JPH0454937B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic material,
More specifically, the present invention relates to a silver halide photographic material containing a novel pentamethane sensitizing dye, which has increased sensitivity and improved photographic properties. Conventionally, in the production of silver halide photographic light-sensitive materials, the technology of optically sensitizing silver halide emulsions by adding and containing sensitizing dyes to expand the photosensitive length range of the silver halide emulsions has been well known. ing. 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'' by T.H.
(Ed.), 1966, Macmillan Publishing, N.Y., pp. 198~
Examples include cyanine dyes, merocyanine dyes, and xanthene dyes described on page 228. When these sensitizing dyes are normally applied to silver halide emulsions, they must not only simply expand the sensitive wavelength range of the silver halide emulsions, but must also satisfy the following conditions. (1) The spectral sensitization range is appropriate. (2) It must have good sensitization efficiency and be able to obtain sufficiently high sensitivity. (3) No fogging should occur. (4) Small variations in sensitivity due to temperature changes during exposure. (5) No adverse interaction with various additives, such as stabilizers, antifoggants, coating aids, color formers, etc. (6) Silver halide emulsions containing sensitizing dyes should not exhibit a decrease in sensitivity, especially when stored at high temperatures and high humidity. (7) The added sensitizing dye should not diffuse into other photosensitive layers and cause color turbidity (color mixing) after development. The above-mentioned conditions have an important meaning especially when preparing a red-sensitive silver halide emulsion in a silver halide color photographic light-sensitive material. That is, as sensitizing dyes conventionally used in red-sensitive silver halide emulsions, for example, rhodacyanine dyes, pentamethine dyes, etc. are known, but silver halide emulsions spectrally sensitized with rhodacyanine dyes can be used at high temperatures. , the sensitivity decreases significantly when stored under high humidity, while silver halide emulsions spectrally sensitized with pentamethine dyes do not suffer from a decrease in sensitivity under the above storage conditions, but photographic additives, For example, when used in combination with a color former, sensitivity decreases during storage, and in order to obtain the desired sensitivity, it is necessary to increase the content of the sensitizing dye, resulting in fog in the silver halide emulsion. There are drawbacks. However, a sensitizing dye that exhibits low fog and sufficient sensitizing properties is not necessarily a dye that has small temperature dependence on exposure temperature.Therefore, it is difficult to obtain a sensitizing dye that fully satisfies the above requirements. I have to say that it is really difficult. Therefore, the object of the present invention is, firstly, to provide a silver halide photographic light-sensitive material with improved photographic properties due to the use of a special dye that is highly sensitive and does not cause fogging, and secondly, to Thirdly, it is an object of the present invention to provide a silver halide photographic material with improved sensitivity variations due to changes in
The object of the present invention is to provide a red-sensitive silver halide photographic material which is sensitized with 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. It has been found that silver halide grains can be composed of a silver halide photographic light-sensitive material color-sensitized with a compound represented by the following general formula (). General formula () (In the formula, R represents a lower alkyl group, cycloalkyl group, lower alkenyl group, cycloalkenyl group, lower alkoxy group, aryl group or thienyl group, X represents an anion, Y ₁ and T ₂
Each represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle containing an oxygen atom, a sulfur atom, or a selenium atom together with C--N. R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a lower alkoxy group, and n ₁ and n ₂ represent 2 or 3. ) Hereinafter, the present invention will be explained in more detail. The pentamethine dye according to the present invention has an aromatic heterocycle in which left and right azole rings are bonded to a nitrogen atom and a carbon atom at the α-position of a polymethine chain, respectively, with a group of nonmetallic atoms, as shown by the general formula (). It is characterized in that the carbon atom at the γ-position is substituted. The lower alkoxy group represented by R in the above general formula () may be linear or branched, and may contain substituents including alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, etc. For example, preferable examples include groups such as methoxyethyl, examples of cycloalkoxy groups include cyclohexyl, and examples of lower alkenyl groups include alkenyl groups having 1 to 6 carbon atoms, such as allyl and pentenyl. Examples of the group include groups such as cyclohexenyl. The lower alkoxy group is preferably a group having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy and the like. Furthermore, typical examples of the aryl group represented by R include phenyl, tolyl, and the like. In the general formula (), R ₁ , R ₂ , R ₃ and R ₄
is a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl and hexyl groups.
n ₁ and n ₂ are 2 or 3. Plus Y ₁ and Y ₂
represents a group of nonmetallic atoms forming a nitrogen-containing heterocycle as described above, and the nitrogen-containing heterocycle in this case includes monocyclic ones and those condensed with benzene rings, etc., such as oxazole, thiazole, etc. , thiazoline, selenazole, benzoxazole, benzthiazole, benzselenazole,
There are rings such as naphthoxazole, naphthothiazole, and naphthoselenazole, and these heterocycles are
Furthermore, for example, a nitro group, an alkoxycarbonyl group,
It may be substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group, or the like. Examples of the anion represented by X include chloride ion, bromide ion, iodide ion, perchlorate ion, p-toluenesulfonate ion, ethylsulfate ion, methylsulfate ion, boron tetrafluoride ion, and the like. In the present invention, among the pentamethine sensitizing dyes represented by the general formula (), particularly preferred are dyes represented by the following general formula (). General formula () In the formula, A ₁ , B ₁ , C ₁ , D ₁ , A ₂ , B ₂ , C ₂ and
D ₂ is a hydrogen atom, lower alkyl group, cycloalkyl group, lower alkenyl group, cycloalkenyl group, lower alkoxy group, aryl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, halogen atom, nitro group, hydroxy group, respectively. , cyano group, amino group, acylamino group, sulfonylamino group, acyloxy group, carbamoyl group, sulfamoyl group, sulfonyl group,
represents an acyl group or a heterocyclic group, 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 , or C ₂ and
Each may form a ring with D ₂ . W ₁ and W ₂ each represent an oxygen atom, a sulfur atom or a selenium atom. R, R ₁ , R ₂ , R ₃ , R ₄ , n ₁ , n ₂ and X
are the same groups as defined in the above general formula (). In the above general formula (), A ₁ , B ₁ , C ₁ ,
The lower alkyl group represented by D ₁ , A ₂ , B ₂ , C ₂ and D ₂ is preferably an alkyl group having 1 to 6 carbon atoms, and may be either linear or branched, such as methyl, ethyl , isopropyl, and those having substituents include trifluoromethyl, hydroxyethyl, acetoxymethyl, carboxymethyl, and ethoxycarbonylmethyl. Examples of the cycloalkyl group include cyclohexa. Examples of lower alkenyl groups include allyl groups. Examples of the cycloalkenyl group include groups such as cyclohexylnyl.
Furthermore, examples of the halogen atom include fluorine, chlorine, bromine, and iodine, and examples of the lower alkoxy group include preferably an alkoxy group having 1 to 6 carbon atoms, such as methoxy, isopropoxy, and chloroethoxy groups. It will be done. Furthermore, aryl groups include various groups such as phenyl, naphthyl, and paratolyl; alkyloxycarbonyl groups include ethoxycarbonyl; and aryloxycarbonyl groups include,
It is a group such as phenoxycarbonyl. Examples of the amino group include amino, alkylamino, arylamino, and di-substituted amino, and specific examples include methylamino, diethylamino, anilino, and the like. Examples of the acylamino group include acetamide and benzamide, and examples of the sulfonylamino group include alkoxysulfonylamino and arylsulfonylamino.Specifically, there are groups such as methanesulfonamide and benzsulfonamide. Examples of acyloxy groups include acetoxy and benzoyloxy, and carbamoyl groups include carbamoyl, alkylcarbamoyl, arylcarbamoyl, and di-substituted carbamoyl. Specifically, methyl Examples include groups such as carbamoyl and phenylcarbamoyl. Subsequently, sulfamoyl groups include, for example, sulfamoyl, alkylsulfamoyl, arylsulfamoyl, disubstituted sulfamoyl, etc., and specifically, ethylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc. The following groups can be mentioned. Examples of sulfonyl groups include alkylsulfonyl, arylsulfonyl, heterocyclic sulfonyl, etc.
Specifically, groups such as methylsulfonyl, cyclohexasulfonyl, benzenesulfonyl, para-toluenesulfonyl, pyridinesulfonyl, 1-piperidinesulfonyl, and N-morpholinesulfonyl can be mentioned. Further, acyl groups include, for example, acetyl, benzoyl, 1-piperidinocarbonyl, N-morpholinocarbonyl, etc., and heterocyclic groups include, for example, benzoxazolyl, benzothiazolyl, piperidino, mornerino, succinimide, There are groups such as furyl and thienyl. In the general formula (), A ₁ and B ₁ , B ₁ and
The rings that can be formed by C ₁ , C ₁ and D ₁ , A ₂ and B ₂ , B ₂ and C ₂ , and C ₂ and D ₂ are not only the rings formed by themselves, but also, for example, the above A ₁ ~ _D1 and _A2
~ _D2 may form a naphthalene ring, a quinoline ring, a benzothiophene ring, an isobenzofuran ring, an indole ring, a chroman ring, a tetrahydroquinoline ring, etc. together with the benzene ring to which D2 is bonded, respectively. And these rings are, for example, halogen atoms,
alkyl, aryl, carboxyl, ester,
Nitro, hydroxy, cyano, amino, acylamino, sulfonylamino, acyloxy, carbamoyl, sulfamoyl, sulfonyl, acyl,
It may be substituted with a group such as a heterocycle. The above general formulas () and () according to the present invention
As is clear from the above, the pentamethine dye shown in is, for example, pyrido[2,1-b]benzothiazole, which is formed by bonding the nitrogen atom of the azole ring and the carbon atom at the α-position of the polymethine chain with an alkylene chain. Naphtho [2', 1': 4, 5] Thiazolo [3,
2-a] It is structurally characterized by having aromatic heterocycles such as pyridine symmetrically and being substituted at the γ-position of the polymethine chain. The symmetrical trimethine, pentamethine, and heptamethine cyanine dyes having a heterocyclic nucleus as described above and in which the polymethine chain is unsubstituted are disclosed in British Patent No. 615205 and British Patent No. 615205.
No. 1153342, Special Publication No. 48-5493, No. 52-25331,
Zh. Obshch Khim. 33 (9) 3016 (1963), 34 (7) 2441
(1964) and others, it is a known compound. However, the descriptions in these publications do not suggest anything about the temperature dependence during exposure, which has a large effect on color balance, which is a problem especially in the case of regular, ortho, and panchromatic multilayer photosensitive materials, and the above-mentioned Known pentamethine cyanine dyes have poor temperature dependence during exposure. As mentioned above, the pentamethine dye according to the present invention is a compound in which a substituent is introduced at the γ-position of the polymethine chain, and is more photosensitive than symmetrical dicarbocyanine dyes in which the γ-position is unsubstituted or other known dyes. When used in materials, it exhibits excellent spectral sensitization and improved fogging properties, but its most distinctive effect is that it provides photosensitive materials with extremely small variations in sensitivity due to temperature differences during exposure. . Typical specific examples of pentamethine dyes represented by the general formulas () and () are listed below, but the present invention is not limited thereto. (Exemplary compound) Next, typical synthetic examples of these exemplified compounds will be described. Synthesis Example 1 (Synthesis of Exemplary Compound (4)) 21.6 g of 2,3-tetramethylenebenzthiazorium bromide and β-ethylpropendianyl hydrochloride
Add 22.9 g to a mixed solution of 20 ml of acetic anhydride and 40 ml of acetic acid, and heat under reflux with 20 g of triethylamine in an oil bath for 15 minutes. After cooling, the precipitate is separated and the liquid is precipitated with ether. The supernatant liquid is decanted, and 200 ml of acetone is added to the precipitate and stirred. Remove the precipitated crystals and wash thoroughly with water. Finally, if you wash it with acetone and dry it, you will get 3.9 as crude crystals.
g (yield 18%). Repeated recrystallization from isopropanol yielded 2.0 g of desired dye crystals (yield 9%)
I got it. Melting point 214℃~219℃. The absorption maximum in methanol solution was 670 nm. The pentamethine dye represented by the general formula () is described, for example, in "The
It can be synthesized by referring to "Cyanine Soybean and Related Compounds", Interscience Publishers, N.Y. (1964) and Michael Abstracts, Vol. 61 (1966), 14816. When the pentamethine dye according to the present invention obtained as described above is added to a silver halide emulsion, the pentamethine dye according to the present invention is about 1×10 ^-5 mol to 2× mol per mol of silver halide.
It can be used effectively at a concentration of 10 ^-3 molar. When adding the above pentamethine dye to a silver halide emulsion, the dye may be directly dispersed in the silver halide emulsion.
Organic solvents such as ethanol and dimethylformamide may be used alone or as a mixed solvent, and after being dissolved in these solvents, it may be added to the silver halide emulsion. The pentatimene dye according to the present invention may be added at any time during the manufacturing process of the light-sensitive material, but generally during the second ripening of the silver halide emulsion or immediately after the second ripening. It is preferable to add it to the emulsion. The pentamethine dye according to the present invention can be used in combination with other cyanine dyes, merocyanine dyes, composite merocyanine dyes, styryl dyes, etc., as necessary, to provide spectral sensitization or superchromatic sensitization. The silver halide emulsion used in the present invention is usually prepared by mixing a water-soluble silver salt (for example, silver nitrate) solution with 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 halide may be any halogen compound used in ordinary silver halide photographic materials, such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. Silver can be used. These silver halide emulsions are prepared 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 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, so-called compound emulsions, Lippmann emulsions, covered grain emulsions, or grains that have been optically treated in advance. Alternatively, it may 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 can be prepared by various methods, such as the generally accepted ammonia method, neutral method, and acid method. Further, the type of silver halide, content and mixing ratio of silver halide, average grain size, size distribution, etc. are appropriately selected depending on the type and use of the photographic light-sensitive material. These methods are described in Chimie et al. by P. Glafkides.
Physique Photographique (published by Paul Montel)
1967), Photographic Emulsion by GFDuffin
Chemistry (The Focal Press, 1966), VL
Making and Coating by Zelikman et al
Photogeaphic Emulsion (published by The Focal Press)
1964). In order to form a photographic light-sensitive material, silver halide is dispersed in a suitable protective colloid to constitute a photosensitive layer, and the layer structure of the photosensitive layer and other auxiliary layers such as an intermediate layer, a protective layer, a filter layer, etc. The protective colloid used for this purpose is generally alkali-treated gelatin, and other types include acid-treated gelatin, derivatized gelatin, colloidal albumin, cellulose derivatives, and synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone. Used in combination. The above silver halide emulsion can be 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 roughly divided 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. These chemical sensitization methods are described, for example, in U.S. Pat.
No. 1574944, No. 1623499, No. 2410689, No. 2448060, No. 2399083, No. 2642361,
Same No. 2487850, Same No. 2518698, Same No. 1623499,
It is described in the same No. 1602592 etc. Further, polyalkylene oxide 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 fatty acids such as mucobromic acid, hardening agents such as epoxy compounds, active halogen compounds, active vinyl compounds, ethyleneimine compounds, saponins, nonionic surfactants, cationic surfactants, etc. surfactants such as surfactants, anionic surfactants, surfactants, azoles, heterocyclic mercapto compounds such as 1-phenyl-5-mercaptretrazole, 4-hydroxy-6-methyl-1,3,3a, Azaindenes such as 7-tetrazaindene, antifoggants or stabilizers such as benzenethiosulfonic acid and benzenesulfinic acid, physical property improvers such as glycerin polymer aqueous dispersion (latex), 5-pyrazolone magenta couplers, Dye image-forming couplers and colored couplers such as acylacetanilide yellow couplers or phenol and naphthol cyan couplers, compeding couplers for improving image sharpness and graininess or adjusting gradation, and development inhibitor-releasing couplers. couplers such as (DIR coupler), dibutyl phthalate,
Dispersants also used as coupler solvents such as triphenyl phosphate, tricresyl phosphate, N,N-diethyl laurylamide, ethyl acetate, butyl acetate, chloroform, methanol, etc., benzotriazoles, triazines, benzophenone compounds UV absorbers such as nuclear-substituted hydroquinones, P-alkoxyphenols, 6-chromanols, 6,6'-dihydroxy-2,2'-spirocoumarone and their alkoxy derivatives, and anti-fading agents. Inhibitors, brighteners such as stilbene, triazine, oxazole or coumarin, filter dyes such as oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and anti-irradiation dyes, etc. Photographic additives may be added. 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 processing. In this case, the support may be, for example, cellulose nitrate 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. Can be used. These supports can be subjected to various surface treatments such as hydrophilic treatment for the purpose of improving adhesion with the photographic emulsion layer, such as saponification treatment, corona discharge treatment, subbing treatment, setting treatment, etc. 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, Auxiliary layers such as an antihalation layer, an anticurl layer, a back layer, a protective layer, etc. may be appropriately combined and overlaid. The present invention can also be applied to multilayer color light-sensitive materials having at least two different spectral sensitivities on a support. The above-mentioned multilayer color light-sensitive material usually has a structure having 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, but the order of these layers is It 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 different from the above may be included. may be done. In the above-mentioned multilayer color photographic material, the cyan coupler applied to the red-sensitive emulsion layer spectrally sensitized with the sensitizing dye according to the present invention is, for example, US Pat. No. 2,474,293, US Pat.
No. 3476563, Japanese Patent Publication No. 52-18315, No. 53-109630
No. 55-32071, No. 55-163537, No. 56-
It is described in No. 65134 etc. The silver halide photographic material of the present invention can be used, for example, in Research Disclosure, No. 176, 28-
The treatment can be performed using the known treatment method and treatment liquid described on page 30 (RD-17643). The photographic processing method may be a black and white photographic process to obtain a silver image or a color photographic process to obtain a dye image. The processing temperature applied to photographic processing is usually 18 to 50°C, but processing is possible even at temperatures lower than 18°C or at temperatures above 50°C. The pentamethine cyanine sensitizing dye according to the present invention has the above-mentioned excellent properties,
Since it is possible to obtain red-sensitive silver halide photographic materials with high sensitivity and good storage stability, it is not only useful as an excellent red-sensitizing dye for color photographic materials, but also useful for various photographic materials, such as black and white. It can be applied to photosensitive materials, various photosensitive materials for plate making, and even color photosensitive materials containing colored dyes produced by silver bleaching. EXAMPLES 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 iodobromide emulsion containing 7 mol% of silver iodide was subjected to a second ripening (chemical ripening) using a gold sensitization method and a sulfur sensitization method in a conventional manner, and the emulsion after this ripening was divided. As shown in Table 1 below, a sensitizing dye as an exemplary compound of the present invention and a comparative sensitizing dye as shown below were each added as a solution dissolved in methanol. The emulsion containing the sensitizing dye was coated on an acetyl cellulose base and dried to obtain samples 1 to 10 of red-sensitive photographic materials, respectively. Next, each sample was heated to 5
After performing light wedge exposure at ℃ and 50℃, respectively, develop with a developer having the following composition at 20℃ for 6 minutes, stop,
After fixing and washing with water, it was dried. (Developer composition) Metol 2g Anhydrous sodium sulfite 40g Hydroquinone 4g Sodium carbonate monohydrate 28g Potassium bromide 1g Add water to make 1. 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 sensitivity was the fog +0.20 point. The results obtained are shown in Table 1 as relative values. Furthermore, the sensitivity of the sample obtained by exposure at a temperature of 5°C is defined as S ₅ , and the sensitivity of the sample obtained by exposure at a temperature of 50°C is defined as S ₅₀ , respectively (S ₅₀ /
Table 1 shows the values of S ₅ )×100 (%) and the relative sensitivity and fog values of the samples obtained by exposure at a temperature of 5°C.

[Table] As is clear from the results in the table above, samples sensitized with the dyes according to the present invention (sample No. 1 to
It can be seen that Samples No. 7) all have superior sensitization properties compared to samples sensitized with comparative dyes (Samples Nos. 8 to 10). At the same time, it was also found that the samples according to the present invention had extremely small fluctuations in sensitivity due to temperature changes during exposure, and that the temperature dependence of sensitivity was significantly improved compared to samples using comparative dyes. This is a completely unexpected effect of the present invention and is an excellent feature of the dye according to the present invention. Example 2 A sample of a multilayer color photosensitive material was prepared by coating each of the following constituent layers on polyethylene coated paper in order from the support side. 1st layer... Blue-sensitive emulsion layer Blue-sensitive silver chlorobromide emulsion layer (contains 90 mol% silver bromide)
A layer containing 400 g of gelatin per mole of silver halide and 0.2 mole of the following yellow coupler dissolved and dispersed in dibutyl phthalate per mole of silver halide, and coated so that the amount of silver was 400 mg/ ^m2 . It is. Second layer: Intermediate layer This layer is a gelatin layer containing 2,5-di-t-octylhydroquinone and is coated at a gelatin concentration of 1.5 g/m ² . Third layer...Green-sensitive emulsion layer Green-sensitive silver chlorobromide emulsion layer (containing 80 mol% silver bromide)
is 500 g of gelatin per mole of silver halide,
The following Magellan coupler dissolved and dispersed in dibutyl phthalate was added at a rate of 0.2 per mole of silver halide.
mole, 0.05 mole of 2,5-di-t-octylhydroquinone per mole of magenta coupler, 1,4
This layer contains 0.3 mol of -di-octyloxy-2,5-di-t-amylbenzene per 1 mol of magenta coupler, and is coated in a silver amount of 500 mg/m ² . 4th layer...Intermediate layer 2, which is dissolved and dispersed in dibutyl phthalate,
5-di-t-octylhydroquinone 30mg/m ²
and a gelatin layer containing 0.7 mg/m ² of 2-(benzotriazol-2-yl)-4,6-di-t-butylphenol as an ultraviolet absorber,
This layer is coated with gelatin of 1.5 g/m ² . Fifth layer...Red-sensitive emulsion layer Red ^- sensitive silver chlorobromide emulsion layer (silver bromide 80 Contains 500 g of gelatin per mole of silver halide and 0.2 mole of the following dian coupler dissolved and dispersed in dibutyl phthalate per mole of silver halide,
This layer is coated with a silver content of 500 mg/m ² . 6th layer...middle layer A gelatin layer containing 0.4 g/m ² of the above-mentioned ultraviolet absorber dissolved and dispersed in dibutyl phthalate,
This layer is coated with gelatin of 1.5 g/m ² . 7th layer...Protective layer This is a gelatin layer coated with a gelatin amount of 1.5 g/m ² . The silver halide emulsions for each of the photosensitive layers mentioned above were prepared by the method described in Japanese Patent Publication No. 46-7772, chemically sensitized using sodium thiosulfate pentahydrate, and stabilizers. as 4-hydroxy-
It contained 6-methyl-1,3,3a,7-tetrazaindene, as well as tetrakis-(vinylsulfonylmethyl)methyl as a hardening agent and saponin as a coating aid. The sample thus obtained was designated as Sample 11. Furthermore, the exemplary compound of the present invention in the above fifth layer
Sample 12 was a sample prepared in exactly the same manner as above except that (4) was replaced with comparative dye (3). Samples 11 and 12 were exposed to light at temperatures of 10°C and 40°C, respectively, using ordinary color negatives to produce color prints. The prints obtained from sample 11 produced two prints with good color balance regardless of temperature changes during exposure, while the prints obtained from sample 12 had different color balance due to temperature changes during exposure. Two prints were obtained. That is, the color photosensitive material using the sensitizing dye according to the present invention has no temperature dependence during exposure;
It was found that this is a photosensitive material that can always form dye images of constant quality.

Claims (1)

[Scope of Claims] 1. 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 ( ) A silver halide photographic material characterized by being color sensitized with a compound represented by: General formula () (In the formula, R represents a lower alkyl group, cycloalkyl group, lower alkenyl group, cycloalkenyl group, lower alkoxy group, aryl group or thienyl group, X represents an anion, and Y ₁ and Y ₂
Each represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle containing an oxygen atom, a sulfur atom, or a selenium atom together with C--N. R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a lower alkyl group, and n ₁ and n ₂ represent 2 or 3. 2. The silver halide photographic material according to claim 1, wherein the compound represented by the general formula () is represented by the following general formula (). General formula () (where A ₁ , B ₁ , C ₁ , D ₁ , A ₂ , B ₂ , C ₂ and
_D2 is a hydrogen atom, a lower alkyl group, a lower alkoxy group, an aryl group, a carboxyl group,
Alkoxycarbonyl group, aryloxycarbonyl group, halogen atom, nitro group, hydroxy group, cyano group, amino group, acylamino group, sulfonylamino group, acyloxy group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group or heterocyclic group. Expressed, 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 , or C ₂ and D ₂ may be linked to each other to form a ring. W ₁ and W ₂ each represent an oxygen atom, a sulfur atom or a selenium atom. R, R ₁ , R ₂ , R ₃ , R ₄ , n ₁ , n ₂ and X are groups each having the same meaning as defined in the above general formula (). )