JPH0454936B2 - - 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 sensitized with a new 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'' by T.H. (2013, Macmillan Publishing, NY) pp. 194-234
Cyanine dyes, merocyanine dyes, xanthene dyes, etc. described on page 1 are known. When these sensitizing dyes are normally applied to silver halide emulsions, they must not only simply expand the wavelength range to which the silver halide emulsions are sensitive, but must also satisfy the following conditions. (1) The spectral sensitization range by dye sensitization is appropriate. (2) It must have good sensitization efficiency and be able to obtain sufficiently high sensitivity. (3) No adverse interaction with various additives, such as stabilizers, antifoggants, coating aids, color formers, etc. (4) Small variations in sensitivity due to temperature changes during exposure. (5) No fogging should occur. The above 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.
These dyes do not necessarily have sufficient sensitization efficiency,
Not only is it not possible to obtain the desired sensitivity, but when various additives are used in combination, the sensitivity may decrease during storage of the photosensitive material, and the sensitivity may vary greatly due to temperature changes during exposure. Furthermore, fogging is often caused, and no satisfactory sensitizing dye has been found. The purpose 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 fogging; Thirdly, it is an object of the present invention to provide a silver halide photographic material with improved sensitivity variations due to changes in temperature.
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 this can be achieved by using a silver halide photographic material whose silver halide grains are color sensitized with a compound represented by the following general formula (). General formula () (where A ¹ , B ¹ , C ¹ , D ¹ , A ² , B ² , C ² and
D ² is 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,
represents a cyano group, amino group, acylamino group, sulfonylamino group, alkyloxy group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group or 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 D ² may be linked to each other to form a ring. Y ¹ represents an oxygen atom, a sulfur atom, or a selenium atom, and T ² represents an oxygen atom, a sulfur atom, a selenium atom, or a N-R ⁵ group (wherein R ⁵ represents an alkyl group or an aryl group). Further, R ¹ represents a hydrogen atom, a halogen atom, a lower alkyl group, an aryl group, a lower alkoxy group or a heterocyclic group, and Y ² represents an alkyl group. R ³ and R ⁴ represent a hydrogen atom or a lower alkyl group, X ^- is an anion, m is 0 or 1, and n is 2
Or represents 3. ) Hereinafter, the present invention will be explained in more detail. In the present invention, the lower alkyl groups represented by A ¹ to D ¹ and A ² to D ² in the general formula () are preferably those with 1 to 6 carbon atoms, and may be linear, branched, or cyclic, or It may be saturated or unsaturated. Furthermore, it may have a substituent, such as methyl, ethyl, iso-propyl,
cyclohexyl, allyl, trifluoromethyl,
Hydroxyethyl, acetoxymethyl, carboxymethyl, ethoxycarbonylmethyl and the like can be mentioned. In addition, the lower alkoxy group has 1 to 6 carbon atoms.
These are preferred, and may further have a substituent, such as methoxy, iso-propoxy, chloroethoxy and the like. Furthermore, as the aryl group, for example, phenyl,
Examples of alkoxycarbonyl groups include naphthyl, p-tolyl, and ethoxycarbonyl.
Examples of aryloxycarbonyl groups include butoxycarbonyl and phenoxycarbonyl. And as halogen atoms, fluorine, chlorine,
Contains bromine and iodine. Examples of amino groups include amino, alkylamino, arylamino, disubstituted amino, and specific examples include methylamino,
Diethylamino, anilino, etc. can be mentioned. 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 the acyloxy group include acetoxy, benzoyloxy, etc., and examples of the carbamoyl group include carbamoyl, alkylcarbamoyl, arylcarbamoyl, disubstituted carbamoyl, etc., and specific examples include methylcarbamoyl, phenylcarbamoyl, etc. . Examples of the sulfamoyl group include sulfamoyl, alkylsulfamoyl, arylsulfamoyl, and di-substituted sulfamoyl, and specific examples include ethylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, and the like. . Further, sulfonyl groups include alkylsulfonyl, arylsulfonyl, heterocyclic sulfonyl, etc., such as methanesulfonyl, cyclohexanesulfonyl, benzenesulfonyl, p-
Toluenesulfonyl, pyridinesulfonyl, 1-
Examples include piperidine sulfonyl and N-morpholinosulfonyl. Next, examples of the acyl group include acetyl, benzoyl, 1-piperidinocarbonyl, N-morpholinosulfonyl, etc., and examples of the heterocyclic group include henzoxazolyl, benzothiazolyl, piperodino, morpholino, axinimide, etc. , frill, thienyl, etc. Next, as mentioned above, A ¹ and B ¹ , B ¹ and C ¹ , C ¹ and D ¹
Also, A ² and B ² , B ² and C ² , and C ² and D ² can be linked to each other to form a ring, but the ring that can be formed is the benzene ring substituted by A ¹ to D ² above. For example, a naphthalene ring, a quinoline ring, a henzothiophene ring, an isobenzofuran ring, an indole ring, a chroman ring, a tetrahydroquinoline ring, etc. can be mentioned. In addition, these rings have further substituents such as alkyl, halogen atoms, aryl,
Carboxy, alkoxycarbonyl, aryloxycarbonyl, nitro, hydroxy, cyano,
Each group such as amino, acylamino, sulfonylamino, acyloxy, carbamoyl, sulfamoyl, sulfonyl, acyl, and heterocycle may be substituted. Furthermore, T ² in the above general formula () represents -N-R ³
The group R ³ represents an alkyl group, and the alkyl group may be linear, branched, or cyclic, and may be saturated or unsaturated. Furthermore, it may have various kinds of substituents. Specific examples include methyl, ethyl, cyclohexyl, n-heptyl, benzyl, hydroxylethyl, acetoxyethyl, acetoxypropyl, ethoxyethyl, hydroxyethoxyethyl, and sulfopropyl. Examples of the aryl group represented by R ³ include phenyl and p-tolyl. The lower alkyl group for R ³ and R ⁴ has 1 to 1 carbon atoms.
6, such as methyl, ethyl, propyl, butyl,
Preferred examples include pentyl and hexyl groups. The lower alkyl group represented by R ¹ in the general formula () 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, such as methyl, ethyl, isopropyl, cyclohexyl, etc. Aryl groups include phenyl, p-tolyl, 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, and chloroethoxy groups. Furthermore, examples of the heterocyclic group include furyl, thienyl, imidazolyl, etc. Among the above, alkyl groups and aryl groups are particularly preferred. Next, the alkyl group represented by R ² in the general formula () includes substituted alkyl groups normally used in cyanine dyes, such as alkyl groups without substituents (methyl, ethyl, butyl, etc.), hydroxylalkyl groups, etc. (2-hydroxyethyl, 4-hydroxybutyl, etc.), acetoxyalkyl group (2-hydroxyethyl, 4-hydroxybutyl, etc.), acetoxyalkyl group (2-hydroxyethyl, 4-hydroxybutyl, etc.),
-acetoxyethyl, 3-acetoxypropyl, etc.), alkoxyalkyl groups (2-methoxyethyl, 2-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 (benzyl, phenylethyl, etc.). The anions ^represented by ion, ethyl sulfate ion, etc. And m represents an integer of 0 or 1, and m is 0 when the compound forms an inner salt. The compound represented by the general formula () of the present invention is an aromatic heterocyclic ring (for example, pyrido [2,1-b] It is a pentamethine dye having a structural feature of having benzothiazole, naphtho[2',1':4,5]thiazolo[3,2-a]pyridine, etc.) on one side. Symmetrical trimethine having a heterocyclic nucleus as described above,
Pentamethine and heptamethine cyanine dyes are disclosed in British Patent No. 615205, British Patent No. 1153342, and British Patent No. 1153342.
No. 5493, No. 52-25331, Zh. Obshch. Khim. 33 (9)
It is a known compound as described in 3016 (1963), 34 (7) 2441 (1964), etc. however,
The descriptions in these publications do not suggest anything about the temperature dependence during exposure, which has a great effect on the color balance of sensitizing dyes. inferior in gender. Therefore, no one could have predicted that the asymmetric cyanine dye represented by the general formula () derived from the symmetric cyanine dye according to the present invention would have good temperature survival characteristics 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 fogging, but it also improves sensitivity variations due to temperature changes during exposure. I have to say that this point is a particularly important feature. Typical specific examples of the sensitizing dye represented by the above general formula () are shown below. (Exemplary compound) Next, typical synthetic examples of the above compounds will be described. Synthesis Example 1 (Synthesis of Exemplary Compound (1)) Chemical Abstracts, Volume 70 (1969)
115047h, 2,3-dihydro-1H-pyrido[2,1-b]benzothiazole (the above compound []) was synthesized. Next, according to the reaction scheme, 23.3 g of β-ethylpropendianil hydrochloride was added to 360 ml of acetic anhydride, and while stirring, 14.0 g of the above compound [] was added little by little. After reacting at room temperature for 2 hours, most of the reaction solution was concentrated and ethyl acetate was added to precipitate a solid, which was collected and recrystallized from a mixed solvent of methanol and ethyl acetate. 11.6 g of the above compound [ ] is obtained as a yellow-green solid. Yield 37%, melting point 146℃ (decomposition)
It was hot. Next, 4-[2-(N-acetylanilinomethylidene)butylidene]-1,2, obtained as above,
3,4-tetrahydroviride [2,1-b]benzothiazolium chloride (the above compound []
11.0 g and anhydro-2-methyl-3-sulfobutylbenzothiazolium hydroxide 5.7
g with 6.1 g of triethylamine and 70 g of ethanol.
ml and heated to reflux with stirring for 40 minutes. The reaction compound was allowed to cool, and the precipitated solid was collected and recrystallized from a mixed solvent of fluorinated alcohol and ethanol to obtain 1.5 g of crystals (yield: 14%). This crystal is an exemplary compound () with a melting point of 210°C (decomposition). Synthesis Example 2 (Synthesis of Exemplary Compound (3)) According to the reaction scheme, 13.9 g of β-ethylpropendianyl was dissolved in 80 ml of acetic anhydride, and 7.0 g of the above compound [] was added little by little while stirring at room temperature. After stirring at room temperature for 30 min, the reaction mixture was
-Toluenesulfonic acid monohydrate (10.5 g) was added, and the mixture was reacted for an additional 4 hours at room temperature. Ether was added to the reaction mixture, washing was repeated several times, and the mixture was concentrated and dried to obtain 20.7 g (yield: 100%) of red caramel. 4-[2-(N-acetylanilinomethylidene)butylidene]1,2,3,4 obtained above
-Tetrahydropyrid[2,1-b]benzothiazolium p-toluenesulfonate (13.5 g of the above compound []) and 6.8 g of 2-methyl-3-hydroxyethylbenzothiazolium p-toluenesulfonate were mixed with triethylamine. The mixture was heated to reflux with stirring for 40 minutes in 100 ml of ethanol together with 5.6 g. The reaction mixture was allowed to cool, the precipitated solid was collected, and recrystallized from methanol to give a blood-colored product of 1.8 g (yield:
16%) of Exemplary Compound (3) was obtained. Melting point: 230°C (decomposition) Typical synthesis examples of the sensitizing dye according to the present invention have been described above. It can be synthesized by referring to "Soybean and Related Compound" (Interscience Publishers, New York, 1964). The pentamethine cyanine sensitizing dye according to the invention is used at a concentration of about 1.times.10.sup. ^-5 mol to 2.times.10.sup.- ³ mol per mol of silver halide 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 be added to the emulsion after that. It can be added at any time during the photosensitive material manufacturing process, but
Generally, it is preferable to add it to the silver halide emulsion during or immediately after the second ripening. Of course, the cyanine 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. be able to. 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. It will be done. 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 photographic materials formed separately may be mixed. Furthermore, even if the crystal structure of silver halide grains is uniform inside, there are also those with a layered structure with different inside and outside, so-called compound emulsions, Lippmann emulsions, etc.
It may be a copper grain emulsion or one that has been optically or 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 generally accepted methods such as an ammonia method, a neutral method, and an acid method. Also, the type of silver halide,
The 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 material. These methods are described in Chimie et al. by P. Glafkides.
Physique Photographique (published by Paul Montel)
1967), Photographiqhic by GFDuffin
Emulsion Chemistry (published by The Focal Press)
(1966), Making and VL Zelikman et al.
Coating Photo-graphie Emulsion (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, derivative gelatin, colloidal albumin, cellulose derivatives, and synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone, which may be used alone or in combination. It is used as The above silver halide emulsion can be sensitized with a chemical sensitizer. Chemical sensitizers include noble metal sensitizers (potassium aurithiocyanate, ammonium chloroparadate, potassium chlorobratinate, 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. These chemical sensitization methods are described, for example, in U.S. Patent No.
No. 1574944, No. 1623499, No. 2410689, No. 1574944, No. 1623499, No. 2410689, No.
No. 2448060, No. 2399083, No. 2642361, No.
No. 2487850, No. 2518698, No. 1623499, No.
It is described in No. 1602592, etc. Further, polyalkylene oxaside 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, amphoteric surfactants, azoles, heterocyclic mercapto compounds such as 1-phenyl-5-mercaptotetrazole, 4-hydroxy-6-methyl-1,3,3a, Azaindenes such as 7-tetrazaindene, antifoggants or stabilizers such as benzenethiosulfonic acid and henzenesulfinic acid, physical property improvers such as glycerin polymer aqueous dispersion (latex), 5-pyrazolone-based magenta binder, Dye image-forming couplers and colored couplers such as acylacetanilide yellow couplers or phenol and naphthol cyan couplers, compounding grapplers for improving image sharpness and graininess and adjusting gradation, and development inhibitor-releasing types. couplers such as dibutyl phthalate, triphenyl phosphate, tricresyl phosphate, N,N-diethyl laurylamide,
Dispersants used as coupler solvents such as ethyl acetate, butyl acetate, chloroform, methanol, etc., ultraviolet absorbers such as benzotriazoles, triazines, benzophenone compounds, etc., nuclear-substituted hydroquinones, p-alkoxyphenols, 6 - anti-staining and anti-fading agents such as chromanols, 6,6'-dihydroxy-2,2'-spirocoumarone and their alkoxy derivatives, brighteners such as stilbenes, triazines, oxazoles or coumarins; Various photographic additives such as filter dyes such as oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and anti-irradiation dyes 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 a magenta coupler, and the blue-sensitive emulsion layer 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). This photographic processing method may be black and white photographic processing to obtain a silver image or color photographic processing to obtain a colored image. The processing temperature applied to photographic processing is usually 18°C 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 exposed to a light wedge according to a conventional method, and then a developer with the following composition was used.
After developing at 20℃ for 6 minutes, stopping, fixing, and washing with water,
Dry. (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 used to determine the sensitivity was the fog +0.20 point. The results obtained are shown in Table 1 as relative values.

【table】

For the above samples 1 to 3, Fig. 1~
FIG. 3 shows the spectral sensitivity curve. It is clear from Table 1 and the drawings that all the samples optically sensitized with the sensitizing dye according to the present invention are stable against fog and have high sensitivity. 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, a chemically ripened silver chlorobromide emulsion (silver bromide ⁸⁰ mol%
The above-mentioned cyan coupler dispersion was added to (containing) 1 in an amount containing 0.2 mol of cyan coupler per 1 mol of silver halide. Next, as a hardening agent, N, N′,
10 ml of a 2% methanol solution of N''-triacryloyl-6H-S-triazine was added, coated on polyethylene coated paper, and dried. Samples 13 to 20 as shown in Table 2 below were obtained. (Cyan coupler) Each of these samples was divided, and in order to examine the photographic characteristics of each sample due to temperature changes during exposure, each of the divided samples was subjected to light wedge exposure at temperatures of 10°C and 30°C, and then colored using the following processing method. It was developed and its photographic properties were investigated. Processing process (32.8℃) Processing time Color development 3 minutes 30 seconds Bleach-fixing 1 minute 30 seconds Water washing 3 minutes 30 seconds (color developer composition) N-ethyl-N-β-methylsulfonamidoethyl-3-methyl-4 -aminoaniline sulfate
4.0g Hydroxylamine sulfate 2.0g Potassium carbonate 25.0g Sodium chloride 0.1g Sodium bromide 0.2g Anhydrous sodium sulfite 2.0g Benzyl alcohol 10.0ml Polyethylene glycol (average degree of polymerization 400)
Add 3.0ml of water to bring the volume to 1, and adjust the pH to 10.0 using sodium hydroxide. (Bleach-fix solution composition) Ethylenediaminetetraacetic acid iron sodium salt
60.0g Ammonium thiosulfate 100.0g Sodium bisulfite 20.0g Sodium metabisulfite 5.0g Add water to make 1, and adjust to PH7.0 using sulfuric acid. Redox potential -70 mV Sensitivity was determined from the density value at fog +0.6 using an optical densitometer through a red filter.
The sensitivity of the sample obtained by exposure at a temperature of 5°C is defined as S ₅ , and that at a temperature of 50°C is defined as S5.
S ₅₀ is shown in Table 2 below as a value of S ₅₀ /S ₅ ×100 (%).

【table】

【table】

As is clear from the above results, it can be seen that the sensitizing dye according to the present invention exhibits little fluctuation in sensitivity due to temperature changes during exposure and low temperature dependence.
This was a completely unexpected effect considering that the comparative dye had greater temperature dependence than comparative dye 5, which had a similar structure to the dye according to the present invention. Example 3 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. First layer: Intermediate layer This is a layer of gelatin containing 2,5-di-t-ocrylhydroquinone and coated with gelatin 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 magenta 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...middle layer 2,5 dissolved and dispersed in dibutyl phthalate
- A gelatin layer containing 30 mg/m ² of di-t-octylhydroquinone and 0.7 mg/m ² of 2-(benzotriazol-2-yl)-4,6-di-t-butylphenol as an ultraviolet absorber. hand,
This layer is coated with gelatin of 1.5 g/m ² . 5th ^layer ...Red-sensitive emulsion layer Red-sensitive silver chlorobromide emulsion layer (silver bromide 80 (mol% content) contains 500 g of gelatin per mole of silver halide and 0.2 mole of the cyan coupler described in Example 2 above dissolved and dispersed in dibutyl phthalate per mole of silver halide. This is a layer coated so that the amount is 500 mg/m ² . 6th layer...Intermediate layer This is a gelatin layer containing 0.4g/ ^m2 of the above-mentioned ultraviolet absorber dissolved and dispersed in dibutyl phthalate, and is coated so that the coated gelatin is 1.5g/ ^m2 . . 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 above-mentioned photosensitive layers were prepared by the method described in Japanese Patent Publication No. 7772/1972, 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 21. Furthermore, the exemplary compound of the present invention in the above fifth layer
Sample 22 was a sample prepared in exactly the same manner as above, except that dye (1) was replaced with comparative dye (4). Samples 21 and 22 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 21 had two prints with good color balance regardless of the temperature change during exposure, while the prints obtained with Sample 22 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.

[Brief explanation of drawings]

1, 2, and 3 are spectral sensitivity curve diagrams corresponding to Sample 1, Sample 2, and Sample 3 in Example 1, respectively.

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 () (where A ¹ , B ¹ , C ¹ , D ¹ , A ² , B ² , C ² and
D ² is 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,
represents a cyano group, amino group, acylamino group, sulfonylamino group, alkyloxy group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group or 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 D ² may be linked to each other to form a ring. Y ¹ represents an oxygen atom, a sulfur atom, or a selenium atom, and T ² represents an oxygen atom, a sulfur atom, a selenium atom, or a N-R ⁵ group (herein, R ⁵ represents an alkyl group or an aryl group). Further, R ¹ represents a hydrogen atom, a halogen atom, a lower alkyl group, an aryl group, a lower alkoxy group or a heterocyclic group, and Y ² represents an alkyl group. R ³ and R ⁴ represent a hydrogen atom or a lower alkyl group, X ^- is an anion, m is 0 or 1, and n is 2
Or represents 3. )