Compound, functional material, and silver halide photographic sensitive material

Abstract

The present invention pertains to: a compound represented by general formula (1); a functional material having a layer containing the compound represented by general formula (1) as a dye; and a silver halide photographic sensitive material.　In general formula (1), A represents a phenyl group or a chlorine atom, R1 and R2 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an aryl group, or a heteroaryl group, R3 represents a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an aryl group, or a heteroaryl group, and one of R1 and R2 has a sulfonic acid group and the other does not have a sulfonic acid group or a carboxylic acid group.

Description

Compounds, functional materials, and silver halide photographic photosensitive materials

[0001] This disclosure relates to compounds, functional materials, and photographic photosensitive materials of silver halide.

[0002] Conventionally, in spectral sensitization techniques for silver halide photographic materials, various sensitizing dyes have been added to improve spectral sensitivity.

[0003] As a spectrally sensitized silver halide photographic emulsion with high green sensitivity, a silver halide photographic emulsion containing at least two types of sensitizing dyes is known (see Patent Document 1 or Patent Document 2). Furthermore, as a silver halide color photographic photosensitive material for motion pictures with a simple development process, in a silver halide color photographic photosensitive material for motion pictures with a specific layer structure, it is known that each of the blue-sensitive silver halide emulsion, red-sensitive silver halide emulsion, and green-sensitive silver halide emulsion contains multiple sensitizing dyes (see Patent Document 3, Examples).

[0004] Patent Document 1: Japanese Unexamined Patent Publication No. 59-188641 Patent Document 2: Japanese Unexamined Patent Publication No. 60-108838 Patent Document 3: Japanese Unexamined Patent Publication No. 2007-264269

[0005] In silver halide photographic photosensitive materials, there is a need for sensitizing dyes that offer superior photographic performance, including photographic sensitivity and color reproduction.

[0006] This disclosure has been made in view of the circumstances described above. One of the problems that one embodiment of this disclosure aims to solve is to provide a novel compound. Another of the problems that one embodiment of this disclosure aims to solve is to provide a functional material or silver halide photographic photosensitive material that is excellent in sensitivity and color reproduction and excellent in storage stability.

[0007] The following embodiments are specific means for solving the above problems: <1> A compound represented by general formula (1).

[0008]

[0009] In general formula (1), A represents a phenyl group or a chlorine atom, and R １ and R ２each independently represents a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an aryl group, or a heteroaryl group, and R ３ represents a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an aryl group, or a heteroaryl group, and R １ and R ２ one of them has one sulfonic acid group, and the other has neither a sulfonic acid group nor a carboxylic acid group. <2> The compound according to <1>, wherein A in General Formula (1) represents a phenyl group. <3> The compound according to <1> or <2>, which is a dye. <4> A functional material having a layer containing the compound according to any one of <1> to <3>. <5> A silver halide photographic light-sensitive material having a layer containing the compound according to any one of <1> to <3>. <6> The silver halide photographic light-sensitive material according to <5>, wherein the layer further contains a dye represented by General Formula (2).

[0010]

[0011] In General Formula (2), R ４ and R ５ each independently represents a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an aryl group, or a heteroaryl group, and R ６ represents an alkyl group having 4 or less carbon atoms, and X １ and X ４ each independently represents a hydrogen atom, an alkyl group, or a chlorine atom, and X ２ and X ５ each independently represents an alkyl group having 4 or less carbon atoms, an alkoxy group, a halogen atom, a hydrogen atom, a hydroxy group, or a phenyl group, and X １ and X ２ , or X ４ and X ５ may be linked to each other to form a benzene ring, X ３ is linked to X ２ to form a benzene ring, or is a hydrogen atom, and X ６ is linked to X ５ to form a benzene ring, or is a hydrogen atom. <7> In General Formula (2), X １ , X ３ , X ４ , and X ６ each represent a hydrogen atom, and X２ and X ５ <6> represents a phenyl group, respectively, as described in the silver halide photographic photosensitive material. <8> The layer containing the compound is a silver halide photographic photosensitive material according to <6> or <7>, wherein the amount of dye represented by general formula (2) used is 0.1 to 1.0 times by mass compared to the amount of compound represented by general formula (1). <9> A diffusion transfer type silver halide photographic photosensitive material according to any one of <5> to <8>.

[0012] According to one embodiment of the present disclosure, a novel compound is provided. Furthermore, according to one embodiment of the present disclosure, a functional material or silver halide photographic photosensitive material is provided that is excellent in sensitivity and color reproduction and has excellent storage stability.

[0013] The following provides a detailed description of this disclosure. While the requirements described below may be based on typical embodiments of this disclosure, this disclosure is not limited to such embodiments and may be modified as appropriate within the scope of the purposes of this disclosure.

[0014] In this disclosure, a numerical range indicated using "~" means a range that includes the numerical values ​​before and after "~" as the lower and upper limits, respectively. In numerical ranges described in stages in this disclosure, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described in this disclosure, the upper or lower limit stated in one numerical range may be replaced with the values ​​shown in the examples.

[0015] In this disclosure, when referring to the amount of each component in a composition, if there are multiple substances corresponding to each component in the composition, it means the total amount of all multiple components present in the composition unless otherwise specified.

[0016] In this disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

[0017] In this disclosure, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as their intended purpose is achieved.

[0018] In this disclosure, "transparent" means that the average transmittance of visible light with wavelengths of 400 nm to 700 nm is 80% or more, and preferably 90% or more. In this disclosure, "transmittance" is a value measured using a spectrophotometer. As a spectrophotometer, for example, a spectrophotometer manufactured by Hitachi, Ltd. (model number: U-3310) can be used. However, the spectrophotometer is not limited to this.

[0019] In this disclosure, unless otherwise specified, the weight-average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC). The GPC measurement is the polystyrene-converted value measured by a GPC analyzer using TSKgel® GMHxL, TSKgel® G4000HxL, or TSKgel® G2000HxL (all product names of Tosoh Corporation) as the column, tetrahydrofuran (THF) as the eluent, a differential refractometer as the detector, and polystyrene as the standard substance.

[0020] In this disclosure, "solvent" means water and organic solvents.

[0021] In this disclosure, "n-" means normal, "s-" means secondary, and "t-" means tertiary.

[0022] In this disclosure, “light” means, for example, ultraviolet light, visible light, and infrared light. In this disclosure, “ultraviolet light” means light in the wavelength range of 200 nm to less than 400 nm, “visible light” means light in the wavelength range of 400 nm to less than 780 nm, and “infrared light” means light in the wavelength range of 780 nm to less than 1000 nm.

[0023] [Compound] The compound relating to this disclosure is a compound represented by general formula (1).

[0024]

[0025] In general formula (1), A represents a phenyl group or a chlorine atom, and R １ and R ２ Each of these independently represents a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an aryl group, or a heteroaryl group, and R ３ R represents a hydrogen atom, alkyl group, aralkyl group, alkenyl group, aryl group, or heteroaryl group. １ and R ２ One of them has one sulfonic acid group, while the other does not have a sulfonic acid group or a carboxylic acid group.

[0026] The compound relating to this disclosure has a betaine-type structure represented by the above formula (1), and A, R １ , R ２ This is a novel compound characterized by a combination of five groups: Cl and CN, and can be used as a sensitizing dye. For example, when the compound according to this disclosure is used as a sensitizing dye in a photographic photosensitive material, it results in a photographic photosensitive material with excellent photographic sensitivity and color reproducibility, as well as high storage stability. Furthermore, when a mixture of the sensitizing dye compound according to this disclosure and another type of sensitizing dye compound different from the compound according to this disclosure is used as a sensitizing dye, it also results in a photographic photosensitive material with even better photographic sensitivity and color reproducibility, as well as high storage stability. This is presumed to be because the compound according to the present invention can suppress interactions with other types of sensitizing dye compounds and form a chemically stable, homogeneous mixture.

[0027] In formula (1), A may be either a phenyl group or a chlorine atom, but it is preferable that A represents a phenyl group.

[0028] R in equation (1) １ and R ２ The alkyl group represented by R may be linear, branched, or cyclic. １ and R ２ The alkyl group represented by is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 5 carbon atoms. １ and R ２Examples of alkyl groups represented by include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decylcyclopropyl, cyclopentyl, cyclohexyl, and 1-norbornyl groups. From the viewpoint of sensitivity and color reproducibility, linear alkyl groups having 1 to 5 carbon atoms are more preferred.

[0029] R in equation (1) １ and R ２ The aralkyl group represented by is preferably an aralkyl group having 6 to 18 carbon atoms. １ and R ２ The alkyl group in the aralkyl group represented by includes, for example, an alkyl group having a linear or branched alkyl chain with 1 to 4 carbon atoms. In this disclosure, R １ and R ２ The aralkyl group represented by includes alkenyl groups such as vinyl groups. １ and R ２ The aryl group in the aralkyl group represented by R is, for example, a phenyl group. １ and R ２ Examples of aralkyl groups represented by R include the benzyl group and the styryl group. １ and R ２ From the viewpoint of sensitivity and color reproducibility, the benzyl group is preferred as the aralkyl group represented by .

[0030] R in equation (1) １ and R ２ The alkenyl group represented by can be either linear or branched. In formula (1), R １ and R ２ The alkenyl group represented by is preferably an alkenyl group having 6 to 12 carbon atoms, and more preferably an alkenyl group having 2 to 8 carbon atoms. １ and R ２ Examples of alkenyl groups represented by include vinyl groups, allyl groups, or 3-buten-1-yl groups.

[0031] R in equation (1) １ and R ２The aryl group represented by may have a single aromatic ring or multiple aromatic rings. １ and R ２ The aryl group represented by is preferably an aryl group having 6 to 18 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. １ and R ２ Examples of aryl groups represented by this include the phenyl group and the naphthyl group.

[0032] R in equation (1) １ and R ２ The heteroaryl group represented by may be a monocyclic heteroaryl group, a bicyclic or complex-ring heteroaryl group, or a polycyclic heteroaryl group. A complex-ring heteroaryl group refers to a structure in which at least two or more aromatic rings are bonded adjacent to each other and share common atoms (usually two or more), such as quinoline, indole, benzimidazole, and benzotriazole. １ and R ２ The heteroaryl group represented by is preferably a heteroaryl group having 1 to 18 carbon atoms, and more preferably a heteroaryl group having 1 to 8 carbon atoms. １ and R ２ Examples of heteroaryl groups represented by include 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, and benzotriazole-1-yl group.

[0033] R in equation (1) １ and R ２ The alkyl group, aralkyl group, alkenyl group, aryl group, or heteroaryl group represented by may each have substituents. Examples of substituents include sulfo groups (including sulfonic acid groups), carboxyl groups (i.e., carboxylic acid groups), cyano groups, halogen atoms, hydroxyl groups, alkoxycarbonyl groups, alkoxy groups, aryloxy groups, acyloxy groups, acyl groups, carbamoyl groups, sulfamoyl groups, and aryl groups.

[0034] R in equation (1) １ and R２ Each of the substituents may be independently substituted with one or more substituents in combination. １ and R ２ The substituents on each of them may be the same or different.

[0035] Examples of substituent halogen atoms include fluorine, chlorine, and bromine atoms. The substituent alkoxycarbonyl group is preferably a carbon-2 to carbon-12 alkoxycarbonyl group, such as a methoxycarbonyl group, ethoxycarbonyl group, or benzyloxycarbonyl group. The substituent alkoxy group is preferably a carbon-1 to carbon-12 alkoxy group, such as a methoxy group, ethoxy group, propoxy group, 1-butoxy group, 2-butoxy group, or benzyloxy group. Examples of substituent aryloxy groups include phenoxy group, 1-naphthoxy group, and p-tolyloxy group. Examples of substituent acyloxy groups include acetyloxy group, propionyloxy group, and pivaloyloxy group. The substituent acyl group is preferably a carbon-1 to carbon-12 acyl group, such as an acetyl group, propionyl group, benzoyl group, or mesyl group (i.e., methanesulfonyl group). The substituted carbamoyl group is preferably a carbamoyl group having 1 to 12 carbon atoms, for example, a carbamoyl group, N,N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, morpholinocarbamoyl group, or piperidinocarbamoyl group. The substituted sulfamoyl group is preferably a sulfamoyl group having 1 to 12 carbon atoms, for example, a sulfamoyl group, N,N-dimethylsulfamoyl group, N-ethyl-N-octylsulfamoyl group, morpholinosulfonyl group, or piperidinosulfonyl group. The substituted aryl group is preferably an aryl group having 6 to 24 carbon atoms, for example, a phenyl group, naphthyl group, or p-sulfophenyl group.

[0036] R in equation (1) １ and R ２each is preferably a hydrogen atom, an alkyl group, an aralkyl group, or an alkenyl group, particularly from the viewpoints of sensitivity, color reproducibility and synthesis suitability.

[0037] In R in formula (1) １ and R ２ , one of R １ and R ２ has one sulfonic acid group, and the other has no sulfonic acid group or carboxylic acid group. Any of R １ and R ２ may have a sulfonic acid group. For example, when R １ has a sulfonic acid group, R ２ does not have a sulfonic acid group or a carboxylic acid group. In this case, R ２ may have a substituent other than a sulfonic acid group or a carboxylic acid group. Alternatively, when R ２ has a sulfonic acid group, R １ does not have a sulfonic acid group or a carboxylic acid group. In this case, R １ may have a substituent other than a sulfonic acid group or a carboxylic acid group.

[0038] Each of the alkyl group, aralkyl group, alkenyl group, aryl group, or heteroaryl group represented by R ３ in formula (1) is the same as described above for R １ and R ２ respectively.

[0039] When the compound represented by formula (1) is used as a sensitizing dye, it is presumed that λmax is sharply localized in the green region due to the intramolecular conjugated system, thereby maximizing the selective absorption for the green photosensitive layer. It is also presumed that the introduction of a substituent provides steric protection so that intermolecular interactions are suppressed. Therefore, when mixed with other types of sensitizing dyes, unnecessary complexes, aggregation and the like between molecules are less likely to occur, each sensitizing dye acts cooperatively while maintaining its respective spectral characteristics, and when used as a mixture, the selective absorption characteristics and photosensitivity in the green photosensitive layer are not impaired, and the effect can be exhibited synergistically.

[0040] Furthermore, the compound represented by formula (1), being a betaine rather than an anionic compound, is presumed to enable molecular stabilization through internal ion pairs, enhanced hydrophobicity, and control of interactions with other sensitizing dyes. In the betaine structure, strong ion pairs are formed internally, and this internal stabilization effect suppresses oxidation and decomposition by moisture from the outside, thereby improving storage stability. In addition, sensitivity reduction and fogging after development and during long-term storage can be suppressed. Moreover, it is presumed that the charge interactions within the molecule give the entire molecule a certain degree of steric stability and facilitate the formation of hydrophobic domains around it. This is presumed to enable efficient adsorption in the emulsion or on the surface of silver halide particles, contributing to the optimization of the spectral sensitization effect. Therefore, when the compound represented by formula (1) is used as a sensitizing dye, the storage stability of the photographic material is improved, and high photographic performance can be maintained over a long period of time in practical use.

[0041] Furthermore, the above effects are not achieved simply by using a betaine-type compound. It is presumed that in the compound represented by formula (1), the selective absorption of the green photosensitive layer is maximized and the extinction coefficient is improved by the appropriate construction of the intramolecular conjugated system. In addition, it is presumed that in the compound represented by formula (1), the electron density and oxidation potential of the molecule are adjusted by electron-withdrawing or electron-donating substituents, resulting in a high sensitization effect in a narrow band. Moreover, as mentioned above, it is presumed that in the compound represented by formula (1), intermolecular interactions are suppressed due to the three-dimensional structure of the molecule, maintaining a more uniform mixing state with other sensitizing dyes. As a result, even when mixing multiple sensitizing dyes, the spectral characteristics of each sensitizing dye are effectively expressed, making it possible to improve the overall photographic performance.

[0042] As described above, the compound relating to this disclosure is preferably a compound represented by formula (1-1), in which A is a phenyl group, from the viewpoint of sensitivity, color reproducibility, and storage stability.

[0043]

[0044] In equation (1-1), R １ , R ２ and R ３, in the above, R in formula (1) １ , R ２ and R ３ are the same as those described above, respectively.

[0045] Specific examples of the compounds according to the present disclosure, compounds (A-1) to (A-56), are shown below respectively. The compounds according to the present disclosure are not limited to the following specific examples.

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054] The compound according to the present disclosure is preferably a dye. The compound according to the present disclosure has favorable properties as a dye. In particular, when a functional material including a silver halide photographic light-sensitive material is provided with a layer containing the compound according to the present disclosure, a functional material or silver halide photographic light-sensitive material excellent in photographic sensitivity, color reproducibility and storage stability can be obtained.

[0055] The compound represented by formula (1) can be synthesized based on the methods described in Japanese Patent Publication No. 2-52252, “Heterocyclic compounds - Cyanine dyes and related compounds,” chapter V, pages 116-147, by F.M. Hamer, published by John Wiley & Sons (New York, London) in 1964, and “Heterocyclic Compounds - Special topics in heterocyclic chemistry,” chapter VIII, section IV, pages 482-515, by D.M. Turmer, published by John Wiley & Sons (New York, London) in 1977.

[0056] [Functional Material] The functional material according to this disclosure has a layer containing a compound represented by formula (1). Preferably, the functional material according to this disclosure has a support and a layer on the support containing a compound represented by general formula (1) (i.e., the compound according to this disclosure).

[0057] The functional materials relating to this disclosure are not particularly limited as long as they have a layer containing the compound relating to this disclosure on a support, but other functional films that require light absorption characteristics in a specific wavelength range are preferably mentioned, such as silver halide photographic photosensitive materials, diffusion transfer type silver halide photographic photosensitive materials, and X-ray photosensitive materials such as intensifying screens, as described later. In particular, with silver halide photographic photosensitive materials, having a layer containing the compound relating to this disclosure allows for selective absorption of light energy in the green photosensitive layer, improving exposure efficiency and gradation reproduction. This increases sensitivity (i.e., responsiveness to exposure), provides accurate color reproduction, and enables the realization of high-quality images overall. Furthermore, with diffusion transfer type silver halide photographic photosensitive materials, having a layer containing the compound relating to this disclosure allows for high photosensitivity and rich gradation during development after exposure, and the photosensitive characteristics do not deteriorate easily during storage, contributing to improved stability and color reproduction of the transferred image. Other specific examples of functional materials include dye-sensitized solar cell materials.

[0058] [Silver Halogen Photosensitive Material] The silver halogen photosensitive material according to this disclosure has a layer containing a compound represented by formula (1) (i.e., the compound according to this disclosure). The silver halogen photosensitive material according to this disclosure has at least one photosensitive layer provided on a support. The silver halogen photosensitive material according to this disclosure preferably includes a layer containing the compound according to this disclosure as a photosensitive layer that is sensitive to green light.

[0059] The silver halide photographic photosensitive material according to this disclosure only requires that at least one photosensitive layer be provided on a support. A typical example is a silver halide photographic photosensitive material having at least one photosensitive layer on a support, which consists of multiple silver halide emulsion layers that are substantially the same in color sensitivity but have different degrees of photosensitivity. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic photosensitive material, the unit photosensitive layers are generally arranged in the order of red-sensitive layer, green-sensitive layer, and blue-sensitive layer from the support side. However, the above arrangement order may be reversed depending on the purpose, or an arrangement order in which different photosensitive layers are sandwiched between the same color-sensitive layers may be adopted. Non-photosensitive layers may be provided between the above silver halide photosensitive layers and at the top and bottom layers. These may include couplers, DIR compounds, color mixing inhibitors, etc., as described later. It is preferable that the multiple silver halide emulsion layers constituting each unit photosensitive layer consist of two layers, a high-sensitivity emulsion layer and a low-sensitivity emulsion layer, arranged such that the photosensitivity decreases sequentially toward the support, as described in DE1,121,470 or GB923,045. Alternatively, as described in Japanese Patent Publication Nos. 57-112751, 62-200350, 62-206541, and 62-206543, the low-sensitivity emulsion layer may be placed on the side further away from the support and the high-sensitivity emulsion layer on the side closer to the support.

[0060] As a specific example, the layers can be arranged from the side furthest from the support in the following order: low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL); BH / BL / GL / GH / RH / RL; or BH / BL / GH / GL / RL / RH.

[0061] Furthermore, as described in Japanese Patent Publication No. 55-34932, the layers can also be arranged in the order of blue photosensitive layer / GH / RH / GL / RL from the side furthest from the support. Also, as described in Japanese Patent Publication Nos. 56-25738 and 62-63936, the layers can also be arranged in the order of blue photosensitive layer / GL / RL / GH / RH from the side furthest from the support. Another arrangement, as described in Japanese Patent Publication No. 49-15495, is one in which the upper layer is a silver halide emulsion layer with the highest photosensitivity, the middle layer is a silver halide emulsion layer with a lower photosensitivity, and the lower layer is a silver halide emulsion layer with an even lower photosensitivity than the middle layer, resulting in an arrangement consisting of three layers with progressively lower photosensitivity towards the support. Even when composed of three layers with different photosensitivity, as described in Japanese Patent Publication No. 59-202464, the medium-sensitivity emulsion layer, the high-sensitivity emulsion layer, and the low-sensitivity emulsion layer may be arranged in the same color-sensitive layer from the side furthest from the support.

[0062] In addition, the layers may be arranged in the order of high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer, or low-sensitivity emulsion layer / medium-sensitivity emulsion layer / high-sensitivity emulsion layer. Furthermore, the arrangement may be changed as described above even when there are four or more layers. To improve color reproducibility, it is preferable to arrange a donor layer (CL) with a layering effect that has a different spectral sensitivity distribution from the main photosensitive layers such as BL, GL, and RL adjacent to or near the main photosensitive layer, as described in U.S. Patent No. 4,663,271, 4,705,744, 4,707,436, Japanese Patent Publication No. 62-160448, and Japanese Patent Publication No. 63-89850.

[0063] Preferred silver halides used in this disclosure are silver iobromide, silver iodide chloride, or silver iodide bromide containing about 30 mol% or less of silver iodide. Particularly preferred are silver iobromide or silver iodide bromide containing about 2 mol% to about 10 mol% of silver iodide.

[0064] The silver halide particles in the photographic emulsion may have regular crystal structures such as cubes, octahedra, or tetrahedra, irregular crystal shapes such as spheres or plates, crystal defects such as twin planes, or composite forms thereof. The particle size of the silver halide may range from particles of approximately 0.2 μm or less to large particles with a projected area diameter of up to approximately 10 μm, and the emulsion may be polydisperse or monodisperse.

[0065] Silver halide photographic emulsions that can be used in this disclosure are, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pp. 22-23, “I. Emulsion preparation and types,” and Research Disclosure No. 18716 (November 1979), p. 648, Research Disclosure No. 307105 (November 1989), pp. 863-865, "Physics and Chemistry of Photography" by Glafkides, published by Paul Montel (P. Glafkides, Chemistry et Physique Photographes, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffin, Photograph Emulsion Chemistry, Focal Press, 1966), "Making and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V.L. Zelikman, et al., Making and Coating Photographic Emulsions) It can be prepared using the methods described in Emulsion, Focal Press, 1964, etc.

[0066] Monodisperse emulsions described in U.S. Patent No. 3,574,628, No. 3,655,394, and GB1,413,748 are also preferred. Furthermore, plate-like particles with an aspect ratio of approximately 3 or more can also be used in this disclosure. Particularly for improved shelf life, an emulsion can be used in which 50% or more of the total projected area is occupied by silver halide plate particles with an aspect ratio of 8 or more. There is no particular upper limit to the aspect ratio, but 30 or less is preferred. Plate-like particles can be easily prepared by the methods described in Gutoff, *Photographic Science and Engineering*, Vol. 14, pp. 248-257 (1970); U.S. Patents No. 4,434,226, 4,414,310, 4,433,048, 4,439,520 and GB2,112,157.

[0067] The crystal structure may be uniform, or it may consist of halogen compositions that differ between the interior and exterior, or it may have a layered structure. Silver halides of different compositions may be joined by epitaxial bonding, or they may be joined with compounds other than silver halides, such as silver rhodane or lead oxide. A mixture of particles of various crystal forms may also be used.

[0068] The above emulsion may be a surface latent image type that primarily forms latent images on the surface, an internal latent image type that forms latent images inside the particles, or a type that has latent images on both the surface and inside, but it must be a negative type emulsion. Among the internal latent image types, it may be a core / shell type internal latent image emulsion as described in Japanese Patent Publication No. 63-264740, and the preparation method for this is described in Japanese Patent Publication No. 59-133542. The thickness of the shell of this emulsion varies depending on the development process, but is preferably 3 nm to 40 nm, and particularly preferably 5 nm to 20 nm.

[0069] Silver halide emulsions are typically used after physical maturation, chemical maturation, and spectral sensitization. Additives used in these processes are described in RD No. 17643, No. 18716, and No. 307105, and the relevant sections are summarized in the table below.

[0070] The silver halide photographic photosensitive material according to this disclosure can be used by mixing two or more emulsions in the same layer, each having at least one different characteristic of the photosensitive silver halide emulsion: particle size, particle size distribution, halogen composition, particle shape, and sensitivity. It is preferable to apply silver halide particles with a surface coating as described in U.S. Patent No. 4,082,553, silver halide particles with an internal coating as described in U.S. Patent No. 4,626,498 and Japanese Patent Publication No. 59-214852, or colloidal silver, to the photosensitive silver halide emulsion layer and / or a substantially non-photosensitive hydrophilic colloid layer. Silver halide particles with an internal or surface coating refer to silver halide particles that can be developed uniformly (i.e., non-image-like) regardless of whether the photosensitive material is unexposed or exposed, and the method for preparing them is described in U.S. Patent No. 4,626,498 and Japanese Patent Publication No. 59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide particles, which have their interiors coated, may have different halogen compositions. Any of the silver halides that can be used to coat the inside or surface of the particles can be silver chloride, silver bromide, silver iodide, or silver iodide. The average particle size of these coated silver halide particles is preferably 0.01 μm to 0.75 μm, and particularly preferably 0.05 μm to 0.6 μm. The particle shape may be regular particles or a polydisperse emulsion, but it is preferable that it be monodisperse (for example, at least 95% of the mass or number of silver halide particles have a particle size within ±40% of the average particle diameter).

[0071] In this disclosure, it is preferable to use non-photosensitive particulate silver halide. Non-photosensitive particulate silver halide refers to silver halide particles that are not photosensitive during image exposure to obtain a dye image and are substantially undeveloped during the development process, and it is preferable that they are not pre-coated. The particulate silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferably, it contains 0.5 to 10 mol% silver iodide. The particulate silver halide has an average particle size (i.e., the average value of the circular diameter of the projected area) of 0.01 μm to 0.5 μm, and more preferably 0.02 μm to 0.2 μm.

[0072] Particulate silver halides can be prepared in the same manner as ordinary photosensitive silver halides. The surface of the silver halide particles does not need to be optically sensitized, nor is spectral sensitization required. However, it is preferable to add a known stabilizer such as a triazole, azaindene, benzothiazolium, or mercapto compound or a zinc compound before adding it to the coating solution. Colloidal silver can be incorporated into this particulate silver halide particle-containing layer.

[0073] The amount of silver coating in the silver halide photographic photosensitive material related to this disclosure is 6.0 g / m². ２ The following is preferable: 4.5 g / m ２ The following are preferable.

[0074] The photographic additives that can be used in this disclosure are also listed in the RD, and the relevant sections are shown in Table 1 below.

[0075]

[0076] Various dye-forming couplers can be used in the silver halide photographic photosensitive material relating to this disclosure, but the following couplers are particularly preferred: Yellow coupler: Coupler represented by formulas (I) and (II) of EP 502,424A; Coupler represented by formulas (1) and (2) of EP 513,496A (especially Y-28 on page 18); Coupler represented by formula (I) of claim 1 of EP 568,037A; Coupler represented by general formula (I) of rows 45-55 of column 1 of U.S. Patent No. 5,066,576; General formula (I) of paragraph 0008 of Japanese Patent Application Publication No. 4-274425 Couplers represented by; couplers described in claim 1 on page 40 of EP 498,381A1 (especially D-35 on page 18); couplers represented by formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y-54 (page 41)); couplers represented by formulas (II) to (IV) in rows 36-58 of column 7 of U.S. Patent No. 4,476,219 (especially II-17, 19 (column 17), II-24 (column 19)).

[0077] Magenta coupler; Japanese Patent Publication No. 3-39737 (L-57 (page 11, bottom right), L-68 (page 12, bottom right), L-77 (page 13, bottom right); A-4-63 (page 134), A-4-73, -75 (page 139) of EP456, 257; M-4, -6 (page 26), M-7 (page 27) of EP486, 965; M-45 (page 19) of EP571, 959A; (M-1) (page 6) of Japanese Patent Publication No. 5-204106; M-22 of paragraph 0237 of Japanese Patent Publication No. 4-362631.

[0078] Cyan coupler: CX-1, 3, 4, 5, 11, 12, 14, 15 (pages 14-16) of Japanese Patent Publication No. 4-204843; C-7, 10 (page 35), 34, 35 (page 37), (I-1), (I-17) (pages 42-43) of Japanese Patent Publication No. 4-43345; a coupler represented by general formula (Ia) or (Ib) of claim 1 of Japanese Patent Publication No. 6-67385.

[0079] Polymer coupler: Pages P-1, P-5 (page 11) of Japanese Patent Publication No. 2-44345. As a coupler in which the color-developing dye has appropriate diffusivity, those described in U.S. Patent No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,873B, and German Patent No. 3,234,533 are preferred.

[0080] Preferred couplers for correcting unwanted absorption of colorants are the yellow colored cyan couplers represented by formulas (CI), (CII), (CIII), and (CIV) described on page 5 of European Patent Application Publication No. 456,257A1 (especially YC-86 on page 84), the yellow colored magenta couplers ExM-7 (page 202), EX-1 (page 249), and EX-7 (page 251) described on European Patent Application Publication No. 456,257A1, the magenta colored cyan couplers CC-9 (column 8) and CC-13 (column 10) described on U.S. Patent No. 4,833,069, (2) (column 8) of U.S. Patent No. 4,837,136, and the colorless masking couplers represented by formula (A) of claim 1 of International Publication No. 92 / 11575 (especially the exemplary compounds on pages 36-45).

[0081] Examples of couplers that release photogenically useful groups include: Development inhibitor-releasing compounds: Compounds represented by formulas (I), (II), (III), and (IV) described on page 11 of European Patent Application Publication No. 378,236A1 (especially T-101 (page 30), T-104 (page 31), T-113 (page 36), T-131 (page 45), T-144 (page 51), and T-158 (page 58)), and compound represented by formula (I) described on page 7 of European Patent Application Publication No. 436,938A2 (especially D-49 (page 51)), and European Patent Application Publication Compounds represented by formula (1) in Publication No. 568,037A (especially (23) (page 11)), compounds represented by formulas (I), (II), (III) described on pages 5-6 of European Patent Application Publication No. 440,195A2 (especially I-(1) on page 29); bleach accelerator-releasing compounds: compounds represented by formulas (I), (I') on page 5 of European Patent Application Publication No. 310,125A2 (especially (60), (61) on page 61), and claim 1 of Japanese Patent Application Publication No. Hei 6-59411 Compounds represented by formula (I) (especially (7) (page 7); Ligand-releasing compounds: Compounds represented by LIG-X as described in claim 1 of U.S. Patent No. 4,555,478 (especially the compounds in rows 21-41 of column 12); Leuco-dye-releasing compounds: Compounds 1-6 in columns 3-8 of U.S. Patent No. 4,749,641; Fluorescent-dye-releasing compounds: Compounds represented by COUP-DYE as described in claim 1 of U.S. Patent No. 4,774,181 (especially the compounds in columns 7-1 Compounds 0 (1-11); Development accelerator or cabracing agent releasing compounds: Compounds represented by formulas (1), (2), and (3) in column 3 of U.S. Patent No. 4,656,123 (especially (I-22) in column 25) and ExZK-2 on page 75, lines 36-38 of EP450,637A2; Compounds that release a group that becomes a pigment only after detachment: Compounds represented by formula (I) in claim 1 of U.S. Patent No. 4,857,447 (especially Y-1 to Y-19 in columns 25-36).

[0082] In addition to couplers, the following additives are preferred: Dispersion medium for oil-soluble organic compounds: P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 (pages 140-144) of Japanese Patent Publication No. 62-215272; Latex for impregnation of oil-soluble organic compounds: Latex as described in U.S. Patent No. 4,199,363; Developer main oxidizer scavenger: Compounds represented by formula (I) in rows 54-62 of column 2 of U.S. Patent No. 4,978,606 (especially I-, (1), (2), (6), (12) (columns 4-5), and the color compound of U.S. Patent No. 4,923,787. Formulas in rows 5-10 of column 2 (especially compound 1 (column 3); stain inhibitors: formulas (I) to (III) in rows 30-33 on page 4 of European Patent Application Publication No. 298321A, especially I-47, 72, III-1, 27 (pages 24-48); fade inhibitors: A-6, 7, 20, 21, 23, 24, 25, 26, 30, 37, 40, 42, 48, 63, 90, 92, 94, 164 (pages 69-118) of European Patent Application Publication No. 298321A, II-1 to III-23 in columns 25-38 of U.S. Patent No. 5,122,444, especially III-10, I-1 to III-4, particularly II-2, on pages 8 to 12 of European Patent Application Publication No. 471347A; A-1 to A-48, particularly A-39, A-42, on columns 32 to 40 of U.S. Patent No. 5,139,931; Materials that reduce the amount of color enhancers or color mixing inhibitors used: I-1 to II-15, particularly I-46, on pages 5 to 24 of European Patent Application Publication No. 411324A; Formalin scavengers: SCV-1 to A-28, particularly SCV-8, on pages 24 to 29 of European Patent Application Publication No. 477932A; Hardening agents: page 17 of Japanese Patent Publication No. 1-214845 H-1, 4, 6, 8, 14, compounds represented by formulas (VII) to (XII) in columns 13 to 23 of U.S. Patent No. 4,618,573 (H-1 to 54), compounds represented by formula (6) in the lower right of page 8 of Japanese Patent Publication No. 2-214852 (H-1 to 76), particularly H-14, the compound described in claim 1 of U.S. Patent No. 3,325,287; developer inhibitors / precursors: P-24, 37, 39 (pages 6 to 7) of Japanese Patent Publication No. 62-168139; compounds described in claim 1 of U.S. Patent No. 5,019,492, particularly 28, 29 in column 7;Preservatives, antifungal agents: I-1 to III-43, particularly II-1, 9, 10, 18, and III-25, columns 3 to 15 of U.S. Patent No. 4,923,790; stabilizers, antifungal agents: I-1 to (14), particularly I-1, 60, (2), and (13), columns 6 to 16 of U.S. Patent No. 4,923,793; compounds 1 to 65, particularly 36, from columns 25 to 32 of U.S. Patent No. 4,952,483; chemical sensitizers: triphenylphosphine selenide; compound 50 from Japanese Patent Publication No. 5-40324; dyes: from pages 15 to 18 of Japanese Patent Publication No. 3-156450. -1 to b-20, especially a-1, 12, 18, 27, 35, 36, b-5, V-1 to 23 on pages 27 to 29, especially V-1, F-I-1 to F-II-43 on pages 33 to 55 of European Patent Application Publication No. 445627A, especially F-I-11, F-II-8, III-1 to 36 on pages 17 to 28 of European Patent Application Publication No. 457153A, especially III-1, 3, microcrystalline dispersions of Dye-1 to 124 on pages 8 to 26 of International Publication No. 88 / 04794, compounds 1 to 22 on pages 6 to 11 of EP319999A, especially compound 1, European Patent Application Publication No. Compounds D-1 to D-87 represented by formulas (1) to (3) of 519306A (pages 3 to 28), compounds 1 to 22 represented by formula (I) of U.S. Patent No. 4,268,622 (columns 3 to 10), compounds (1) to (31) represented by formula (I) of U.S. Patent No. 4,923,788 (columns 2 to 9); UV absorbers: compounds (18b) to (18r), 101 to 427 represented by formula (1) of Japanese Patent Publication No. 46-3335 (pages 6 to 9), compounds (3) to (66) represented by formula (I) of European Patent Application Publication No. 520938A (pages 10 to 44) and compounds HBT-1 to 10 represented by formula (III) of European Patent Application Publication No. 521823A (page 14), compounds (1) to (31) represented by formula (1) of European Patent Application Publication No. 521823A (columns 2 to 9). ;

[0083] This disclosure can be applied to various color photosensitive materials such as black and white photographic paper, black and white negative film, X-ray film, general-purpose or motion picture color negative film, slide or television color inversion film, color paper, color positive film, and color inversion paper. It is also suitable for the lens-equipped film units described in Japanese Patent Publication No. 2-32615 and Japanese Utility Model Publication No. 3-39784.

[0084] Suitable supports that can be used in this disclosure are described, for example, on page 28 of RD. No. 17643, on the right column of page 647 to the left column of page 648 of RD. No. 18716, and on page 879 of RD. No. 307105.

[0085] The silver halide photographic photosensitive material according to this disclosure preferably has a total film thickness of 28 μm or less for the entire hydrophilic colloidal layer on the side having the emulsion layer, more preferably 23 μm or less, even more preferably 18 μm or less, and particularly preferably 16 μm or less. Also, the film swelling rate T １／２ It is preferable that the time is 30 seconds or less, and more preferably 20 seconds or less. １／２ This is defined as the time it takes for the film thickness to reach half of the saturation film thickness, which is defined as 90% of the maximum swelling film thickness achieved when treated with a color developing solution at 30°C for 3 minutes and 15 seconds. Film thickness refers to the film thickness measured under controlled conditions of 25°C and 55% relative humidity (2 days). １／２ This can be measured using a suelometer (also called a swelling meter) of the type described in A. Green et al.'s *Photographic Science and Engineering*, Vol. 19, pp. 2, pp. 124-129. １／２ This can be adjusted by adding a hardening agent to the gelatin used as a binder, or by changing the time-dependent conditions after application. Furthermore, a swelling rate of 150% to 400% is preferred. The swelling rate can be calculated from the maximum swollen film thickness under the above conditions using the formula: (maximum swollen film thickness - film thickness) / film thickness.

[0086] The silver halide photographic photosensitive material according to this disclosure preferably has a hydrophilic colloidal layer (referred to as a back layer) on the side opposite to the side having the emulsion layer, with a total dry film thickness of 2 μm to 20 μm. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardening agent, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling rate of this back layer is preferably 150% to 500%.

[0087] The silver halide photographic photosensitive material relating to this disclosure can be developed by the conventional methods described on pages 28-29 of RD. No. 17643, left column 651-right column of RD. No. 18716, and pages 880-881 of RD. No. 307105.

[0088] Furthermore, in this disclosure, antistatic agents are preferably used. Examples of such antistatic agents include polymers containing carboxylic acids and carboxylates, sulfonates, cationic polymers, ionic surfactant compounds, and π-electron conjugated conductive polymers. Preferred antistatic agents include ZnO and TiO ２ , SnO ２ Al ２ O ３ In ２ O ３ SiO ２ , MgO, BaO, MoO ３ , V ２ O ５ At least one volume resistivity selected from among them is 10 ７ Ω·cm or less, more preferably 10 ５ The particles are crystalline metal oxides or composite oxides thereof (Sb, P, B, In, S, Si, C, etc.) with a particle size of 0.001 μm to 1.0 μm and Ω·cm or less, or sol-like metal oxides or composite oxides thereof. The content in the silver halide photographic photosensitive material is 5 mg / m². ２ ~500 mg / m² ２ Preferably, and especially preferably, 10 mg / m² ２ ~350 mg / m² ２The ratio of the amount of conductive crystalline oxide or its composite oxide to the binder is preferably 1 / 300 to 100 / 1, and more preferably 1 / 100 to 100 / 5. Examples of π-electron conjugated conductive polymers include polythiophene compounds, polypyrrole compounds, and polyfuran compounds. Preferably, a latex-like aqueous dispersion containing a polythiophene compound and a polymeric polyanion compound can be used. The detailed structure of the compound, the composition of the dispersion, and preferred embodiments with the dispersant used in combination can be found in the methods described in Japanese Patent Publication No. 2003-330145, Japanese Patent No. 4244541, Japanese Patent Publication No. 2016-120650, and Japanese Patent Publication No. Hei 8-211615.

[0089] The silver halide photographic photosensitive material according to this disclosure preferably has lubricity. The lubricant-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferred lubricity is a dynamic friction coefficient of 0.01 to 0.25. This measurement is based on a 5 mm diameter stainless steel sphere transported at 60 cm / min (25°C, 60% RH). In this evaluation, substituting the photosensitive layer surface as the mating material yields approximately the same value.

[0090] Lubricants usable in this disclosure include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, and esters of higher fatty acids and higher alcohols. Examples of polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, polystyrenemethylsiloxane, and polymethylphenylsiloxane. The outermost or back layer of the emulsion layer is preferred as the additive layer. Polydimethylsiloxane or esters having long-chain alkyl groups are particularly preferred.

[0091] The silver halide photographic photosensitive material according to this disclosure preferably contains a matting agent. The matting agent may be added to either the emulsion surface or the back surface, but it is particularly preferable to add it to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and it is preferable to use both in combination. For example, polymethyl methacrylate, poly(methyl methacrylate / methacrylic acid = 9 / 1 or 5 / 5 (molar ratio)), and polystyrene particles are preferred. The particle size is preferably 0.8 μm to 10 μm, and a narrow particle size distribution is also preferred, with 90% or more of the total number of particles preferably contained between 0.9 and 1.1 times the average particle size. In addition, it is also preferable to add particles of 0.8 μm or less at the same time to enhance the matting properties, for example, polymethyl methacrylate (0.2 μm), poly(methyl methacrylate / methacrylic acid = 9 / 1 (molar ratio), 0.3 μm), polystyrene particles (0.25 μm), and colloidal silica (0.03 μm).

[0092] The silver halide photographic photosensitive material relating to this disclosure may contain other known additives in each layer. Furthermore, even if the silver halide photographic photosensitive material relating to this disclosure is not photosensitive to X-ray irradiation, the configuration and components of a silver halide photographic photosensitive material that is photosensitive to X-ray irradiation may be used as necessary.

[0093] (Silver Halide Emulsion) The silver halide emulsion used in this disclosure will be described. The silver halide emulsion used in this disclosure includes the compound relating to this disclosure as a spectrally sensitizing dye.

[0094] 1) Halogen composition: Photosensitive silver halide particles can be silver chloride, silver bromide salt, silver bromide, silver iodide, or silver iodide salt. However, as mentioned above, from the viewpoint of rapid processing, it is preferable that the amount of iodine contained in the photosensitive silver halide particles is 0 mol% or more and 0.45 mol% or less on average. More preferably, this amount of iodine is 0.05 mol% or more and 0.40 mol% or less on average, and even more preferably 0.10 mol% or more and 0.30 mol% or less. Here, the "average" amount of iodine contained in the photosensitive silver halide particles means the average value of the iodine content determined from the halogen composition of each individual photosensitive silver halide particle. The distribution of halogen composition within the photosensitive silver halide particles may be uniform, the halogen composition may change in steps, or it may change continuously. In addition, photosensitive silver halide particles having a core / shell structure can also be used as photosensitive silver halide particles.

[0095] 2) As part of the particle shape, photosensitive silver halide particles, so-called halogen conversion type (also called conversion type) particles, as described in British Patent No. 635,841 and U.S. Patent No. 3,622,318, are also suitable. The halogen conversion is usually carried out by adding an aqueous halogen solution with a smaller solubility product with silver than the halogen composition on the particle surface before halogen conversion. For example, for silver chloride or silver bromide plate-shaped particles, an aqueous potassium bromide and / or potassium iodide solution is added to cause conversion, and for silver bromide or silver iodide plates, an aqueous potassium iodide solution is added to cause conversion. The concentration of these added aqueous solutions is preferably low, preferably 30% or less, and more preferably 10% or less. Furthermore, it is preferable to add the conversion halogen solution at a rate of 1 mol% or less per minute per mole of silver halide before halogen conversion. Furthermore, during halogen conversion, some or all of the sensitizing dye and / or the silver halide adsorbent may be present, and silver bromide, silver iodide, or silver iodide silver halide particles may be added instead of the halogen conversion aqueous solution. The size of these fine particles is preferably 0.2 μm or less, preferably 0.1 μm or less, and particularly preferably 0.05 μm or less. The halogen conversion method is not limited to the method described above, and can be used in appropriate combinations depending on the purpose.

[0096] 3) Particle size: Methods for forming photosensitive silver halide particles are well known in the industry and can be prepared by using methods such as those described in Japanese Patent Application Publication No. 2-68539, U.S. Patent No. 3,700,458, and Research Disclosure No. 17029 of June 1978.

[0097] 4) Chemical Sensitization Methods As chemical sensitization methods, the methods described in Japanese Patent Publication No. 2-68539, page 10, upper right column, line 13 to lower left column, line 16, Japanese Patent Publication No. 5-313282, and Japanese Patent Publication No. 6-110144 can be used. Specifically, as methods for chemical sensitization of silver halide emulsion, known methods such as sulfur sensitization, selenium sensitization, reduction sensitization, and gold sensitization can be used in the presence of a silver halide adsorbent, and these can be used alone or in combination.

[0098] Among the precious metal sensitization methods, the gold sensitization method is representative and uses gold compounds, mainly gold complex salts. It is also acceptable to include complex salts of other precious metals, such as platinum, palladium, and iridium. Specific examples are described in U.S. Patent No. 2,448,060 and British Patent No. 618,061, among others. As sulfur sensitizers, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines can be used. Specific examples are described in U.S. Patents No. 1,574,944, 2,278,947, 2,410,689, 2,728,668, 5,501,313, and 3,656,955. Furthermore, selenium sensitizers are described in Japanese Patent Publication No. 6-110144. The combined use of sulfur sensitization with thiosulfates, selenium sensitization, and gold sensitization is useful. As reductive sensitizers, stannous salts, amines, formamine disulfide, and silane compounds can be used.

[0099] 5) Anti-fogging agents and stabilizers As anti-fogging agents and stabilizers, those described in Japanese Patent Publication No. 2-68539, from line 17 in the lower left column of page 10 to line 7 in the upper left column of page 11 and from line 2 in the lower left column of page 3 to line 4 in the lower left column may be used.

[0100] Specifically, compounds that can be added include azoles (e.g., benzothiazolium salts, etroidazoles, nitrobenzimidazoles, chlorobenzimidazoles, chromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds (e.g., mercaptotheazoles, mercaptobenzithiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles, mercaptopyrimidizi, mercaptotriazines, etc.); thioketo compounds such as oxadrinthion; azaidenes (e.g., triazaidenes, tetraazaidenes (especially 4-hydroxysubstituted (1,3,3a,7) tetraazaidenes), pentaazaidenes, etc.); and compounds known as anti-fogging agents or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, and benzenesulfonamide.

[0101] In particular, nitrones and their derivatives described in Japanese Patent Publication No. 60-76743 and No. 60-87322, mercapto compounds described in Japanese Patent Publication No. 60-80839, heterocyclic compounds described in Japanese Patent Publication No. 57-164735, and complex salts of heterocyclic compounds with acids (e.g., 1-phenyl-5-mercaptotetrazoles) can be preferably used.

[0102] Furthermore, purines or nucleic acids, or polymer compounds described in Japanese Patent Publication No. 61-36213, Japanese Patent Application Publication No. 59-90844, etc., can also be used. Among these, azaidenes, purines, and nucleic acids are particularly preferred. The amount of these compounds added is preferably 0.5 mmol to 5.0 mmol, more preferably 0.5 mmol to 3.0 mmol, per mole of silver halide.

[0103] 6) Color correcting agents Examples of color correcting agents include those described in Japanese Patent Publication No. 62-276539, page 2, bottom left, line 7 to page 10, bottom left, line 20, and Japanese Patent Publication No. 3-94249, page 6, bottom left, line 15 to page 11, top right, line 19. Specifically, the covering strength of the silver halide photographic emulsion layer is 60 or more, and the silver halide photographic emulsion layer and / or other layers may contain a dye having a maximum absorption wavelength between 520 nm and 560 nm and a dye having a maximum absorption wavelength between 570 nm and 700 nm, such that the increase in optical density due to the contained dyes in the transmittance of the post-exposure area after development is 0.03 or less.

[0104] Typical emulsions that provide a covering strength of 60 or more for the silver halide photographic emulsion layer include plate-shaped emulsions and particle emulsions. In particular, when the silver halide photographic emulsion consists of plate-shaped silver halide particles with a particle thickness of 0.4 μm or less, or when a mixed emulsion of a high-iodine surface photosensitive emulsion and an emulsion consisting of particles whose interiors are covered with other particles is used, the effect of improving color tone is significant. Dyes that can be used for improving color tone preferably include a dye having a maximum absorption wavelength between 520 nm and 560 nm, more preferably between 530 nm and 555 nm, and a combination of a dye having a maximum absorption wavelength between 570 nm and 700 nm, more preferably between 580 and 650 nm. The maximum absorption wavelength refers to the maximum absorption wavelength when the dye is present in the photosensitive material.

[0105] As dyes, for example, those having a predetermined maximum wavelength are selected from anthraquinone dyes, azo dyes, azomethine dyes, indoaniline dyes, oxonol dyes, carbocyanine dyes, styryl dyes, triphenylmethane dyes, etc. Considering stability to development processing, lightfastness, and the impact on photographic performance such as desensitization, fogging, and staining, preferred dyes are used from anthraquinone dyes, azo dyes, azomethine dyes, and indoaniline dyes. Preferred compounds are described in Japanese Patent Publication No. 62-276539, from the 5th line in the upper left column of page 3 to the 9th line in the upper left column of page 9. Such dyes can be dispersed in emulsion layers or other hydrophilic colloidal layers (intermediate layers, protective layers, anti-halation layers, filter layers, etc.) by various known methods, specifically described in Japanese Patent Publication No. 62-276539, from the 14th line in the upper left column of page 9 to the 20th line in the lower left column of page 10.

[0106] 7) Spectroscopy-sensitizing dyes The spectroscopy-sensitizing dyes include compounds represented by formula (1) according to the present invention (i.e., dyes represented by formula (1)) as spectroscopy-sensitizing dyes for green light.

[0107]

[0108] In general formula (1), A represents a phenyl group or a chlorine atom, and R １ and R ２ Each of these independently represents a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an aryl group, or a heteroaryl group, and R ３ R represents a hydrogen atom, alkyl group, aralkyl group, alkenyl group, aryl group, or heteroaryl group. １ and R ２ One of them has one sulfonic acid group, while the other does not have a sulfonic acid group or a carboxylic acid group.

[0109] A, R １ , R ２ and R ３ The preferred range and specific examples are the same as those described above for formula (1), which is the compound according to the present invention.

[0110] Preferably, the spectrally sensitizing dye includes, in addition to the dye represented by formula (1), a dye represented by general formula (2).

[0111]

[0112] In general formula (2), R ４ and R ５ Each of these independently represents a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an aryl group, or a heteroaryl group. ６ X represents an alkyl group with 4 or fewer carbon atoms. １ and X ４ Each of these independently represents a hydrogen atom, an alkyl group, or a chlorine atom. ２ and X ５ Each of these independently represents an alkyl group, alkoxy group, halogen atom, hydrogen atom, hydroxyl group, or phenyl group having four or fewer carbon atoms. １ and X ２ , or X ４ and X ５ They may be linked together to form a benzene ring. ３ is, X ２ It is either linked to form a benzene ring, or it is a hydrogen atom. ６ is, X ５ It is either linked to form a benzene ring, or it is a hydrogen atom.

[0113] The dye represented by formula (2) is a different type of sensitizing dye than the dye represented by formula (1). As described above, the three-dimensional structure of the molecule of the dye represented by formula (1) suppresses intermolecular interactions, and it is presumed that a more uniform mixing state is maintained with other types of sensitizing dyes such as the dye represented by formula (2). As a result, even when mixing multiple sensitizing dyes including the dye represented by formula (1) and the dye represented by formula (2), the spectral characteristics of each sensitizing dye are effectively expressed, making it possible to improve the overall photographic performance. The dye represented by formula (1) and the dye represented by formula (2) in this disclosure can be mixed nicely without forming a complex. Therefore, by mixing the dye represented by formula (1) and the dye represented by formula (2), it is possible to effectively express the desired spectral characteristics from the spectral characteristics of each dye.

[0114] In formula (2), R ４ and R ５ For each of the alkyl, aralkyl, alkenyl, aryl, or heteroaryl groups represented by R, the preferred range and specific examples are as follows: １ and R ２ This is similar to what was explained earlier.

[0115] In formula (2), R ６ The alkyl group with four or fewer carbon atoms represented by may be linear, branched, or cyclic, but linear is preferred. ６ Examples of alkyl groups with four or fewer carbon atoms represented by include methyl, ethyl, or propyl groups.

[0116] In formula (2), X １ or X ４ The alkyl group represented by may be linear, branched, or cyclic. １ or X ４ Examples of alkyl groups represented by include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decylcyclopropyl, cyclopentyl, cyclohexyl, and 1-norbornyl groups. １ or X ４ Preferably, each of these is a hydrogen atom.

[0117] In formula (2), X ２ or X ５ The alkyl group having four or fewer carbon atoms represented by may be linear, branched, or cyclic, but linear is preferred. ２ or X ５ Examples of alkyl groups with four or fewer carbon atoms represented by include methyl, ethyl, or propyl groups.

[0118] In formula (2), X ２ or X ５ The alkoxy group with four or fewer carbon atoms represented by can be linear or branched, but linear is preferred. ２or X ５ Examples of alkoxy groups having four or fewer carbon atoms represented by include methoxy, ethoxy, propoxy, 1-butoxy, or 2-butoxy groups. In formula (2), X ２ or X ５ Examples of halogen atoms with four or fewer carbon atoms represented by this symbol include fluorine, chlorine, and bromine atoms.

[0119] In equation (2), for example, R ６ is an ethyl group or a propyl group, X ２ and X ５ Each of these is an alkoxy group, a chlorine atom, a hydrogen atom, or an aryl group having 4 or fewer carbon atoms, and X １ and X ４ X is a hydrogen atom. １ and X ３ Each is either a hydrogen atom or X ２ It is preferable that it is linked to form a benzene ring. Also, R ６ is an ethyl group, X ２ and X ５ Each of these is a chlorine atom, a hydrogen atom, or a phenyl group, and X １ and X ４ X is a hydrogen atom. １ and X ３ Each is either a hydrogen atom or X ２ A more preferable material is one that connects to form a benzene ring.

[0120] The compound represented by formula (2) is, in formula (2), X １ , X ３ , X ４ , and X ６ Each of these represents a hydrogen atom, X ２ and X ５ Preferably, the compound is represented by formula (2-1), where each represents a phenyl group. This allows for the formation of a more homogeneous mixture with the compound represented by formula (1) without forming complexes, and this mixture effectively brings out the spectral characteristics of each sensitizing dye represented by formula (1) and formula (2), thereby improving the overall photographic performance.

[0121]

[0122] In equation (2-1), R １ , R ２ and R ３ In the above, R in equation (2) １ , R ２ and R ３ The information provided is the same as what was written about the other items.

[0123] The following are specific examples of the dyes represented by formula (2) in this disclosure, namely compounds (B-1) to (B-13). The dyes represented by (2) are not limited to the following specific examples.

[0124]

[0125]

[0126]

[0127] Regarding the amounts of the dye represented by formula (1) and the dye represented by formula (2) used, the amount of the dye represented by formula (2) is preferably 0.1 to 1.0 times, more preferably 0.12 to 0.90 times, and even more preferably 0.14 to 0.80 times, on a mass basis, relative to the amount of the dye represented by formula (1). Within this range, when a mixture of the dye represented by formula (1) and the dye represented by formula (2) is used as a sensitizing dye in a silver halide photographic photosensitive material, desirable spectral characteristics can be obtained in green light. Specifically, when a mixture of the dye represented by formula (1) and the dye represented by formula (2) is used as a sensitizing dye, the desired spectral waveform can be obtained by measuring the reflectance spectrum in the silver halide emulsion. Therefore, when a mixture of the dye represented by formula (1) and the dye represented by formula (2) is used as a sensitizing dye in a silver halide photographic photosensitive material, the desired spectral characteristics can be achieved.

[0128] In addition to the dyes represented by formula (1) and formula (2), the following spectrally sensitizing dyes can be used. Examples of such spectrally sensitizing dyes are those described in the lower right column of page 4 to the lower right column of page 8 of Japanese Patent Publication No. 2-68539. Specifically, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holoporanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used. Sensitizing dyes include, for example, U.S. Patent Nos. 3,522,052, 3,617,197, 3,713,828, 3,615,643, 3,615,632, 3,617,293, 3,628,964, 3,703,377, 3,666,480, 3,667,960, 3,679,428, 3,672,897, 3,769,026, 3,556,800, 3,615,613, and 3,613. This is described in Japanese Patent Publication No. 638, Nos. 3,615,635, 3,705,809, 3,632,349, 3,677,765, 3,770,449, 3,770,440, 3,769,025, 3,745,014, 3,713,826, 3,567,458, 3,625,698, 2,526,632, 2,503,776, Japanese Patent Publication No. 48-76525, Belgian Patent No. 691807, etc. The amount of sensitizing dye added is preferably 0.5 mmol or more and less than 4 mmol per mole of silver halide, more preferably 0.5 mmol or more and less than 1.5 mmol. Specific examples of sensitizing dyes include II-1 to II-47, described on pages 5 to 8 of Japanese Patent Publication No. 2-68539.

[0129] 8) Antistatic Agents In this disclosure, surfactants described in the upper left column of page 11, line 14 to the upper left column of page 12 of Japanese Patent Publication No. 2-68539 may be used as coating aids, antistatic agents, or electrostatic modifiers. In addition, compounds related to this disclosure may be used as coating aids, antistatic agents, or electrostatic modifiers. Specific examples of surfactants used for this purpose include nonionic surfactants such as saponins (steroids), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, silicone polyethylene oxide compounds), and alkyl esters of sugars; anionic surfactants such as alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, N-acyl-N-alkyl taurines, sulfosuccinates, and sulfoalkyl polyoxyethylene alkylphenyl ethers; amphoteric surfactants such as alkyl betaines and alkyl sulfobetaines; and cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, pyridinium salts, and imidazolium salts.

[0130] Of these, anions such as saponins, sodium dodecylbenzenesulfonate, sodium di-2-ethylhexyl α-sulfosuccinate, sodium p-octylphenoxyethoxyethanesulfonate, sodium dodecyl sulfate, sodium triisopropylnaphthalenesulfonate, and sodium N-methyl-oleoyl taurate are particularly preferred; cations such as dodecyltrimethylammonium chloride, N-oleoyl-N',N',N'-trimethylammoniumdiaminopropane bromide, and dodecylpyridinium chloride are preferred; betaines such as N-dodecyl-N,N-dimenal carboxybetaine and N-oleyl-N,N-dimethylsulfobutylbetaine are preferred; and nonions such as poly(average degree of polymerization n-10)oxyethylene cetyl ether, poly(n=25)oxyethylene p-nonylphenol ether, and bis(1-poly(n=15)oxyethylene-oxy-2,4-di-t-pentylphenyl)ethane are particularly preferred. Furthermore, as antistatic agents, nonionic surfactants described in Japanese Patent Publication No. 60-80848, No. 61-112144, No. 62-172343, No. 62-173459, etc., alkali metal nitrates, conductive tin oxide, zinc oxide, vanadium pentoxide, or composite oxides obtained by doping these with antimony, etc., can be preferably used.

[0131] 9) Matting agents, lubricants and plasticizers Examples of matting agents, lubricants and plasticizers include those described in the 10th line of the upper left column to the 10th line of the upper right column on page 12 of Japanese Patent Publication No. 2-68539, and the 10th line of the lower left column to the 1st line of the lower right column on page 14. Specifically, as matting agents, fine particles of polymethyl methacrylate homopolymers or copolymers of methyl methacrylate and methacrylic acid as described in U.S. Patent Nos. 2,992,101, 2,701,245, 4,142,894, and 4,396,706 can be used, as well as organic compounds such as starch, silica, titanium dioxide, sulfuric acid, and strontium barium. The particle size is preferably 1.0 μm to 10 μm, and particularly preferably 2 μm to 5 μm. In addition to silicone compounds described in U.S. Patent No. 3,489,576 and No. 4,047,958, and colloidal silica described in Japanese Patent Publication No. 56-23139, paraffin wax, higher fatty acid esters, starch derivatives, etc., can be used as lubricants for the surface layer of the silver halide photographic photosensitive material according to this disclosure.

[0132] In the hydrophilic colloidal layer of the silver halide photographic photosensitive material according to this disclosure, polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers. Furthermore, the emulsion layer of the silver halide photographic photosensitive material according to this disclosure may contain plasticizers such as polymers and emulsions to improve the pressure properties. For example, methods using heterocyclic compounds are disclosed in British Patent No. 738618, alkyl phthalates in British Patent No. 738637, alkyl esters in British Patent No. 738639, polyhydric alcohols in US Patent No. 2,960,404, carboxylalkylcellulose in US Patent No. 3,121,060, paraffin and carboxylates in Japanese Patent Publication No. 49-5017, and alkyl acrylates and organic acids in Japanese Patent Publication No. 53-28086, and these methods can also be used in this disclosure.

[0133] 10) Hydrophilic colloids As a binder or protective colloid that can be used in the emulsion layer, intermediate layer and surface protective layer of the silver halide photographic photosensitive material relating to this disclosure, gelatin is advantageous, but other hydrophilic colloids can also be used. Examples of hydrophilic colloids are those described in the upper right column, line 11 to the lower left column, line 16 of page 12 of Japanese Patent Publication No. 2-68539.

[0134] For example, various synthetic hydrophilic polymers can be used, such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate, dextran, and starch derivatives; and single or copolymer forms of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole. In addition to lime-treated gelatin, acid-treated gelatin and enzyme-treated gelatin may also be used as gelatin, and hydrolyzed or enzymatically decomposed gelatin products can also be used. Among these, it is preferable to use dextran or polyacrylamide with an average molecular weight of 100,000 or less together with gelatin. The methods described in Japanese Patent Publication No. 63-68887 and Japanese Patent Publication No. 63-149641 can also be used in this disclosure.

[0135] 11) The photographic emulsion and the non-photosensitive hydrophilic colloid may contain an inorganic or organic hardening agent. Examples of hardening agents are those described in Japanese Patent Publication No. 2-68539, from line 17 in the lower left column of page 12 to line 6 in the upper right column of page 13. Specifically, for example, chromium salts (such as chromium alum and chromium acetate), aldehydes (such as formaldehyde, glyoxal, and darital aldehyde), N-methylol compounds (such as dimethylol urea, methyloldimethyl and dantoin), dioxane derivatives (such as 2,3-dihydroxydioxane), activated vinyl compounds (such as 1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl)methyl ether, and N,N'-methylenebis-(β-(vinylsulfonyl)propionamide)), activated halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine), mucohalic acids (such as mucochloroic acid and mucophenoxycycloic acid), isoxazoles, dialdehyde starch, and 2-chlor-6-hydroxytriazinylated gelatin can be used individually or in combination. Among these, the activated vinyl compounds described in Japanese Patent Publication No. 53-41221, No. 53-57257, No. 59-162546, and No. 60-80846, and the activated halides described in U.S. Patent No. 3,325,287 are preferred.

[0136] Polymeric hardening agents can also be effectively utilized as hardening agents. Examples of polymeric hardening agents include dialdehyde starch, polyacrolein, polymers having aldehyde groups such as the acrolein copolymer described in U.S. Patent No. 3,396,029, polymers having epoxy groups described in U.S. Patent No. 3,623,878, polymers having dichlorotriazine groups described in U.S. Patent No. 3,362,827, Research Disclosure No. 17333 (1978), polymers having active ester groups described in Japanese Patent Publication No. 56-66841, Japanese Patent Publication No. 56-142524, U.S. Patent No. 4,161,407, Japanese Patent Publication No. 54-65033, Research Disclosure No. Examples include polymers having active vinyl groups or precursor groups thereof, as described in 16725 (1978), with polymers having active vinyl groups or precursor groups thereof being preferred, and among these, polymers in which active vinyl groups or precursor groups thereof are bonded to the polymer main chain by long spacers, as described in Japanese Patent Publication No. 56-142524, are particularly preferred. The hydrophilic colloidal layer in the silver halide photographic photosensitive material according to this disclosure is preferably hardened with these hardening agents such that the swelling rate in water is 300% or less, particularly 230% or less.

[0137] 12) Support As a support, see the one described in the upper right column of page 13 of Japanese Patent Publication No. 2-68539, lines 7 to 20. Specifically, polyethylene terephthalate film or cellulose triacetate film is preferred as the support. To improve adhesion with the hydrophilic colloid layer, the surface of the support is preferably treated by corona discharge, glow discharge, or ultraviolet irradiation. Alternatively, an undercoat layer made of styrene-butadiene latex, vinylidene chloride latex, etc., may be provided, or a gelatin layer may be further provided on top of it. Alternatively, an undercoat layer using an organic solvent containing a polyethylene swelling agent and gelatin may be provided. The adhesion of these undercoats to the hydrophilic colloid layer can be further improved by surface treatment.

[0138] 13) Crossover Cut Method It is a well known fact in this industry that crossover light significantly reduces sharpness. As a means of ensuring that the crossover light of photographic photosensitive materials is 12% or less, methods are disclosed in U.S. Patent No. 4,130,429 and Japanese Patent Publication No. 61-116354, in which light with a wavelength matching the emission wavelength of an X-ray fluorescent screen is absorbed using sensitizing dyes or dyes.

[0139] Furthermore, U.S. Patent No. 4,800,150 discloses a technique for having the dye present as a microcrystalline dispersion between the support and the emulsion layer so that the crossover light is 10% or less. In addition, Japanese Patent Publication No. 63-305345 discloses a technique for fixing anions or dyes to a specific layer using a cationic polymer latex, and Japanese Patent Publication No. 1-166031 discloses a technique for making the dye-fixed layer an undercoat layer on the support. Any of these methods can be used in the photosensitive material according to this disclosure, but it is preferable that the colored layer with the dye be an undercoat layer, and that the dye be fixed by the method described in Japanese Patent Publication No. 1-166031, and in particular it is desirable that the dye be fixed to the undercoat layer in the form of a microcrystalline dispersion as described in U.S. Patent No. 4,803,150. In this disclosure, it is possible to combine these methods as appropriate. Preferred dyes include those described in the lower left column of page 4 to the upper right column of page 9 of Japanese Patent Publication No. 2-264944. Furthermore, as the mordant layer, the one described in the lower right column to the upper right column of page 9 to section 14 of Japanese Patent Publication No. 2-264944 can be used.

[0140] 14) Polyhydroxybenzenes Examples of polyhydroxybenzenes include those described in the upper left column of page 11 to the lower left column of page 12 of Japanese Patent Publication No. 3-39948 and in the specification of European Patent Application Publication No. 452772A. Specifically, examples include the compound of general formula (III) described in the upper left column of page 11 of Japanese Patent Publication No. 8-39948, and the specific compounds thereof, compounds (III)-1 to 25 described in the lower left column of page 11 to the lower left column of page 12 of the same publication. The amount of these polyhydroxybenzene compounds to be added is 5 × 10 per mole of silver halide. －１It is sufficient if it is less than a mole, preferably 5 × 10 per mole of silver halide. －３ Moles ~ 1 x 10 －１ This is the amount added in moles.

[0141] The silver halide photographic photosensitive material according to this disclosure comprises a silver halide emulsion layer (i.e., a photosensitive layer) containing photosensitive silver halide particles on a support, and at least one non-photosensitive hydrophilic colloidal layer such as an intermediate layer, a surface protective layer, a back layer, a back surface protective layer, an anti-halation layer, or a filter layer. However, there are no particular restrictions on the emulsion sensitization method or various additives used, and those described in Japanese Patent Application Publication No. 2-68539, for example, can be suitably used.

[0142] 15) Surface protective layer and back protective layer The silver halide photographic photosensitive material according to this disclosure preferably has a surface protective layer and a back protective layer, and the surface protective layer and the back protective layer contain various chemicals with a hydrophilic colloid such as gelatin as a binder. If the main component of the layer is gelatin, preservatives and the like are necessary. In addition, it is preferable to include matting agents, lubricants, plasticizers, antistatic agents, surfactants, hardening agents, thickeners, dyes, conductive substances, etc. as needed.

[0143] 16) Development Processing Methods As development processing methods for silver halogen photographic photosensitive materials relating to this disclosure, the methods described in Japanese Patent Publication No. 2-103037, from the 7th line in the upper right column of page 16 to the 15th line in the lower left column of page 19, Japanese Patent Publication No. 2-115837, from the 5th line in the lower right column of page 3 to the 10th line in the upper column of page 6, and Japanese Patent Publication No. 2000-112078, from the 42nd line in the left column of page 34 to the 2nd line in the left column of page 35. Furthermore, for thermally developable photosensitive materials, the methods described in Japanese Patent Publication No. 2001-255617, from the 40th line in the left column of paragraph 37 to the 43rd line in the left column of page 35, etc., can be adopted.

[0144] One embodiment of the silver halide photographic material relating to this disclosure is a photosensitive thermally developable photographic material. The technology is described in paragraphs 16 to 189 of Japanese Patent No. 5623921. In this embodiment, the desired effect can be obtained when the surfactant described in paragraphs 181 to 183 of the said publication is the one described in this application.

[0145] (Diffusion Transfer Type Silver Halogen Photosensitive Material) The silver halogen photosensitive material according to this disclosure may be a diffusion transfer type silver halogen photosensitive material. The diffusion transfer type silver halogen photosensitive material preferably comprises a photosensitive sheet and a transparent cover sheet and an alkali-treated composition-containing material spread between them.

[0146] [1] Alkali Treatment Composition Container The alkali treatment composition container is uniformly spread on the photosensitive sheet after exposure and has the function of developing the photosensitive layer, and together with the light-shielding layer provided on the back of the transparent support of the photosensitive sheet or within the photosensitive sheet, it has the function of completely blocking the photosensitive layer from external light. For this reason, the alkali treatment composition container typically contains alkali, thickener, light-shielding agent, developer, as well as development accelerators to adjust the development, development inhibitors, antioxidants to prevent deterioration of the developer, etc.

[0147] (a) The alkali is not particularly limited as long as it raises the pH of the solution to 12 or higher. Examples of alkalis include alkali metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, and lithium hydroxide), alkali metal phosphates (e.g., potassium phosphate), guanidines, and quaternary amine hydroxides (e.g., tetramethylammonium hydroxide). Potassium hydroxide and sodium hydroxide are preferred among these.

[0148] (b) Developer Any developer is acceptable as long as it cross-oxidizes the pigment image-forming compound and does not substantially produce stains even after oxidation. The developer may be used alone, in combination of two or more types, or in the form of a precursor. Examples of developers include aminophenols and pyrazolidinones. Of these, pyrazolidinones are particularly preferred because they produce less stain. Specific examples of pyrazolidinones include 1-phenyl-3-pyrazolidinone, 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1-(3'-methylphenyl)-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, and 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone. The developer may be incorporated into an alkali treatment composition or added to an appropriate layer of the photosensitive sheet.

[0149] (c) Light-shielding agent Any material having light-shielding properties can be used as a light-shielding agent without particular limitations. Examples of light-shielding agents include carbon black and biodegradable dyes described in U.S. Patent No. 4,615,966, etc. Of these light-shielding agents, carbon black is preferred. The carbon black is not limited to those obtained by a specific manufacturing method, but can be obtained by any manufacturing method. Examples of methods for producing carbon black include the channel method described in Donnel Voet “Carbon Black” Marcel Dekker, Inc. (1976), as well as the thermal method and the furnace method.

[0150] When using carbon black as a light-shielding agent, it is preferable to prepare the carbon black as an aqueous dispersion beforehand. Aqueous dispersions of carbon black are very commonly used as black materials or light-shielding materials in paints, inks, cosmetics, or photographic light-sensitive materials. To prepare an aqueous dispersion of carbon black, carbon black is added to water in which a suitable dispersant has been dissolved, and the carbon black is roughly dispersed using a coarse disperser (for example, a high-speed stirring disperser such as the dissolver described in Japanese Patent Application No. 54-36045) to an average particle size of about 10 μm to 100 μm. Then, the particle size is further reduced using a fine disperser (for example, a sand grinder, homogenizer, colloid mill, etc.). This process yields an aqueous dispersion of carbon black having an average particle size of approximately 0.1 μm to 10 μm. Alternatively, as described in Japanese Patent Application No. 58-52362, carbon black may be dispersed in an aqueous solution containing an organic solvent, and then the organic solvent may be removed to obtain an aqueous dispersion of carbon black.

[0151] Preferred dispersants include those listed on pages 255-257 and 501-539 of "Comprehensive Data Collection on Dispersion Technology" (Management Development Center Publishing). An example of a commercially available dispersant is Demol N (trade name, manufactured by Kao Corporation).

[0152] The type and / or amount of dispersant affects the sodium ion content, which will be discussed later. The type and / or amount of dispersant must be determined so as to satisfy not only the condition of (a) providing sufficient dispersibility to the light-shielding agent, but also the condition of (b) sodium ion content. To satisfy both the conditions of dispersibility and sodium ion content, it is preferable to add the dispersant in an amount of 2% to 100% by mass relative to the light-shielding agent.

[0153] (d) Optical density The optical density of the alkali-treated composition containing the material is preferably 47 or higher, more preferably 50 or higher, and particularly preferably 55 or higher. When the optical density is 47 or higher, sufficient light shielding is obtained and spot fogging is suppressed. It is preferable to determine the amount of light shielding agent to be added so that the optical density is 47 or higher. Depending on the type of light shielding agent used, it is preferable to add approximately 10% to 40% by mass of the light shielding agent to achieve an optical density of 47 or higher.

[0154] (e) Sodium ion content: The sodium ion content of the alkali-treated composition is preferably 0.4 g / m² in the expanded state. ２ The following applies: The sodium ion content is 0.35 g / m³. ２ It is even more preferable that the following is the case: 0.25 g / m ２ The following is particularly preferable:

[0155] The sodium ion content is determined primarily by the dispersant in the light-shielding agent mentioned above, as well as by the thickening agent. Sodium carboxymethylcellulose is particularly preferred as a thickening agent. Sodium carboxymethylcellulose has sufficient spreadability and stability. Using alkali metal salts other than sodium of polyvinyl alcohol, hydroxyethylcellulose, or carboxymethylcellulose as thickening agents can reduce the sodium ion content. However, these do not have sufficient spreadability and stability, so their use alone is not appropriate. Therefore, it is preferable to use sodium carboxymethylcellulose as the main thickening agent, in combination with alkali metal salts other than sodium of polyvinyl alcohol, hydroxyethylcellulose, or carboxymethylcellulose.

[0156] The sodium ion content is 0.4 g / m² when expanded. ２It is preferable to adjust the degree of etherification and the amount of sodium carboxymethylcellulose added so that the following conditions are met: The degree of etherification of sodium carboxymethylcellulose is preferably 0.5 to 2.7, and more preferably 1.0 to 2.4. The amount of sodium carboxymethylcellulose blended is preferably 1% to 15% by mass, and more preferably 2% to 10% by mass.

[0157] Alkali-treated composition-containing materials satisfying the above-mentioned optical density and sodium ion content exhibit excellent light-shielding and dye transfer properties even when spread thinly on a photosensitive sheet. In this specification, "thinly spread" means that the alkali-treated composition-containing material is spread on a photosensitive sheet to a thickness of 10 μm to 80 μm. A preferred spreading thickness is 10 μm to 70 μm, and a more preferred spreading thickness is 20 μm to 60 μm.

[0158] [2] Photosensitive Sheet (a) First Transparent Support The support of the photosensitive sheet may be any material commonly used for photographic photosensitive materials. The support of the integrated color diffusion transfer film unit must be transparent. The support is preferably smooth. Examples of support materials include cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. To prevent light piping, the support preferably contains a small amount of dye or a pigment such as titanium dioxide. The thickness of the support of the photosensitive sheet is preferably 25 μm to 350 μm, more preferably 50 μm to 210 μm, and particularly preferably 70 μm to 150 μm. It is preferable to provide an undercoat layer (also called an under-coating layer) on the front surface of the support. On the back side of the support, a layer for curl balancing or an oxygen-blocking layer may be provided as needed. The oxygen-blocking layer can be provided by referring to the description in Japanese Patent Publication No. 56-78833.

[0159] (b) The image-receiving layer of the photosensitive sheet (also called the dye image-receiving layer) preferably contains a mordant and a hydrophilic colloid. The image-receiving layer may be a single layer or a structure in which layers having different mordant strengths are laminated. Single-layer and multi-layer image-receiving layers can be provided by referring to the description in Japanese Patent Publication No. 61-252551.

[0160] A polymer mordant is preferred as the mordant. A polymer mordant is a polymer containing secondary and / or tertiary amino groups, a polymer having a nitrogen-containing heterocyclic moiety, or a polymer containing a quaternary cation, and is preferably one with a molecular weight of 5,000 or more, and particularly preferably one with a molecular weight of 10,000 or more. The amount of mordant to be applied is preferably 0.5 g / m². ２ ~10g / m ２ More preferably, 1 g / m ２ ~5g / m ２ The most preferred amount is 2 g / m². ２ ~4g / m ２ That is the case.

[0161] Examples of hydrophilic colloids include gelatin, polyvinyl alcohol, polyacrylamide, and polyvinylpyrrolidone. Gelatin is a preferred hydrophilic colloid.

[0162] The image-receiving layer may contain a fade-preventing agent. There are no particular restrictions on the fade-preventing agent, but for example, those described in Japanese Patent Publication No. 62-30620, Japanese Patent Publication No. 62-30621, and Japanese Patent Publication No. 62-215272 can be used. The thickness of the image-receiving layer may be the same as that of a typical color diffusion transfer film unit.

[0163] (c) The white reflective layer of the photosensitive sheet forms the white background of the color image. The white reflective layer usually contains a white pigment and a hydrophilic binder.

[0164] The whiteness of the white reflective layer is determined by the type of pigment, the mixing ratio of the pigment to the binder, and the amount of pigment applied. When the white pigment is titanium dioxide, the titanium dioxide content is preferably 5 g / m². ２ ~40g / m ２ More preferably, 10 g / m ２ ~25g / m ２ That is the case.

[0165] The light reflectance of the white reflective layer is preferably 70% or higher, and more preferably 78% to 85% for light with a wavelength of 540 nm.

[0166] Examples of white pigments include barium sulfate, zinc oxide, barium stearate, silver flakes, silicates, alumina, zirconium oxide, sodium zirconium sulfate, kaolin, mica, and titanium dioxide. Non-film-forming polymer particles such as polystyrene can also be used as white pigments. Among these, titanium dioxide is preferred, and rutile-type titanium dioxide is particularly preferred. White pigments may be used alone or in combination of two or more. Using two or more white pigments makes it easier to achieve a desirable reflectivity for the white reflective layer.

[0167] As the white pigment, those surface-treated with alumina, silica, zinc oxide, etc., are preferred, and those with a surface treatment amount of 5% or more are more preferred. The white reflective layer containing the surface-treated white pigment exhibits high reflectivity.

[0168] Examples of commercially available titanium dioxide include DuPont's Ti-pure R931 (trade name) and those described in Research Disclosure (RD) No. 15162.

[0169] Examples of hydrophilic binders include alkali-permeable polymer matrices such as gelatin and polyvinyl alcohol, and cellulose derivatives such as hydroxyethylcellulose and carboxymethylcellulose. When the binder is gelatin, the mass ratio of white pigment to gelatin is preferably 1 / 1 to 20 / 1, and more preferably 5 / 1 to 10 / 1.

[0170] The white reflective layer preferably contains a fade inhibitor. There are no particular restrictions on the fade inhibitor, but for example, those described in Japanese Patent Publication No. 62-30620 and Japanese Patent Publication No. 62-30621 can be used.

[0171] (d) Light-shielding layer The light-shielding layer is provided between the white reflective layer and the photosensitive layer. The light-shielding layer preferably contains a light-shielding agent and a hydrophilic binder.

[0172] The light-shielding agent may be one of those described in (c) Light-shielding agent of the alkali-treated composition-containing material in (1) above. The amount of light-shielding agent varies depending on the sensitivity of the photosensitive material to be shielded, but generally an optical density of 5 to 10 is preferred.

[0173] The binder for the light-shielding layer can be any material capable of dispersing light-shielding agents such as carbon black. Gelatin is a preferred binder.

[0174] The thickness of the light-blocking layer is not particularly limited, as long as it provides sufficient light-blocking performance and does not make the photosensitive sheet too thick.

[0175] (e) Photosensitive layer The photosensitive layer is adjacent to the light-shielding layer and preferably contains a dye image-forming compound and a silver halide emulsion. The photosensitive layer may be a multilayer consisting of a silver halide emulsion layer and a dye image-forming compound layer, or a single layer containing both a silver halide emulsion and a dye image-forming compound. The multilayer case will be described below, but the same applies to the single-layer case.

[0176] (f) Pigment-forming compounds Pigment-forming compounds include yellow pigment-forming compounds, magenta pigment-forming compounds, and cyan pigment-forming compounds. Specific examples of yellow pigment-forming compounds are described in U.S. Patent Nos. 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609, 4,139,383, 4,195,992, 4,148,641, 4,148,643, 4,336,322, Japanese Unexamined Patent Publication No. 51-114930, Japanese Unexamined Patent Publication No. 56-71072, Research Disclosure No. 17630 (1978), and Research Disclosure No. 16475 (1977), among others.

[0177] Specific examples of magenta-forming compounds include U.S. Patent No. 3,453,107, U.S. Patent No. 3,544,545, U.S. Patent No. 3,932,380, U.S. Patent No. 3,931,144, U.S. Patent No. 3,932,308, U.S. Patent No. 3,954,476, U.S. Patent No. 4,233,237, U.S. Patent No. 4,255,509, U.S. Patent No. 4,250,246, and U.S. Patent No. 4,142,891. This is described in the following publications: the Japanese Patent Publication No. 4,207,104, the Japanese Patent Publication No. 4,287,292, the Japanese Unexamined Patent Publication No. 52-106727, the Japanese Unexamined Patent Publication No. 53-23628, the Japanese Unexamined Patent Publication No. 55-36804, the Japanese Unexamined Patent Publication No. 56-73057, the Japanese Unexamined Patent Publication No. 56-71060, the Japanese Unexamined Patent Publication No. 55-134, the Japanese Unexamined Patent Publication No. Hei 7-120901, the Japanese Unexamined Patent Publication No. 8-286343, the Japanese Unexamined Patent Publication No. 8-286344, and the Japanese Unexamined Patent Publication No. 8-292537, among others.

[0178] Specific examples of cyanide-forming compounds are found in U.S. Patent Nos. 3,482,972, 3,929,760, 4,013,635, 4,268,625, 4,171,220, 4,242,435, 4,142,891, 4,195,994, and 4,147,544. This is described in the following publications: U.S. Patent No. 4,148,642, British Patent No. 1,551,138, Japanese Unexamined Patent Publication No. 54-99431, Japanese Unexamined Patent Publication No. 52-8827, Japanese Unexamined Patent Publication No. 53-47823, Japanese Unexamined Patent Publication No. 53-143323, Japanese Unexamined Patent Publication No. 54-99431, Japanese Unexamined Patent Publication No. 56-71061, European Patent (EP) No. 53,037, European Patent (EP) No. 53,040, Research Disclosure No. 17,630 (1978), and Research Disclosure No. 16,475 (1977), among others.

[0179] Pigment-forming compounds that form pigments through coupling can also be used as pigment-forming compounds. Examples of pigment-forming compounds that form pigments through coupling are described in Japanese Patent Publication No. 8-286340, Japanese Patent Publication No. 9-152705, Japanese Patent Publication No. 10-186564, Japanese Patent Publication No. 10-293388, etc.

[0180] Positive-type pigment-forming compounds can also be used. Examples of positive-type pigment-forming compounds are described in Japanese Patent Publication No. 4-156542, 4-155332, 4-172344, 4-172450, 4-318844, 4-356046, 5-45824, 5-45825, 5-53279, 5-107710, 5-241302, 5-107708, 5-232659 and U.S. Patent No. 5,192,649, among others. Positive-type pigment image-forming compounds are preferably used in combination with negative-type silver halide emulsions, as described later.

[0181] Positive-type pigment image-forming compounds can be dispersed by the method described on pages 144 to 146 of Japanese Patent Publication No. 62-215272. The dispersion may also contain the compounds described on pages 137 to 144 of Japanese Patent Publication No. 62-215272. The following compounds are specific examples of these pigment image-forming compounds. In the following compounds, Dye represents a pigment group, a temporarily short-wave pigment group, or a pigment precursor group.

[0182]

[0183]

[0184]

[0185] (g) Silver halide emulsion The silver halide emulsion may be a negative-type silver halide emulsion that mainly forms a latent image on the surface of the silver halide particles, or an internal latent-image direct positive silver halide emulsion that forms a latent image inside the silver halide particles. Internal latent-image direct positive silver halide emulsions include, for example, so-called "conversion-type emulsions" made by utilizing the difference in solubility of silver halides, and "core / shell-type emulsions" in which at least the photosensitive sites of silver halide internal core particles (also called cores) that have been doped with metal ions, chemically sensitized, or both are covered with an external shell (also called a silver halide shell), and these This is described in the specifications of U.S. Patent Nos. 2,592,250 and 3,206,313, British Patent No. 1,027,146, U.S. Patent Nos. 3,761,276, 3,935,014, 3,447,927, 2,297,875, 2,563,785, 3,551,662 and 4,395,478, West German Patent No. 2,728,108, and U.S. Patent No. 4,431,730, etc.

[0186] Furthermore, when using an internal latent image type direct positive silver halide emulsion, it is necessary to provide surface flick nuclei using light or a nucleating agent after image exposure. Examples of nucleating agents include hydrazines described in U.S. Patent No. 2,563,785, No. 2,588,982, etc., hydrazines and hydrazones described in U.S. Patent No. 3,227,552, heterocyclic quaternary salt compounds described in British Patent No. 1,283,835, Japanese Unexamined Patent Publication No. 52-69613, U.S. Patent No. 3,615,615, No. 3,719,494, No. 3,734,738, No. 4,094,683, No. 4,115,122, etc., and compounds having nucleating substituents in the dye molecule as described in U.S. Patent No. 3,718,470. Sensitive dyes, thiourea-linked acylhydrazine compounds described in U.S. Patent Nos. 4,030,925, 4,031,127, 4,245,037, 4,255,511, 4,266,013, 4,276,364, and British Patent No. 2,012,443, etc., and acylhydrazine compounds with heterocyclic groups (thioamide rings, triazole rings, tetrazole rings, etc.) linked as adsorbent groups, as described in U.S. Patent Nos. 4,080,270, 4,278,748, and British Patent No. 2,011,391B, etc., can be used. To reduce the sensitivity of the re-inverted negative image and increase the sensitivity of the inverted positive image, it is also preferable to use metal complexes described in Japanese Patent Publication No. 2002-40607 and Japanese Patent Publication No. 2003-107616. For a preferred method of producing a negative-type silver halide emulsion, the method described in Japanese Patent Publication No. 2006-113291 can be preferably used.

[0187] A spectrally sensitizing dye can be used in combination with a silver halide emulsion. The spectrally sensitizing dye includes a compound represented by formula (1) according to the present invention (i.e., a dye represented by formula (1)) as a spectrally sensitizing dye for green light.

[0188]

[0189] In general formula (1), A represents a phenyl group or a chlorine atom, and R １ and R ２Each of these independently represents a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an aryl group, or a heteroaryl group, and R ３ R represents a hydrogen atom, alkyl group, aralkyl group, alkenyl group, aryl group, or heteroaryl group. １ and R ２ One of them has one sulfonic acid group, while the other does not have a sulfonic acid group or a carboxylic acid group.

[0190] A, R １ , R ２ and R ３ The preferred range and specific examples are the same as those described above for formula (1), which is the compound according to the present invention.

[0191] Preferably, the spectrally sensitizing dye includes, in addition to the dye represented by formula (1), a dye represented by general formula (2).

[0192] In general formula (2), R ４ and R ５ Each of these independently represents a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an aryl group, or a heteroaryl group. ６ X represents an alkyl group with 4 or fewer carbon atoms. １ and X ４ Each of these independently represents a hydrogen atom, an alkyl group, or a chlorine atom. ２ and X ５ Each of these independently represents an alkyl group, alkoxy group, halogen atom, hydrogen atom, hydroxyl group, or phenyl group having four or fewer carbon atoms. １ and X ２ , or X ４ and X ５ They may be linked together to form a benzene ring. ３ is, X ２ It is either linked to form a benzene ring, or it is a hydrogen atom. ６ is, X ５ It is either linked to form a benzene ring, or it is a hydrogen atom.

[0193] The dye represented by formula (2) is a different type of sensitizing dye than the dye represented by formula (1). As described above, the three-dimensional structure of the molecule of the dye represented by formula (1) suppresses intermolecular interactions, and it is presumed that a more uniform mixing state is maintained with other types of sensitizing dyes such as the dye represented by formula (2). As a result, even when mixing multiple sensitizing dyes including the dye represented by formula (1) and the dye represented by formula (2), the spectral characteristics of each sensitizing dye are effectively expressed, making it possible to improve the overall photographic performance. The dye represented by formula (1) and the dye represented by formula (2) in this disclosure can be mixed nicely without forming a complex. Therefore, by mixing the dye represented by formula (1) and the dye represented by formula (2), it is possible to effectively express the desired spectral characteristics from the spectral characteristics of each dye.

[0194] The preferred ranges and specific examples of the dyes represented by formula (1) and formula (2) are the same as those described above for the compound represented by formula (1) and the silver halide photographic material of the present disclosure.

[0195] In addition to the dyes represented by formula (1) and formula (2), the following spectrally sensitized dyes can be used as spectrally sensitized dyes. For specific examples of spectrally sensitized dyes, see Japanese Patent Publication No. 59-180550, Japanese Patent Publication No. 60-140335, RD17029, and U.S. Patents No. 1,846,300, 2,078,233, 2,089,129, 2,165,338, 2,231,658, 2,917,516, 3,352,857, 3,411,916, and 2,295,276. This is described in the specifications of Japanese Patent No. 2,481,698, U.S. Patent No. 2,688,545, U.S. Patent No. 2,921,067, U.S. Patent No. 3,282,933, U.S. Patent No. 3,397,060, U.S. Patent No. 3,660,103, U.S. Patent No. 3,335,010, U.S. Patent No. 3,352,680, U.S. Patent No. 3,384,486, U.S. Patent No. 3,623,881, U.S. Patent No. 3,718,470, and U.S. Patent No. 4,025,349, etc.

[0196] (h) Constituent Photosensitive Sheet The photosensitive sheet preferably has at least three silver halide emulsion layers with different color sensitivity and at least two color-mixing prevention layers located between the silver halide emulsion layers and having a non-diffusible reducing agent. In order to impart different color sensitivity to the at least three silver halide emulsion layers, it is effective and preferable to use the above-mentioned spectral sensitizing dyes having different absorption wavelength distributions. When imparting different color sensitivity to silver halide emulsions, it is preferable that their spectral sensitivity distributions do not overlap as much as possible, but it is not necessary to completely separate them. Among the at least three silver halide emulsion layers, if the sensitivity of one emulsion layer at a specific wavelength is at least twice that of the other at least two silver halide emulsion layers, then they can be considered to have different color sensitivity. In the sensitivity relationship between the at least three silver halide emulsion layers, it is desirable that the sensitivity of one emulsion layer at a specific wavelength is preferably at least five times, more preferably at least ten times, that of the other at least two silver halide emulsion layers. There are no restrictions on the specific wavelengths required to establish these relationships; they may be in the visible, ultraviolet, or infrared range. However, it is preferable that the silver halide emulsions in at least three layers of silver halide emulsion are selected from silver halide emulsions that are sensitive to blue, green, red, or infrared light.

[0197] The emulsion and the pigment-forming compound may be in separate layers, or they may be contained in a single layer. If the pigment-forming compound, when applied, has absorption within the spectral sensitivity range of the emulsion combined with it, then separate layers are preferable.

[0198] The emulsion layer may consist of emulsions having different sensitivities. Furthermore, any layer may be present between the emulsion layer and the pigment image-forming compound layer. For example, providing a layer containing a nucleation and development accelerator as described in Japanese Patent Publication No. 60-173541, or a partition layer as described in Japanese Patent Publication No. 60-15267, can increase the color image density, and providing a reflective layer can increase the sensitivity of the photosensitive sheet. The reflective layer is a layer containing a white pigment and a hydrophilic binder; the preferred white pigment is titanium dioxide, and the preferred hydrophilic binder is gelatin. The amount of titanium dioxide applied is 0.1 g / m². ２ ~8g / m ２ Preferably, it is 0.2 g / m ２ ~4g / m ２ It is more preferable that this be the case. An example of a reflective layer is described in Japanese Patent Publication No. 60-91354.

[0199] In the case of a multi-layered photosensitive layer, it is preferable that the combination units of blue-sensitive emulsion, green-sensitive emulsion, and red-sensitive emulsion are arranged sequentially from the exposure side. Any additional layers may be provided between each emulsion layer unit as needed.

[0200] (i) Color mixing prevention layer: In order to prevent undesirable effects of the development of one emulsion layer on other emulsion layer units, it is preferable to have a color mixing prevention layer having a non-diffusible reducing agent located between the emulsion layers. Since at least one color mixing prevention layer is required between each emulsion layer, it is preferable that the photosensitive sheet has at least two color mixing prevention layers.

[0201] Any known compound can be preferably used as the non-diffusive reducing agent for the color-mixing prevention layer. For example, it is also preferable to use the high molecular weight redox compound described in Japanese Patent Publication No. 5-333501, the phenidone or hydrazine compounds described in International Publication No. 98 / 33760, U.S. Patent No. 4,923,787, etc., and the redox compounds described in German Patent Application Publication No. 19618786A1, European Patent Application Publication No. 839623A1, European Patent Application Publication No. 842975A1, German Patent Application Publication No. 19806846A1, and French Patent Application Publication No. 2760460A1, etc. It is also preferable to use the lactones described in Japanese Patent Publication No. 2000-122243. Particularly preferred as the non-diffusive reducing agent for the color-mixing prevention layer are those selected from non-diffusive hydroquinone derivatives, sulfonamidophenol derivatives, sulfonamidonaphthol derivatives, and lactones. Non-diffusible hydroquinone derivatives are particularly preferred, and dialkylhydroquinone derivatives are especially preferred. Here, the alkyl group can be substituted or unsubstituted alkyl groups, and the substituent is not particularly limited as long as it does not inhibit the "non-diffusibility" of the compound. Specific examples include aryl groups, acyl groups, alkoxycarbonyl groups, and aryloxycarbonyl groups. Furthermore, the total number of carbon atoms in the "dialkyl group" is preferably 12 or more, and more preferably 16 or more.

[0202] The molecular weight of the non-diffusible reducing agent is preferably 350 or more, more preferably 390 or more, and particularly preferably 500 or more. When the color-mixing inhibitor is a polymer, its molecular weight is expressed as the number-average molecular weight. The upper limit of the molecular weight of the non-diffusible reducing agent is not particularly limited when the non-diffusible reducing agent is a polymer, but when it is a compound other than a polymer, it is preferably about 1,000 or less. The optimal amount of non-diffusible reducing agent contained in at least two color-mixing inhibitor layers placed between each silver halide emulsion layer varies depending on the amount of silver halide emulsion used, its shape, particle size, the target maximum color density, etc. However, too much non-diffusible reducing agent will lead to a decrease in color density and a delay in image formation time, while too little will cause clouding of the color hue. Therefore, the amount of non-diffusible reducing agent should be set taking these factors into consideration. The decrease in color density when the amount of coated silver is reduced can be effectively suppressed by setting the amount of coated silver halide to these non-diffusible reducing agents in a specific ratio, and by using a specific amount of negative-type silver halide emulsion as the silver halide emulsion. The total number of moles of silver halide applied is in the range of 5 to 10 times the total number of moles of the non-diffusible reducing agent used in the color mixing prevention layer. The total number of moles of the non-diffusible reducing agent applied is preferably 0.5 mmol / m². ２ ~1.5mmol / m ２ The range, more preferably 0.8 mmol / m² ２ ~1.2mmol / m ２ This is within the scope of [the specified range]. Specific examples of non-diffusible reducing agents are given below, but this disclosure is not limited to these.

[0203]

[0204] The non-diffusible reducing agent is preferably dissolved in a high-boiling point organic solvent and present in the color-mixing prevention layer as fine oil droplets obtained by emulsification dispersion. The high-boiling point organic solvent is preferably one with a dielectric constant in the range of 4.0 to 8.0. The high-boiling point organic solvent may be a mixture of two or more types. Examples of preferred high-boiling point organic solvents include esters such as phthalates and phosphate esters, organic acid amides, and ketones. Here, the dielectric constant was measured using the transformer bridge method (Ando Electric TRS-10T) under conditions of 25°C and 10kHz. The boiling point of the high-boiling point organic solvent is preferably 140°C or higher and its melting point is preferably 100°C or lower, and more preferably 160°C or higher and its melting point is 70°C or lower. The high-boiling point organic solvent may be a solid at room temperature, in which case the dielectric constant is the value measured in a liquid (supercooled state). The amount (by weight) of high-boiling point organic solvent used relative to the non-diffusible reducing agent in the color-mixing prevention layer is preferably 0.3 to 20, more preferably 0.5 to 10, and even more preferably 1 to 8.

[0205] As long as it provides sufficient color reproduction capabilities and does not make the photosensitive sheet too thick, the thickness of the photosensitive layer is not particularly limited.

[0206] (j) The photosensitive sheet may have an irradiation prevention layer, a UV absorber layer, a protective layer, etc., as needed. The thickness of the photosensitive sheet is not particularly limited, as long as it does not make the color diffusion transfer film unit too thick.

[0207] [3] Transparent cover sheet (a) Second transparent support The support of the transparent cover sheet may be any smooth transparent support commonly used for photographic photosensitive materials. Preferred supports include cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. The support preferably contains a small amount of dye to prevent light piping. It is also preferable to provide an undercoat layer on the support.

[0208] (b) Neutralizing layer The neutralizing layer (also called the neutralizing layer) is a layer containing a sufficient amount of acidic substance to neutralize the alkali introduced from the alkali treatment composition. If necessary, it may also be a multilayer structure consisting of layers such as a neutralization rate adjustment layer (also called the neutralization timing layer) and an adhesion strengthening layer.

[0209] Preferred acidic substances include substances containing acidic groups with a pKa of 9 or less (or precursor groups that produce acidic groups with a pKa of 9 or less by hydrolysis), and even more preferred acidic substances are higher fatty acids such as oleic acid as described in U.S. Patent No. 2,983,606, polymers of acrylic acid, methacrylic acid, or maleic acid and their partial esters or acid anhydrides as disclosed in U.S. Patent No. 3,362,819; copolymers of acrylic acid and acrylic acid esters as disclosed in French Patent No. 2,290,699; and latex-type acidic polymers as disclosed in U.S. Patent No. 4,139,383 and RD No. 16102 (1977). In addition, acidic substances disclosed in U.S. Patent No. 4,088,493, Japanese Unexamined Patent Publication No. 52-153739, Japanese Unexamined Patent Publication No. 53-1023, Japanese Unexamined Patent Publication No. 53-4540, Japanese Unexamined Patent Publication No. 53-4541, Japanese Unexamined Patent Publication No. 53-4542, etc. are also preferred.

[0210] Other examples of acidic polymers include copolymers of vinyl monomers such as ethylene, vinyl acetate, and vinyl methyl ether with maleic anhydride and their n-butyl esters, copolymers of butyl acrylate and acrylic acid, cellulose, and acetate hydrodienphthalate.

[0211] Acidic polymers can be used in combination with hydrophilic polymers. Examples of hydrophilic polymers include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified forms), carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and polymethyl vinyl ether. Among these, polyvinyl alcohol is preferred. Other polymers besides hydrophilic polymers, such as cellulose acetate, may also be mixed with the acidic polymer.

[0212] The amount of acidic polymer applied is determined by the amount of alkali in the alkali treatment composition. The equivalent ratio of acidic polymer to alkali per unit area is preferably 0.9 to 2.0. If there is too little acidic polymer, the hue of the transfer dye will change or stains will occur in the white areas. If there is too much, it will also cause problems such as changes in hue or a decrease in lightfastness. A more preferable equivalent ratio is 1.0 to 1.3. The amount of hydrophilic polymer mixed in will also degrade the quality of the photograph if it is too much or too little. The mass ratio of hydrophilic polymer to acidic polymer is preferably 0.01 to 10, more preferably 0.1 to 3.0.

[0213] Additives can be incorporated into the neutralization layer for various purposes. For example, general film-forming agents may be added to harden the neutralization layer, or polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, and glycerin may be added to improve the brittleness of the film. In addition, antioxidants, fluorescent whitening agents, development inhibitors, and their precursors may be added as needed.

[0214] Useful materials for the neutralization timing layer used in combination with the neutralization layer include polymers that reduce alkali permeability, such as gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, and partially hydrolyzed polyvinyl acetate; latex polymers that increase the activation energy of alkali permeation by copolymerizing a small amount of hydrophilic comonomers such as acrylic acid monomers; and polymers having lactone rings.

[0215] In particular, timing layers using cellulose acetate as disclosed in Japanese Patent Publication No. 54-136328, U.S. Patent No. 4,267,262, U.S. Patent No. 4,009,030, U.S. Patent No. 4,029,849, etc.; acrylic as disclosed in Japanese Patent Publication No. 54-128335, Japanese Patent Publication No. 56-69629, Japanese Patent Publication No. 57-6843, U.S. Patent No. 4,056,394, U.S. Patent No. 4,061,496, U.S. Patent No. 4,199,362, U.S. Patent No. 4,250,243, U.S. Patent No. 4,256,827, U.S. Patent No. 4,268,604, etc. Latex polymers copolymerized in small amounts with hydrophilic comonomers such as acids; polymers having monoacrylic or monomethacrylic esters of polyhydric alcohols, as disclosed in Japanese Patent Publication No. 11-2890; polymers having lactone rings, as disclosed in U.S. Patent No. 4,229,516; and polymers disclosed in other publications such as Japanese Patent Publication No. 56-25735, Japanese Patent Publication No. 56-97346, Japanese Patent Publication No. 57-6842, European Patent (EP) Publication No. 31,957A1, European Patent Publication No. 37,724A1, and European Patent Publication No. 48,412A1 are particularly useful.

[0216] In addition, the following documents may also be used: U.S. Patent No. 3,421,893, U.S. Patent No. 3,455,686, U.S. Patent No. 3,575,701, U.S. Patent No. 3,778,265, U.S. Patent No. 3,785,815, U.S. Patent No. 3,847,615, U.S. Patent No. 4,088,493, U.S. Patent No. 4,123,275, U.S. Patent No. 4,148,653, U.S. Patent No. 4,201,587, U.S. Patent No. 4,288,523, U.S. Patent No. 4,297,431, West German Patent Application Publication (OLS) No. 1,622,936, West German Patent Application Publication No. 2,162,277, RD15162, No. 151 (1976), etc.

[0217] The neutralization timing layer may contain a developer inhibitor and / or its precursor disclosed in U.S. Patent No. 4,009,029, West German Patent Application (OLS) No. 2,913,164, West German Patent Application Publication No. 3,014,672, Japanese Unexamined Patent Publication No. 54-155837, Japanese Unexamined Patent Publication No. 55-138745, etc., or a hydroquinone precursor disclosed in U.S. Patent No. 4,201,578, or other photographic additives or their precursors. Furthermore, providing an auxiliary neutralization layer as described in Japanese Unexamined Patent Publication No. 63-168648 and Japanese Unexamined Patent Publication No. 63-168649 is effective in reducing changes in transfer concentration over time after processing.

[0218] The neutralization timing layer may contain multiple of these materials. Multiple materials may be included in one layer, or they may be included in separate layers.

[0219] (c) Other layers: In addition to the layer having a neutralizing function, the transparent cover sheet may also have layers with auxiliary functions, such as a back layer, a protective layer, a filter dye layer, etc.

[0220] The back layer is provided to adjust curl and provide slipperiness. The back layer may contain filter dyes. The protective layer is mainly used to prevent adhesion to the back surface of the cover sheet and to prevent adhesion to the protective layer of the photosensitive material when the photosensitive material and the cover sheet are stacked. If the transparent cover sheet contains dyes, the sensitivity of the photosensitive layer can be adjusted. Filter dyes may be added to the support of the cover sheet, to the neutralizing layer, the back layer, the protective layer, the mordant capture layer, etc. Alternatively, a layer of filter dye alone may be provided.

[0221] The diffusion transfer type silver halide photographic photosensitive material relating to this disclosure may contain other known additives in each layer.

[0222] The present disclosure will be further explained with reference to the following examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not deviate from the spirit of the present disclosure. Therefore, the scope of the present disclosure is not limited to the following specific examples. In these examples, unless otherwise specified, "%" and "parts" mean "mass percent" and "parts by mass," respectively.

[0223] (Synthesis Example 1) Intermediate 1-1 was synthesized according to the following synthesis scheme. 100 g of 2-methyl-5-phenylbenzoxazole and 345 g of ethyl p-toluenesulfonate were added and mixed, then stirred at 150°C for 2 hours. After the reaction was complete, 240 mL of acetone and 1440 mL of ethyl acetate were added at 50°C, and the precipitated solid was filtered off and washed with 100 mL of acetone and 240 mL of ethyl acetate to obtain 146 g of intermediate 1-1 (yield 75%).

[0224]

[0225] (Synthesis Example 2) Next, intermediates 1-2 were synthesized according to the following synthesis scheme. 75 g of intermediate 1-1, 53.9 g of N,N'-diphenylformamidine, 23.4 g of acetic anhydride, and 375 mL of acetic acid were added and mixed, then stirred at 125°C for 3 hours. After the reaction was complete, 225 mL of methanol and 1275 mL of ethyl acetate were added at 60°C, and the precipitated solid was filtered off and washed with 900 mL of ethyl acetate to obtain 76.5 g of intermediate 1-2 (yield 82%).

[0226]

[0227] (Synthesis Example 3) Intermediate 2-1 was synthesized according to the following synthesis scheme. 50 g of 2,4-dichlorobenzonitrile, 100 mL of concentrated sulfuric acid, and 100 mL of methanesulfonic acid were added and mixed, then cooled to 0°C. 100 mL of fuming nitric acid was added dropwise at 10°C or below, and the mixture was stirred at 10°C or below for 3 hours. After the reaction was complete, the reaction solution was added dropwise to 2000 mL of water, the precipitated solid was filtered off, and then washed with 250 mL of water to obtain 61.8 g of intermediate 2-1 (yield 98%).

[0228]

[0229] (Synthesis Example 4) Next, intermediate 2-2 was synthesized according to the following synthesis scheme. 40 g of intermediate 2-1, 400 mL of methanol, and 36.9 mL of a 70% aqueous solution of ethylamine were added and mixed, then stirred at 40°C for 4 hours. After the reaction was complete, 800 mL of water was added, and the precipitated solid was filtered off and washed with 700 mL of water to obtain 38.2 g of intermediate 2-2 (yield 92%).

[0230]

[0231] (Synthesis Example 5) Next, intermediates 2-3 were synthesized according to the following synthesis scheme. 32.2 g of reduced iron, 0.72 g of ammonium chloride, 189 mL of 2-propanol, 26.1 mL of water, and 0.720 mL of acetic acid were mixed and stirred at 75°C for 1 hour. 30 g of intermediate 2-3 and 117 mL of tetrahydrofuran were mixed and added dropwise to the reaction mixture. After addition, the mixture was stirred for 1 hour, then 12 mL of water, 1.1 g of sodium hydroxide, 0.72 g of activated carbon, and 18.0 g of CeLite® were added. After filtering off the insoluble matter, the mixture was washed with a mixed solvent of 150 mL of tetrahydrofuran and 10 mL of water. 1200 mL of water was added to the obtained filtrate, and the precipitated solid was filtered off and washed with 180 mL of water to obtain 23.7 g of intermediate 2-3 (yield 91%).

[0232]

[0233] (Synthesis Example 6) Next, intermediate 2-4 was synthesized according to the following synthesis scheme. 30 g of intermediate 2-3, 135 mL of acetic acid, and 54.0 mL of acetic anhydride were added and mixed, then stirred at 130°C for 4 hours. After the reaction was complete, 600 mL of water was added, and the precipitated solid was filtered off and washed with 240 mL of water to obtain 27.6 g of intermediate 2-4 (yield 82%).

[0234]

[0235] (Synthesis Example 7) Next, intermediate 2-5 was synthesized according to the following synthesis scheme. 40 g of intermediate 2-4, 186 g of 1,4-butanesultone, and 200 mL of anisole were added and mixed, then stirred at 160°C for 6 hours. After the reaction was complete, 600 mL of ethyl acetate was added, and the precipitated solid was filtered off and washed with 320 mL of ethyl acetate to obtain 64.2 g of intermediate 2-5 (yield 99%).

[0236]

[0237] (Example 1) (Synthesis of Compound A-1) Next, Compound A-1 was synthesized according to the following synthesis scheme. 68.6 g of intermediate 1-2, 40.0 g of intermediate 2-5, 500 mL of acetonitrile, 500 mL of N,N-dimethylformamide, 34.4 g of acetic anhydride, and 68.3 g of triethylamine were added and mixed, then stirred at 100°C for 2 hours. After the reaction was complete, the precipitated solid was filtered off and washed with 400 mL of acetonitrile. The obtained solid was mixed with 2200 mL of methanol, stirred at 60°C for 1 hour, filtered off the solid, and washed with 320 mL of methanol to obtain 66.0 g of Compound A-1 (yield 97%).

[0238] Compound A-1 is the compound of A-1 as follows: １ Confirmed by H-NMR. １ The chemical shift (δ) values ​​obtained by 1H-NMR analysis were as follows: １ H-NMR (CDCl ３ / MeOD=1 / 1): δ 8.16 (m, 2H), 7.77 (s, 1H), 7.60-7.40 (m, 8H), 6.06 (d, 1H), 5.78 (d, 1H), 4. 41 (m, 4H), 4.19 (q, 2H), 3.01 (t, 2H), 2.12 (m, 4H), 1.63 (t, 3H), 1.54 (t, 3H)

[0239]

[0240] (Example 2) (Synthesis of Compound A-2) Compound A-2 was obtained in the same manner as in Synthesis Examples 1 to 8, except that 1,3-propanesultone was used instead of ethyl p-toluenesulfonate in Synthesis Example 1, and ethyl p-toluenesulfonate was used instead of 1,4-butanesultone in Synthesis Example 7.

[0241] Compound A-2 is the compound of A-2 as follows: １ Confirmed by H-NMR. １ The chemical shift (δ) values ​​obtained by 1H-NMR analysis were as follows: １ H-NMR (CDCl ３ / MeOD=1 / 1): δ 8.13 (t, 1H), 7.95 (s, 1H), 7.77 (s, 1H), 7.60-7.40 (m, 8H), 6.16 (d, 1H), 6. 03 (d, 1H), 4.43 (m, 6H), 3.02 (t, 2H), 2.36 (m, 2H), 1.63 (m, 3H), 1.61 (t, 3H)

[0242]

[0243] (Example 3) (Synthesis of Compound A-3) Compound A-3 was obtained in the same manner as in Synthesis Examples 1 to 8, except that benzyl bromide was used instead of ethyl p-toluenesulfonate in Synthesis Example 1.

[0244] Compound A-3 is the compound of A-3 described below. １ Confirmed by H-NMR. １ The chemical shift (δ) values ​​obtained by 1H-NMR analysis were as follows: １ H-NMR (CDCl ３ / MeOD=1 / 1): δ 8.17 (m, 2H), 7.83 (s, 1H), 7.60-7.40 (m, 13H), 6.09 (d, 1H), 5.78 (d, 1H), 5.32 (s, 2H), 4.41 (m, 4H), 3.00 (t, 2H), 2.10 (m, 4H), 1.61 (t, 3H)

[0245]

[0246] (Example 4) (Synthesis of Compound A-4) Compound A-4 was obtained in the same manner as in Synthesis Examples 1 to 8, except that allylamine was used instead of a 70% aqueous solution of ethylamine in Synthesis Example 4.

[0247] Compound A-4 is the compound A-4 described below. １ Confirmed by H-NMR. １ The chemical shift (δ) values ​​obtained by 1H-NMR analysis were as follows: １ H-NMR (CDCl ３ / MeOD=1 / 1): δ 8.16 (m, 2H), 7.72 (s, 1H), 7.60-7.40 (m, 8H), 6.21 (m, 1H), 6.07 (d, 1H), 5.80 (d, 1H), 5.56 (d, 1 H), 5.30 (d, 1H), 5.01 (m, 2H), 4.39 (t, 2H), 4.19 (q, 2H), 3.01 (t, 2H), 2.10 (m, 4H), 1.52 (t, 3H)

[0248]

[0249] (Example 5) (Synthesis of Compound A-5) Compound A-5 was obtained in the same manner as in Synthesis Examples 1 to 8, except that pentyl p-toluenesulfonate was used instead of ethyl p-toluenesulfonate in Synthesis Example 1.

[0250] Compound A-5 is the compound of A-5 as follows: １ Confirmed by H-NMR. １ The chemical shift (δ) values ​​obtained by 1H-NMR analysis were as follows: １ H-NMR (CDCl ３ / MeOD=1 / 1): δ 8.16 (m, 2H), 7.83 (s, 1H), 7.60-7.40 (m, 8H), 6.08 (d, 1H), 5.78 (d, 1H), 4.41 (m, 4H), 4. 12 (q, 2H), 3.01 (t, 2H), 2.12 (m, 4H), 1.96 (m, 2H), 1.62 (t, 3H), 1.47 (m, 4H), 0.96 (t, 3H)

[0251]

[0252] (Example 6) (Synthesis of Compound A-6) Compound A-6 was obtained in the same manner as in Synthesis Examples 1 to 8, except that 1,3-propanesultone was used instead of ethyl p-toluenesulfonate in Synthesis Example 1, and benzyl bromide was used instead of 1,4-butanesultone in Synthesis Example 7.

[0253] Compound A-6 is the compound of A-6 as follows: １ Confirmed by H-NMR. １ The chemical shift (δ) values ​​obtained by 1H-NMR analysis were as follows: １ H-NMR (CDCl ３ / MeOD=1 / 1): δ 7.99 (t, 1H), 7.88 (s, 1H), 7.85 (s, 1H), 7.60-7.30 (m, 13H), 6.14 (d, 1H), 5.95 (d, 1H), 5.63 (s, 2H), 4.44 (q, 2H), 4.35 (t, 2H), 2.98 (t, 2H), 2.30 (m, 2H), 1.60 (t, 3H)

[0254]

[0255] (Example 7) (Synthesis of Compound A-7) Compound A-7 was obtained in the same manner as in Synthesis Examples 1 to 8, except that 2-methyl-5-chlorobenzoxazole was used instead of 2-methyl-5-phenylbenzoxazole in Synthesis Example 1.

[0256] Compound A-7 is the compound of A-7 as follows: １ Confirmed by H-NMR. １ The chemical shift (δ) values ​​obtained by 1H-NMR analysis were as follows: １ H-NMR (CDCl ３ / MeOD=1 / 1): δ 8.26 (s, 1H), 8.07 (dd, 1H), 7.86 (s, 1H), 7.60 (s, 1H), 7.41 (d, 1H), 7.26 (dd, 1H), 6.17 (d, 1H), 5 .80 (d, 1H), 4.60-4.40 (m, 4H), 4.19 (q, 2H), 3.01 (t, 2H), 2.12 (m, 4H), 1.63 (t, 3H), 1.54 (t, 3H)

[0257]

[0258] (Comparative Compounds) The comparative compounds (D-1) to (D-4) used in the comparative examples are as follows.

[0259]

[0260] (Examples 8 to 20 and Comparative Examples 1 to 7) <Preparation of Substrate for Photosensitive Material> As a coating solution for the substrate and the sixth layer, composition (A) was prepared containing the components shown in Table 2 per 1,000 g of the finished coating solution. The remaining component in composition (A) is water.

[0261]

[0262] Furthermore, the above composition (A) listed in Table 2 has a gelatin coating amount of 0.29 g / m² in Table 3. ２ It was applied in such a way that it would look like this.

[0263] A separate substrate was prepared by laminating a back layer onto a polyethylene terephthalate support, followed by the lamination of the substrate-1st layer and the substrate-2nd layer. On this substrate, four layers, from the substrate-3rd layer to the substrate-6th layer, were simultaneously extruded from a gyser onto a sliding surface at a coating speed of 60 m / min. The image receiving film after coating was stored at 25°C and 55% relative humidity for 7 days to harden. The composition of each layer is shown in Table 3 below.

[0264]

[0265] The details of the compounds used in Table 3 are as follows.

[0266] Surfactants (1): The following compounds

[0267]

[0268] Surfactants (6): The following compounds

[0269]

[0270] Surfactants (7): The following compounds

[0271]

[0272] Additive (1): The following compound

[0273]

[0274] Additive (5): the following compound

[0275]

[0276] Additive (8): carboxymethyl cellulose (CMC Cellogen 6A manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) Additive (10): the following compound

[0277]

[0278] Additive (12): the following compound

[0279]

[0280] Additive (18): the following compound

[0281]

[0282] Hardener (1): the following compound; Hardener (2): the following compound; Hardener (4): the following compound

[0283]

[0284] Polymer mordant (1): the following compound

[0285]

[0286] Ultraviolet absorber (2): the following compound; Ultraviolet absorber (3): the following compound

[0287]

[0288] <Preparation of Silver Halide Emulsion (Emulsion D)> Each emulsion was prepared according to the method for internal latent image type direct positive emulsion D (hereinafter also referred to as emulsion D) described in Japanese Patent Application Laid-Open No. 2002-40607. With respect to the emulsion D described in Japanese Patent Application Laid-Open No. 2002-40607, the type and amount of the sensitizing dye were replaced as shown in Table 5, to prepare Emulsion 1 (Example 8) to Emulsion 13 (Example 20), and Comparative Emulsion 1 (Comparative Example 1) to Comparative Emulsion 7 (Comparative Example 7). That is, as shown in Table 5, emulsion D was prepared using each of the compounds (A-1) to (A-7) according to the present disclosure and comparative compounds (D-1) to (D-4). In Table 5, "-" is indicated when the corresponding compound is not added.

[0289] Provided that the dye was prepared into a solution by the following method: 1 kg of this emulsion was weighed into a pot, heated to 70°C and dissolved. First, 7.7 ml of 0.01% sodium thiosulfate pentahydrate aqueous solution and 5.3 ml of 0.1% additive (a) aqueous solution were added, followed by stirring for 2 hours. Thereafter, after the temperature was lowered to 60°C, 1.6 ml of 30% potassium bromide aqueous solution was added, and 20 ml of water, a predetermined amount of dye solution A and a predetermined amount of dye solution B were added respectively. After stirring for 20 minutes, 1.8 ml of 10% additive (b) aqueous solution was added. Additive (a), additive (b), dye solution A and dye solution B were each prepared as follows.

[0290] Additive (a) is a compound represented by the following formula (3), and has a Mw of 40000. Additive (b) is a compound represented by the following formula (4).

[0291]

[0292]

[0293] Dye solution A was prepared by adding dye A to a mixture of a 20 wt% aqueous solution of surfactant (a) and phenoxyethanol to obtain a 0.75% solution. Surfactant (a) is a compound represented by the following formula (5).

[0294]

[0295] Dye solution B was prepared as follows. 1.3 cc of 1N sodium hydroxide aqueous solution, 200 g of dye B, 5 g of sensitizing dye (1) and 1.1 g of sensitizing dye (2) were mixed and dissolved in 14.2 L of water at 50°C to prepare a first solution. Sensitizing dye (1) is a compound represented by the following formula (6), and sensitizing dye (2) is a compound represented by the following formula (7). Next, a second solution was prepared by mixing 1330 g of gelatin, 75 cc of phenoxyethanol, and 300 cc of 1N sodium hydroxide aqueous solution into 10.7 L of water. Then, the first solution and the second solution were mixed to obtain dye solution B.

[0296]

[0297]

[0298] <Preparation of Photosensitive Material> On the substrate (Subs-1) prepared as described above, five layers, the 7th, 8th, 10th, 11th, and 12th layers, were simultaneously extruded from the gieser onto the slide surface and coated at a coating speed of 60 m / min. The emulsion D of the 10th layer was selected from emulsion 1 (Example 8) to emulsion 13 (Example 20) and comparative emulsion 1 (Comparative Example 1) to comparative emulsion 7 (Comparative Example 7), as shown in Table 5. After coating, the photosensitive material was stored for 7 days under environmental conditions of 25°C and 55% RH relative humidity to allow the hardening reaction to proceed. The sample obtained in this way was designated as silver halide photographic photosensitive material 101. The composition of each layer is shown in Table 4.

[0299]

[0300] The following details each component, which is listed using abbreviations other than those mentioned above in Table 4.

[0301] Additives (2): The following compounds

[0302]

[0303] Additives (3): The following compounds

[0304]

[0305] Additives (10): The following compounds

[0306]

[0307] Additive (11): The compound below Additive (13): The compound below

[0308]

[0309] Additives (14): The following compounds

[0310]

[0311] Nucleating agent (1): The following compound

[0312]

[0313] Surfactants (4): The following compounds

[0314]

[0315] Surfactants (5): The following compounds

[0316]

[0317] High-boiling organic solvent (1): the following compound; High-boiling organic solvent (2): the following compound

[0318]

[0319] Magenta dye-releasing compound (1): the following compound

[0320]

[0321] (Evaluation) The following evaluations were performed using each photosensitive transfer material of Examples 8 (Emulsion 1) to 20 (Emulsion 13) and Comparative Examples 1 (Comparative Emulsion 1) to 7 (Comparative Emulsion 7). The evaluation results are shown in Table 5.

[0322] 1. Photographic Performance Evaluation After subjecting silver halide photographic light-sensitive material 101 to gray gradation exposure, a processing solution was developed under environmental conditions of 25°C and 55% RH, and the density of the image formed by transfer after 24 hours was measured. The maximum density value was measured as Dmax, and the required exposure amount (logarithm) at the point giving a density of 0.7 was measured as sensitivity, and evaluation was performed according to the following evaluation criteria. The measured values and evaluation results are shown in Table 5.

[0323] (Evaluation Criteria for Sensitivity) A: Sensitivity value is 0.65 or more B: Sensitivity value is 0.60 or more and less than 0.65 C: Sensitivity value is less than 0.60

[0324] 2. Evaluation of Oxygen Storage Stability After coating, silver halide photographic light-sensitive material 101 was stored for 7 days under environmental conditions of 25°C and a relative humidity of 55% RH, and additionally stored for 7 days under an oxygen pressure of 10 atm. After subjecting the light-sensitive materials stored under both conditions to gray gradation exposure, a processing solution was developed under environmental conditions of 25°C and 55% RH, and the density of the image formed by transfer after 24 hours was measured. The sensitivity change at the point giving a density of 0.7 was evaluated by the amount of sensitivity change calculated by the following formula. The amounts of sensitivity change and evaluation results are shown in the storage stability column of Table 5.

[0325] Amount of sensitivity change (storage stability) ΔE=E0-E1

[0326] E0: Required exposure to a point to obtain a concentration of 0.7 after 7 days of storage under environmental conditions of 25°C and 55°C and RH. E1: Required exposure to a point to obtain a concentration of 0.7 after 7 days of storage under additional environmental conditions of 10 atm oxygen.

[0327] (Sensitivity evaluation criteria) AA: ΔE is 0.080 or less A: ΔE is greater than 0.080 and 0.10 or less B: ΔE is greater than 0.010 and 0.15 or less C: ΔE is greater than 0.15

[0328] 3. The emulsion from which the reflectance spectrum was obtained was dissolved at 40°C. Titanium oxide was used as the target sample, and the emulsion was placed in a quartz cell (10 mm thick, 30 x 50 mm), and the reflectance from 380 to 800 nm was measured. The obtained reflectance spectrum was subjected to Kubelka-Munk transformation using the following conversion formula to calculate the maximum absorption wavelength (λmax) and the absorption coefficient at the maximum absorption (absorption coefficient @λmax). A larger absorption coefficient @λmax indicates that the sensitizing dye and silver halide are strongly adsorbed, giving the desired absorption. The absorption coefficient at the maximum absorption (absorption coefficient @λmax) and the evaluation results are shown in Table 5.

[0329] Kubelka-Munk conversion formula for absorption coefficient K = (1 - (reflectance / 100)) ２ ) / (2×reflectance / 100)

[0330] (Evaluation criteria for λmax) A: λmax is 560 nm or greater and 570 nm or less B: λmax is less than 560 nm and greater than 570 nm

[0331] (Evaluation criteria for absorption coefficient @λmax) A: Absorption coefficient @λmax value is 9.0 or higher B: Absorption coefficient @λmax value is 8.5 or higher and less than 9.0 C: Absorption coefficient @λmax value is less than 8.5

[0332] Furthermore, for each sample, the ratio of the absorption coefficient at λmax (absorption coefficient @λmax / absorption coefficient @550nm) was calculated when the absorbance at a wavelength of 550 nm was set to 1, and evaluated according to the following criteria. When this value falls within an appropriate range, it means that the two sensitizing dyes are properly mixed and the desired spectral characteristics are achieved. The ratio of the absorption coefficient at λmax (absorption coefficient @λmax / absorption coefficient @550nm) when the absorbance at a wavelength of 550 nm is set to 1, and the evaluation results are shown in Table 5.

[0333] (Evaluation criteria for absorption coefficient @λmax / absorption coefficient @550nm) A: Absorption coefficient @λmax / absorption coefficient @550nm is 1.30 or greater and 1.60 or less B: Absorption coefficient @λmax / absorption coefficient @550nm is 1.25 or greater and less than 1.30, or greater than 1.60 and less than 1.70 C: Absorption coefficient @λmax / absorption coefficient @550nm is less than 1.25, or greater than 1.70

[0334]

[0335] (Example 21) <Preparation of Substrate for Photosensitive Material> As shown in Table 3 of Example 8 above, a back layer was laminated onto a polyethylene terephthalate support, and then substrate layers 1 through 6 were laminated to obtain a laminated substrate (Subs-1). This laminated substrate (Subs-1) was stored for 7 days under environmental conditions of 25°C and 55% RH relative humidity after coating.

[0336] <Preparation of Silver Halide Emulsions (Emulsion E and Emulsion F)> Emulsion E was prepared in the same manner as Emulsion D in Example 8, except that the spherical equivalent diameter was changed from 1.1 μm to 1.0 μm and the aspect ratio was changed from 7 to 5.

[0337] Emulsion F was prepared in the same manner as emulsion D in Example 8, except that the equivalent sphere diameter was changed from 1.1 μm to 0.9 μm and the aspect ratio was changed from 7 to 4.

[0338] <Preparation of Photosensitive Material> For the 18th layer of the silver halide photosensitive material, a composition (P-A) was prepared containing the components shown in Table 6 per 1,000 g of the finished coating solution.

[0339]

[0340] Furthermore, the composition (P-A) listed in Table 6 above has a gelatin coating amount of 0.20 g / m² in Table 6. ２ It was applied in such a way that it would look like this.

[0341] On the substrate (Subs-1) prepared as described above, 18 layers, from the 1st to the 18th layer, were simultaneously extruded from the Gieser onto a slide surface and coated at a coating speed of 60 m / min. After coating, the photosensitive material was stored for 7 days under environmental conditions of 25°C and 55% RH relative humidity to allow the hardening reaction to proceed. The sample obtained in this way was designated as the silver halide photographic photosensitive material 201 of Example 21. The composition of each layer is shown in Tables 7 to 9. In addition, in the above composition (P-A), coarse particles with a diameter of 6 μm were intentionally added to the composition in order to forcibly evaluate the stability against repulsion during coating. By intentionally adding coarse particles that are mixed in at a very low frequency, it is possible to evaluate repulsion in a small coating area.

[0342]

[0343]

[0344]

[0345] The details of the compounds used in Tables 7 to 9, other than those mentioned above, are as follows.

[0346] Additive (4): Compound listed below Additive (6): Compound listed below Additive (7): Compound listed below Additive (9): Polyvinyl alcohol (PVA-220E manufactured by Kuraray Co., Ltd., degree of polymerization approximately 2,000, degree of saponification 88%)

[0347]

[0348] Surfactants (3): The following compounds

[0349]

[0350] Dural agents (3): The following compounds

[0351]

[0352] Yellow pigment-releasing compound (1): The following compound Cyanide pigment-releasing compound (1): The following compound

[0353]

[0354] UV absorber (1): The following compounds

[0355]

[0356] The latent direct positive emulsions A to C and the latent direct positive emulsions G to I were prepared in accordance with the emulsion of sample 101 in Japanese Patent Publication No. 2002-40607. Emulsion G for the fourth layer was prepared in accordance with emulsion RM12 described in paragraphs 0052 to 0053 and 0057 to 0061. Details of the latent direct positive emulsions A to C and the latent direct positive emulsions G to I are shown in Tables 10 and 11. The latent direct positive emulsion D is the emulsion D used in Example 8 (see Table 5). The latent direct positive emulsion E is the emulsion E. The latent direct positive emulsion F is the emulsion F.

[0357]

[0358]

[0359] Sensitizing dyes (1) to (5), (8), and (9): The following compounds

[0360]

[0361]

[0362]

[0363] (Evaluation) The same photographic performance evaluation, oxygen storage stability evaluation, and reflectance spectrum evaluation were performed on the silver halide photographic photosensitive material 201 as in Example 8, and similar results were obtained. Specifically, when the silver halide photographic photosensitive material 201 was evaluated, the sensitivity was rated A, the storage stability was rated AA, the λmax was rated A, the absorption coefficient @λmax was rated A, the absorption coefficient @λmax / absence coefficient @550nm was rated A, and Dmax was 2.26.

[0364] (Examples 22-24) <Preparation of Silver Iodide Microparticle Emulsion YYA-1> 1800 ml of water, 40 g of alkali-treated gelatin with an average molecular weight of 40,000, and 0.5 g of potassium iodide were added to a reaction vessel kept at 40°C and stirred and mixed. Subsequently, 800 ml of a 180 g / l concentration silver nitrate aqueous solution and 800 ml of an aqueous solution containing 175 g / l potassium iodide were added over 50 minutes using a double jet method. After that, the mixture was washed with water using the usual flocculation method, and then alkali-treated gelatin and water were added to adjust the emulsion to contain 60 g of silver and 40 g of gelatin per 1 kg, thereby preparing Silver Iodide Microparticle Emulsion YYA-1 with an equivalent spherical diameter of 0.04 μm.

[0365] <Preparation of Silver Halide Emulsions (Emulsions 14 to 16)> (Preparation of Emulsion 14) Emulsion 14 was prepared in the same manner as in Example 8, except that 0.3 g of silver iodide microparticle emulsion YYA-1 was added after adding a 30% potassium bromide aqueous solution and left for 5 minutes. (Preparation of Emulsion 15) Emulsion 15 was prepared in the same manner as in Example 8, except that 0.6 g of silver iodide microparticle emulsion YYA-1 was added after adding a 30% potassium bromide aqueous solution and left for 5 minutes. (Preparation of Emulsion 16) Emulsion 16 was prepared in the same manner as in Example 8, except that 1.2 g of silver iodide microparticle emulsion YYA-1 was added after adding a 30% potassium bromide aqueous solution and left for 5 minutes.

[0366] <Preparation of Photosensitive Material> The silver halide photographic photosensitive material 101 of Examples 22 to 24 was prepared in the same manner as in Example 8, except that emulsions 14 to 16 prepared above were used instead of emulsion D of the 10th layer.

[0367] (Evaluation) The silver halide photographic photosensitive material 101 of Examples 22 to 24 was evaluated for photographic performance, oxygen storage stability, and reflectance spectrum in the same manner as in Example 8. The evaluation results are shown in Table 12 below. As shown in Table 12, Examples 22 to 24 showed excellent photographic performance, similar to Example 8, and it was confirmed that sensitivity and storage stability were further improved.

[0368]

[0369] From the results shown in Table 5 and the results for the silver halide photographic photosensitive material 201 described above, the silver halide photographic photosensitive material according to this disclosure was excellent in all aspects: λmax, the absorption coefficient at λmax, the ratio of the absorption coefficient at λmax to the absorbance at a wavelength of 550 nm (which is set to 1), sensitivity, and Dmax. Therefore, it was demonstrated that the silver halide photographic photosensitive material according to this disclosure has excellent photographic performance, including photographic sensitivity and color reproducibility. Furthermore, it was demonstrated that the silver halide photographic photosensitive material according to this disclosure also has excellent storage stability. Therefore, it was demonstrated that the silver halide photographic photosensitive material according to this disclosure is excellent in all aspects, including photographic performance, including photographic sensitivity and color reproducibility, and storage stability, and is overall superior.

[0370] The disclosure of Japanese Patent Application No. 2025-057239, filed on 28 March 2025, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. A compound represented by general formula (1). In general formula (1), A represents a phenyl group or a chlorine atom, and R １ and R ２ Each of these independently represents a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an aryl group, or a heteroaryl group, R ３ R represents a hydrogen atom, alkyl group, aralkyl group, alkenyl group, aryl group, or heteroaryl group. １ and R ２ One of them has one sulfonic acid group, while the other does not have a sulfonic acid group or a carboxylic acid group.

2. The compound according to claim 1, wherein A in general formula (1) represents a phenyl group.

3. The compound according to claim 1 or claim 2, which is a pigment.

4. A functional material having a layer containing the compound described in claim 3.

5. A photographic photosensitive material having a layer containing the compound described in claim 3.

6. The silver halide photographic light-sensitive material according to claim 5, wherein said layer further comprises a dye represented by general formula (2). In general formula (2), R ４ and R ５ each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an aryl group, or a heteroaryl group, and R ６ represents an alkyl group having 4 or less carbon atoms, and X １ and X ４ each independently represent a hydrogen atom, an alkyl group, or a chlorine atom, and X ２ and X ５ each independently represent an alkyl group having 4 or less carbon atoms, an alkoxy group, a halogen atom, a hydrogen atom, a hydroxy group, or a phenyl group. X １ and X ２ , or X ４ and X ５ may be linked to each other to form a benzene ring, X ３ is linked to X ２ to form a benzene ring, or is a hydrogen atom, and X ６ is linked to X ５ to form a benzene ring, or is a hydrogen atom.

7. In general formula (2), X １ , X ３ , X ４ , and X ６ Each of these represents a hydrogen atom, X ２ and X ５ The silver halide photographic photosensitive material according to claim 6, wherein each of the terms represents a phenyl group.

8. The silver halide photographic photosensitive material according to claim 6, wherein the layer containing the compound is such that the amount of dye represented by general formula (2) used is 0.1 to 1.0 times by mass compared to the amount of compound represented by general formula (1).

9. The silver halide photographic photosensitive material according to claim 5, which is a diffusion transfer type silver halide photographic photosensitive material.

Images