JPH0364054B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a color reversal photographic material, and particularly to a color reversal photographic material with improved suitability for sensitization processing. (Prior Art) Color photographic materials are usually prepared by using a support with different color sensitivities (color sensitivity refers to the property of being sensitive to light in one of the three regions of the visible spectrum, namely red, green, and blue). The emulsion layer has at least one silver halide emulsion layer each having the following properties. In the field of color photographic materials, especially color reversal materials often used by professional photographers,
Highly sensitive color photosensitive materials are required for shooting special scenes such as sports photography that requires a fast shutter speed or stage photography where the amount of light required for exposure is insufficient. There are few color photographic materials that meet this requirement. Under these circumstances, sensitivity adjustment is performed through processing to compensate for the lack of exposure. Sensitivity adjustment by this process is usually called "sensitization process", and in the case of color reversal photosensitive materials, it is carried out by extending the time of the first development (black and white development) from the time of standard processing. However, conventional color reversal photosensitive materials do not necessarily have sufficient suitability for sensitization processing, and may not be sensitized unless the first development time is much longer than standard processing, or the high-speed layer may be replaced with a low-sensitivity layer. In light-sensitive materials that have a structure divided into layers, the suitability of development processing for both layers is different, so sensitization may cause a change in gradation, or the degree of sensitization may be changed by extending the first development time. Attempting to increase the color density may cause a significant decrease in color development density, or the color balance may deteriorate when sensitized due to differences in development processing suitability between the red, green, and blue sensitive layers. There was something that caused this. Therefore, it has been desired to develop a technique that can solve the above-mentioned drawbacks, can freely control the degree of sensitization, and does not cause any adverse effects during standard processing. The present inventors have previously developed a silver halide emulsion layer as a technique that does not cause gradation changes or deterioration of color balance even after sensitization treatment, and can relatively reduce the degree of decrease in color image density. Or, he invented a technique in which a silver halide emulsion having fog nuclei inside is added to the adjacent layer, and the fog nuclei function to advance development during sensitization processing (Japanese Patent Application No. 1982-
No. 88939). In this technology, sensitization is carried out by changing the ratio of the silver halide emulsion having internal fog nuclei to the photosensitive silver halide emulsion and the thickness of the outer shell of silver halide that covers the fog nuclei. This allows you to adjust the color balance afterwards. However, when this technique is used, there is a drawback that the maximum image density of color photographs subjected to sensitization tends to be low in some cases. (Object of the invention) Therefore, the object of the present invention is to
The object of the present invention is to provide a color reversal photographic material that can ensure a high maximum image density when improving the suitability of sensitization using the technique described in No. 88939. As a result of continuing research in view of the above objectives, the present inventors have found that by using a sensitizing dye with a specific structure as described below in combination with a light-sensitive silver halide emulsion, the maximum image density can be reduced. It has been discovered that sufficient sensitization can be achieved with a small amount. This effect could not be achieved with other sensitizing dyes, and was a unique effect observed only with the sensitizing dye of the present invention. (Structure of the Invention) The object of the present invention is to provide at least two emulsion layers having the same color sensitivity but different sensitivities, each having one or more red-sensitive, green-sensitive, and blue-sensitive emulsion layers on a support. In a color reversal photographic light-sensitive material having layers, of the at least two emulsion layers, the lower-sensitivity emulsion layer has a light-sensitive silver halide emulsion and a carbon atom of a heterocyclic nucleus having both a carboxyl group and a sulfo group. It is characterized by containing a combination of methine dyes that do not have methine dyes, and containing a silver halide emulsion having fog nuclei inside in the lower-sensitivity emulsion layer and/or the non-photosensitive emulsion layer adjacent thereto. This was achieved using a color reversal photographic material. By using the above-mentioned sensitizing dye of the present invention in combination with a light-sensitive silver halide emulsion, the sensitizing effect during sensitization using a silver halide emulsion having internal fog nuclei can be enhanced while maintaining high image density. You can enjoy up to. The reason for this is not clear, but it is probably because the degree of dissolution physical development of the emulsion is controlled by increasing or decreasing the amount of the sensitizing dye of the present invention adsorbed onto the surface of the grains of the photosensitive silver halide emulsion. be interpreted. Although the combination ratio of the sensitizing dye of the present invention and the photosensitive silver halide emulsion can be changed as appropriate, it is generally from 10 ^-5 to 1 mole of photosensitive silver halide.
Good results can be obtained with a concentration of 10 ^-1 mol, especially in the range of 10 ^-4 to 10 ^-2 mol. In the present invention, the sensitizing dye of the present invention and the photosensitive silver halide emulsion are used in the same layer.
When both are mixed, it is desirable that the above-mentioned compound is adsorbed exclusively onto the surface of the above-mentioned silver halide emulsion grains. Therefore, when a silver halide emulsion having internal fog nuclei is incorporated into a red-sensitive, green-sensitive, or blue-sensitive light-sensitive silver halide emulsion layer, the light-sensitive silver halide emulsion is coated with a fog core before mixing both emulsions. Preferably, the compound of the invention is added in advance. In particular, US Patent No. 2735766, US Patent No. 3628960,
It is also possible to apply the method described in JP-A No. 55-26589, etc., in which a dye is added at a stage before the physical ripening of a silver halide emulsion is completed. When silver halide grains having internal fog nuclei are added to the interior of a blue-sensitive emulsion layer or a layer adjacent thereto, the following general sensitizing dyes are particularly preferred as sensitizing dyes to be used together with the light-sensitive silver halide of the blue-sensitive emulsion layer. It is a monomethine cyanine dye represented by formula (A). In addition, when silver halide grains having fog nuclei inside are added inside a green-sensitive emulsion layer or a layer adjacent thereto, or when added inside a red-sensitive emulsion layer or a layer adjacent thereto, general formula (B) is used. Among the trimethine cyanine dyes represented by the above, it is particularly preferable to use a dye having a maximum spectral sensitivity in the range of 500 to 600 nm for the green-sensitive emulsion layer, and a dye having a maximum spectral sensitivity in the range of 600 to 700 nm for the red-sensitive emulsion layer. preferable. General formula (A) In the formula, Z ¹ and Z ² each independently represent an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a thiazole nucleus, a benzthiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a pyridine nucleus or a quinoline nucleus. represents the atomic group necessary to form the heterocyclic nucleus (however, the carbon atoms of these heterocyclic nuclei must not be substituted with carboxyl groups or sulfo groups). R ¹ and R ² each independently represent an alkyl group or a substituted alkyl group. n represents 0 when the dye forms an inner salt, and 1 otherwise. X represents an anion. General formula (B) In the formula, Z ³ and Z ⁴ each independently form a benzoxazole nucleus, a naphthoxazole nucleus, a benzthiazole nucleus, a benzselenazole nucleus, a naphthoselenazole nucleus, a benzimidazole nucleus, a naphthimidazole nucleus, a pyridine nucleus or a quinoline nucleus. (However, the carbon atoms of these heterocyclic nuclei must not be substituted with carboxyl or sulfo groups). R ³ represents a hydrogen atom, an alkyl group or an aralkyl group. R ⁴ and R ⁵ each independently represent an alkyl group or a substituted alkyl group. n represents 0 when the dye forms an inner salt, and 1 otherwise. X represents an anion. The carbon atoms of the nucleus completed by Z ¹ , Z ² , Z ³ and Z ₄ include substituents other than carboxyl or sulfo groups, such as alkyl groups with up to 6 carbon atoms, alkoxy groups with up to 8 carbon atoms, Aryl group with up to 8 carbon atoms, aryloxy group with up to 8 carbon atoms, 8 carbon atoms
It may have an acyl group up to 8 carbon atoms, an alkoxycarbonyl group up to 8 carbon atoms, an acyloxy group up to 3 carbon atoms, a cyano group, a trifluoromethyl group, a halogen atom, etc. The alkyl group represented by R ¹ , R ² , R ⁴ and R ⁵ is preferably one having up to 8 carbon atoms, such as a methyl group, ethyl group, n-propyl group, n-butyl group and the like. Furthermore, the substituted alkyl group represented by R ¹ , R ² , R ⁴ and R ⁵ has a carbon number of 10
The above are preferred, such as hydroxyalkyl groups, acetoxyalkyl groups, alkoxyalkyl groups, alkoxycarbonylalkyl groups, carboxyalkyl groups, sulfoalkyl groups, sulfoalkoxyalkyl groups, allyl groups, cyanoalkyl groups, carbamoylalkyl groups, and aralkyl groups. Examples include. The alkyl group for R ³ preferably has 4 or less carbon atoms, and the aralkyl group preferably has 10 or less carbon atoms. Specific examples of sensitizing dyes suitable for use in the present invention are listed below, but the present invention is not limited thereto. The silver halide emulsion with internal fog nuclei of the present invention is not developed at all by standard processing, and only after being subjected to sensitization processing can it be developed uniformly regardless of whether it is unexposed or exposed. In this case, it is possible to determine whether or not the product can be used using the following test method. That is, a sample prepared by coating the emulsion to be tested on a film support at a coating silver amount of 0.5 g/m ² was prepared (without exposure) at 38°C using a developer with the following formulation. Treat for 2 minutes (standard treatment) and 10 minutes (sensitization treatment) at the same temperature. Developer treated water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g potassium iodide (0.1% solution) Add 2ml water 1 As a result of the above test, the concentration showed almost no increase in the 2-minute treatment, but the concentration increased more than 5 times the concentration in the 2-minute treatment in the 10-minute treatment. The emulsion used in the sample shown is suitable for use as a silver halide emulsion having internal fog nuclei in the present invention. Preferably, the above-mentioned silver halide emulsion having a fogged core inside is a core-shell type silver halide grain consisting of an inner core of silver halide whose surface is fogged and an outer shell of silver halide covering the surface. It is an emulsion consisting of In general, a core-shell type silver halide emulsion with a fogged internal core surface is produced by fogging the surface of the silver halide grain by a chemical method or with light after the formation of silver halide grains in which the internal core is to be formed. and then depositing silver halide on the surface of an inner core silver halide grain to form an outer shell. The above-mentioned fogging step is carried out by adding a reducing agent or gold salt under conditions suitable for PH and pAg, by heating under low pAg, or by applying uniform exposure. be able to. As the reducing agent, stannous chloride, hydrazine compounds, ethanolamine, thiourea dioxide, etc. can be used. The use of the core-shell type silver halide grains described above is advantageous because the timing at which the sensitizing treatment effect appears can be adjusted by changing the thickness of the outer shell. Therefore, the thickness of the outer shell should be determined depending on how long the sensitizing effect is produced when the first development is prolonged.
In the extension time range adopted in normal sensitization processing, the thickness of the outer shell is 50 to 1000A.
It is preferable to set it to (Angstrom),
In particular, good results can be obtained by setting it in the range of 100 to 500A. Even if the silver halide forming the inner core and the silver halide forming the outer shell of core-shell type silver halide grains have the same halogen composition,
They may have different halogen compositions. As the silver halide having an internal fog nucleus, any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used. There is no particular limitation on the grain size of silver halide having internal fogging nuclei, but fine grains are preferable, especially as the average grain size.
0.01-0.75μ, more preferably 0.01-0.5μ. Further, there is no particular limitation on the grain shape of the silver halide emulsion having fog nuclei inside, and it may be either regular grains or irregular grains. Silver halide emulsions with fog nuclei inside are
It may be polydisperse, but monodisperse (particularly one with a coefficient of variation CV of particle size distribution of 20% or less) is preferable. Further, it is preferable that this emulsion has no photosensitivity. In the present invention, the silver halide emulsion having fog nuclei inside is used in a color reversal photographic light-sensitive material having at least two emulsion layers having the same color sensitivity but different sensitivities.
In the lower-sensitivity emulsion layer of the two emulsion layers and/or
Or it is contained in a non-photosensitive emulsion layer adjacent thereto. In the present invention, the layer to which the silver halide emulsion having fog nuclei inside is applied is a red-sensitive emulsion layer of lower sensitivity and/or a non-light-sensitive layer adjacent thereto;
One or more of the following: a green-sensitive emulsion layer with lower sensitivity and/or a non-photosensitive layer adjacent thereto, a blue-sensitive emulsion layer with lower sensitivity and/or a non-photosensitive layer adjacent thereto. In the present invention, a silver halide emulsion having an internal fog nucleus accelerates the development of the adjacent light-sensitive silver halide by sensitization treatment, so that the sensitization characteristics are maintained between the high-speed layer and the low-speed layer. If there is a difference, it is possible to prevent the gradation from deteriorating compared to the standard process by adding it to the layer where the development progresses more slowly due to the sensitization process. In addition, deterioration of color balance (deterioration during sensitization) due to differences in sensitization processing characteristics that exist between different color-sensitive layers,
It can be prevented in the same way. In the present invention, the degree of sensitization when the first development is extended for a certain period of time is changed by changing the ratio of the silver halide emulsion having internal fog nuclei and the photosensitive silver halide emulsion. be able to. Therefore, the usage ratio should be determined depending on the desired sensitization width, but it is usually 0.05 to 50 mol%, especially 0.05 to 50 mol% based on the light-sensitive silver halide emulsion.
In the range of 0.1 to 25 mol%, and even 0.5 to 10 mol%,
A preferable sensitizing effect can be achieved by using a silver halide emulsion having fog nuclei inside. The photosensitive silver halide emulsion used in the present invention does not have fog nuclei inside the grains, and contains silver bromide, silver iodide, silver iodobromide, and salts that can form a latent image upon imagewise exposure. It may be silver bromide, silver chloroiodobromide, or silver chloride. The average grain size of the silver halide grains in the above photographic emulsion (grain diameter for spherical or approximately spherical grains, grain size for cubic grains, and expressed as an average based on projected area) is particularly important. Although it is not, it is preferably 3μ or less. The particle size distribution may be narrow or wide. Silver halide grains in photographic emulsions may have regular crystal shapes such as cubes or octahedrons, or irregular crystal shapes such as spherical or plate shapes. , or a composite form of these crystal forms.
It may also consist of a mixture of particles of various crystalline forms. These photographic emulsions were published by P. Glafkides in Chimie et al.
Physique Photographique (published by Paul Montel)
1967), Photographic Emulsion by GFDuffin
Chemistry (The Focal Press, 1966), VL
Making and Coating by Zelikman et al
Photographic Emulsion (published by The Focal Press)
(1964) and others. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the formation of the reaction between the soluble silver salt and the soluble halogen salt may be performed using any one-sided mixing method, simultaneous mixing method, or a combination thereof. . It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. Although the silver halide emulsion can be used as a so-called primitive emulsion without chemical sensitization, it is usually chemically sensitized. For chemical sensitization, Glafkides or
Zelikman et al.'s book or H. Frieser (ed.)
protse mito zilbelhalogenyden)
Die Grudlagen der Photographischen
Prozesse mit Silberhalogeniden (Akademische
Verlahsgesellschaft, 1968) can be used. That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat.
Described in Nos. 2278947, 2728668, and 3656955. As the reduction sensitizer, soot salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof include US Pat.
Described in Nos. 2518698, 2983609, 2983610, and 2694637. For noble metal sensitization, in addition to gold complex salts, complex salts of metals in the periodic table group such as platinum, iridium, and palladium can be used.
It is described in issues such as No. 618061. Each light-sensitive photographic emulsion layer of the light-sensitive material of the present invention contains a color-forming coupler, which is formed by oxidative coupling with an aromatic primary amine developer (e.g., phenylenediamine derivative, aminophenol derivative, etc.) during color development processing. Contains a compound that can develop color when exposed to heat. For example, magenta couplers used in the green-sensitive emulsion layer include 5-pyrazolone couplers, pyrazolone benzimidazole couplers, cyanoacetylcoumarone couplers, and open-chain acylacetonitrile couplers, and yellow couplers used in the blue-sensitive emulsion layer include acylacetamide couplers. couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc.
Cyan couplers used in the red-sensitive emulsion layer include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent, 4-equivalent, or 2-equivalent to silver ion. A specific example of a magenta coloring coupler is a U.S. patent
No. 2600788, No. 2983608, No. 3062653, No.
No. 3127269, No. 3311476, No. 3419391, No. 3127269, No. 3311476, No. 3419391, No.
No. 3519429, No. 3558319, No. 3582322, No.
No. 3615506, No. 3834908, No. 3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665,
No. 2417945, No. 2418959, No. 2424467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 20826-1971, No. 50-13041
No. 52-58922, No. 49-129538, No. 49-
No. 74027, No. 50-159336, No. 52-42151, No. 49
-74028, 50-60233, 51-26541, same
No. 53-55122, etc. A specific example of a yellow coupler is U.S. Patent No. 2875058.
No. 3265506, No. 3408194, No. 3551155,
3582322, 3725072, 3891445, West German Patent No. 1547868, West German Patent Application No. 2219917,
No. 2261361, No. 2414006, British Patent No. 1425020,
Special Publication No. 51-10783, Japanese Patent Publication No. 47-26133, No. 48-
No. 73147, No. 51-102636, No. 50-6341, No. 50
−123342, No. 50-130442, No. 51-21827,
These are described in No. 52-87650, No. 52-82424, No. 52-115219, etc. Specific examples of cyan couplers are U.S. Patent No. 2369929,
Same No. 2434272, No. 2474293, No. 2521908, Same No.
No. 2895826, No. 3034892, No. 3311476, No. 3458315
No. 3476563, No. 3583971, No. 3591383,
No. 3767411, No. 4004929, West German Patent Application (OLS) No. 2414830, No. 2454329, Japanese Patent Application Laid-Open No. 1973-
No. 59838, No. 51-26034, No. 48-5055, No. 51-
These are those described in No. 146828, No. 52-69624, and No. 52-90932. Other known sensitizing dyes may be used in combination with the sensitizing dye of the present invention. Gelatin is advantageously used as the binder for each light-sensitive photographic emulsion layer and interlayer or other constituent layers of the invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives,
Graft polymers of gelatin and other polymers, proteins such as albumin and casein; Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol and polyvinyl alcohol moieties A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. In addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan, No. 1630 are used as gelatin.
Enzyme-treated gelatin such as that described in Page (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. The present invention uses photosensitive materials such as polyalkylene oxide or its ethers, derivatives such as ester amines, thioether compounds, thiomorpholins, quaternary ammonium salt compounds, urethane derivatives, and urea for the purpose of increasing sensitivity, increasing contrast, or accelerating development. It may also include derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, US Patent No. 2400532, US Patent No. 2423549, US Patent No. 2716062
No. 3617280, No. 3772021, No. 3808003, etc. can be used. The light-sensitive material of the present invention may contain various compounds as antifoggants or stabilizers. Azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercapto. Benzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1
-phenyl-5-mercaptotetrazole), mercaptopyridines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindene; -Hydroxy substitution (1,3,
Many compounds known as antifoggants or stabilizers can be added, such as (3a, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; etc. For more detailed examples of these and how to use them, see, for example, U.S. Pat. No. 3,954,474;
No. 3982947, No. 4021248, specifications or Tokkosho
The description in Publication No. 52-28660 can be referred to. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other constituent layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-
Methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-S-triazine, 1,3-vinylsulfonyl- 2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.),
These can be used alone or in combination. The photographic emulsion layer or other constituent layers of the light-sensitive material of the present invention may contain various additives such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). Various surfactants may be included for this purpose. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic interfaces such as alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator: Alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl tauric acid, sulfosuccinic acid Anion interfaces containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. such as esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters, etc. Activators: Ampholytic surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; Alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, Cationic surfactants such as heterocyclic quaternary ammonium salts such as imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. The light-sensitive material of the present invention may contain a developing agent. As a developing agent, research disclosure,
Those described in the "Developing agents" section of Vol. 176, page 29 can be used. The photographic material produced according to the present invention may contain a dye in the photographic emulsion layer or other constituent layers as a filter dye or for various purposes such as preventing irradiation. As such dyes, Research, Disclosure, Vol. 176
Those described in the "Absorbing and filter dyes" section on pages 25-26 are used. The light-sensitive material of the present invention may also contain antistatic agents, plasticizers, matting agents, lubricants, ultraviolet absorbers, fluorescent whitening agents, air antifoggants, and the like. The silver halide emulsion layer and/or other constituent layers are coated on the support. Research and application method
The method described in "Coating procedures" in Disclosure, Vol. 176, pages 27-28 can be used. For photographic processing of the light-sensitive material of the present invention, for example, the above-mentioned Research Disclosure, Vol. 176, No. 28
Any of the known color imaging methods can be used, such as those described on pages 30-30. The processing temperature is usually preferably set between 18°C and 60°C. The processing of the color reversal light-sensitive material, which is a preferred embodiment of the present invention, usually involves the following steps: black and white development (first development) → stop → water washing → reversal → water washing → color development → stop → water washing → adjustment bath → water washing → bleaching → water washing The following steps are used: → fixation → washing → stabilization → drying. This step may further include a prebath, a predural bath, a neutralization bath, and the like. Further, water washing after stopping, reversing, color development, conditioning bath or bleaching may be omitted. Reversal may be performed in a fogging bath or by re-exposure.
It is also possible to omit the fogging agent by adding it to the color developing bath. Furthermore, the conditioning bath can also be omitted. Known developing agents can be used in the first developer used in the present invention. Examples of developing agents include dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol), 1-phenyl-3-pyrazoline. 1, described in U.S. Pat. No. 4,067,872,
A heterocyclic compound such as a fused 2,3,4-tetrahydroquinoline ring and an indolene ring can be used alone or in combination. The black and white developer used in the present invention may also include preservatives (e.g., sulfites, bisulfites, etc.), buffers (e.g., carbonates, boric acid, borates,
alkanolamines), alkaline agents (e.g. hydroxides, carbonates), solubilizers (e.g. polyethylene glycols, esters thereof), PH regulators (e.g. organic acids such as acetic acid), sensitizers (e.g. , quaternary ammonium salt), a development accelerator, a surfactant, a toning agent, an antifoaming agent, a hardening agent, a viscosity imparting agent, and the like. The first developer used in the present invention must contain a compound that acts as a silver halide solvent, and the above-mentioned sulfite added as a preservative usually plays this role. Specifically, the sulfite and other usable silver halide solvents include:
_KSCN , _NaSCK , _K2SO3 , _{Na2SO3 , K2S2O5 ,}
Examples include Na ₂ S ₂ O ₅ , K ₂ S ₂ O ₃ and Na ₂ S ₂ O ₃ . If the amount of these silver halide solvents used is too small, the progress of development will be slowed down, and if it is too large, it will cause fogging in the silver halide emulsion, so there is a preferable amount to use, but determining the amount is difficult. can be easily accomplished by a person skilled in the art. For example, when using SCN ^- , per developer
It is preferably 0.005 to 0.02 mol, particularly 0.01 to 0.015 mol, and when SO ^32- is used, 0.05 to 1 mol.
It is preferably mol, especially 0.1 to 0.5 mol. Additionally, antifoggants (e.g. potassium bromide,
halides such as sodium bromide, benzimidazoles, benzotriazoles, benzothiazoles, tetrazoles, thiazoles, etc.),
Chelating agents (eg, ethylenediaminetetraacetic acid, alkali metal salts thereof, polyphosphates, nitriloacetates) can be included. The PH value of the developer thus adjusted is selected to be sufficient to provide the desired density and contrast, and is preferably in the range of about 8.5 to about 11.5. In order to carry out sensitization treatment using such a first developer, it is usually sufficient to extend the time up to about three times as long as the standard treatment. If the treatment temperature is raised at this time, the extension time for the sensitization treatment can be shortened. The fogging bath used in the present invention can contain a known fogging agent. Namely, stannous ion-organophosphoric acid complex salt (U.S. Pat. No. 3,617,282), stannous ion-organophosphonocarboxylic acid complex salt (Japanese Patent Publication No. 1983-32616), and stannous ion-aminopolycarboxylic acid complex salt (British patent). No.
1209050)) and other stannous ion complex salt hydrogenated phosmine compounds (US Pat. No. 2984567).
Heterocyclic amine borane compound (UK Patent No. 1011000)
boron compounds, such as those in the patent specification). The pH of this fogging bath (reversal bath) ranges widely from acidic to alkaline, ranging from PH2 to 12,
It is preferably in the range of 2.5 to 10, particularly preferably 3 to 9. The color developer used in the present invention has the composition of a general color developer containing an aromatic primary amine developing agent. Preferred examples of aromatic primary amine color developing agents are p-phenylenediamine derivatives as shown below. N,N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5-(N-ethyl-N-laurylamino)toluene, 4-[N-ethyl-N
-(β-hydroxyethyl)amino]aniline,
2-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline, N-ethyl-N
-(β-methanesulfamidoethyl)-3-methyl-4-aminoaniline, N-(2-amino-5-
diethylaminophenylethyl) methanesulfonamide, N,N-dimethyl-p-phenylenediamine, 4-amino-3-methyl-N- described in U.S. Pat.
Ethyl-N-methoxyethylalinine, 4-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline and 4-amino-3-methyl-
N-ethyl-N-β-butoxyethylaniline and salts thereof (e.g. sulfate, hydrochloride, sulfite,
p-toluenesulfonate, etc.) are preferred representative examples. The color developer may also contain other known developer component compounds. For example, alkali agents, buffering agents, etc. include caustic soda, caustic potash,
Sodium carbonate, potassium carbonate, tertiary sodium phosphate or potassium, potassium metaphosate, borax, etc. are used alone or in combination. Sulfites (for example, sodium sulfite, potassium sulfite, potassium bisulfite, and sodium bisulfite) and hydroxylamine, which are commonly used as preservatives, can be added to the color developing solution. If necessary, any development accelerator can be added to the color developing solution. For example, US Patent No. 2,648,604,
Various pyridinium compounds and other cationic compounds as typified by Japanese Patent Publication No. 44-9503 and US Pat. No. 3,671,247, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate and potassium nitrate, 44-9504, US Patent No. 2533990, US Patent No. 2531832,
Nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc. described in 2950970 and 2577127;
In addition to the organic solvents and organic amines described in Publication No. 9509 and Belgian Patent No. 682862, such as ethanolamine, ethylenediamine, and diethanolamine, L.
Photographic Processing by FAMAson
P40-43 of Chemistry (Focal Press－London－
(1966) can be used. Furthermore, the color developer contains ethylenediaminetetraacetic acid,
Aminopolycarboxylic acids represented by nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and the like can be included as water softeners. Competing couplers and compensating developers can also be added to the color developer. Citrazic acid, J acid, H acid, etc. are useful as competitive couplers. p-aminopheninol, N as a compensating developer
-benzyl-p-aminophenol, 1-phenyl-3-pyrazolidone, etc. can be used. The pH of the color developer is preferably in the range of about 8-13.
The temperature of the color developing solution is selected within the range of 20°C to 70°C, preferably 30°C to 60°C. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Bleach agents include iron (), cobalt (), chromium (), and copper ().
Compounds of polyvalent metals such as, peracids, quinones, nitrone compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, tartaric acid. , complex salts of organic acids such as malic acid; persulfates, permanganates;
Nitrosophenols and the like can be used.
Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Aminopolycarboxylic acid iron() complexes are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. Bleach or bleach-fix solution has US Patent 3042520
Specification of No. 3241966, Special Publication No. 1985-8506
Various additives can be added, including the bleaching accelerators described in Japanese Patent Publication No. 45-8836 and the like. In the fixing bath of the present invention, ammonium salt, sodium salt, potassium salt of thiosulfate is used as a fixing agent in an amount of about 30 g/l to 200 g/l, and in addition, stabilizing salts such as sulfite and isomeric sulfite are used. hardening agents such as potash alum, PH buffering agents such as acetates, borates, phosphates, carbonates, etc. The pH of the fixer is 3-10, more preferably 5-9. The present invention will be described in detail below with reference to Examples. Example 1 A color reversal photographic material was prepared by coating the first to twelfth layers on a triacetate film base in the following order. First layer; antihalation layer (gelatin layer containing black colloidal silver). Second layer; gelatin middle layer. 2,5-di-t-octylhydroquinone,
A non-chemically sensitized fine-grain emulsion (particle size 0.06μ, iodine Contains 1 mol%
silver iodobromide emulsion) 1Kg with 1.5% gelatin
kg and applied to a dry film thickness of 2μ (silver amount 0.4g/m ² ). 3rd layer; low-sensitivity red-sensitive emulsion layer cyan coupler 2-(heptafluorobutyramide)-5-{2'-(2″,4″-di-t-amylphenoxy)butyramide}-phenonol 100
Dissolve g in 100 c.c. of tricresyl phosphonate and 100 c.c. of ethyl acetate, and add 10% aqueous gelatin solution.
500 g of the emulsion obtained by high-speed stirring with Kg and 1 Kg of red-sensitive silver iodobromide emulsion (containing 70 g of silver, 60 g of gelatin, and iodine content of 6 mol%) was mixed to give a dry film thickness of 1 μm. It was applied to. (Amount of silver: 0.5 g/m ² ) 4th layer: Highly sensitive red-sensitive emulsion layer Cyan coupler 2-(heptafluorobutyramide)-5-{2'-(2″,4″-di-t-amylphenoxy) )Butyramide}-phenol 100g
was dissolved in 100 c.c. of tricresyl phosphate and 100 c.c. of ethyl acetate and stirred at high speed with 1 kg of 10% gelatin aqueous solution. 1000 g of the emulsion obtained was mixed with 1 kg of red-sensitive silver iodobromide emulsion ( Contains 70g of silver, 60g of gelatin, and the iodine content is 6 mol%), and the dry film thickness is
Coated to a thickness of 2.5μ (silver amount 0.8g/m ² ) 5th layer; intermediate layer 2,5-di-t-octylhydroquinone,
1 kg of an emulsion obtained by dissolving 100 c.c. of dibutyl phthalate and 100 c.c. of ethyl acetate and stirring at high speed with 1 kg of an aqueous solution in 10% gelatin is mixed with 1 kg of 10% gelatin to obtain a dry film thickness of 1 μm. It was applied like this. 6th layer; low green sensitivity emulsion layer 1-(2,4,6-trichlorophenyl)-3- which is a magenta coupler instead of a cyan coupler
Emulsion obtained in the same manner as the third layer emulsion except that {3-(2,4-di-t-amylphenoxyacetamide)benzamide}-5-pyrazolone was used
300g, green-sensitive silver iodobromide emulsion 1Kg (70g silver,
The mixture contained 60 g of gelatin (7 mol % iodine content) and was coated to a dry film thickness of 1.3 μm.
(Amount of silver: 1.1 g/m ² ) 7th layer: Highly sensitive green-sensitive emulsion layer 1-(2,4,6-trichlorophenyl)-3- which is a magenta coupler instead of a cyan coupler
Emulsion obtained in the same manner as the third layer emulsion except that pyrazolone made from {3-(2,4-di-t-amylphenoxyacetamide)benzamide}- was used.
1000g of green-sensitive silver iodobromide emulsion (1kg of silver 70g,
The mixture contained 60 g of gelatin (with an iodine content of 6 mol%) and was coated to a dry film thickness of 3.5 μm.
(Amount of silver: 1.1 g/m ² ) 8th layer: Yellow filter layer An emulsion containing yellow colloidal silver was coated to a dry film thickness of 1 μm. 9th layer: Low-sensitivity blue-sensitive emulsion layer Instead of cyan coupler, yellow coupler α-(pivaloyl)-α-(1-benzyl-5-
Ethoxy-3-hydantoynyl)-2-chloro-
1000 g of an emulsion obtained in the same manner as the emulsion of the third layer except that 5-dodecyloxycarbonylacetanilide was used was mixed with 1 kg of blue-sensitive silver iodobromide emulsion (silver
(containing 70 g of gelatin and 60 g of gelatin, 7 mol % iodine content) and coated to a dry film thickness of 1.5 μm. (Amount of silver: 0.4 g/m ² ) 10th layer: Highly sensitive green-sensitive emulsion layer α(pivaloyl)-α-(1-benzyl-5-ethoxy-3-hydantoinyl)-2, which is a yellow coupler instead of the cyan coupler -Chloro-5
- 1 kg of blue-sensitive silver iodobromide emulsion (silver 70
(60 g of gelatin, iodine content: 6 mol %) and coated to a dry film thickness of 3 μm. (Amount of silver: 0.8 g/m ² ) 11th layer: 2nd protective layer 1 kg of the emulsion used in the 3rd layer was mixed with 1 kg of 10% gelatin.
Kg and applied to a dry film thickness of 2 μm. 12th layer; 1st protective layer Fine grain emulsion with a surface covered (grain size
A 10% gelatin aqueous solution containing 0.06μ, 1 mol% silver iodobromide emulsion) was applied at a silver coating amount of 0.1g/m ² and a dry film thickness of 0.8μ.
It was applied so that The spectral sensitization of the red-sensitive emulsion coated on the third layer (low-sensitivity red-sensitivity emulsion layer) and fourth layer (high-sensitivity red-sensitivity emulsion layer) of the sample prepared in this way was determined by the sensitizing dye of the present invention ( B-56). Specify this sample as the sample number
101. Next, a silver bromide cubic emulsion with an average grain size of 0.15μ was prepared by the controlled double-jet method, and a low pAg emulsion was prepared using hydrazine and a gold complex.
After covering the surface of the emulsion with 250Å of silver bromide.
The shell was attached to a thickness of . This emulsion was added to the third layer (low-sensitivity red-sensitivity emulsion layer), and the amount of coated silver was 0.017.
Sample 102 was prepared in the same manner as Sample 101, except that the coating was applied so as to give a coating weight of g/m ² . Also, instead of dye (B-56), dye (B-60), (B-64)
Samples 103 and 104 were prepared in the same manner as sample 102, except that . Next, in order to compare the performance with the sensitizing dye of the present invention, a comparative dye represented by the structural formula below was used in the third layer (low red-sensitive emulsion) instead of the sensitizing dye (B-56) of the present invention. Sample 105 was prepared in the same manner as Sample 102, except that it was used for the layer). The obtained sample was exposed to a light source of 4800 〓, and the illuminance of the exposed surface was
Color images were obtained by exposure through a sensitometric wedge with white light at 1000 lux, followed by inversion standard processing and inversion sensitization processing as described below. The treatment steps and treatment liquid used here are as follows. Standard processing process Process Time Temperature First development 6 minutes 38℃ Washing 2 minutes Inversion 2 minutes 38℃ Color development 6 minutes Adjustment 2 minutes Bleaching 6 minutes Fixing 4 minutes Washing 4 minutes Safe Fixing 1 minute Room temperature Drying Drying sensitization process Process Time Temperature First development 10 minutes 38℃ Washing 2 minutes Inversion 2 minutes Color development 6 minutes Adjustment 2 minutes Bleaching 6 minutes Fixing 4 minutes Wash with water 4 minutes Stability 1 minute Dry at room temperature The following composition of the treatment liquid is used. First developer water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-phenyl 4-methyl 4-hydroxymethyl-3-pyrazolidone 2g Potassium bromide 2.5g Thiocyanide Potassium acid 1.2g Potassium iodide (0.1% solution) 2ml Add water to 1000ml (PH10.1) Reverse liquid water 700ml Nitro-N-N-N-trimethylenephosphonic acid 6Na salt 3g Stannous chloride (diwater) Salt) 1g p-aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid 15ml Add water 1000ml color developer water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 7g Sodium triphosphate (12 hydrate) 36g Potassium bromide 1g Iodine Potassium chloride (0.1% solution) 90ml Potassium hydroxide 3g Citrazic acid 1.5g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 11g Ethylenediamine 3g Add water 1000ml adjustment solution Water 700ml Sodium sulfite 12g Ethylenediamine, sodium tetraacetate (2
8g Thioglycerin 0.4ml Glacial acetic acid 3ml Add water 1000ml Bleach water 800g Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Ammonium ethylenediaminetetraacetate (dihydrate) 120.0g Potassium bromide 100.0g Add water to 1000ml fixing solution Water 800ml Ammonium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water 1000ml Stable solution water 800ml Formalin (37% by weight) 5.0ml Fuji Drywell 5.0ml Add water to obtain 1000ml The optical density of the cyan image of the obtained sample was measured through a red filter, and the sensitization developability was evaluated. From the characteristic curve, the sensitivity was expressed as the reciprocal of the exposure amount required to obtain a constant cyan density (D=1.00). The results obtained are shown in Table-1. From Table 1, the sample (sample number 102) in which an emulsion with internal fog nuclei was added to the low red-sensitivity emulsion layer was:
It can be seen that the increase in sensitivity when subjected to sensitization development processing is greater (2.7 to 3 times that of standard processing) compared to the sample without additives (sample number 201). However, when a sensitizing dye other than the present invention is used for spectral sensitization in an emulsion layer to which the emulsion is added and/or an emulsion layer adjacent to the layer to which the emulsion is added, the It was found that the maximum concentration decreased significantly. For example, in sample 105 using the comparative dye,
It can be seen that the maximum density during sensitization and development processing is extremely low. On the other hand, it can be seen that Samples 102 to 104 using the sensitizing dyes of the present invention can achieve sufficient sensitization with less decrease in maximum density when subjected to sensitization and development.

[Table] Example 2 Sample 201 was prepared in the same manner as Sample 101 of Example 1. Next, an emulsion having the same internal fog nuclei as that used in Example 1 was added to the ninth layer (low-sensitivity blue-sensitive emulsion layer) of Example 1, and the amount of coated silver was 0.012.
Sample 202 was prepared in the same manner as Sample 201, except that the coating was applied so as to give a coating weight of 1.5 g/m ² . Sample 201 and
The sensitizing dye (A-9) of the present invention was added to the 9th layer (low-sensitivity blue-sensitive emulsion layer) and the 10th layer (high-sensitivity blue-sensitive emulsion layer) of No. 202. Next, in order to compare the performance with the sensitizing dye (A-9) of the present invention, a comparison dye represented by the following structural formula was used in the ninth layer (low-sensitizing emulsion) instead of the sensitizing dye (A-9). Sample 203 was prepared in the same manner as Sample 202, except that it was used as a layer). The sample thus obtained was exposed and developed in the same manner as in Example 1 to obtain a color image. The optical density of the yellow image of the obtained sample was measured through a blue filter, and the sensitization developability was evaluated. Constant concentration (D=1.00) from the characteristic curve
Sensitivity is also expressed as the reciprocal of the exposure amount required to obtain a yellow density of . The results obtained are shown in Table-2. From Table 2, sample 202, in which the sensitizing dye of the present invention was used in combination with an emulsion having internally fogged nuclei,
It can be seen that sufficient sensitization can be achieved with less decrease in the maximum density when sensitized and developed in the same manner as in Example 1.

【table】

Claims (1)

[Scope of Claims] 1. A color reversal photograph having at least two emulsion layers having the same color sensitivity but different sensitivities, each having one or more red-sensitive, green-sensitive, and blue-sensitive emulsion layers on a support. In the light-sensitive material, the lower-sensitivity emulsion layer of the at least two emulsion layers combines a light-sensitive silver halide emulsion and a methine dye having neither a carboxyl group nor a sulfo group on a carbon atom of a heterocyclic nucleus. A color reversal photographic light-sensitive material characterized in that a silver halide emulsion having internal fog nuclei is contained in the lower-sensitivity emulsion layer and/or the non-light-sensitive emulsion layer adjacent thereto. . 2. The silver halide emulsion having a fogged core inside is composed of core-shell type silver halide grains consisting of a silver halide inner core with a fogged surface and a silver halide outer shell covering the surface. The color reversal photographic material according to claim 1, which is an emulsion.