methanol, ultraviolet absorbers such as benzotriazoles, triazines, benzophenone compounds, etc.
Nuclear-substituted hydroquinones, p-alkoxyphenols, 6-chromanols, 6,6'-dihydroxy-2,
Anti-staining agents and anti-fading agents such as 2'-subirocumaquarin and their alkoxy derivatives, brighteners such as stilbene-based, triazine thread, oxazole-based or coumarin-based, oxonol dyes, hemioxonol dyes, styryl dyes, Various photographic additives may be added, such as filter dyes such as merocyanine dyes, cyanine dyes, azo dyes, and anti-irradiation dyes.

The silver halide photographic material of the present invention is produced by coating it on a support that has good flatness, good dimensional stability and little dimensional change during the manufacturing process or during processing. Supports in this case include, for example, cellulose film, cellulose ester film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, glass, paper, metal, paper coated with polyolefin, such as polyethylene, polypropylene, etc. etc. can be used.

The Kowara support can be subjected to various surface treatments such as hydrophilic treatment in order to improve its adhesion with the photographic emulsion layer, such as saponification treatment, corona discharge treatment, subbing treatment, and setting treatment. The following processing is performed.

The silver halide photographic material of the present invention basically consists of a support and a light-sensitive emulsion layer, but depending on the type of silver halide photographic material, it may include a subbing layer, an intermediate layer, a filter layer, an anti-halation layer, etc. Auxiliary layers such as a layer, an anti-curl layer, a backing layer, a protective layer, etc. may be appropriately combined and stacked.

The present invention can also be applied to multilayer color light-sensitive materials having at least two different spectral sensitivities on the support.

29- The above-mentioned multilayer color light-sensitive material usually has at least one layer each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer in order from the support side on a support.
The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan coupler, the green-sensitive emulsion layer contains a magenta coupler, and the blue-sensitive emulsion layer contains a yellow coupler, but in some cases a combination K different from the above may be used. May be included.

In the above-mentioned multilayer color light-sensitive material, the cyan coupler applied to the red-sensitive emulsion layer spectrally sensitized with the sensitizing dye according to the present invention is disclosed in, for example, U.S. Pat.
No. 293, No. 2,895,826, No. 3,476
．． No. 563, JP-A-52-18315, JP-A No. 53-10
No. 9630, No. 55-32071, No. 55-1635
No. 37, No. 56-65134, etc.

The silver halide photographic light-sensitive material of the present invention is processed using the known processing method and processing solution described, for example, in Research Disclosure, No. 176, pages 20-30-30 (RD-1764-3). be able to. This photographic processing method may be black and white photographic processing to obtain a silver image or color photographic processing to obtain a color image. The processing temperature applied in photographic processing is usually 18
℃ to 50℃, but even at temperatures lower than 18℃, 50℃
Processing is possible even at higher temperatures.

The pentamethine cyanine sensitizing dye according to the present invention has the above-mentioned excellent properties and can provide a red-sensitive silver halide photographic material with high sensitivity and good storage stability, so it is suitable for special pressure color photography. Not only is it useful as a red-sensitive sensitizing dye, but it can also be used in various photosensitive materials,
For example, it can be applied to black-and-white photosensitive materials, various photosensitive materials for plate making, and color photosensitive materials containing colored dyes produced by silver bleaching.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 A silver iodochloride emulsion containing 7 mol % of silver iodide was subjected to second ripening (chemical ripening) by gold sensitization and sulfur sensitization in a conventional manner, and the emulsion after this ripening was divided. As shown in Table 1 below, a sensitizing dye which is an exemplary compound of the present invention and a comparative sensitizing dye as described above were dissolved in methanol and 1-
It was added as a solution. The emulsion containing the sensitizing dye was coated on acetyl cellulose paste and dried to obtain red-sensitive photographic materials Samples 1 to 10, respectively. Next, each sample was exposed to light according to a conventional method, and then a developer of the following composition was used for 20 minutes.
It was developed at .degree. C. for 6 minutes, stopped 1.about., fixed, washed with water, and then dried.

(Developer Composition) The density of each sample treated as described above was measured using an optical densitometer, and the sensitivity and fog were measured. The optical density reference point for determining the sensitivity was the fog +0.20 point. The obtained results are shown in Table 1 as relative values1
-It is.

33- Comparative Dye (1) Comparative Dye (2) Spectral sensitivity curves for the above samples 1 to 3 are shown in FIGS. 1 to 3, respectively.

From Table 1 and the drawings above, it is clear that all the samples optically sensitized with the sensitizing dye according to the present invention are stable against fog and have a high sensitivity of 34-.

Example 2 A solution of the cyan coupler shown below dissolved in dibutyl phthalate and ethyl acetate was added to an aqueous gelatin solution containing sodium dodecylbenzenesulfonate, and then dispersed with a homogenizer to obtain a cyan coupler dispersion.

On the other hand, the above chemically ripened silver chlorobromide emulsion (containing 80 mol% silver bromide) 17 was added with 2.0 x 10' mol of sensitizing dyes as shown in Table 2 below per mol of silver halide. cyan coupler dispersion per mole of silver halide.
．． It was added in an amount containing 2 moles of cyan coupler. Next, as a hardening agent, N, N'', N''-triacryloyl-
6I (-8-triazine dissolved in 2% methanol)
was added, coated on polyethylene coated paper, and dried. Samples 11 to 18 as shown in Table 2 below were obtained.

We divided each of these samples and examined the photographic characteristics of each sample due to temperature changes during exposure.
After exposing each of the divided samples to light, they were subjected to color development using the following processing method and their photographic properties were investigated.1. -6 Processing step (32.8°C) Processing time Color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Water washing 3 minutes 30 seconds (Color developer composition) 36- Adjust to pH 10.0 using water.

(Composition of Bleach-Fix Solution) Sensitivity was determined from the density value at a turn point of lj 0.6 using an optical densitometer through a red filter.

Then, let the sensitivity of the sample obtained by exposure at a temperature of 5°C be S, and let the sensitivity of the sample at a temperature of 50°C be 85°, and the value of 850/s, x 100 (!%) will be expressed as follows:
Shown in the table.

37- (Table 2) Comparative dye (4) Comparative dye (5) 38- As is clear from the above results, the sensitizing dye according to the present invention has little sensitivity fluctuation due to humidity changes during exposure. , it can be seen that there is no temperature dependence. The stiffness was a completely unexpected effect considering that the comparative dye has greater temperature dependence than the comparative dye (5), which has a similar structure to the dye according to the present invention.

Example 3 A sample f1 of a multilayer color light-sensitive material was prepared by applying each of the following constituent layers onto polyethylene coated paper under normal pressure from the support side.

1st layer - Blue-sensitive emulsion layer Blue-sensitive silver chlorobromide emulsion layer (containing 90 mol% silver bromide) contains the following yellow coupler dissolved and dispersed in 400 g of gelatin and dibutyl phthalate per mol of silver halide. contains 0.2 mol per mol of silver halide, and the amount of silver is 400
This is a layer coated to give Tng/771'.

Second layer: Intermediate layer This is a gelatin layer containing 2.5-di-t-octylhydroquinone and coated with ceratin of 1.5 g/m.

Seratin 500.9 per mole of silver halide, 0.2 mole of the following magenta coupler dissolved and dispersed in dibutyl phthalate per mole of silver halide, and magenta coupler of 2.5-di-t-octylhydroquinone. 0.05 mole per mole, 1,4-di-octyloxy-2
, 0.3 mol of 5-di-t-amylbenzene per mol of magenta coupler, and the amount of silver is 500 ■
This is a layer that is applied so that the color is 0.

4th layer: 2,5-di-t dissolved and dispersed in intermediate layer dibutyl phthalate
- octylhydroquinone at 30 μ/co and 2-(benzotriazol-2-yl)-4 as a UV absorber.
,6-di-t-butylphenol o,7rrvi/go containing gelatin layer, the coated gelatin is 1.5
It is a layer coated to give g/m.

51st threat...Red-sensitive emulsion layer The sensitizing dye of the exemplary compound (1) of the present invention is silver halide 1
The red-sensitive silver chlorobromide emulsion layer (containing 80 mol% silver bromide) was dissolved and dispersed in dibutyl phthalate and 500 g of gelatin per 1 mol of silver halide. The material described in Example 2 above was coated containing 0.2 mol of cyanide dollar per mol of silver halide and coated at a silver content of 500 μ/lri.
It is.

6th layer: Intermediate layer A gelatin layer containing 0.4.9/m' gold of the ultraviolet absorber dissolved and dispersed in dibutyl phthalate, so that the coated gelatin is 1.5 jj/rrl. It is a coated layer.

71st Emperor...The amount of gelatin in the protective layer is 1.5,! It is a gelatin layer applied to i'/rrl.

41- (Yellow coupler) C/ (Magenta coupler) Shi! Incidentally, the silver halide emulsion of each of the above-mentioned photosensitive layers is
-7'172, chemically sensitized using sodium thiosulfate pentahydrate, and 4-hydroxy-6-methyl-1 as a stabilizer.
, 3,3a, 7-titrazaindene, as well as tetrakis-(vinylsulfonylmethyl)methane as a hardening agent and saponin as a coating aid. The sample thus obtained was designated as sample 19.

Furthermore, Sample 20 was prepared in the same manner as above, except that Comparative Dye (4) was used in place of Exemplary Compound 42-(1) of the present invention in the fifth layer.

Samples 19 and 20 were exposed to light at temperatures of 10° C. and 40° C., respectively, using ordinary color negatives to produce color prints. The prints obtained with sample 19 had two prints with good color balance regardless of the temperature change during exposure, while the prints obtained with sample 20 had different color balance due to the temperature change during exposure. Two prints were obtained. That is, it was found that the color photosensitive material using the sensitizing dye according to the present invention is a photosensitive material that is free from temperature dependence during exposure and can always form dye images of constant quality.

[Brief explanation of the drawing]

1, 2 and 3 are sample 1 in Example 1.
, spectral sensitivity curve diagrams corresponding to Sample 2 and Sample 3, respectively. Agent Yoshimi Kuwahara 43- Procedural amendment 2 Name of the invention Silver halide photographic light-sensitive material 3 Relationship to the case of the person filing Supplement 11- Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name Name (+27) Roku Konishi Photo Industry Co., Ltd. Seven Directors Kawa
Nobuhiko Moto 4 Agent Address: 5, Konishiroku Photo Industry Co., Ltd., 1 Sakura-cho, Hino-shi, Tokyo, 191, Japan, 81 of the order for amendment 6, ``Detailed Description of the Invention'' column of the specification to be amended 7. Contents of amendment The detailed description of the invention shall be amended as follows. 2-

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide grains contained in the silver halide emulsion layer have the following general formula (I ) A silver halide photographic material characterized by being color sensitized with a compound represented by: General formula (I) (wherein, AZ B1.CI, pZ A", B
2. C2 and B2 are each a hydrogen atom, a lower alkyl group, a lower alkoxy group, an aryl group, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom, a nitro group, a hydroxy group, a cyano group, an amino group, and an acylamine group. , 7 sulfonyl amide groups,
Acyloxy group, carbamoyl group, sulfamoyl group,
l= represents a sulfonyl group, acyl group or heterocyclic group,
A' and B1, B1 and C1, CI and Dl, A2 and B2, B
2 and C2 or C2 and B2 may be connected to each other to form a ring. Yl represents an oxygen atom, sulfur atom, or selenium atom, and Y2 represents an oxygen atom, sulfur atom, selenium atom, or N-R
2 represents an atomic group necessary to form a 5- to 7-membered ring with -N-C=C-. . Moreover, R1 is a hydrogen atom, a halogen atom, a lower alkyl group,
It represents an aryl group, a lower alkoxy group or a heterocyclic group, and R2 represents an alkyl group. X- represents an anion, and m represents O or an integer of 1. )