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(11) | EP 0 510 960 B1 |
| (12) | EUROPEAN PATENT SPECIFICATION |
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Silver halide photographic light sensitive material Photographisches lichtempfindliches Silberhalogenidmaterial Matériau photographique à l'halogénure d'argent sensible à la lumière |
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| Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). |
[0001] The present invention relates to a silver halide photographic light-sensitive material, specifically to a silver halide photographic light-sensitive material which is improved in sharpness and sensitivity, and hardly undergoes fogging when exposed to safe light.
[0002] In recent years, there has been an increasing demand for a silver halide color photographic light-sensitive material (hereinafter often abbreviated as "a color photographic light-sensitive material") improved in image quality and handling properties.
[0003] To improve image quality, it is important to increase sharpness. It is well known in the art that sharpness can be increased by coloring silver halide emulsion layers or other hydrophilic colloidal layers with a dye that absorbs light of specific wavelength, whereby the optical characteristics of a support can be improved and a light-sensitive material can be protected from halation or irradiation.
[0004] Dyes are employed in a light-sensitive material normally for the following purposes:
(1) To eliminate unnecessary absorption of light; specifically, to adjust the spectral composition of light incident upon an emulsion layer to a preferable one, or, to change the amount of incident light to control sensitivity. For this purpose, a layer colored with a dye is provided on the side of an emulsion layer which is far away from a support. Such colored layer is called "a filter layer" and may be provided between two adjacent emulsion layers, when a light-sensitive material comprises a plurality of emulsion layers.
(2) To prevent light, that has passed through an emulsion layer and has been reflected at the interface between the emulsion layer and a support or at the opposite side of the support, from re-entering into the emulsion layer (that is, to prevent halation which makes a photographic image get blurred). For this purpose, a layer colored with a dye is provided between an emulsion layer and a support or on the opposite side (as viewed from an emulsion layer) of a support. Such colored layer is called "an anti-halation layer" and may be provided between two adjacent emulsion layers, when a light-sensitive material comprises a plurality of emulsion layers.
(3) To eliminate light scattering caused by the action of silver halide grains contained in an emulsion layer. Such scattering of light is called "irradiation". For this purpose, an emulsion layer itself is colored with a dye.
[0005] Dyes employed for these purposes must satisfy the following requirements:
- They must have spectral absorption characteristics suited to the purpose;
- They must be capable of being bleached or released from a light-sensitive material during processing to eliminate a fear of contaminating a photographic image.
- They must not affect adversely a photographic emulsion that has been spectrally sensitized. In other words, they must not allow an emulsion to get sensitized, desensitized or fogged.
- They must not fade or discolor with the passage of time.
[0006] For improved sharpness, it is preferred that the spectral sensitivity distribution characteristics of a silver halide emulsion that has been spectrally sensitized and the spectral absorption characteristics of a dye be well-matched. If not, employment of a large amount of a dye will be necessary. Use of a large amount of a dye, however, results in a lowering in sensitivity. If the spectral sensitivity characteristics of an emulsion and the spectral absorption characteristics of a dye differ considerably, sharpness cannot be improved even when a large amount of a dye is employed.
[0007] In the case of a color photographic light-sensitive material for direct appreciation, a cyan dye image must be improved in sharpness to make users feel the photograph has a good image quality. For improved cyan dye image sharpness, in the negative-to-positive method, it is required that the spectral sensitivity distribution of a red-sensitive emulsion layer of a light-sensitive material for direct appreciation should not differ greatly from the spectral absorption distribution of a cyan dye image of an original. In addition, a red-sensitive emulsion layer of a light-sensitive material for direct appreciation is spectrally sensitized such that its spectral sensitivity distribution will culminate within the range of 670 to 720 nm, whereby the spectral sensitivity distribution of a red-sensitive emulsion layer can be prevented from overlapping with the longer wavelength region of the spectral sensitivity distribution of a green-sensitive layer. It is, therefore, preferred that a dye to be contained in a light-sensitive material have an absorption maxima in this wavelength region.
[0008] Many attempts were made to find a dye which satisfies the above requirement. Dyes which were found to satisfy the requirement include oxonol dyes (British Patent No. 506,385, U.S. Patent No. 3,247,127, Japanese Patent Examined Publication Nos. 22069/1964 and 13168/1968); styryl dyes (U.S. Patent No. 1,845,404); merocyanine dyes (U.S. Patent No. 2,493,747, British Patent No. 1,542,807); cyanine dyes (U.S. Patent Nos. 2,843,486 and 3,294,539); and anthraquinone dyes (U.S. Patent No. 2,865,752).
[0009] Of these dyes, oxonol dyes and anthraquinone dyes have been widely employed in silver halide photographic light-sensitive materials for direct appreciation due to their relatively small negative affects on photographic emulsions.
[0010] The inventors made extensive studies to find a dye which satisfies all of the requirements, i.e., a dye having spectral absorption distribution characteristics which are well-matched with the spectral sensitivity distribution characteristics of a silver halide emulsion; capable of being bleached completely in a processing liquid and released readily from a light-sensitive material, and hence, unlikely to contaminate a photographic image; producing no adverse effects, such as sensitization and desensitization, on a silver halide emulsion that has been spectrally sensitized; and exhibiting good time stability in a solution or in a light-sensitive material.
[0011] Through the studies, the inventors found several dyes that satisfied the above requirements. However, when employed in an amount sufficient to improve the sharpness of an image, these dyes adversely affect the sensitivity, which is a matter of crucial importance for a light-sensitive material for direct appreciation. In addition, the inventors found that these dyes deteriorated the safe light suitability of a light-sensitive material.
[0012] During the production or processing of a light-sensitive material, safe light which has spectral energy distribution characteristics suited to the spectral sensitivity distribution characteristics of the light-sensitive material is normally employed for enhanced working efficiency. In the case of color paper, of which the spectral sensitivity distribution has no peaks in the green-sensitive region (green lack), a colored filter which has a maximum transmittance at around 590 nm (generally called "a safe light filter") is employed. A light-sensitive material is required to have a higher sensitivity but not to safe light. Having a lower sensitivity to safe light will be referred to as "safe light suitability".
[0013] Japanese Patent Publication Open to Public Inspection (hereinafter referred to as "Japanese Patent O.P.I. Publication") No. 20830/1977, U.S. Patent No. 3,746,539 and FDR Patent No. 2,928,184 disclose use of specific oxonol dyes for improved safe light suitability.
[0014] However, these oxonol dyes do not fully satisfy the above requirements. In addition, to improve safe light suitability, these dyes must be employed in a large amount, which results in lowered sensitivity. Another serious problem is that these oxonol dyes tend to sensitize or desensitize a silver halide emulsion.
[0015] Japanese Patent O.P.I. Publication No. 235046 discloses the use of a specific oxonol dye in combination with other dyes, by which safe light suitability can be improved without adversely affecting a silver halide emulsion.
[0016] This method is, however, still unsatisfactory in respect of sharpness. In addition, it cannot improve the safe light suitability of a light-sensitive material prepared from an emulsion with a higher silver chloride content, which is suited to rapid processing. In short, this method cannot improve sharpness and safe light suitability without affecting adversely sensitivity.
[0017] An object of the invention is to provide a silver halide photographic light-sensitive material which is improved in sharpness, sensitivity and safe light suitability.
[0018] Another object of the invention is to provide a silver halide photographic light-sensitive material which contains a novel dye which does not produce negative effects, such as sensitization, desensitization and fogging, on a silver halide emulsion; exhibits good time stability in a solution or in a light-sensitive material; and is readily released from a light-sensitive material after processing, therefore, arises no fear of contaminating a photographic image.
[0019] The above object can be attained by a silver halide photographic light-sensitive material comprising a support and provided thereon at least one light-sensitive silver halide emulsion layer, wherein at least one layer selected from said light-sensitive emulsion layer and other hydrophilic colloidal layers contains at least one dye having an absorption maxima at 630-680 nm (the first dye) and at least one dye having an absorption maxima at 680 to 750 nm (the second dye), chosen from Formulae XII to XV below, as measured when they are present in a gelatin film.
[0020] In the present invention, the first dye having an absorption maxima at 630-680 nm is preferably a compound represented by any one of Formulae I to XI, and the second dye having an absorption maxima at 680-750 nm is a compound represented by any one of Formulae XII to XV. Explanation will be made on these compounds.
wherein R1 and R2 each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOH, -COOC2H5, -NHCON(CH3)2, -NHCOCH3 or a cyano group; R3 and R4 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or a heterocyclic group; L1, L2, L3, L4 and L5 each represent a methine group; n1 and n2 each represent 0 or 1; and R5 and R6 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or a heterocyclic group. R5 and R6 may combine with each other to form a 5- or 6-membered ring.
wherein R7 and R8 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -NR9R10, -N(R9)CONR10R11, -N(R9)COR10 or -N(R9)SO2R10; Z1 and Z2 each represent a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring; L6, L7, L8, L9 and L10 each represent a methine group; n3 and n4 each represent 0 or 1; and R9, R10 and R11 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or a heterocyclic group. R9 and R10 may combine with each other to form a 5- or 6-membered ring. The same can be applied to R10 and R11.
wherein R12 and R13 each represent an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -NR16R17, -OR16, -N(R16)COR17, -N(R16)SO2R17, -N(R16)CONR17R18, -COR16, -CONR16R17, -SO2R16, -SO2NR16R17, -COOR16 -S-CH3 or a cyano group; R14 and R15 each have the same meaning as R7 or R8; R16, R17 and R18 each have the same meaning as R9, R10 or R11; L11, L12, L13, L14 and L15 each represent a methine group; and n5 and n6 each represent 0 or 1.
wherein R19 has the same meaning as R7 or R8; Y1 represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or =CR20R21; R20 and R21 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or a heterocyclic group; Z3 and Z4 each represent a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring; L16, L17, L18 and L19 each represent a methine group; and n7 and n8 each represent 0 or 1. R20 and R21 may combine with each other to form a 5- or 6-membered ring.
wherein R22 represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOC2H5 or a cyano group; R23 has the same meaning as R3 or R4; R24 and R25 each have the same meaning as R9 or R10; R26, R27 and R28 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyano group, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, N-(R29)CONR30R31, -SR29, -COOR29 or -SO2NR29R30; R29 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an alkenyl group; R30 and R31 each represent an alkyl group, an aryl group, a heterocyclic group or an alkenyl group; L20, L21 and L22 each represent a methine group; and n9 represents 0 or 1. R24 and R25 may combine with each other to form a 5- or 6-membered ring.
wherein R32 has the same meaning as R7 or R8; R33 and R34 each have the same meaning as R9 or R10; R35 and R36 each have the same meaning as R26, R27 or R28; Y2 has the same meaning as Y1; Z5 has the same meaning as Z3; L23 and L24 each represent a methine group; n10 represents 0, 1 or 2; X1 represents a group capable of being dissociated into anions; and n11 represents 0, 1 or 2. R33 and R34 may combine with each other to form a 5- or 6-membered ring.
wherein R37 and R38 each have the same meaning as R7 or R8; Y3 and Y4 each represent an oxygen atom, a sulphur atom, a selenium atom, a tellurium atom, 〉NC2H5 or =CR20R21; R20 and R21 each represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; Z6 and Z7 each have the same meaning as Z1 or Z2; L25, L26, L27, L28 and L29 each represent a methine group; n12 and n13 each represent 0 or 1; X2 has the same meaning as X1; and n14 represents 0, 1 or 2.
wherein R39, R40, R41, R42, R43 and R44 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; R39 and R40 may combine with each other to form a 5- or 6-membered ring, R41 and R42 may combine with each other to form a 5- or 6-membered ring, R43 and R44 may combine with each other to form a 5- or 6-membered ring, R45, R46, R49 and R50 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyano group, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31 , -SR29, -COOR29 or -SO2NR29R30; R47 and R48 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyano group, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29, -SO3-, -SO3Na, -SO3K or -SO2NR29R30; R29, R30 and R31 each represent an alkyl group, an aryl group, a heterocyclic group or an alkenyl group; X3 has the same meaning as X1; n15 represents 0, 1 or 2; and m represents 0 or 1. R39 and R40 may combine with each other to form a 5- or 6-membered ring. The same can be applied to R41 and R42, and R43 and R44.
wherein R51 and R52 each have the same meaning as R7 or R8; Z8 and Z9 each have the same meaning as Z1 or Z2; L30, L31, L32, L33 and L34 each represent a methine group; and n16 and n17 each represent 0 or 1.
wherein R53 and R54 each have the same meaning as R7 or R8; Z10 and Z11 each have the same meaning as Z1 or Z2; L35, L36, L37, L38 and L39 each represent a methine group; and n18 and n19 each represent 0 or 1.
wherein R55, R56, R57 and R58 each have the same meaning as R7 or R8; X1, X2, X3, X4, X5 and X6 each represent an oxygen atom, a sulfur atom or -NR59R60; R59 and R60 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic atom, a hydroxyl group or -OR61; R61 represents an alkyl group or an aryl group; L40, L41, L42, L43 and L44 each represent a methine group; and n20 and n21 each represent 0 or 1.
wherein R62 and R63 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, - SOR5, -COOH, -COOC2H5, -NHCON(CH3)2, -NHCOCH3,
or a cyano group; R64 and R65 each have the same meaning as R3 or R4; L45, L46, L47, L48 and L49 each represent a methine group; and n32 and n33 each represent 1 or 2.
wherein R66 and R67 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5 or a cyano group; R5 and R6 are each as defined above; Z12 and Z13 each have the same meaning as Z1 or Z2; L50, L51, L52, L53 and L54 each represent a methine group; and n34 and n35 each represent 1 or 2.
wherein R68 and R69 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5 or a cyano group; R5 and R6 are each as defined above; R70 and R71 each have the same meaning as R12 or R13; X7, X8, X9 and X10 each have the same meaning as X1, X2, X3, X4, X5 or X6; L55, L56, L57, L58 and L59 each represent a methine group; and n36 and n37 each represent 1 or 2.
wherein R72 and R73 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6 , -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5 or a cyano group; R74, R76, R77, R78, R80 and R81 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyano group, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29 or -SO2NR29R30; R75 and R79 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyano group, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29, -SO2NR29R30 or -SO3K; R29 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an alkenyl group; R29 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an alkenyl group; R30 and R31 each represent an alkyl group, an aryl group, a heterocyclic group or an alkenyl group; X11 and X12 each have the same meaning as X1, X2, X3, X4, X5 or X6; L60, L61, L62, L63 and L64 each represent a methine group; n38 and n39 each represent 0, 1 or 2.
[0022] Examples of the alkyl group represented by any one of R1 to R81 include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, cyclopentyl and cyclohexyl. These alkyl groups each may be substituted with a hydroxyl group, a cyano group, a sulfo group, a carboxyl group, a halogen atom, an alkoxy group (e.g. methoxy, ethoxy), an aryloxy group (e.g. phenoxy, 4-sulfophenoxy, 2,4-disulfophenoxy), an aryl group (e.g. phenyl, 4-sulfophenyl, 2,5-disulfonyl), an alkoxycarbonyl (e.g. methoxycarbonyl, ethoxycarbonyl) or an aryloxycarbonyl (e.g. phenoxycarbonyl).
[0023] Examples of the aryl group represented by any one of R1 to R81 include phenyl and naphthyl. These aryl groups each may be substituted. Suitable substituents include the alkyl groups represented by any one of R1 to R81 and the groups mentioned above as the substituents for the alkyl group.
[0024] Examples of the heterocyclic group represented by any one of R1 to R81 include pyridyl, thiazolyl, oxazolyl, imidazolyl, furyl, pyrrolyl, pyrazinyl, pyrizinyl, pyridazinyl, purinyl, selenazolyl, sulforanyl, piperidinyl, pyrazolyl and tetrazolyl. These heterocyclic groups each may be substituted. Suitable substituents include the alkyl groups represented by any one of R1 to R81 and the groups mentioned above as the substituents for the alkyl group.
[0025] Examples of the alkenyl group represented by any one of R1 to R81 include vinyl, allyl and butenyl. These alkenyl groups may be substituted. Suitable substituents include the alkyl groups represented by any one of R1 to R81 and the groups mentioned above as the substituents for the alkyl group. Examples of the 5- or 6-membered ring formed by any one of Z1 to Z13 include benzene, naphthalene, thiophene, pyrrole, furan, pyrazole, indole, quinoline, pyridine, pyrazine, pyrimidine, cyclohexene and cyclopentene. These rings each may be substituted. Suitable substituents include the alkyl groups represented by any one of R1 to R81 and the groups mentioned above as the substituents for the alkyl group.
[0026] The methine group represented by any one of L1 to L64 may have a substituent. Suitable substituents include an alkyl group (e.g. methyl, ethyl, i-butyl), an aryl group (e.g. phenyl, p-tolyl, p-carboxyphenyl), an aralkyl group (e.g. benzyl, phenethyl), alkoxy (e.g. methoxy, ethoxy), an aryloxy group (e.g. phenoxy), a halogen atom and a cyano group.
[0027] Representative examples of the dye represented by any one of Formulae I to XV are given below:
[0028] The first dye used according to the invention is characterized in that it has an absorption maxima, as measured when contained in a gelatin film, at from 630 to 680 nm, preferably from 640 to 670 nm. The second dye used according to the invention is characterized in that it has an absorption maxima, as measured when contained in a gelatin film, at from 680 to 750 nm, preferably from 690 to 740 nm.
[0029] It is preferred that the maximum absorption wavelength of the second dye should be longer than that of the first dye by from 20 to 100 nm.
[0030] The dyes used in the invention are contained in a silver halide emulsion layer or in a hydrophilic colloidal layer other than the emulsion layer. Good results can be obtained when these dyes are contained in a layer adjacent to a red-sensitive emulsion layer. If the dyes are diffusible, good results can also be obtained even when they are added to a layer far away from a red-sensitive layer (e.g. an intermediate layer, a protective layer).
[0031] The amounts of the dyes are not limitative, but are preferably from 1 to 200 mg/m2 for the first dye, and from 3 to 100 mg/m2 for the second dye.
[0032] The first and second dyes may be added either simultaneously or at an interval. They may be added in the form of two different solutions or dispersions, or in the form of a mixture.
[0033] The amount ratio of the first dye to the second dye is not limitative, but is preferably from 1:10 to 5:1.
[0034] The dyes used in the invention are contained in a silver halide emulsion layer or in a hydrophilic colloidal layer other than the emulsion layer by the following method: A dye or its organic or inorganic salt is dissolved in an aqueous solution or an organic solvent (e.g. alcohols, glycols, cellosolves, dimethylformamide, dibutyl phthalate, tricresyl phosphate), and emulsified, if necessary. The resultant is added to a coating composition.
[0035] Silver halides usable in the invention include silver iodide, silver iodobromide, silver iodochloride, silver bromide, silver chlorobromide and silver chloride, which have been widely employed in the photographic industry. It is preferable to use silver halide grains having a silver chloride content of 95 mol% or more, a silver bromide content of 5 mol% or less and a silver iodide content of 0.5 mol% or less.
[0036] Preferably, the total amount of binders contained in the silver halide eight-sensitive emulsion layers and other hydrophilic colloid layers is 8.0 g/m2 or less.
[0037] It is possible to employ two or more kinds of silver halide grain differing in halide composition.
[0038] If a silver halide emulsion layer comprises silver halide grains with a silver chloride content of 95 mol% or more, the amount of such grains accounts for 60 wt% or more, preferably 80 wt% or more, of the total amount of silver halide grains contained therein.
[0039] The halide composition of a silver halide grain may be uniform within the entire grain. Alternatively, the halide composition may change, either continuously or discontinuously, with the distance from the center of the grain.
[0040] The size of a silver halide grain is not limitative, but is preferably from 0.2 to 1.6 µm, still preferably from 0.25 to 1.2 µm, for the attainment of rapid processing and improved sensitivity. Grain size measurement can be conducted by a known method, such as that described in Labrand: Grain Size Analysis Method (A.S.T.M. Symposium on Light Microscopy, 1955, pp. 94 to 122) or in Mees & James: Theory of Photographic Process (3rd ed., MacMillan Company, 966, Chapter 2).
[0041] A grain size can be measured by using the area of a projected image of a grain or the approximate value of a grain diameter. An accurate grain size distribution can be obtained based on the project image area or the diameter, as long as grains are in substantially the same shape.
[0042] The size distribution of silver halide grains to be used in the invention may be either monodispersed or polydispersed. In the invention, monodispersed silver halide grains having a variation coefficient of 0.22 or less are preferable. Still preferable are monodispersed silver halide grains with a variation coefficient of 0.15 or less.
[0043] Variation coefficient represents the width of size distribution, and is defined by the following equation: Variation coefficient=Standard deviation of grain size distribution/average grain size Grain size represents the diameter of a grain when the grain is spherical. In the case of a grain which is cubic or in other shapes, grain size represents the diameter of a circle having the same area as that of the projected image of the grain.
[0044] Silver halide grains to be employed in the invention can be prepared by any of the neutral method, the acid method or the ammonia method. Use of seed grains is permissible. Formation of seed grains and growing of silver halide grains may be performed by the same method.
[0045] The shape of a silver halide grain is not limitative. Preferred is a cubic grain having a (100) face as a crystal face. Octahedral, tetradecahedral and dodecahedral silver halide grains may also be employed. Methods of preparing these grains are described in U.S. Patent Nos. 4,183,756, 4,225,666, Japanese Patent O.P.I. Publication No. 26589/1980, Japanese Patent Examined Publication No. 42737/1980 and The Journal of Photographic Science, 21, 39 (1973). Also usable are silver halide grains with a twin crystal face. Silver halide grains may be either identical or different in shape.
[0046] In the invention, it is possible to add a metal ion to a silver halide grain during forming and/or growing the grain so that the metal ion can be contained in its inside and/or on its surface. For this purpose, use can be made of cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (or complex salts), rhodium salts (or complex salts) or iron salts (or complex salts). A reduction sensitization nucleous can be formed in the inside and/or on the surface of a grain in a reductive atmosphere.
[0048] A silver halide emulsion is chemically sensitized by a known method, including the sulfur sensitization method (activated gelatin or a compound containing sulfur which is reactive to a silver ion is used as a sensitizer), the selenium sensitization method, the reduction sensitization method and the noble metal sensitization method. These sensitization methods can be applied either alone or in combination.
[0049] A silver halide emulsion can be spectrally sensitized to a prescribed wavelength region with a sensitizing dye such as a cyanine dye, a merocyanine dye, a composite cyanine dye, a composite merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye and a hemioxanol dye.
[0050] In the invention, it is preferred that a silver halide emulsion for forming a red-sensitive emulsion layer be spectrally sensitized with a sensitizing dye represented by the following Formula RSI or RSII.
wherein R1 and R2 each represent an alkyl group or an aryl group; L1, L2, L3, L4 and L5 each represent a methine group; Y1 and Y2 each represent an oxygen atom, a sulfur atom or a selenium atom; R3 and R4 each represent a lower alkyl group; A1, A2, B1, B2, C1, C2, D1 and D2 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, a cyano group, a nitro group or an alkoxycarbonyl group; X+ represents an acid anion; and n and 1 each represent 0 or 1, provided that 1 is 0 when the compound forms an intramolecular salt. At least one combination selected from A1 and B1, B1 and C1, C1 and D1, A2 and B2, B2 and C2, and C2 and D2 may form a benzene ring by condensation.
[0051] Specific examples of the above groups are given in Japanese Patent Application Specification No. 305532/1990, page 33, line 3 to page 34, line 19.
[0053] These sensitizing dyes may be employed either singly or in combination. They also may be used together with a dye which does not have a sensitizing effect or with a supersensitizer consisting of a compound which does not absorb UV rays, which serves to enhance the sensitizing effect of a sensitizing dye.
[0054] The amount of a sensitizing dye is not limitative, but is preferably from 1 × 10-7 to 1 x 10-3 mol, still preferably from 5 × 10-6 to 5 × 10-4 mol, per mol silver halide.
[0056] For example, a sensitizing dye may be added in the form of a solution obtained by dissolving it in a water-soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellusolve, acetone or a mixture thereof, and optionally, diluting with water. Water may be used instead of a water-solubloe solvent. Use of ultrasonic vibration is advisable to facilitate dissolving. Alternatively, as described in U.S. Patent No. 3,469,987, a dye may be added in the form of a dispersion obtained by dissolving it in a volatile organic solvent and dispersing the resulting solution in a hydrophilic colloid. In the case of a water-insoluble dye, the dye may be added in the form of a dispersion obtained by dispersing it in a water-soluble solvent (see Japanese Patent Examined Publication No. 24185/1971).
[0057] It is also possible to add a sensitizing dye in the form of a dispersion prepared by the acid dissolving dispersion method. Also applicable are methods described in U.S. Patent Nos. 2,912,345, 3,342,605, 2,996,287 and 3,425,835.
[0058] When two or more sensitizing dyes are employed, it is possible to dissolve them separately in different solvents, and mix the resulting solutions before adding to an emulsion. The dye solutions may be added separately without mixing, in which case the order of addition, timing and interval are determined according to the purpose.
[0059] A sensitizing dye may be added to a silver halide emulsion at any time during the process of preparing the emulsion, but preferably immediately before, during or immediately after the chemical ripening.
[0060] The present invention can be applied to both single-colored and multi-colored light-sensitive materials including color negative films, color positive films, color printing paper, light-sensitive materials for display, and the like. The effects of the invention, however, can be produced most satisfactorily when applied to light-sensitive materials for direct appreciation.
[0061] When the invention is applied to a color photographic light-sensitive material, a dye-forming coupler is normally employed. Normally, a silver halide emulsion layer contains a dye-forming coupler which can absorb spectral light to which the emulsion layer is sensitive. Therefore, a yellow dye-forming coupler, a magenta dye-forming coupler and a cyan dye-forming coupler are generally contained in a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, respectively. Combination of a coupler and an emulsion layer, however, is not limited thereto.
[0062] In the invention, acylacetoanilide-based couplers are preferable as a yellow dye-forming coupler. Of acylacetoanilide-based couplers, benzoylacetoanilide-based compounds and pivaloylacetoanilide-based compounds, in particular, example compound Nos. Y-1 to Y-146 described in Japanese Patent O.P.I. Publication No. 85631/1988, example compound Nos. Y-1 to Y-98 described in Japanese Patent O.P.I. Publication No. 97951/1988, example compound Nos. I-1 to I-50 described in Japanese Patent O.P.I. Publication No. 298943/1990 and example compound Nos. Y-1 to Y-24 described in Japanese Patent O.P.I. Publication No. 156748/1989 are advantageous.
[0064] As a magenta dye-forming coupler, 5-pyrazolone-based compounds, pyrazoloazole-based compounds and pyrazolobenzimidazole-based compounds can be preferably employed.
[0066] Also usable are compound Nos. 1 to 4, 8 to 17, 19 to 24, 26 to 43, 45 to 59, 61 to 104, 106 to 121, 123 to 162, 164 to 233 described from page 18, upper right column to page 32, upper right column of Japanese Patent O.P.I. Publication No. 166339/1987, and compound Nos. M-1 to M-29 described in pages 5 to 6 of Japanese Patent O.P.I. Publication No. 100048/1990.
[0067] As a cyan dye-forming coupler, naphthol-based compounds and phenol-based compounds are preferable.
[0068] In the case of a light-sensitive material for direct appreciation (e.g. color printing paper), for improved fastness of a dye image and color reproducibility, it is advisable to employ a 2,5-diacylaminophenol-based compound described in U.S. Patent No. 2,895,826, Japanese Patent O.P.I. Publication Nos. 112038/1975, 109630/1978, 163537/1980 and 96656/1988 and a phenol-based compound containing an alkyl group with 2 or more carbon atoms at the 5th position.
[0069] Examples of a 2,5-diacylaminophenol-based compound include example compound Nos. C-1 to C-25 described in Japanese Patent O.P.I. Publication No. 96656/1988 and examples of a phenol-based compound include example compound Nos. IV-1 to IV-19 described in Japanese Patent O.P.I. Publication No. 196048/1989.
[0070] Also usable are phenol-based compounds described in Japanese Patent O.P.I. Publication No. 132437/1990, pages 31 to 32, in each of which a nitrogen-containing heterocyclic ring is condensed to a phenol nucleous, and phenylimidazole-based compounds.
[0072] A dye-forming coupler is normally added to a hydrophilic colloidal layer in the form of a dispersion obtained by dissolving it in a high-boiling solvent (boiling point: 150°C or more) or a water-insoluble high-molecular substance (if need arises, a low-boiling and/or a water-soluble organic solvent are used in combination), and dispersing the resulting solution in a hydrophilic binder such as an aqueous gelatin solution in the presence of a surfactant. When a low-boiling solvent is employed, it may be removed at the time of dispersing a coupler solution in a binder.
[0073] As a high-boiling solvent, a compound with a dielectric constant (at 30°C) of 6.5 or less, such as esters including phosphoric esters, organic acid amides, ketones and hydrocarbons, are preferable. Combined use of two or more different types of high-boiling solvent is possible.
[0074] A high-boiling solvent is employed in an amount of 0 to 400 wt%, preferably 10 to 100 wt%, based on the amount of a coupler.
[0076] Either lime-treated gelatin or acid-treated gelatin is usable, and there is no restrictions on the raw material (a bone or hide of a cow, a hide of a pig) of gelatin. In the invention, however, it is preferable to use a lime-treated gelatin made from a bone of a cow.
[0077] Silver halide emulsion layers and other hydrophilic colloidal layers may be hardened by the addition of one or more hardeners. Hardeners serve to allow molecules of a binder (or protective colloid) to be cross-linked, thus making these layers tougher.
[0078] Hydrophilic colloidal layers such as a protective layer and an intermediate layer may contain a UV absorber, which serves to prevent fogging caused by electric discharge which is generated when a light-sensitive material is electrified by friction, as well as to prevent UV rays from adversely affecting the quality of a photographic image.
[0079] A light-sensitive material of the invention may contain auxiliary layers such as a filter layer, an anti-halation layer and/or an anti-irradiation layer. These layers and/or silver halide emulsion layers each may contain a dye other than the dye defined herein, which can be released from a light-sensitive material or can be bleached during processing.
[0080] A light-sensitive material of the invention may contain a fluorescent brightener, such as those described in Japanese Patent O.P.I. Publication No. 71049/1984 and 71050/1984. By the addition of a fluorescent brightener, it is possible to obtain a visually clear photographic image. In the case of a water-soluble fluorescent brightener, a fluorescent brightener trapping agent may be added to prevent the brightener from flowing out.
[0081] Any type of compound may be employed as long as it can trap a fluorescent brightener. Advantageous are hydrophilic polymers, such as polyvinyl pyrrolidone, a copolymer containing vinyl pyrrolidone as a repeating unit, a hydrophilic polymer containing a cationic nitrogen-containing active group (described in Japanese Patent O.P.I. Publication No. 42732/1973) and a copolymer of vinyl alcohol and vinyl pyrrolidone (described in Japanese Patent Examined Publication No. 20738/1972).
[0082] Silver halide emulsion layers and/or other hydrophilic colloidal layers each may contain a matting agent, which serves to make a light-sensitive material less glossy, two improve writability and to prevent a light-sensitive material from adhering to other light-sensitive materials.
[0083] A light-sensitive material of the invention may contain a lubricant which serves to minimize slide abrasion.
[0084] A light-sensitive material of the invention may contain an anti-static agent. An anti-static agent may be contained in an anti-static layer provided on the opposite side of a support (where no emulsion layer is provided), or in a silver halide emulsion layer and/or a protective colloidal layer other than an emulsion layer provided on the emulsion layer side of a support.
[0085] Silver halide emulsion layers and/or other hydrophilic colloidal layers each may contain a surfactant as a coating aid, an anti-static agent, a lubricant, an emulsifier, and to prevent a light-sensitive material from adhering to other light-sensitive materials, as well as to improve photographic properties (e.g. to accelerate development, to harden the layers of a light-sensitive material, to sensitize emulsions).
[0086] Silver halide emulsion layers and other component layers of a light-sensitive material of the invention are provided on a variety of supports, in particular, a film of a semisynthetic or synthetic polymer such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide, as well as on paper supports, such as those which coated with baryta or a polymer of an α-olefin (an α-olefin layer may be one which can be removed readily), flexible reflective supports such as synthetic paper, and a rigid material such as glass, metals and ceramics. An extremely thin reflective support of 120 to 160 µm in thickness is also usable.
[0087] A support to be employed in the invention may be either reflective or transparent. To make a support reflective, a white pigment may be contained in the support, or, a white pigment-containing hydrophilic colloidal layer may be provided on the support. Preferable white pigments include barium sulfate and titanium oxide.
[0088] If need arises, a support may be subjected to corona discharge treatment or flame treatment, or exposed to UV rays prior to the provision of layers. Between a support and layers, an undercoating layer may be formed to increase adhesion between the support and the layers, to prevent a light-sensitive material from getting electrified, as well as to improve the dimensional stability, abrasion resistance, hardness, anti-halation property, frictional characteristics and/or other photographic characteristics of a light-sensitive material. Provision of two or more undercoating layers is possible.
[0090] Examples include aminophenol-based compounds and p-phenylenediamine-based compounds. These compounds are normally employed in the form of a salt (e.g. hydrochloride, sulfate), since they are more stable in a salt form than in a free state. The amounts of these compounds are preferably 0.1 to 30 g, still preferably 1 to 15 g, per 1 l of a color developer.
[0091] The most effective primary aromatic amine-based developing agent is an N,N-dialkyl-p-phenylenediamine-based compound. In this compound, the alkyl group and the phenyl group each may be substituted with a substituent.
[0092] In addition to a primary aromatic amine-based color developing agent, a color developer may also contain various known additives, such as an alkalizing agent (e.g. sodium hydroxide, sodium carbonate, potassium carbonate), an alkali metal sulfite, an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener and a thickener.
[0094] Color developing is performed at 15°C or more, normally 20°C to 50°C. For rapid processing, 30°C or more is preferable. Color developing is performed preferably for 20 to 60 seconds, still preferably 30 to 50 seconds.
[0095] A light-sensitive material of the invention is subjected to bleaching and fixing after color developing. Bleaching may be performed simultaneously with fixing.
[0096] After fixing, a light-sensitive material is normally rinsed. Rinsing may be replaced by or performed simultaneously with stabilization. A stabilizer may contain a pH controller, a chelating agent, a fungicide or other additives.
[0097] Conditions of color developing are described in Japanese Patent O.P.I. Publication No. 134636/1983.
EXAMPLES
Example 1
[0099] One side of a paper support was coated with polyethylene, and the other side thereof was coated with polyethylene containing titanium oxide. Then, layers of the following compositions were provided on the polyethylene layer side of the support, whereby a multilayer silver halide color photographic light-sensitive material was obtained (Sample Nos. 1-1). Coating compositions were prepared by the method described below.
[0100] Sample Nos. 1-2 to 1-25 were prepared in substantially the same manner as in the preparation of Sample No. 1-1, except that the type and amount (mg/m2) of dyes contained in the 4th layer were changed to those shown in Table 1. In the table, dyes having an absorption maxima at 580 to 630 nm, dyes having an absorption maxima at 630 to 680 nm and dyes having an absorption maxima at 680 to 750 nm are designated as group A, group B and group C, respectively.
Preparation of Coating Compositions
Coating Composition for the 1st Layer
[0101] Sixty (60) ml of ethyl acetate was dissolved in a mixture of 26.7 g of a yellow coupler (YC-8), 10.0 g of a dye image stabilizer (ST-1), 6.67 g of another dye image stabilizer (ST-2), 0.67 g of an anti-stain agent (HQ-1) and 6.67 g of a high-boiling solvent (DNP). The resulting solution was dispersed in 220 ml of an aqueous 10% gelatin solution that contained 7 ml of a 20% surfactant (SU-1) by means of a ultrasonic homogenizer, whereby a yellow coupler dispersion was obtained. The dispersion was mixed with a blue-sensitive silver halide emulsion (silver content: 10 g) that had been prepared by the method described below, thereby to obtain a coating composition for the 1st layer.
[0102] Coating compositions for the 2nd to 7th layers were prepared in substantially the same manner as in the preparation of the 1st layer coating composition except for ingredients.
[0103] As a hardener, H-1 and H-2 were added to the 2nd layer coating composition and the 4th layer coating composition, respectively. Surfactants SU-1 and SU-2 were added to each coating composition to adjust the surface tension.
Table 1
| Layer | Ingredient | Amount (g/m2) |
| 7th layer (protective layer) | Gelatin | 1.00 |
| Anti-stain agent HQ-2 | 0.002 | |
| Anti-stain agent HQ-3 | 0.002 | |
| Anti-stain agent HQ-4 | 0.004 | |
| Anti-stain agent HQ-5 | 0.02 | |
| DIDP | 0.005 | |
| Fungicide F-1 | 0.002 | |
| 6th layer (UV absorbing layer) | Gelatin | 0.40 |
| UV absorber UV-1 | 0.10 | |
| UV absorber UV-2 | 0.04 | |
| UV absorber UV-3 | 0.16 | |
| Anti-stain agent HQ-5 | 0.04 | |
| DNP | 0.20 | |
| PVP | 0.03 | |
| 5th layer (red-sensitive layer) | Gelatin | 1.30 |
| Red-sensitive silver chlorobromide emulsion Em-R | 0.21 | |
| Cyan coupler CC-8 | 0.17 | |
| Cyan coupler CC-2 | 0.25 | |
| Dye image stabilizer ST-1 | 0.20 | |
| Anti-stain agent HQ-1 | 0.01 | |
| HBS-1 | 0.20 | |
| DOP | 0.20 | |
| 4th layer (UV absorbing layer) | Gelatin | 0.94 |
| UV absorber UV-1 | 0.28 | |
| UV absorber UV-2 | 0.09 | |
| UV absorber UV-3 | 0.38 | |
| Anti-stain agent HQ-5 | 0.10 | |
| DNP Dye (shown in Table 1) | 0.40 |
Table 2
The amount of each silver halide emulsion was indicated as the amount of silver contained
therein.
| Layer | Ingredient | Amount (g/m2) |
| 3rd layer (green-sensitive layer) | Gelatin | 1.40 |
| Green-sensitive silver chlorobromide emulsion Em-G | 0.17 | |
| Magenta coupler MC-10 | 0.23 | |
| Dye image stabilizer ST-3 | 0.20 | |
| Dye image stabilizer ST-4 | 0.17 | |
| DIDP | 0.13 | |
| DBP | 0.13 | |
| 2nd layer (intermediate layer) | Gelatin | 1.20 |
| Anti-stain agent HQ-2 | 0.03 | |
| Anti-stain agent HQ-3 | 0.03 | |
| Anti-stain agent HQ-4 | 0.05 | |
| Anti-stain agent HQ-5 | 0.23 | |
| DIDP | 0.06 | |
| Compound F-1 | 0.002 | |
| 1st layer (blue-sensitive layer) | Gelatin | 1.20 |
| Gelatin, Blue-sensitive silver chlorobromide emulsion Em-B | 0.26 | |
| Yellow coupler YC-8 | 0.80 | |
| Dye image stabilizer ST-1 | 0.30 | |
| Dye image stabilizer ST-2 | 0.20 | |
| Anti-stain agent HQ-1 | 0.02 | |
| DNP | 0.20 | |
| Support | Polyethylene-coated paper | |
- DBP:
- Dibutyl phthalate
- DOP:
- Dioctyl phthalate
- DNP:
- Dinonyl phthalate
- DIDP:
- Diisodecyl phthalate
- PVP:
- Polyvinyl pyrrolidone
H-1 C(CH2SO2CH=CH2)4
Preparation of Blue-sensitive Silver Halide Emulsion
[0104] To 1,000 ml of an aqueous 2% gelatin solution that had been heated to 40°C, liquids A and B were added by the double-jet method over a period of 30 minutes, while controlling pAg and pH to 6.5 and 3.0, respectively. Then, liquids C and D were added over a period of 180 minutes, while controlling pAg and pH to 7.3 and 5.5, respectively. pAg was controlled according to the method described in Japanese Patent O.P.I. Publication No. 45437/1983, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.
| Liquid A | |
| Sodium chloride | 3.42 g |
| Potassium bromide | 0.03 g |
| Water was added to make the total quantity 200 ml. | |
| Liquid B | |
| Silver nitrate | 10 g |
| Water was added to make the total quantity 200 ml. | |
| Liquid C | |
| Sodium chloride | 102.7 g |
| Potassium bromide | 1.0 g |
| Water was added to make the total quantity 600 ml. | |
| Liquid D | |
| Silver nitrate | 300 g |
| Water was added to make the total quantity 600 ml. | |
[0105] After the addition, desalting was performed by using an aqueous 5% solution of Demor N (manufactured by Kao Atlas Co., Ltd) and an aqueous 20% solution of magnesium sulfate. The resultant was then mixed with an aqueous gelatin solution to obtain an emulsion consisting of monodispersed cubic grains with an average grain size of 0.85 µm, a variation coefficient of 0.07 and a silver chloride content of 99.5 mol% (EMP-1).
[0106] EMP-1 was chemically sensitized to an optimum level by using the following compounds, whereby a blue-sensitive silver halide emulsion was obtained (Em-B).
| Sodium thiosulfate | 0.8 mg/mol AgX |
| Chlorauric acid | 0.5 mg/mol AgX |
| Stabilizer STAB-1 | 6 × 10-4 mol/mol AgX |
| Sensitizing dye BS-1 | 4 × 10-4 mol/mol AgX |
| Sensitizing dye BS-2 | 1 × 10-4 mol/mol AgX |
Preparation of Green-sensitive Silver Halide Emulsion
[0107] An emulsion consisting of monodispersed cubic grains with an average grain size of 0.43 µm, a variation coefficient of 0.08 and a silver chloride content of 99.5% (EMP-2) was prepared in substantially the same manner as in the preparation of EMP-1, except that the addition time of liquids A and B and the addition time of liquids C and D were changed.
[0108] EMP-2 was then chemically sensitized at 55°C to an optimum level by using the following compounds, whereby a green-sensitive silver halide emulsion (Em-G) was obtained.
| Sodium thiosulfate | 1.5 mg/mol AgX |
| Chlorauric acid | 1.0 mg/mol AgX |
| Stabilizer STAB-1 | 6 × 10-4 mol/mol AgX |
| Sensitizing dye GS-1 | 4 × 10-4 mol/mol AgX |
Preparation of Red-sensitive Emulsion
[0109] An emulsion consisting of monodispersed cubic grains with an average grain size of 0.50 µm, a variation coefficient of 0.08 and a silver chloride content of 99.5% (EMP-3) was prepared in substantially the same manner as in the preparation of EMP-1, except that the addition time of liquids A and B and the addition time of liquids C and D were changed, and that the following metallic compounds were added to liquid C.
| K2IrC16 | 3.8 × 10-8 mol/mol AgX |
| K4Fe(CN)6 | 1.2 × 10-5 mol/mol AgX |
[0110] EMP-3 was then chemically sensitized at 60°C to an optimum level by using the following compounds, whereby a red-sensitive silver halide emulsion (Em-R) was obtained.
| Sodium thiosulfate | 1.8 mg/mol AgX |
| Chlorauric acid | 2.0 mg/mol AgX |
| Stabilizer STAB-1 | 6 × 10-4 mol/mol AgX |
| Sensitizing dye RS-12 | 1 × 10-4 mol/mol AgX |
Table 1
| Dyes in 4th Layer (mg/m2) | |||
| Sample No. | Group A | Group B | Group C |
| 1-1 | - | - | - |
| 1-2 | - | I-10 (25) | - |
| 1-3 | - | 1-9 (30) | - |
| 1-4 | - | 1-5 (30) | - |
| 1-5 | - | 1-5 (45) | - |
| 1-6 | - | - | D-5 (35) |
| 1-7 | - | - | XIV-4 (30) |
| 1-8 | - | - | XII-3 (40) |
| 1-9 | D-2 (33) | - | - |
| 1-10 | D-1 (20) | - | - |
| 1-11 | D-1 (15) | 1-5 (26) | - |
| 1-12 | D-3 (12) | 1-5 (26) | - |
| 1-13 | D-3 (12) | - | XIV-1 (20) |
| 1-14 | D-1 (15) | - | D-5 (20) |
| 1-15 | D-1 (15) | - | D-4 (25) |
| 1-16 | D-1 (25) | - | D-4 (15) |
| 1-17 | - | I-1 (12) | XII-18 (20) |
| 1-18 | - | 1-18 (15) | XIII-1 (23) |
| 1-19 | - | VII-2 (12) | XIV-1 (20) |
| 1-20 | - | 1-5 (15) | XII-8 (23) |
| 1-21 | - | VI-7 (15) | XII-8 (23) |
| 1-22 | - | IX-4 (15) | XII-8 (30) |
| 1-23 | - | X-1 (15) | XII-8 (23) |
| 1-24 | - | 1-28 (12) | XII-8 (23) |
| 1-25 | - | 1-28 (18) | XII-8 (23) |
| Group A: 580 nm≦λmax≦630 nm Group B: 630 nm≦λmax≦680 nm Group C: 680 nm≦λmax≦750 nm |
|||
Comparative dyes
[0112] Each of the so-obtained light-sensitive materials was exposed to light in the usual way, and processed according to the following procedure.
| Processing procedure | Temperature | Time |
| Color developing | 35.0 ±0.3°C | 45 sec |
| Bleach-fixing | 35.0 ±0.5°C | 45 sec |
| Stabilizing | 30 to 34°C | 90 sec |
| Drying | 60 to 80°C | 60 sec |
| Color developer | |
| Pure water | 800 ml |
| Triethanolamine | 10 g |
| N,N-diethylhydroxylamine | 5 g |
| Potassium bromide | 0.02 g |
| Potassium chloride | 2 g |
| Potassium sulfite | 0.3 g |
| 1-hydroxyethylidene-1,1-diphosphonic acid | 1.0 g |
| Ethylenediaminetetracetic acid | 1.0 g |
| Disodium catechol-3,5-disulfonate | 1.0 g |
| N-ethyl-N-β-methanesulfoneamideethyl-3-methyl-4-aminoaniline sulfate | 4.5 g |
| Fluorescent brightener (4,4-diaminostilbene disulfonic acid derivative) | 1.0 g |
| Potassium carbonate | 27 g |
| Water was added to make the total quantity 1 liter, and pH was adjusted to 10.10. | |
| Bleach-fixer | |
| Dihydrate of ferric ammonium ethylenediaminetetracetate | 60 g |
| Ethylenediaminetetracetic acid | 3 g |
| Ammonium thiosulfate (aqueous 70% solution) | 100 ml |
| Ammonium sulfite (aqueous 40% solution) | 27.5 ml |
| Water was added to make the total quantity 1 liter, and pH was adjusted to 5.7 with potassium carbonate or glacial acetic acid. | |
| Stabilizer | |
| 5-chloro-2-methyl-4-isothiazoline-3-one | 1.0 g |
| Ethylene glycol | 1.0 g |
| 1-hydroxyethylidene-1,1-diphosphonic acid | 2.0 g |
| Ethylenediaminetetracetic acid | 1.0 g |
| Ammonium hydroxide (aqueous 20% solution) | 3.0 g |
| Fluorescent brightener (4,4-diaminostilbene disulfonic acid derivative) | 1.5 g |
| Water was added to make the total quantity 1 liter, pH was adjusted to 7.0 with sulfuric acid or potassium hydroxide. | |
[0113] Then, each light-sensitive material was evaluated for sensitivity, gradation, sharpness, whiteness of background and safe light suitability.
<Sensitivity and Gradation>
[0114] Sensitivity and gradation (γvalue) were examined by means of a densitometer (PDA-65, manufactured by Konica Corp.).
- Sensitivity (S):
- Reciprocal of an exposure which gives a reflectance density of 0.8.
- Gradation (γ) :
- Gradient of a straight line connecting a point (log. exposure) at which the reflectance density becomes 0.5 and a point at which the reflectance density becomes 1.5.
<Sharpness>
[0115] Using each light-sensitive material, a resolving power testing chart was photographed using red light, and the same processing as mentioned above was performed. Each of the resulting cyan dye image was examined for density by means of a microdensitometer (PDM-5, manufactured by Konica Corp.).
- Sharpness (%) :
- (Difference between the maximum density and the minimum density of a portion of an image which contains 5 lines per mm)/(Difference between the maximum density and the minimum density of a portion of an image which contains no lines)
<Whiteness of background>
[0117] Each light-sensitive material was subjected to continuous processing using a color printer processor (CL-PP1701QA, manufactured by Konica Corp.). CPK-2-20 (manufactured by Konica Corp.) was employed as a processing liquid. The processing was continued until the amount of a replenisher exceeded that immediately after the start. The red light reflectance density (DR) of the non-exposed area was measured by the same method as mentioned above.
[0118] Smaller DR values represent higher whiteness. DR should be 0.02 or less. If it exceeds 0.02, users notice the deteriorated whiteness of the non-exposed area. A DR value exceeding 0.025 makes the photographic image practically unusable.
<Safe light suitability>
[0119] A safe light glass for color printing paper (No. 9B, manufactured by Konica Corp.) was fixed to a tungsten light bulb. The resultant was employed as a light source. Each of the light-sensitive materials was exposed to this safe light through an optical wedge for 20 minutes, followed by the same processing as mentioned above.
[0120] Each light-sensitive material was then examined for red light reflectance density by means of the same densitometer as mentioned above (PDA-65).
Safe light sensitivity (SSL):
Reciprocal of the amount of safe light exposure that gives a reflectance density higher than the minimum density by 0.1.
Safe light suitability:
where SSL represents safe light sensitivity, and SR represents sensitivity obtained by exposing to red light through a red filter (KodaküLs wratten filter No. 29) for 0.1 sec.
[0121] Safe light suitability is indicated as a value relative to that of a control sample (set at 0). Smaller rel. SF values represent higher safe light suitability.
[0122] The results are shown in Table 2.
Table 2
| Sample No. | Relative sensitivity | Sharpness | Safe light suitability (rel. SF) | Whiteness of background |
| 1-1 (Comparative) | 188 | 0.39 | +0.31 | 0.014 |
| 1-2 (Comparative) | 101 | 0.69 | +0.02 | 0.015 |
| 1-3 (Comparative) | 97 | 0.68 | +0.03 | 0.016 |
| 1-4 (Comparative) | 100 | 0.67 | 0 | 0.018 |
| 1-5 (Comparative) | 70 | 0.74 | -0.05 | 0.021 |
| 1-6 (Comparative) | 117 | 0.72 | +0.21 | 0.022 |
| 1-7 (Comparative) | 112 | 0.74 | +0.19 | 0.019 |
| 1-8 (Comparative) | 120 | 0.73 | +0.23 | 0.017 |
| 1-9 (Comparative) | 159 | 0.47 | -0.05 | 0.018 |
| 1-10(comparative) | 175 | 0.44 | -0.03 | 0.017 |
| 1-11 (Comparative) | 94 | 0.68 | -0.02 | 0.019 |
| 1-12 (Comparative) | 95 | 0.67 | -0.01 | 0.019 |
| 1-13 (Comparative) | 108 | 0.72 | +0.02 | 0.018 |
| 1-14 (Comparative) | 111 | 0.71 | +0.03 | 0.023 |
| 1-15 (Comparative) | 106 | 0.71 | +0.02 | 0.021 |
| 1-16 (Comparative) | 107 | 0.60 | -0.01 | 0.020 |
| 1-17 (Invention) | 103 | 0.75 | -0.03 | 0.017 |
| 1-18 (Invention) | 101 | 0.80 | -0.02 | 0.016 |
| 1-19 (Invention) | 99 | 0.82 | -0.02 | 0.017 |
| 1-20 (Invention) | 107 | 0.79 | -0.01 | 0.017 |
| 1-21 (Invention) | 116 | 0.77 | -0.05 | 0.017 |
| 1-22 (Invention) | 104 | 0.84 | -0.03 | 0.015 |
| 1-23 (Invention) | 105 | 0.84 | -0.02 | 0.017 |
| 1-24 (Invention) | 107 | 0.80 | -0.04 | 0.015 |
| 1-25 (Invention) | 100 | 0.83 | -0.03 | 0.016 |
[0123] Sensitivity was indicated as a value relative to that of sample No. 1-4 which was set at 100. Also, safe light suitability was indicated as a value relative to that of sample No. 1-4 which was set at 0.
[0124] From the results, it is understood that the combined use of a dye of group B (630 nm≦λmax≦680 nm) and a dye of group C (630 nm≦λmax≦750 nm) (sample Nos. 17-25) resulted in significantly improved sharpness and safe light suitability. Comparative sample Nos. 1 to 16, in each of which dyes were employed in the combination manner falling outside the scope of the invention, were not satisfactory in sharpness, safe light suitability, sensitivity and whiteness. The samples of the invention were also found to be excellent in sensitivity and whiteness of background.
Example 2
[0125] Light-sensitive materials (Sample Nos. 2-1 to 17) were prepared in substantially the same manner as in the preparation of Sample No. 1-1, except that the yellow coupler Y-8, the magenta coupler MC-10 in the 3rd layer and the cyan coupler in the 5th layer were replaced by YC-10, MC-13 and CC-3 (equimolar), respectively, a dye AI-2 was added to the intermediate layer in an amount of 7 mg/m2, the red-sensitive emulsion Em-R in the 5th layer was replaced by those shown in Table 3, and the dye in the 4th layer was changed to those shown in Table 3.
Preparation of Red-sensitive Silver Halide Emulsion
[0126] To 1,000 ml of an aqueous 2% gelatin solution that had been heated to 40°C, liquids A and B were added by the double-jet method over a period of 15 minutes, while controlling pAg and pH to 6.5 and 3.0, respectively. Then, liquids C and D were added also by the double-jet method over a period of 110 minutes, while controlling pAg and pH to 7.5 and 5.5, respectively.
| Liquid A | |
| Sodium chloride | 3.18 g |
| Potassium bromide | 0.35 g |
| Water was added to make the total quantity 200 ml. | |
| Liquid B | |
| Silver nitrate | 10 g |
| Water was added to make the total quantity 200 ml. | |
| Liquid C | |
| Sodium chloride | 95.9 g |
| Potassium bromide | 13.7 g |
| K2IrC16 | 0.03 mg |
| K4Fe(CN)6 | 8.0 mg |
| Water was added to make the total quantity 600 ml. | |
| Liquid D | |
| Silver nitrate | 300 g |
| Water was added to make the total quantity 600 ml. | |
[0127] After the addition, desalting was performed by using an aqueous 5% solution of Demor N (manufactured by Kao Atlas, Co., Ltd.) and an aqueous 20% solution of magnesium sulfate. The resultant was then mixed with an aqueous gelatin solution, whereby an emulsion consisting of cubic monodispersed grains with an average grain size of 0.52 µm, a variation coefficient of 0.08 and a silver chloride content of 93.0 mol% (EMP-4).
[0128] EMP-4 was then subjected to chemical ripening to an optimum level at 60°C by using the following compounds, thereby to obtain a red-sensitive silver halide emulsion (Em-R-11).
| Sodium thiosulfate | 2.2 mg/mol AgX |
| Chlorauric acid | 2.0 mg/mol AgX |
| Stabilizer STAB-2 | 5 × 10-4 mol/mol AgX |
| Sensitizing dye SR-15 | 1.5 × 10-4 mol/mol AgX |
Table 3
| Sample No. | Red-sensitive emulsion in the 5th layer | Dyes in the 4th layer (mg/m2) | ||
| Group A | Group B | Group C | ||
| 2-1 | Em-R-II | - | 1-24 (30) | - |
| 2-2 | Em-R-II | D-1 (25) | - | - |
| 2-3 | Em-R-II | D-1 (15) | 1-24 (25) | - |
| 2-4 | Em-R-II | D-1 (15) | - | D-4 (20) |
| 2-5 | Em-R-II | - | 1-9 (15) | D-4 (20) |
| 2-6 | Em-R-II | - | VII-2 (12) | XII-3 (20) |
| 2-7 | Em-R-II | - | 1-7 (15) | XV-1 (20) |
| 2-8 | Em-R-II | - | 1-22 (15) | XII-18 (20) |
| 2-9 | Em-R | - | 1-24 (30) | - |
| 2-10 | Em-R | D-1 (25) | - | - |
| 2-11 | Em-R | D-1 (15) | 1-24 (25) | - |
| 2-12 | Em-R | D-1 (15) | - | D-4 (20) |
| 2-13 | Em-R | - | 1-9 (15) | D-4 (20) |
| 2-14 | Em-R | - | VII-2 (12) | XII-3 (20) |
| 2-15 | Em-R | - | 1-7 (15) | XV-1 (20) |
| 2-16 | Em-R | - | 1-22 (15) | XII-18 (20) |
| 2-17 | Em-R | - | 1-6 (15) | XII-18 (20) |
| Group A: 580 nm≦λmax≦630 nm Group B: 630 nm≦λmax≦680 nm Group C: 680 nm≦λmax≦750 nm |
||||
[0129] Each of the samples was exposed, processed and evaluated in the same manner as in Example 1, and the results obtained are shown in Table 4.
Table 4
| Sample No. | Relative sensitivity | Sharpness | Safe light suitability (rel. SF) | Whiteness of background |
| 2-1 | 82 | 0.64 | -0.05 | 0.014 |
| 2-2 | 135 | 0.43 | -0.17 | 0.013 |
| 2-3 | 77 | 0.66 | -0.12 | 0.014 |
| 2-4 | 86 | 0.69 | -0.09 | 0.017 |
| 2-5 | 83 | 0.78 | -0.08 | 0.017 |
| 2-6 | 86 | 0.80 | -0.08 | 0.014 |
| 2-7 | 84 | 0.84 | -0.09 | 0.014 |
| 2-8 | 85 | 0.82 | -0.11 | 0.014 |
| 2-9 | 100 | 0.63 | 0 | 0.015 |
| 2-10 | 167 | 0.43 | -0.05 | 0.014 |
| 2-11 | 95 | 0.65 | -0.02 | 0.015 |
| 2-12 | 106 | 0.68 | +0.02 | 0.020 |
| 2-13 | 102 | 0.78 | -0.01 | 0.021 |
| 2-14 | 107 | 0.79 | -0.04 | 0.017 |
| 2-15 | 104 | 0.83 | -0.05 | 0.018 |
| 2-16 | 106 | 0.81 | -0.07 | 0.016 |
| 2-17 | 103 | 0.83 | -0.05 | 0.016 |
1. A silver halide photographic light-sensitive material comprising a support and provided
thereon at least one silver halide light-sensitive emulsion layer, wherein at least
one layer selected from the light-sensitive emulsion layer and other hydrophilic colloidal
layers contains at least one dye having an absorption maximum at 630-680 nm (the first
dye) and at least one dye having an absorption maximum at 680-750 nm (the second dye),
as measured when they are present in a gelatin film, wherein the second dye is a dye
chosen from Formula XII, Formula XIII, Formula XIV, Formula XV and compound XV-16;
wherein R62 and R63 each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOH, -COOC2H5, -NHCON(CH3)2, -NHCOCH3,
or a cyano group; R5 and R6 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; R5 and R6 may combine with each other to form a 5- or 6-membered ring; R64 and R65 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; L45, L46, L47, L48 and L49 each represent a methine group; n32 and n33 each represent 1 or 2;
wherein R66 and R67 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, - COR5, -SO2NR5R6, -SOR5 or a cyano group; R5 and R6 are each as defined above; Z12 and Z13 each represent a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring; L50, L51, L52, L53 and L54 each represent a methine group; n34 and n35 each represent 1 or 2;
wherein R68 and R69 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, - COR5, -SO2NR5R6, -SOR5 or a cyano group; R5 and R6 are each as defined above; R70 and R71 each represent an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -NR16R17, -OR16, -N(R16)COR17, -N(R16)SO2R17, - N(R16)CONR17R18, -COR16, -CONR16R17, -SO2R16, -SO2NR16R17, - COOR16 or a cyano group; R16, R17 and R18 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or a heterocyclic group; X7, X8, X9, and X10 each represent an oxygen atom, a sulphur atom or -NR59R60; R59 and R60 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a hydroxy group or -OR61, where R61 represents an alkyl group or an aryl group; L55, L56, L57, L58 and L59 each represent a methine group; n36 and n37 each represent 1 to 2;
wherein R72 and R73 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, - COR5, -SO2NR5R6, -SOR5 or a cyano group; R74, R76, R77, R78, R80 and R81 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyano group, -COR29, -CONR29R30, - NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29 or -SO2NR29R30; R75 and R79 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyano group, -COR29, -CONR29R30, -NR29R30, -OR29, - SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, - COOR29, -SO2NR29R30 or -SO3K; R29 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an alkenyl group; R30 and R31 each represent an alkyl group, an aryl group, a heterocyclic group or an alkenyl group; X11 and X12 each represent an oxygen atom, a sulphur atom or -NR59R60; R59 and R60 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a hydroxy group or -OR61; R61 represents an alkyl group or an aryl group; R5 and R6 are each as defined above; L60, L61, L62, L63 and L64 each represent a methine group; n38 and n39 each represent 0, 1 or 2,
wherein R62 and R63 each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOH, -COOC2H5, -NHCON(CH3)2, -NHCOCH3,
or a cyano group; R5 and R6 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; R5 and R6 may combine with each other to form a 5- or 6-membered ring; R64 and R65 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; L45, L46, L47, L48 and L49 each represent a methine group; n32 and n33 each represent 1 or 2;
wherein R66 and R67 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, - COR5, -SO2NR5R6, -SOR5 or a cyano group; R5 and R6 are each as defined above; Z12 and Z13 each represent a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring; L50, L51, L52, L53 and L54 each represent a methine group; n34 and n35 each represent 1 or 2;
wherein R68 and R69 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, - COR5, -SO2NR5R6, -SOR5 or a cyano group; R5 and R6 are each as defined above; R70 and R71 each represent an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -NR16R17, -OR16, -N(R16)COR17, -N(R16)SO2R17, - N(R16)CONR17R18, -COR16, -CONR16R17, -SO2R16, -SO2NR16R17, - COOR16 or a cyano group; R16, R17 and R18 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or a heterocyclic group; X7, X8, X9, and X10 each represent an oxygen atom, a sulphur atom or -NR59R60; R59 and R60 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a hydroxy group or -OR61, where R61 represents an alkyl group or an aryl group; L55, L56, L57, L58 and L59 each represent a methine group; n36 and n37 each represent 1 to 2;
wherein R72 and R73 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, - COR5, -SO2NR5R6, -SOR5 or a cyano group; R74, R76, R77, R78, R80 and R81 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyano group, -COR29, -CONR29R30, - NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29 or -SO2NR29R30; R75 and R79 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyano group, -COR29, -CONR29R30, -NR29R30, -OR29, - SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, - COOR29, -SO2NR29R30 or -SO3K; R29 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an alkenyl group; R30 and R31 each represent an alkyl group, an aryl group, a heterocyclic group or an alkenyl group; X11 and X12 each represent an oxygen atom, a sulphur atom or -NR59R60; R59 and R60 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a hydroxy group or -OR61; R61 represents an alkyl group or an aryl group; R5 and R6 are each as defined above; L60, L61, L62, L63 and L64 each represent a methine group; n38 and n39 each represent 0, 1 or 2,
2. A silver halide photographic light-sensitive material according to claim 1, wherein
the first dye is a dye chosen from Formula I, Formula II, Formula III, Formula IV,
Formula V, Formula VI, Formula VII, Formula VIII, Formula IX, Formula X, Formula XI
and compound VIII-3;
wherein R1 and R2 each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOH, -COOC2H5, -NHCON(CH3)2,-NHCOCH3 or a cyano group; R3 and R4 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; L1, L2, L3, L4 and L5 each represent a methine group; n1 and n2 each represent 0 or 1; and R5 and R6 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; R5 and R6 may combine with each other to form a 5-or 6-membered ring,
wherein R7 and R8 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -NR9R10, -N(R9)CONR10R11, -N(R9)COR10 or -N(R9)SO2R10; Z1 and Z2 each represent a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring; L6, L7, L8, L9 and L10 each represent a methine group; n3 and n4 each represent 0 or 1; and R9, R10 and R11 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; R9 and R10 may combine with each other to form a 5- or 6-membered ring, R10 and R11 may combine with each other to form a 5- or 6-membered ring,
wherein R12 and R13 each represent an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -NR16R17, -OR16, -N(R16)COR17, -N(R16)SO2R17, -N(R16)CONR17R18, -COR16, -CONR16R17, -SO2R16, -SO2NR16R17, -COOR16, -SCH3 or a cyano group; R14 and R15 are defined as for R7 and R8 above; R16, R17 and R18 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, R16 and R17 may combine with each other to form a 5- or 6-membered ring, R17 and R18 may combine with each other to form a 5- or 6-membered ring; L11, L12, L13, L14 and L15 each represent a methine group; n5 and n6 each represent 0 or 1,
wherein R19 is as defined for R7 or R8 above; Y1 represents an oxygen atom, a sulphur atom, a selenium atom, a tellurium atom or =CR20R21; R20 and R21 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; Z3 and Z4 each represent a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring; L16, L17, L18 and L19 each represent a methine group; n7 and n8 each represent 0 or 1; R20 and R21 may combine with each other to form a 5- or 6-membered ring,
wherein R22 represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOC2H5 or a cyano group; R5 and R6 are each as defined above; R23 represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; R24 and R25 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; R24 and R25 may combine with each other to form a 5- or 6-membered ring; R26, R27 and R28 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyano group, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29 or -SO2NR29R30; R29 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an alkenyl group; R30 and R31 each represent an alkyl group, an aryl group, a heterocyclic group or an alkenyl group; L20, L21 and L22 each represent a methine group; and n9 represents 0 or 1;
wherein R32 is defined as for R7 or R8 above; R33 and R34 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; R33 and R34 may combine with each other to form a 5- or 6-membered ring; R35 and R36 are defined as for R26, R27 or R28 above; Y2 represents an oxygen atom, a sulphur atom, a selenium atom, a tellurium atom or =CR20R21; R20 and R21 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; Z5 represents a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring; L23 and L24 each represent a methine group; n10 represents 0, 1 or 2; X1 represents a group capable of being dissociated into anions; and n11 represents 0, 1 or 2; R33 and R34 may combine with each other to form a 5- or 6-membered ring,
wherein R37 and R38 are each defined as for R7 and R8 above; Y3 and Y4 each represent an oxygen atom, a sulphur atom, a selenium atom, a tellurium atom, 〉NC2H5 or =CR20R21; R20 and R21 each represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; Z6 and Z7 each represent a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring; L25, L26, L27, L28 and L29 each represent a methine group; n12 and n13 each represent 0 or 1; X2 represents a group capable of being dissociated into anions; and n14 represents 0, 1 or 2,
wherein R39, R40, R41, R42, R43 and R44 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; R39 and R40 may combine with each other to form a 5- or 6-membered ring, R41 and R42 may combine with each other to form a 5- or 6-membered ring, R43 and R44 may combine with each other to form a 5- or 6-membered ring, R45, R46, R49 and R50 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyano group, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29 or -SO2NR29R30; R47 and R48 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyano group, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29, -SO3-, -SO3Na, -SO3K or -SO2NR29R30; R29, R30 and R31 each represent an alkyl group, an aryl group, a heterocyclic group or an alkenyl group; X3 represents a group capable of being dissociated with anions; and n15 represents 0, 1 or 2, m represents 0 or 1;
wherein R51 and R52 are each defined as for R7 or R8 above; Z8 and Z9 each represent a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring; L30, L31, L32, L33 and L34 each represent a methine group; n16 and n17 each represent 0 or 1;
wherein R53 and R54 are each defined as for R7 or R8 above; Z10 and Z11 each represent a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring; L35, L36, L37, L38 and L39 each represent a methine group; n18 and n19 each represent 0 or 1;
wherein R55, R56, R57 and R58 are each defined as for R7 or R8 above; X1, X2, X3, X4, X5 and X6 each represent an oxygen atom, a sulphur atom or -NR59R60; R59 and R60 each represent a hydrogen atom, an alkyl group, an aryl group an alkenyl group, a heterocyclic group, a hydroxy group or -OR61; R61 represents a alkyl group or an aryl group; L40, L41, L42, L43 and L44 each represent a methine group; and n20 and n21 each represent 0 or 1;
wherein R1 and R2 each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOH, -COOC2H5, -NHCON(CH3)2,-NHCOCH3 or a cyano group; R3 and R4 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; L1, L2, L3, L4 and L5 each represent a methine group; n1 and n2 each represent 0 or 1; and R5 and R6 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; R5 and R6 may combine with each other to form a 5-or 6-membered ring,
wherein R7 and R8 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -NR9R10, -N(R9)CONR10R11, -N(R9)COR10 or -N(R9)SO2R10; Z1 and Z2 each represent a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring; L6, L7, L8, L9 and L10 each represent a methine group; n3 and n4 each represent 0 or 1; and R9, R10 and R11 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; R9 and R10 may combine with each other to form a 5- or 6-membered ring, R10 and R11 may combine with each other to form a 5- or 6-membered ring,
wherein R12 and R13 each represent an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -NR16R17, -OR16, -N(R16)COR17, -N(R16)SO2R17, -N(R16)CONR17R18, -COR16, -CONR16R17, -SO2R16, -SO2NR16R17, -COOR16, -SCH3 or a cyano group; R14 and R15 are defined as for R7 and R8 above; R16, R17 and R18 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, R16 and R17 may combine with each other to form a 5- or 6-membered ring, R17 and R18 may combine with each other to form a 5- or 6-membered ring; L11, L12, L13, L14 and L15 each represent a methine group; n5 and n6 each represent 0 or 1,
wherein R19 is as defined for R7 or R8 above; Y1 represents an oxygen atom, a sulphur atom, a selenium atom, a tellurium atom or =CR20R21; R20 and R21 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; Z3 and Z4 each represent a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring; L16, L17, L18 and L19 each represent a methine group; n7 and n8 each represent 0 or 1; R20 and R21 may combine with each other to form a 5- or 6-membered ring,
wherein R22 represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOC2H5 or a cyano group; R5 and R6 are each as defined above; R23 represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; R24 and R25 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; R24 and R25 may combine with each other to form a 5- or 6-membered ring; R26, R27 and R28 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyano group, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29 or -SO2NR29R30; R29 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an alkenyl group; R30 and R31 each represent an alkyl group, an aryl group, a heterocyclic group or an alkenyl group; L20, L21 and L22 each represent a methine group; and n9 represents 0 or 1;
wherein R32 is defined as for R7 or R8 above; R33 and R34 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; R33 and R34 may combine with each other to form a 5- or 6-membered ring; R35 and R36 are defined as for R26, R27 or R28 above; Y2 represents an oxygen atom, a sulphur atom, a selenium atom, a tellurium atom or =CR20R21; R20 and R21 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; Z5 represents a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring; L23 and L24 each represent a methine group; n10 represents 0, 1 or 2; X1 represents a group capable of being dissociated into anions; and n11 represents 0, 1 or 2; R33 and R34 may combine with each other to form a 5- or 6-membered ring,
wherein R37 and R38 are each defined as for R7 and R8 above; Y3 and Y4 each represent an oxygen atom, a sulphur atom, a selenium atom, a tellurium atom, 〉NC2H5 or =CR20R21; R20 and R21 each represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; Z6 and Z7 each represent a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring; L25, L26, L27, L28 and L29 each represent a methine group; n12 and n13 each represent 0 or 1; X2 represents a group capable of being dissociated into anions; and n14 represents 0, 1 or 2,
wherein R39, R40, R41, R42, R43 and R44 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group; R39 and R40 may combine with each other to form a 5- or 6-membered ring, R41 and R42 may combine with each other to form a 5- or 6-membered ring, R43 and R44 may combine with each other to form a 5- or 6-membered ring, R45, R46, R49 and R50 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyano group, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29 or -SO2NR29R30; R47 and R48 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyano group, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29, -SO3-, -SO3Na, -SO3K or -SO2NR29R30; R29, R30 and R31 each represent an alkyl group, an aryl group, a heterocyclic group or an alkenyl group; X3 represents a group capable of being dissociated with anions; and n15 represents 0, 1 or 2, m represents 0 or 1;
wherein R51 and R52 are each defined as for R7 or R8 above; Z8 and Z9 each represent a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring; L30, L31, L32, L33 and L34 each represent a methine group; n16 and n17 each represent 0 or 1;
wherein R53 and R54 are each defined as for R7 or R8 above; Z10 and Z11 each represent a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring; L35, L36, L37, L38 and L39 each represent a methine group; n18 and n19 each represent 0 or 1;
wherein R55, R56, R57 and R58 are each defined as for R7 or R8 above; X1, X2, X3, X4, X5 and X6 each represent an oxygen atom, a sulphur atom or -NR59R60; R59 and R60 each represent a hydrogen atom, an alkyl group, an aryl group an alkenyl group, a heterocyclic group, a hydroxy group or -OR61; R61 represents a alkyl group or an aryl group; L40, L41, L42, L43 and L44 each represent a methine group; and n20 and n21 each represent 0 or 1;
3. A silver halide photographic light-sensitive material according to any of claims 1
or 2, wherein at least one of the silver halide light-sensitive emulsion layers comprises
a silver halide emulsion with a silver chloride content of 95 mol % or more.
4. A silver halide photographic light-sensitive material according to any preceding claim,
wherein the total amount of binders contained in the silver halide light-sensitive
emulsion layers and other hydrophilic colloidal layers is 8.0 g/m2 or less.
1. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial mit einem
Schichtträger und mindestens einer darauf vorgesehenen lichtempfindlichen Silberhalogenid-emulsionsschicht,
wobei mindestens eine Schicht, die aus der lichtempfindlichen Emulsionsschicht und
sonstigen hydrophilen Kolloidschichten ausgewählt ist, mindestens einen Farbstoff
eines Absorptionsmaximums bei 630 - 680 nm (erster Farbstoff) und mindestens einen
Farbstoff eines Absorptionsmaximums bei 680 - 750 nm (zweiter Farbstoff) - gemessen
bei ihrer Anwesenheit in einem Gelatinefilm - enthält, wobei der zweite Farbstoff
aus einem solchen der Formeln XII, XIII, XIV, XV und der Verbindung XV-16 ausgewählt
ist:
worin bedeuten:
worin bedeuten:
R62 und R63 jeweils unabhängig voneinander ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe,
eine Alkenylgruppe, eine heterocyclische Gruppe, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOH, -COOC2H5, -NHCON(CH3)2, -NHCOCH3,
oder eine Cyanogruppe;
R5 und R6 jeweils unabhängig voneinander ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe oder R5 und R6 zusammen einen 5- oder 6-gliedrigen Ring;
R64 und R65 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe oder eine heterocyclische Gruppe;
L45, L46, L47, L48 und L49 jeweils eine Methingruppe und n32 und n33 jeweils 1 oder 2;
worin bedeuten:
R66 und R67 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5 oder eine Cyanogruppe, wobei R5 und R6 jeweils der zuvor angegebenen Definition entsprechen;
Z12 und Z13 jeweils eine Gruppe von zur Bildung eines 5- oder 6-gliedrigen Rings erforderlichen
nichtmetallischen Atomen; L50, L51, L52, L53 und L54 jeweils eine Methingruppe und n34 und n35 jeweils 1 oder 2;
worin bedeuten:
R68 und R69 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5 oder eine Cyanogruppe, wobei R5 und R6 jeweils der zuvor angegebenen Definition genügen;
R70 und R71 jeweils eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe, -NR16R17, -OR16, -N(R16)COR17, -N(R16)SO2R17, -N(R16)CONR17R18, -COR16, -CONR16R17, -SO2R16, -SO2NR16R17, -COOR16 oder eine Cyanogruppe;
R16, R17 und R18 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe oder eine heterocyclische Gruppe;
X7, X8, X9 und X10 jeweils ein Sauerstoffatom, ein Schwefelatom oder -NR59R60;
R59 und R60 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe, eine Hydroxygruppe oder -OR61 mit R61 gleich einer Alkylgruppe oder einer Arylgruppe;
L55, L56, L57, L58 und L59 jeweils eine Methingruppe und n36 und n37 jeweils 1 bis 2;
worin bedeuten:
R72 und R73 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5 oder eine Cyanogruppe;
R74, R76, R77, R78, R80 und R81 jeweils ein Wasserstoffatom, ein Halogenatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe, eine Cyanogruppe, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29 oder -SO2NR29R30;
R75 und R79 jeweils ein Wasserstoffatom, ein Halogenatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe, eine Cyanogruppe, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29, -SO2NR29R30 oder -SO3K;
R29 ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine heterocyclische Gruppe oder eine Alkenylgruppe;
R30 und R31 jeweils eine Alkylgruppe, eine Arylgruppe, eine heterocyclische Gruppe oder eine Alkenylgruppe;
X11 und X12 jeweils ein Sauerstoffatom, ein Schwefelatom oder -NR59R60;
R59 und R60 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe, eine Hydroxygruppe oder -OR61;
R61 eine Alkylgruppe oder eine Arylgruppe;
R5 und R6 jeweils dieselben Reste wie oben definiert;
L60, L61, L62, L63 und L64 jeweils eine Methingruppe und n38 und n39 jeweils 0, 1 oder 2;
2. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial nach Anspruch
1, wobei der erste Farbstoff aus einem solchen der Formeln I, II, III, IV, V, VI,
VII, VIII, IX, X und XI und der Verbindung VIII-3 ausgewählt ist:
worin bedeuten:
worin bedeuten:
R1 und R2 jeweils unabhängig voneinander ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOH, -COOC2H5, -NHCON(CH3)2, -NHCOCH3 oder eine Cyanogruppe;
R3 und R4 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe oder eine heterocyclische Gruppe;
L1, L2, L3, L4 und L5 jeweils eine Methingruppe;
n1 und n2 jeweils 0 oder 1, und
R5 und R6 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe
oder eine heterocyclische Gruppe oder R5 und R6 zusammen einen 5- oder 6-gliedrigen Ring;
worin bedeuten:
R7 und R8 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe, -NR9R10, -N(R9)CONR10R11, -N(R9)COR10 oder -N(R9)SO2R10;
Z1 und Z2 jeweils eine Gruppe von zur Bildung eines 5- oder 6-gliedrigen Rings erforderlichen nichtmetallischen Atomen;
L6, L7, L8, L9 und L10 jeweils eine Methingruppe;
n3 und n4 jeweils 0 oder 1 und
R9, R10 und R11 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe
oder eine heterocyclische Gruppe oder R9 und R10 zusammen einen 5- oder 6-gliedrigen Ring oder R10 und R11 zusammen einen 5- oder 6-gliedrigen Ring;
worin bedeuten:
R12 und R13 jeweils eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe, -NR16R17, -OR16, -N(R16)COR17, -N(R16)SO2R17, -N(R16)CONR17R18, -COR16, -CONR16R17, -SO2R16, -SO2NR16R17, -COOR16, -SCH3 oder eine Cyangruppe;
R14 und R15 die Reste entsprechend der obigen Definition für R7 und R8;
R16, R17 und R18 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe oder eine heterocyclische Gruppe oder R16 und R17 zusammen einen 5- oder 6-gliedrigen Ring oder R17 und R18 zusammen einen 5- oder 6-gliedrigen Ring;
L11, L12, L13, L14 und L15 jeweils eine Methingruppe und
n5 und n6 jeweils 0 oder 1;
worin R19 der obigen Definition für R7 oder R8 genügt und worin bedeuten:
Y1 ein Sauerstoffatom, ein Schwefelatom, ein Selenatom, ein Telluratom oder =CR20R21;
R20 und R21 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe oder eine heterocyclische Gruppe oder R20 und R21 zusammen einen 5- oder 6-gliedrigen Ring;
Z3 und Z4 jeweils eine Gruppe von zur Bildung eines 5- oder 6-gliedrigen Rings erforderlichen nichtmetallischen Atomen;
L16, L17, L18 und L19 jeweils eine Methingruppe und
n7 und n8 jeweils 0 oder 1;
worin bedeuten:
R22 ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOC2H5 oder eine Cyanogruppe mit R5 und R6 jeweils in der zuvor angegebenen Bedeutung;
R23 ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe oder eine heterocyclische Gruppe;
R24 und R25 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe oder eine heterocyclische Gruppe oder R24 und R25 zusammen einen 5- oder 6-gliedrigen Ring;
R26, R27 und R28 jeweils ein Wasserstoffatom, ein Halogenatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe, eine Cyanogruppe, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29 oder -SO2NR29R30;
R29 ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine heterocyclische Gruppe oder eine Alkenylgruppe;
R30 und R31 jeweils eine Alkylgruppe, eine Arylgruppe, eine heterocyclische Gruppe oder eine Alkenylgruppe;
L20, L21 und L22 jeweils eine Methingruppe und
n9 0 oder 1;
worin R32 der obigen Definition für R7 oder R8 genügt und worin bedeuten:
R33 und R34 jeweils ein Waserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe oder R33 und R34 zusammen einen 5- oder 6-gliedrigen Ring;
R35 und R36 jeweils dieselben Reste wie für R26, R27 oder R28 definiert;
Y2 ein Sauerstoffatom, ein Schwefelatom, ein Selenatom, ein Telluratom oder =CR20R21;
R20 und R21 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe oder eine heterocyclische Gruppe;
Z5 eine Gruppe von zur Bildung eines 5- oder 6-gliedrigen Rings erforderlichen nichtmetallischen Atomen;
L23 und L24 jeweils eine Methingruppe;
n10 0, 1 oder 2;
X1 eine zu Anionen dissoziierbare Gruppe und
n11 0, 1 oder 2;
worin bedeuten:
R37 und R38 dieselben Reste wie sie zuvor für R7 und R8 angegeben wurden;
Y3 und Y4 jeweils ein Sauerstofatom, ein Schwefelatom, ein Selenatom, ein Telluratom, 〉NC2H5 oder =CR20R21 mit R20 und R21 jeweils gleich einem Wasserstoffatom, einer Alkylgruppe, einer Arylgruppe, einer Alkenylgruppe oder einer heterocyclischen Gruppe;
Z6 und Z7 jeweils eine Gruppe von zur Bildung eines 5- oder 6-gliedrigen Rings erforderlichen nichtmetallischen Atomen;
L25, L26, L27, L28 und L29 jeweils eine Methingruppe;
n12 und n13 jeweils 0 oder 1;
X2 eine zu Anionen dissoziierbare Gruppe und
n14 0, 1 oder 2;
worin bedeuten:
R39, R40, R41, R42, R43 und R44 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe oder eine heterocyclische Gruppe oder R39 und R40 zusammen einen 5- oder 6-gliedrigen Ring oder R41 und R42 zusammen einen 5- oder 6-gliedrigen Ring oder R43 und R44 zusammen einen 5- oder 6-gliedrigen Ring;
R45, R46, R49 und R50 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe, eine Cyanogruppe, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29 oder -SO2NR29R30;
R47 und R48 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe, eine heterocyclische Gruppe, eine Cyanogruppe, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29, -SO3-, -SO3K oder -SO2NR29R30 mit R29, R30 und R31 jeweils gleich einer Alkylgruppe, einer Arylgruppe, einer heterocyclischen Gruppe oder einer Alkenylgruppe;
X3 eine mit Anionen dissoziierbare Gruppe;
n15 0, 1 oder 2 und
m 0 oder 1;
worin R51 und R52 der zuvor angegebenen Definition für R7 oder R8 genügen, Z8 und Z9 jeweils eine Gruppe von zur Bildung eines 5- oder 6-gliedrigen Rings erforderlichen
nichtmetallischen Atomen darstellt, L30, L31, L32, L33 und L34 jeweils eine Methingruppe bedeuten und n16 und n17 jeweils = 0 oder 1;
worin R53 und R54 jeweils der zuvor angegebenen Bedeutung für R7 oder R8 genügen, Z10 und Z11 jeweils eine Gruppe von zur Bildung eines 5- oder 6-gliedrigen Rings erforderlichen
nichtmetallischen Atomen darstellen, L35, L36, L37, L38 und L39 jeweils eine Methingruppe bedeuten und n18 und n19 jeweils = 0 oder 1;
worin R55, R56, R57 und R58 jeweils der zuvor angegebenen Bedeutung für R7 oder R8 entsprechen, X1, X2, X3, X4, X5 und X6 jeweils ein Sauerstoffatom, ein Schwefelstom oder -NR59R60 mit R59 und R60 jeweils gleich einem Wasserstoffatom, einer Alkylgruppe, einer Arylgruppe, einer
Alkenylgruppe, einer heterocyclischen Gruppe, einer Hydroxygruppe oder -OR61 mit R61 gleich einer Alkylgruppe oder einer Arylgruppe bedeuten, L40, L41, L42, L43 und L44 jeweils eine Methingruppe darstellen und n20 und n21 jeweils = 0 oder 1;
3. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial nach einem
der Ansprüche 1 oder 2, wobei mindestens eine der lichtempfindlichen Silberhalogenidemulsionsschichten
eine Silberhalogenidemulsion eines Silberchloridgehalts von 95 Mol-% oder mehr umfaßt.
4. Lichtempfindliches photographisches Silberhalogenid-Aufzeichnungsmaterial nach einem
der vorhergehenden Ansprüche, wobei die Gesamtmenge an in den lichtempfindlichen Silberhalogenidemulsionsschichten
und sonstigen hydrophilen Kolloidschichten enthaltenen Bindemitteln 8,0 g/m2 oder weniger beträgt.
1. Un matériau photographique photosensible à l'halogénure d'argent, comprenant un support
et, appliquée sur celui-ci, au moins une couche d'émulsion photosensible à l'halogénure
d'argent, dans laquelle au moins une couche choisie parmi la couche d'émulsion photosensible
et d'autres couches colloïdales hydrophiles contient au moins un colorant ayant un
maximum d'absorption à 630-680 nm (le premier colorant) et au moins un colorant ayant
un maximum d'absorption à 680-750 nm (le second colorant), mesurés lorsqu'ils sont
présents dans un film de gélatine, le second colorant étant un colorant choisi parmi
la formule XII, la formule XIII, la formule XIV, la formule XV et le composé XV-16
;
dans laquelle R62 et R63 représentent, chacun indépendamment, un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOH, -COOC2H5, -NHCON(CH3)2, -NHCOCH3,
ou un groupe cyano ;
R5 et R6 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; R5 et R6 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons ; R64 et R65 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; L45, L46, L47, L48 et L49 représentent chacun un groupe méthine ; n32 et n33 représentent chacun 1 ou 2 ;
dans laquelle R66 et R67 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5 ou un groupe cyano ; R5 et R6 sont chacun tels que définis ci-dessus ; Z12 et Z13 représentent chacun un groupe d'atomes non métalliques qui sont nécessaires pour former un cycle à 5 ou 6 chaînons ; L50, L51, L52, L53 et L54 représentent chacun un groupe méthine ; n34 et n35 représentent chacun 1 ou 2 ;
dans laquelle R68 et R69 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5 ou un groupe cyano ; R5 et R6 sont chacun tels que définis ci-dessus ; R70 et R71 représentent chacun un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -NR16R17, -OR16, -N(R16)COR17, -N(R16)SO2R17, -N(R16)CONR17R18, -COR16, -CONR16R17, -SO2R16, -SO2NR16R17, -COOR16 ou un groupe cyano ; R16, R17 et R18 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle ou un groupe hétérocyclique ; X7, X8, X9 et X10 représentent chacun un atome d'oxygène, un atome de soufre ou -NR59R60 ; R59 et R60 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, un groupe hydroxy ou -OR61, où R61 représente un groupe alkyle ou un groupe aryle ; L55, L56, L57, L58 et L59 représentent chacun un groupe méthine ; n36 et n37 représentent chacun 1 à 2 ;
dans laquelle R72 et R73 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5 ou un groupe cyano ; R74, R76, R77, R78, R80 et R81 représentent chacun un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, un groupe cyano, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29 ou -SO2NR29R30 ; R75 et R79 représentent chacun un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, un groupe cyano, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29, -SO2NR29R30 ou -SO3K ; R29 représente un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe hétérocyclique ou un groupe alcényle ; R30 et R31 représentent chacun un groupe alkyle, un groupe aryle, un groupe hétérocyclique ou un groupe alcényle ; X11 et X12 représentent chacun un atome d'oxygène, un atome de soufre ou -NR59R60 ; R59 et R60 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, un groupe hydroxy ou -OR61; R61 représente un groupe alkyle ou un groupe aryle ; R5 et R6 sont chacun tels que définis ci-dessus ; L60, L61, L62, L63 et L64 représentent chacun un groupe méthine ; n38 et n39 représentent chacun 0, 1 ou 2,
dans laquelle R62 et R63 représentent, chacun indépendamment, un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOH, -COOC2H5, -NHCON(CH3)2, -NHCOCH3,
ou un groupe cyano ;
R5 et R6 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; R5 et R6 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons ; R64 et R65 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; L45, L46, L47, L48 et L49 représentent chacun un groupe méthine ; n32 et n33 représentent chacun 1 ou 2 ;
dans laquelle R66 et R67 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5 ou un groupe cyano ; R5 et R6 sont chacun tels que définis ci-dessus ; Z12 et Z13 représentent chacun un groupe d'atomes non métalliques qui sont nécessaires pour former un cycle à 5 ou 6 chaînons ; L50, L51, L52, L53 et L54 représentent chacun un groupe méthine ; n34 et n35 représentent chacun 1 ou 2 ;
dans laquelle R68 et R69 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5 ou un groupe cyano ; R5 et R6 sont chacun tels que définis ci-dessus ; R70 et R71 représentent chacun un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -NR16R17, -OR16, -N(R16)COR17, -N(R16)SO2R17, -N(R16)CONR17R18, -COR16, -CONR16R17, -SO2R16, -SO2NR16R17, -COOR16 ou un groupe cyano ; R16, R17 et R18 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle ou un groupe hétérocyclique ; X7, X8, X9 et X10 représentent chacun un atome d'oxygène, un atome de soufre ou -NR59R60 ; R59 et R60 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, un groupe hydroxy ou -OR61, où R61 représente un groupe alkyle ou un groupe aryle ; L55, L56, L57, L58 et L59 représentent chacun un groupe méthine ; n36 et n37 représentent chacun 1 à 2 ;
dans laquelle R72 et R73 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5 ou un groupe cyano ; R74, R76, R77, R78, R80 et R81 représentent chacun un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, un groupe cyano, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29 ou -SO2NR29R30 ; R75 et R79 représentent chacun un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, un groupe cyano, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29, -SO2NR29R30 ou -SO3K ; R29 représente un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe hétérocyclique ou un groupe alcényle ; R30 et R31 représentent chacun un groupe alkyle, un groupe aryle, un groupe hétérocyclique ou un groupe alcényle ; X11 et X12 représentent chacun un atome d'oxygène, un atome de soufre ou -NR59R60 ; R59 et R60 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, un groupe hydroxy ou -OR61; R61 représente un groupe alkyle ou un groupe aryle ; R5 et R6 sont chacun tels que définis ci-dessus ; L60, L61, L62, L63 et L64 représentent chacun un groupe méthine ; n38 et n39 représentent chacun 0, 1 ou 2,
2. Un matériau photographique photosensible à l'halogénure d'argent selon la revendication
1, dans lequel le premier colorant est un colorant choisi parmi la formule I, la formule
II, la formule III, la formule IV, la formule V, la formule VI, la formule VII, la
formule VIII, la formule IX, la formule X, la formule XI et le composé VIII-3 ;
dans laquelle R1 et R2 représentent, chacun indépendamment, un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOH, -COOC2H5, -NHCON(CH3)2, -NHCOCH3 ou un groupe cyano ; R3 et R4 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; L1, L2, L3, L4 et L5 représentent chacun un groupe méthine ; n1 et n2 représentent chacun 0 ou 1 ; et R5 et R6 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; R5 et R6 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons,
dans laquelle R7 et R8 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -NR9R10, -N(R9)CONR10R11, -N(R9)COR10 ou -N(R9)SO2R10 ; Z1 et Z2 représentent chacun un groupe d'atomes non métalliques qui sont nécessaires pour former un cycle à 5 ou 6 chaînons ; L6, L7, L8, L9 et L10 représentent chacun un groupe méthine ; n3 et n4 représentent chacun 0 ou 1 ; et R9, R10 et R11 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; R9 et R10 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons, R10 et R11 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons,
dans laquelle R12 et R13 représentent chacun un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -NR16R17, -OR16, -N(R16)COR17, -N (R16)SO2R17, -N(R16)CONR17R18, -COR16, -CONR16R17, -SO2R16, -SO2NR16R17, -COOR16, -SCH3 ou un groupe cyano ; R14 et R15 sont définis comme pour R7 et R8 ci-dessus ; R16, R17 et R18 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, R16 et R17 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons, R17 et R18 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons ; L11, L12, L13, L14 et L15 représentent chacun un groupe méthine ; n5 et n6 représentent chacun 0 ou 1,
dans laquelle R19 est tel que défini pour R7 ou R8 ci-dessus ; Y1 représente un atome d'oxygène, un atome de soufre, un atome de sélénium, un atome de tellure ou =CR20R21 ; R20 et R21 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; Z3 et Z4 représentent chacun un groupe d'atomes non métalliques qui sont nécessaires pour former un cycle à 5 ou 6 chaînons ; L16, L17, L18 et L19 représentent chacun un groupe méthine ; n7 et n8 représentent chacun 0 ou 1; R20 et R21 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons,
dans laquelle R22 représente un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOC2H5 ou un groupe cyano ; R5 et R6 sont chacun tels que définis ci-dessus ; R23 représente un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; R24 et R25 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; R24 et R25 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons ; R26, R27 et R28 représentent chacun un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, un groupe cyano, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29) CONR30R31, -SR29, -COOR29 ou -SO2NR29R30 ; R29 représente un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe hétérocyclique ou un groupe alcényle ; R30 et R31 représentent chacun un groupe alkyle, un groupe aryle, un groupe hétérocyclique ou un groupe alcényle ; L20, L21 et L22 représentent chacun un groupe méthine ; et n9 représente 0 ou 1 ;
dans laquelle R32 est défini comme pour R7 ou R8 ci-dessus ; R33 et R34 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; R33 et R34 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons ; R35 et R36 sont définis comme pour R26, R27 ou R28 ci-dessus ; Y2 représente un atome d'oxygène, un atome de soufre, un atome de sélénium, un atome de tellure ou =CR20R21 ; R20 et R21 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; Z5 représente un groupe d'atomes non métalliques qui sont nécessaires pour former un cycle à 5 ou 6 chaînons ; L23 et L24 représentent chacun un groupe méthine ; n10 représente 0, 1 ou 2 ; X1 représente un groupe apte à être dissocié en anions ; et n11 représente 0, 1 ou 2 ; R33 et R34 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons,
dans laquelle R37 et R38 sont chacun définis comme pour R7 et R8 ci-dessus ; Y3 et Y4 représentent chacun un atome d'oxygène, un atome de soufre, un atome de sélénium, un atome de tellure, >NC2H5 ou =CR20R21 ; R20 et R21 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; Z6 et Z7 représentent chacun un groupe d'atomes non métalliques qui sont nécessaires pour former un cycle à 5 ou 6 chaînons ; L25, L26, L27, L28 et L29 représentent chacun un groupe méthine ; n12 et n13 représentent chacun 0 ou 1 ; X2 représente un groupe apte à être dissocié en anions ; et n14 représente 0, 1 ou 2,
dans laquelle R39, R40, R41, R42, R43 et R44 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; R39 et R40 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons, R41 et R42 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons, R43 et R44 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons, R45, R46, R49 et R50 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, un groupe cyano, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29 ou -SO2NR29R30 ; R47 et R48 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, un groupe cyano, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29, -SO3-, -SO3Na, -SO3K ou -SO2NR29R30 ; R29, R30 et R31 représentent chacun un groupe alkyle, un groupe aryle, un groupe hétérocyclique ou un groupe alcényle ; X3 représente un groupe apte à être dissocié en anions ; et n15 représente 0, 1 ou 2, m représente 0 ou 1 ;
dans laquelle R51 et R52 sont chacun définis comme pour R7 ou R8 ci-dessus ; Z8 et Z9 représentent chacun un groupe d'atomes non métalliques qui sont nécessaires pour former un cycle à 5 ou 6 chaînons ; L30, L31, L32, L33 et L34 représentent chacun un groupe méthine ; n16 et n17 représentent chacun 0 ou 1 ;
dans laquelle R53 et R54 sont tels que définis pour R7 ou R8 ci-dessus ; Z10 et Z11 représentent chacun un groupe d'atomes non métalliques qui sont nécessaires pour former un cycle à 5 ou 6 chaînons ; L35, L36, L37, L38 et L39 représentent chacun un groupe méthine ; n18 et n19 représentent chacun 0 ou 1 ;
dans laquelle R55, R56, R57 et R58 sont chacun définis comme pour R7 ou R8 ci-dessus ; X1, X2, X3, X4, X5 et X6 représentent chacun un atome d'oxygène, un atome de soufre ou -NR59R60 ; R59 et R60 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, un groupe hydroxy ou -OR61 ; R61 représente un groupe alkyle ou un groupe aryle ; L40, L41, L42, L43 et L44 représentent chacun un groupe méthine ; et n20 et n21 représentent chacun 0 ou 1 ;
dans laquelle R1 et R2 représentent, chacun indépendamment, un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOH, -COOC2H5, -NHCON(CH3)2, -NHCOCH3 ou un groupe cyano ; R3 et R4 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; L1, L2, L3, L4 et L5 représentent chacun un groupe méthine ; n1 et n2 représentent chacun 0 ou 1 ; et R5 et R6 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; R5 et R6 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons,
dans laquelle R7 et R8 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -NR9R10, -N(R9)CONR10R11, -N(R9)COR10 ou -N(R9)SO2R10 ; Z1 et Z2 représentent chacun un groupe d'atomes non métalliques qui sont nécessaires pour former un cycle à 5 ou 6 chaînons ; L6, L7, L8, L9 et L10 représentent chacun un groupe méthine ; n3 et n4 représentent chacun 0 ou 1 ; et R9, R10 et R11 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; R9 et R10 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons, R10 et R11 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons,
dans laquelle R12 et R13 représentent chacun un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -NR16R17, -OR16, -N(R16)COR17, -N (R16)SO2R17, -N(R16)CONR17R18, -COR16, -CONR16R17, -SO2R16, -SO2NR16R17, -COOR16, -SCH3 ou un groupe cyano ; R14 et R15 sont définis comme pour R7 et R8 ci-dessus ; R16, R17 et R18 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, R16 et R17 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons, R17 et R18 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons ; L11, L12, L13, L14 et L15 représentent chacun un groupe méthine ; n5 et n6 représentent chacun 0 ou 1,
dans laquelle R19 est tel que défini pour R7 ou R8 ci-dessus ; Y1 représente un atome d'oxygène, un atome de soufre, un atome de sélénium, un atome de tellure ou =CR20R21 ; R20 et R21 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; Z3 et Z4 représentent chacun un groupe d'atomes non métalliques qui sont nécessaires pour former un cycle à 5 ou 6 chaînons ; L16, L17, L18 et L19 représentent chacun un groupe méthine ; n7 et n8 représentent chacun 0 ou 1; R20 et R21 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons,
dans laquelle R22 représente un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5, -COOC2H5 ou un groupe cyano ; R5 et R6 sont chacun tels que définis ci-dessus ; R23 représente un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; R24 et R25 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; R24 et R25 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons ; R26, R27 et R28 représentent chacun un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, un groupe cyano, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29) CONR30R31, -SR29, -COOR29 ou -SO2NR29R30 ; R29 représente un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe hétérocyclique ou un groupe alcényle ; R30 et R31 représentent chacun un groupe alkyle, un groupe aryle, un groupe hétérocyclique ou un groupe alcényle ; L20, L21 et L22 représentent chacun un groupe méthine ; et n9 représente 0 ou 1 ;
dans laquelle R32 est défini comme pour R7 ou R8 ci-dessus ; R33 et R34 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; R33 et R34 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons ; R35 et R36 sont définis comme pour R26, R27 ou R28 ci-dessus ; Y2 représente un atome d'oxygène, un atome de soufre, un atome de sélénium, un atome de tellure ou =CR20R21 ; R20 et R21 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; Z5 représente un groupe d'atomes non métalliques qui sont nécessaires pour former un cycle à 5 ou 6 chaînons ; L23 et L24 représentent chacun un groupe méthine ; n10 représente 0, 1 ou 2 ; X1 représente un groupe apte à être dissocié en anions ; et n11 représente 0, 1 ou 2 ; R33 et R34 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons,
dans laquelle R37 et R38 sont chacun définis comme pour R7 et R8 ci-dessus ; Y3 et Y4 représentent chacun un atome d'oxygène, un atome de soufre, un atome de sélénium, un atome de tellure, >NC2H5 ou =CR20R21 ; R20 et R21 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; Z6 et Z7 représentent chacun un groupe d'atomes non métalliques qui sont nécessaires pour former un cycle à 5 ou 6 chaînons ; L25, L26, L27, L28 et L29 représentent chacun un groupe méthine ; n12 et n13 représentent chacun 0 ou 1 ; X2 représente un groupe apte à être dissocié en anions ; et n14 représente 0, 1 ou 2,
dans laquelle R39, R40, R41, R42, R43 et R44 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique ; R39 et R40 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons, R41 et R42 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons, R43 et R44 peuvent se combiner entre eux pour former un cycle à 5 ou 6 chaînons, R45, R46, R49 et R50 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, un groupe cyano, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29 ou -SO2NR29R30 ; R47 et R48 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, un groupe cyano, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29, -SO3-, -SO3Na, -SO3K ou -SO2NR29R30 ; R29, R30 et R31 représentent chacun un groupe alkyle, un groupe aryle, un groupe hétérocyclique ou un groupe alcényle ; X3 représente un groupe apte à être dissocié en anions ; et n15 représente 0, 1 ou 2, m représente 0 ou 1 ;
dans laquelle R51 et R52 sont chacun définis comme pour R7 ou R8 ci-dessus ; Z8 et Z9 représentent chacun un groupe d'atomes non métalliques qui sont nécessaires pour former un cycle à 5 ou 6 chaînons ; L30, L31, L32, L33 et L34 représentent chacun un groupe méthine ; n16 et n17 représentent chacun 0 ou 1 ;
dans laquelle R53 et R54 sont tels que définis pour R7 ou R8 ci-dessus ; Z10 et Z11 représentent chacun un groupe d'atomes non métalliques qui sont nécessaires pour former un cycle à 5 ou 6 chaînons ; L35, L36, L37, L38 et L39 représentent chacun un groupe méthine ; n18 et n19 représentent chacun 0 ou 1 ;
dans laquelle R55, R56, R57 et R58 sont chacun définis comme pour R7 ou R8 ci-dessus ; X1, X2, X3, X4, X5 et X6 représentent chacun un atome d'oxygène, un atome de soufre ou -NR59R60 ; R59 et R60 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle, un groupe hétérocyclique, un groupe hydroxy ou -OR61 ; R61 représente un groupe alkyle ou un groupe aryle ; L40, L41, L42, L43 et L44 représentent chacun un groupe méthine ; et n20 et n21 représentent chacun 0 ou 1 ;
3. Un matériau photographique photosensible à l'halogénure d'argent selon l'une quelconque
des revendications 1 ou 2, dans lequel au moins l'une des couches d'émulsion photosensibles
à l'halogénure d'argent comprend une émulsion d'halogénure d'argent ayant une teneur
en chlorure d'argent de 95 % en moles ou plus.
4. Un matériau photographique photosensible à l'halogénure d'argent selon l'une quelconque
des revendications précédentes, dans lequel la quantité totale de liants contenus
dans les couches d'émulsion photosensibles à l'halogénure d'argent et les autres couches
colloïdales hydrophiles est de 8,0 g/m2 ou moins.