JPS6024462B2 - Color photographic image forming method - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an image forming method for color photographic materials. More specifically, the present invention relates to a method of forming color photographic images having high image density and low fog density, and further relates to a method of forming color photographic images with improved sharpness in high temperature rapid processing. Generally, in order to process a silver halide color photographic light-sensitive material to form a color photographic image, the light-sensitive material is exposed to an image material, and developed with a color photographic developer containing an aromatic primary amine color developer.
A method is used in which the silver halide is reduced to silver, the developer is oxidized at the same time, and the oxidation product of the generated developer is combined with the coupler to form a dye corresponding to the developed silver. ing. Further, in the above color image forming method, for example, a silver halide color photographic light-sensitive material containing a non-diffusible coupler is imagewise exposed, then processed with a color photographic developer, and further desilvered and fixed to form a color negative image. There is also an internal development method in which a silver halide color photographic light-sensitive material is exposed in a crosswise pattern, then black and white first development is performed, and then the remaining silver halide emulsion is uniformly exposed to form an internal color photograph. Processed with developer,
Furthermore, there is a method of forming a reversed color photographic image by desilvering and fixing, and also a film having a color negative image formed by the above method on a multicolor reflective photosensitive material in which a color photographic emulsion layer is provided on an opaque support. There are methods such as printing, color photographic development, and desilvering and fixing to form a color positive image. An active p-phenylenediamine developer is used in any of these various color image forming methods. Conventionally, when a silver halide color photographic light-sensitive material is processed with such a p-phenylenediamine developer to form a color photographic image, all the silver halide grains that have been exposed to light and formed a port image are effectively converted into silver and dyes. Rather than being converted, a considerable amount of the silver halide that formed the dissolved image is dissolved in the fixing solution and discarded without being effectively utilized. If silver halide grains were effectively converted into silver and dyes without waste, it would be possible to produce excellent color images with higher contrast, and the amount of silver would be reduced accordingly, making it possible to make thin films of photosensitive materials. Therefore, rapid development processing is also possible, and many advantages such as the ability to obtain high-resolution color images should be obtained. These advantages have become more strongly desired in recent years as automatic processors have been used to rapidly process large quantities. On the other hand, silver halide color photographic materials that block the subtractive color principle of the three primary colors are
It consists of an emulsion layer that develops a yellow color when exposed to blue light, an emulsion layer that develops a magenta color when exposed to green light, and an emulsion layer that develops a cyan color when exposed to red light.Each emulsion layer produces a yellow color. Acylacetamide or dibenzoylmethane derivatives are commonly used as couplers, 5-pyrazolone, cyanoacetyl, indazolone, or pyrazolone benzimidazole derivatives are commonly used as magenta color-forming couplers, and phenol or Q-naphthol derivatives are used as cyan color-forming couplers. ing. To form a color image using a photographic light-sensitive material containing a coupler whose active site is unsubstituted among the above couplers, 4 equivalents of silver halide are required per molecule. In general, this so-called 4-equivalent type coupler has low coupling reaction activity with N,N'-p-phenylenediamine type developers, and not only does it not provide a sufficient amount of coloring dye, but it also has a negative effect on silver halide emulsions. This delays development and makes quick development difficult. In addition, the well-known N,N'-p-phenylene diamine-based developer used in development efficiently converts the latent silver halide image obtained by imagewise flashing of a silver halide color photographic light-sensitive material. It is difficult to say that it converts into reduced silver, resulting in wasted silver halide, and furthermore, it lacks permeability and adsorption to the silver halide emulsion layer, making it difficult to say that it is a developer with a high color development speed. Therefore, in order to obtain a high-density colored image, a large amount of silver halide and a large amount of coupler are required. On the other hand, incorporating a large amount of silver halide and coupler into a light-sensitive material increases the scattering of light in the emulsion, which in turn reduces the sharp image storage ability of the light-sensitive material, and further reduces the processing speed of the light-sensitive material. etc., resulting in performance deterioration. In order to solve these shortcomings,
A color image forming method using a developer having a very high coupling rate as described in Japanese Patent No. 7-111534 and Japanese Patent No. 50-1131526 has been proposed. However, when these developers are simply used, although high-density images can be obtained, they also have the disadvantage of causing fog. In order to improve these drawbacks of 4-equivalent type couplers, US Pat. No. 3,408,194 and US Pat.
7928, specifications of British Patent No. 1092506, etc., Tokukan Sho 48-129432, Sho 48-6 Mura No. 34, Sho 49
Publications such as -10736, 47-26133, 50-12 Spot No. 34, U.S. Patent No. 3419391, 11
No. 476, Samurai Kaisho No. 50-13041, No. 49-129
Publication No. 5, US Patent No. 2801171, British Patent No. 10
Capable of releasing one of the active hydrogen atoms as described in the specifications of Masu No. 48 Pi, etc., and publications such as Hakama Kaisho No. 50-10135, Hakama Kaisho No. 50-25 Matsu No. 8, Hakama Kaisho No. 47-37425, etc. Use of group-substituted active point-substituted couplers and U.S. Patent 3
Specifications of 51yo No. 29, No. 31276, etc., Mochiseki Sho 4
9-29 Musi No. 9 German Patent No. 2211018, No. 2
Anilino-type pyrazolone couplers as described in specifications such as No. 357122, publications such as JP-A-49-74027 and JP-A-51-44927, and British Patent No. 1142.
The use of ureido-type pyrazolone couplers, such as those described in US Pat. No. 5,553, has been proposed. The so-called 2-equivalent coupler manufactured by active point layer f requires only 2 equivalents of silver halide as an oxidizing agent to form one molecule of dye.
Therefore, the amount of silver halide contained in the light-sensitive material can be reduced, and since the rate of coupling with the oxidation product of the developer is fast, the amount of coupler can also be reduced. Furthermore, the sharpness of the image can be improved by reducing light scattering in the photosensitive material, and furthermore, since the formation of the dye is completed during the development process, there is no need to use a special oxidizing agent in post-processing. It has features such as simplifying the development process. Also, the aniline type pyrazolone coupler and the ureido type pyrazolone coupler have a very fast coupling rate with the oxidation product of the developer, and therefore have the same characteristics as the two-equivalent type coupler. However, these couplers have a serious drawback in that they tend to cause considerable fog during development, which is a major obstacle when using these couplers in light-sensitive materials. In order to eliminate this drawback, the use of compounds capable of forming poorly soluble silver salts such as active sulfur compounds, the use of colorless competitive couplers, or the use of U.S. Pat.
No. 60290, No. 2403721, No. 2728659
No. 2732300, No. 2735765, No. 24
No. 18613, No. 2675314, No. 2710801
No. 2816028, No. 2360290, French Patent No. 5 H.2, British Patent No. 113350, U.S. Patent No. 2336327, No. 2403721, No. 570
79, Japanese Patent Publication No. 43-13496, US Pat. No. 2, No. 4658, etc., techniques using reducing compounds are known. However, the techniques using these compounds have little effect on color fog removal, and when used in sufficient suppressive amounts, the conventionally used N,N'-p
- Image forming methods using phenylenediamine-based developers have the drawback of lowering sensitivity and maximum density. Furthermore, in a multilayer color light-sensitive material having two or more silver halide emulsion layers with different photosensitive regions on a support, if these couplers are applied to one of the emulsion layers, there will be a Exchange of oxidation products of the color developer occurs, producing so-called warm colors in which the correspondence between the color sensitivity of the emulsion layer and the dyes formed is out of order, resulting in unfavorable results in terms of color reproduction. Since the coupling activity of conventional N,N'-p-phenylenediamine developers is low, this green color could be improved by conventionally known methods such as providing an intermediate layer. However, since the developer used in the image forming method of the present invention has a very high coupling activity, it is difficult to improve it using conventional techniques. Therefore, an object of the present invention is to provide a method for forming a color image that is less likely to cause color fog during color development and has sufficiently high image density and high color sensitivity. Another object of the present invention is to provide a color photographic image forming method that allows rapid color development without deteriorating image quality. Another object of the present invention is to provide a color photographic material that is less likely to cause color fog and has high color image density without color mixing. The above objects, and other objects which will become apparent below, include a red-sensitive silver halide emulsion layer containing a cyan-forming coupler, a green-sensitive silver halide emulsion layer containing a magenta-forming coupler, and a yellow-forming coupler. It has a sound-sensitive silver halide emulsion layer on a support, and is in contact with at least one surface of at least one silver halide emulsion layer and has the following general formula [1], [B], [
A silver halide color photographic light-sensitive material having a non-photosensitive barrier layer containing a compound represented by [m], [W], [V] or [W] is imagewise exposed to produce a material represented by the following general formula [skin]. This is achieved by a color photographic image forming method characterized by developing with a developer containing a compound or a salt thereof and forming a color photographic image in response to the imagewise exposure. General formula [1] (In the formula, Q represents a group of nonmetallic atoms necessary to form a hydrocarbon ring or a heterocycle, × represents a hydrogen atom or a halogen atom, and Y represents a sulfur atom of a thioether bond released Represents a group that forms a compound with a sulfur atom when combined with a sulfur atom. ) General formula

[0] (In the formula, R represents a substituted or unsubstituted aliphatic hydrocarbon group, aryl group, or heterocyclic residue, and x and Y each have the same meaning as in general formula [1].) General formula [m] [In the formula, A and A' each represent a hydrogen atom or a group whose bond with oxygen under alkaline conditions is cleaved, and B, C and D
each represents a hydrogen atom, a substituted or unsubstituted alkyl group, an IJyl group, an amino group or a heterocyclic residue, a halogen atom, a hydroxyl group, a group represented by the formula -S-Y (
Y is the same rhombus as in general formula [1]. ), or a group represented by the formula -○-W (W represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic residue).
), C and D may be bonded to each other to form a carbon ring, and Y has the same meaning as in general formula [1].
] General formula [W] [In the formula, R2 and R3 each represent a hydrogen atom or an unsubstituted alkyl group (however, at least one of R2 and R3 is an unsubstituted alkyl group), A and A has the same meaning as in general formula [m].
] General formula [V] (wherein R4 represents a substituted or unsubstituted alkyl group or a / group, R5 is a substituted or substituted alkyl group,
represents a phenyl group, an alkoxy group or a phenoxy group,
R6 represents a substituted or unsubstituted aryl group. ) General formula [M] [In the formula, R7 represents an aliphatic residue, R8 is a hydrogen atom,
Ha. Gen atom, substituted or unsubstituted alkyl group, aryl group or heterocyclic residue, formula 101W (where W represents a substituted or unsubstituted alkyl group, aryl group, heterocyclic residue or acyl group) ), a group represented by the formula -COV (wherein V represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic residue), a group represented by the formula (however, R
9, R, and o each represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic residue. ), (however, V and V2 each have the same meaning as V above) or a group represented by the formula -S1V, where Q' forms a 5- or 6-membered heterocycle r is an integer of 0 or 1, Ahe represents an anion, and Y has the same meaning as in general formula [1]. ] General formula [Skin] [In the formula, R'11' formula - (R■○)m1 (R'7}0
)n-R■ (in the formula, R■ and R{71' each represent a substituted or unsubstituted direct mirror alkylene group having 1 to 6 carbon atoms, and R(8}' represents a hydrogen atom or a substituted or unsubstituted straight mirror alkylene group) represents a substituted aryl group, aralkyl group, or alkyl group having 1 to 6 carbon atoms, m and n are each an integer of 0 or more, and the sum of m and n is an integer of 1 or more, but m and n When the sum of R and R' is 1, it is a linear alkylene group having 1 to 6 carbon atoms and having a substituent.), where R is a hydrogen atom, a substituted or Represents an unsubstituted alkyl group having 1 to 6 carbon atoms or a group represented by R[1' above, R'3}, R'4'
and R'51 are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group, a sulfonamide group, an alkylsulfonamide group, an acylamido group, an amine/group, or a monomer group. Alternatively, it represents a dialkylamino group. ] The present invention will be explained in detail below. In the silver halide color photographic material of the present invention, the non-photosensitive barrier layer provided in contact with one surface of at least one photosensitive silver halide emulsion layer is made of a hydrophilic colloid. Gelatin and gelatin derivatives are preferred as hydrophilic colloids. U.S. Patent No. 2,594,293, U.S. Patent No. 2,614,928,
Same No. 2763, No. 9, No. 3118766, No. 31
No. 32945, No. 3186843, No. 32235
Specifications such as No. 28, No. 125, No. 3328257, British Patent No. 968892, No. 101579
Any of the gelatin derivatives described in the specification of Japanese Patent Publication No. 42-2 Gikka No. 5, etc. can be used in the non-photosensitive barrier layer of the present invention. Also, so-called grafted gelatin to which other polymeric substances are bound, such as U.S. Pat.
7 So No. 625, Hina No. 2 Hina No. 1767, Madaratsuchi No. 295, etc., Polymer Letters Vol. 5, p. 595 (1967
), Photographic Science and Engineering Vol. 9, p. 148 (1965), Journal of Polymer Science Part A-1, Vol. 9, p. 3199 (1971).
) etc. can also be used in the present invention. The single layer of the non-photosensitive barrier is the one-pronged type [1],

[0]
, [m], [W], [V] or [W]. As a typical compound represented by the above general formula [1], Q in the formula is, for example, a 5-, 6-, or 7-membered saturated or unsaturated hydrocarbon group, nitrogen, oxygen, or sulfur. It is a heterocycle containing atoms such as, for example, sik. pentan, cyclohexane, cyclohexenone, piberidone (e.g. 2-piveridone, 3-piveridone,
Representative examples include lactones (e.g., 4- to 7-membered rings), lactams (e.g., pyrrolidone), hydanthins, etc., and these hydrocarbon rings and heterocycles include alkyl groups, aryl groups, alkoxy groups, Including those having one or more substituents such as aryloxy group, acyl group, halogen atom, etc., or including those in which the hydrocarbon ring or heterocycle forms a fused ring at an appropriate position (
For example, indanone, benzcyclohexenone, benzcycloheptenone, oxindole). Alternatively, these hydrocarbon rings or heterocycles may have one or more -SY groups (Y is the same as above) on the carbon atom adjacent to the carbonyl group. In the formula, x represents a hydrogen atom or a halogen atom such as fluorine, chlorine, or bromine. On the other hand, when the sulfur atom of the thioether bond is released, Y in the formula combines with the sulfur atom to inhibit the development of compounds such as allylmercapto compounds, heterocyclic compounds, thioglycolic acid series compounds, cysteine, or glutathione. It is a group that forms a compound with For example, representative mercapto compounds of Y include multi-hata cyclic 〆capto compounds, such as mercaptotetrazole compounds, particularly 1-phenyl-2-〆captotetrazole, 1-nitrophenyl-5-mercaptotetrazole, 1-naphthyl-5-mercaptotetrazole. or mercaptothiazole compounds, especially 2-mercaptobenzthiazole, mercaptonaphthothiazole, etc., or mercaptooxadiazole compounds, mercaptopiveridine compounds, mercaptothiadiazole compounds, especially 2-mercaptothiadiazolotriazine, etc., or mercaptotriazine. Examples include mercaptotriazole-based compounds, mercaptobenzene-based compounds, particularly 1-mercapto-2-monobenzoic acid, 1-mercapto-2-nitrobenzene, 1-mercapto-3-heptadecanoylaminobenzene, and the like. Among the above-mentioned compounds, preferred in the present invention is when Y is a heterocyclic residue and the ring formed by Q is a hydrocarbon ring. The compound represented by the general formula [1] is described, for example, in Samurai Seki Publications No. 49-77635 and No. 51-
It can be synthesized according to the methods described in Japanese Patent No. 6724, Japanese Patent No. 51-64927, and the like. As a typical compound represented by the above general formula [B], the aliphatic hydrocarbon group R in the formula is preferably a saturated or olefinically unsaturated aliphatic group having up to 18 carbon atoms, and halogen , hydroxyl group, phenyl group, etc. The heterocyclic residue of R is a 5- to 6-membered double cyclic group, which can have one or more heteroatoms such as N, 0, or S atoms, and includes a benzene ring, a naphthalene ring, etc. A condensed one may also be used. Further, the aryl group of R is typically a phenyl group or a naphthyl group, and these may be substituted with a halogen, hydroxyl group, alkoxy group, alkyl group, or the like. Further, X represents a hydrogen atom or a halogen atom, preferably a halogen atom, and particularly preferably bromine. On the other hand, when the sulfur atom of the thioether bond is released, Y in the formula combines with the sulfur atom to inhibit the development of compounds such as IJ lumercapto compounds, heterocyclic compounds, thioglycolic acid series compounds, cysteine, or glutathione. It is a group that forms a compound having the same meaning as shown above. As detailed above - general formula

Among the compounds represented by [0], the one that exhibits preferable effects in the present invention is
is a halogen atom, especially a bromine atom. The compound represented by this general formula m] is Hakama Sekisho 49-12
It can be synthesized according to the methods described in Publications No. 6217, Taruko Sho 46-Matsu No. 514, and the like. In the compound represented by the general formula [Rainbow], A and H each represent a hydrogen atom or a group whose bond with oxygen is cleaved under alkaline conditions, such as an acyl group, an alkoxycarbonyl group, an alkoxyoxalyl group, and the like. B, C and D are each hydrogen atoms; c. Gen atom; hydroxy group;
Substituted or substituted alkyl groups such as methyl group, allyl group, ethyl group, octyl group, dodecyl group: phenyl group,
Substituted or unsubstituted aryl group such as tolyl group; substituted or unsubstituted heterocyclic residue such as tetrazole group, thiazolyl group, quinolinyl group, etc.; substituted or terminally substituted family/group: formula -S-Y or a group represented by the formula -○-W (W is a substituted or unsubstituted alkyl group, aryl group, or heterocyclic residue); D can also be condensed with each other to form a ring-closed ring with a carbon ring. Y has the same meaning as above. The compound represented by the general formula (b) can be rendered non-diffusible by having a ballast group at B, C, O or Y, or by bonding it to a polymer with a residue of B, C or D. The compound represented by the general formula [m] is disclosed in U.S. Pat. No. 3,379,529.
No. 33, No. 3620746, etc., Tsubaki Sekisho No. 49-129536, No. 50-111963
It can be synthesized according to the method described in No. 1, No. 50-37435, etc. Compounds represented by general formula [W] include US Pat.
No. 0210, No. 2722556, No. 272865
No. 9, No. 2732300, No. 3062, No. 323, British Patent No. 55775, No. 5
Specifications such as No. 57802, Hakamoseki Publication No. 46-2128, Journal of Organic Chemistry (J.
g. Chem) Vol. 22, pp. 772-774, etc., monoalkyl-substituted hydroquinone, U.S. Patent No. 23
No. 36327, No. 236029, No. 24037
21, No. 2360290, No. 273230, Oka No. 2735765, etc. are packaged. In the general formula [W], R2 and R3 may be the same or different, and may be a straight chain or a branched chain.
These compounds can be synthesized according to the descriptions in the above-mentioned publications, specifications, or literature. The compound represented by the general formula [V] is
Compounds are described in publications such as No. 155676 and No. 11 Iso 76y, and specifications such as U.S. Pat. The compound represented by the general formula [W] is Hakama Sekisho 51-724
It can be synthesized according to the method described in No. 33. The compounds represented by -Gaishi formulas [1] to [W] have been described in detail above, but in the present invention, they are contained in a non-photosensitive barrier layer provided in contact with at least one silver halide emulsion layer. Those that exhibit more favorable effects and require a smaller amount to be added to obtain the same effect are those of general formula [1],
Among the compounds represented by [ro], [m] or [N], where X is a halogen atom, the compound represented by the general formula [1] exhibits even more preferable effects. General formula [1] used in the present invention,

[0], [m], [
Representative compounds represented by N], [V] or [W] are shown below. The compound represented by the above general formula [1], [b], [m], [W], [V] or [W] is generally used to form the above-mentioned non-photosensitive barrier at a concentration of 0.01 to 1 night per unit. It is preferable to include it in the layer. The hydrophilic colloid constituting the non-photosensitive barrier layer contains the general formula [1], [B], [m], [W], [V] or [
In order to incorporate the compound represented by W], any known method used for incorporating a color-forming coupler into a hydrophilic colloid can be used. That is, a method in which a high boiling point solvent such as dibutyl phthalate or tricresyl phosphate is dispersed together in a hydrophilic colloid,
A method of adding it to a hydrophilic colloid as an alkaline aqueous solution can be applied. In the non-photosensitive barrier layer of the present invention, a portion of the hydrophilic colloid binder is incorporated into US Pat.
Specifications such as No. 5389, British Patent No. 1052487,
It may be replaced with a vinylpyrrolidone-based polymer compound as described in the specification such as No. 1226158. The vinyl pyrrolidone polymer compound is preferably used in an amount of about 4% by weight of the hydrophilic colloid binder.
A vinylpyrrolidone-based polymer compound can be easily mixed into a hydrophilic colloid in the form of an aqueous solution. The non-photosensitive barrier layer of the present invention may further contain photographic additives such as hardeners, coating aids, antifoggants, paints, etc., if necessary. In addition, the dry film thickness of the non-photosensitive barrier layer is generally 0.1
It is at least micron, preferably 0.5 to 3 micron. The silver halide color photographic light-sensitive material used in the present invention has three light-sensitive silver halide emulsion layers with different photosensitive areas on a support, and has a red-sensitive halide emulsion layer containing a cyan color-forming coupler on the support. A silver emulsion layer, a green-sensitive silver halide emulsion layer containing a magenta color-forming coupler, a blue-sensitive emulsion layer containing a 2-equivalent alpha acylacetamide yellow-forming coupler, and provided in contact with one side of any one of the emulsion layers. In addition, non-photosensitive auxiliary layers such as a surface protective layer and an intermediate layer may be provided. Silver halide in the light-sensitive silver halide emulsion layer of the silver halide photographic light-sensitive material used in the present invention includes silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, silver chloride, etc. Any of those commonly used in silver halide photographic emulsions are included. These silver halides may be coarse grained or fine grained, and can be prepared by any known method.
Publications such as Samurai Ko No. 46-7772, U.S. Patent No. 25
92250, French Patent No. 3276877, French Patent No. 155728y, US Patent No. 17322, French Patent No. 2
No. 222264, No. 3320069, No. 3271
No. 157, No. 3206313, No. 3367778
No. 3447927, Mukai No. 2996 Paper No. 2, No. 2184013, No. 2541472, No. 350
No. 1307, No. 2563785, No. 24569
No. 2861 Spot No. 5, British Patent No. 72301y,
Specifications such as French Patent No. 1520821, “Journal of Photographic Science (J.P.
hot. Sci), Volume 12, No. 5 (September, October issue)
, 19 I, pp. 242-251, No. 1 can be used. It is also possible to mix and use silver halides prepared by different methods. It is preferable that soluble salts be removed from the halogenated emulsion used in the present invention, but those from which soluble salts are not removed may also be used. In the silver halide photographic light-sensitive material of the present invention, hydrophilic colloids advantageously used to prepare a light-sensitive silver halide emulsion include gelatin, colloidal albumin, agar, gum arabic, alginic acid, and hydrolyzed cellulose. Acetate acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polypynylacetate,
For example, British Patent No. 523661, West German Patent No. 55
No. 711, No. 2046632, U.S. Patent No. 3341
332, water-soluble polymers, gelatin derivatives (e.g., US Pat. No. 26149
phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in U.S. Pat. No. 28, U.S. Pat. No. 2,525,753; These hydrophilic colloids can be used as constituent layers of photographic materials that do not contain silver halide. It can also be advantageously used, for example, in the production of filter layers, protective layers, intermediate layers, etc. The silver halide emulsion applied to the silver halide photographic light-sensitive material used in the present invention can be sensitized with various chemical sensitizers. Sensitizers include activated gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate), selenium sensitizers (N,N-dimethylselenurea, selenium urea), reduction Sensitizers (triethylenetetramine, stannic chloride), noble metal sensitizers such as gold sensitizers (potassium chloride, potassium aurithiocyanate, potassium chlorooleate, 2-ourosulfobenzothiazole methyl chloride), etc. used. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent. Other sensitizers such as palladium, platinum, and iridium salts (ammonium chloroparadate, potassium chloroplatinate, and sodium chloroparadite) can be used alone or in combination as appropriate. The blue-sensitive emulsion, green-sensitive emulsion and red-sensitive emulsion used in the silver halide photographic light-sensitive material of the present invention are optically sensitized using appropriate sensitizing dyes in order to impart photosensitivity to the desired wavelength range. It is felt. Various sensitizing dyes can be used, and one type or a combination of two or more types of sensitizing dyes can be used. Examples of the sensitizing dyes that can be advantageously used in the present invention include the following. That is, useful sensitizing dyes generally include methine dyes and styryl dyes such as cyanine, merocyanine, hemicyanine, rhodacyanine, oxol/hemioxonol, and the like. More specifically, the sensitizing dyes described in the following patents or literature are effective. U.S. Patent (hereinafter referred to as US) 1 Tsuchisuji No. 01, USI Shigeru No. 6302, U
No. SI939201, No. U61990507, US20
No. 72908, US2112140, US21653
Madara No., US Matsu No. 13995, US No. 2269234, U
S2270378, US2442710, US24
No. 54629, US2493748, US25037
No. 76, US2519001, US2666761, US2739149, US2739964, US
294 Group No. 63, British Patent (BP) No. 424559, BP438420, BP450958, BP50
No. 5979, German patent (hereinafter referred to as DP) No. 929080, D
P2049967, Special Publication No. 43-10251, Special Publication No. 10252, Special Publication No. 10252, Special Publication No. 10252, Special Publication No. 21, Special Publication No. 132753, Special Publication No. 44-32753, Special Publication No. 27672, Special Publication No. 45-27672, Special Publication No. 27673, Special Publication No. 1973, Special Publication No. 1977- 27674, Special Publication No. 45-127675, Special Publication No. 46-18106,
Special Publication No. Sho 46-18108, Special Publication No. 47-1741, Special Publication No. 47-23573, Special Publication No. 47-137443,
Japanese Patent Publication No. 48-78930, Mies/James, The.
Theory of the Photographic Process Part 3
Edition (1966 King) Harmer, Cyanindas &
Related Compound (King 1964). Among these patents or documents, US2213995
No., US2503775, US2945763, D
No. P929080, No. DP2049967, Kimiaki Tsubaki 43
No. 11, No. 21, Tsubaki Kosho No. 44-132753, Mochikosho No. 46
-18108, Tsubaki Publication No. 47-8741, Special Publication No. 47
The sensitizing dyes described in No. 37443 and Samurai Kaisho 48-7893 are particularly effective in the present invention. Couplers useful in the silver halide photographic material used in the present invention include closed ketomethylene yellow couplers, pyrazolone magenta couplers, and phenolic or naphthol cyan couplers.These couplers can be combined with silk to form an automask. It is also possible to use azo-type colored couplers, osazone-type compounds, development-diffusible dye-releasing couplers, and the like. Typical yellow coverrs that can be used in the present invention include those represented by the following general formula [K]. General formula [K] In the formula, R9 represents a substituted or unsubstituted aliphatic hydrocarbon group, aryl group or heterocyclic group, R and o represent a substituted or unsubstituted aryl group or heterocyclic group, Z represents a hydrogen atom or a coupling-off group. Among the yellow couplers represented by the general formula [K], those having a more preferable effect in the present invention are R, in the general formula [K]. is a substituted or unsubstituted phenyl group, and Z is a coupling-off group, and substituents for the phenyl group include a halogen atom, an amine group, an acylamino group, a trifluoromethyl group, and a sulfonamide group. , ureido group,
Preferred examples include an alkyl group, an alkoxy group, an aryloxy group, a carboxy group, an alkoxycarponyl group, a carbamyl group, a sulfo group, a sulfamoyl group, and an imido group. Furthermore, as mentioned above, alpha acylacetanilide type couplers exhibit more preferable effects in the present invention, and among these, pivalyl acetanilide type and penzoylacetanilide type couplers are preferred. Examples of the pivallylacetanilide type 4-equivalent yellow coupler include those described in French Patent No. 129111, and examples of the benzoylacetanilide type 4-equivalent yellow coupler include those described in Publication No. 46-19031 and U.S. Patent No. 2875051.
The ones described in the specification of No. 1 are effective, and the ones described in the specification of US Pat.
Active point 1○-acyl substituted as described in Han No. 8 Specification; Active point hydanthin compound substituted as described in Tokuseki Sho 48-29432 Publication; Active point urazole as described in Tokoseki Shogome-6 Spotted Milk Publication Compound substitution; Japanese Patent Publication No. 49-1357
The active point substituted with a succinimide compound described in Publication No. 6: The active point substituted with a succinimide compound described in JP-A-50-12-34; The active point substituted with a succinimide compound described in JP-A-49-10736; Compound-substituted ones; Active points described in British Patent No. 94449 and fluorine substituted; Active points described in British Patent No. 780507 and active points substituted with chlorine or bromine; Active points described in British Patent No. 1092506. 10-sulfonyl substituted; JP-A-5
1-3631 with active point substitution; JP-A No. 1-3631;
Active point substituted as described in Publication No. 0-65231; Active point substituted as described in Tokkoki Sho 50-134232; Active point substituted as described in Tsubaki Kai No. 50-117423;
The active point substitution method described in Mochiseki No. 51-50734 is more effective in the present invention. These can be synthesized according to the descriptions in each publication or specification. Further, particularly preferable 2-equivalent yellow couplers are those described in Tokuseki No. 48-29432, U.S. Pat. It is.
Magenta couplers that can be used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazo-1'nobenzimidazole-based, and indazolone-based compounds. As pyrazolone magenta couplers, US3127269, US2600788, US3
No. 519429, US3419391, US3062
No. 653, BPI No. 142553, DP2162778
No., Special Publication No. 49-2963y, Special Publication No. 48-2793
Pyrazolotriazole magenta couplers are described in DP1810464, Belgian Patent (hereinafter referred to as BELG) No. 762525, pyrazolotriazole magenta couplers are described in US3061432, BEL is an indazolone magenta coupler described in Japanese Patent Publication No. 46-60479 and DP2156111.
The one described in G769116 is used.
Others: Tokusekki No. 49-111631, No. 49-129
No. 538, No. 49-74027, No. 49-74028
No. 49-122335, No. 50-13041,
No. 50-159336, No. 50-60233, No. 5
1-32 spot number, 51-26 I number 1, 51-36 already 8
DP336498 and DP211018 can also be effectively used in the present invention. These can be synthesized according to each publication or specification. Particularly preferable magenta couplers in the present invention include those described in Hakama Kosho No. 48-2793 and US Pat. No. 3,127,269.
Examples include the 3-anilinopyrazolone mazesoda coupler described in No. Useful cyan couplers that can be used in the present invention include, for example, US2423730
No., US281171, US2895826, BE
LG779512' Phenol compound described herein, U
No. S2474293, BPI No. 08448' Active point 1○-aryl-substituted naphthol compounds described herein, JP-A-4
No. 7-448, JP-A No. 47-37425, JP-A No. 5
No. 0-10135, JP-A-50-25228, Tokkoku-Kei No. 50-112038, JP-A-50-120334,
Mochikai Sho 50-1117422, Special Seki Sho 50-13044
Examples include phenol and naphthol compounds described in No. 1, No. 51-6551, and DP129201. These can be synthesized according to the descriptions in each publication or specification. Couplers contained in the photographic material used in the present invention include, but are not limited to, the following. Yellow coupler The yellow coupler, magenta coupler or cyan coupler used in the present invention is generally contained in the blue-sensitive, green-sensitive or red-sensitive emulsion layer in an amount of 0.1 to 5.0 mmol. Each emulsion layer may contain two or more same color forming couplers. A conventional method may be used to make it contain. For example, as described in U.S. Pat. No. 23-027, it can be dissolved in a high-boiling point solvent, and as described in U.S. Pat. No. 280,117, a coupler with a high-boiling point It is also possible to separately disperse the solvent into fine particles and then mix them together for use, and in these methods of dispersion, it is also preferable to use a low boiling point solvent. In this case, the compound represented by the above general formula used in the present invention can be mixed and dispersed with the coupler, or can be used separately from the coupler, and when a low boiling point solvent is used. It is also possible to remove the low boiling point solvent from the dispersion liquid by the method described in US Pat. No. 2,801,171 or Tsubaki Kensho No. 44-76273. Among the applicable solvents, particularly preferred are dibutyl phthalate, dioctifthalate, diisodecyl phthalate, triphenyl phosphate, tricresyl phosphate, diethyl laurylamide, dibutyl laurylamide, benzyl phthalate, monophenyl phthalate, as high boiling point solvents. P-t-butynolephenyl/rephosphate, phenoxyethanol, diethylene glycol, monophenyl ether, dimethoxyethylphthalate, hexamethylphosphoramide, as well as U.S. Patent No. 3779765, Hakama Kaisho 49-90523,
Examples include high boiling point organic solvents that are immiscible with water and are described in Hakamako Sho 48-2906 Pishi Publication. Examples of low boiling point solvents include methyl isobutyl ketone, 8-utoxyethyl acetate, methoxy triglycol acetate, acetone, methyl acetone, methanol, ethanol, acetonitrile, dioxane,
Examples include dimethylformamide, dimethyl sulfoxide, ethyl acetate, butyl acetate, inbropylacetate, butanol, chloroform, cyclohexane, cyclohexanol, fluorinated alcohol, etc., and these low-boiling point solvents should be used in place of high-boiling point solvents. In addition, it can be used in combination with a high boiling point solvent, and each of these solvents can be used alone or in combination of two or more. Alternatively, in the case of a coupler having a water-soluble group and a compound represented by the above general formula, it is also possible to use the Fischer type, that is, by dissolving it in an alkaline solution. It is also possible to add one in the same layer by a dispersion method and the other by a Fischer type method. As a colored magenta coupler, a compound according to the activity rule of a colorless magenta coupler having a arylazo substitution or a heteroarylazo substitution is used, for example, U63.
No. 005712, US2983608, US2801
Compounds described in No. 171, BP Maki No. 7621, and Chigan No. 44-1-33 are used. As colored cyan couplers, active point arylazo substitution US30348 rudder number, US2521908, BP
No. 1255111, the compound described in Tokuiso Sho 46-55665, and furthermore the compound described in Tokuiso Sho 46-5782y, Samurai Sho 48.
16 job number 66, Samurai Isoaki number 49-16057, Tokusardo number 49
-25 Ibarakongo, Tokugao 49-3716bi No., BPI08
Masking couplers of the type described in US Pat. No. 4,480, which react with oxidized developer and cause the dye to flow into the processing bath may also be used. In order to incorporate these couplers into the silver halide emulsion layer, it is possible to apply the various techniques mentioned above that have been used for couplers in the related art. In the present invention, the photosensitive emulsion layer can contain various photographic additives. For example, hardeners include commonly used photographic hardeners, aldehyde-based hardeners, aziridine-based hardeners [for example, rB Report 19921, US Patent (hereinafter referred to as US) 295019]
No. 7, US2964404, US2 disaster P611, U
No. S3271175, those described in Japanese Patent Publication No. 46-14 Female Spot], isoxazole series (for example, US331609
No. 5), epoxy systems (e.g. US 304
No. 73, West German Patent (hereinafter referred to as DP) No. 1085663, British Patent (hereinafter referred to as BP) No. 1033518, Special Publication No. 1973-3
(mentioned in Nezumi No. 95), vinyl sulfones (for example, PB Report No. 19920, DPIIOO Kou No. 2, BP
No. 1251091, Akisho Hakama No. 45-Hiroshi No. 236, Special Request No. 4
No. 8-110996, Japanese Patent Application No. 115745, U.
S3539644, US Milk No. 90911), acryloyl type (e.g. Samuraibuta 48-27949)
No. 1, US3M0720), carbodimide series (e.g.
No. 715, those described in Tokuiso Sho No. 49-15095),
Maleimides (e.g. US2992109, US3
2327), acetylene series (for example, those described in DP2130483), methanesulfonic acid ester series (for example, those described in US2726162, US2130483),
816125), mucohalogenated acids (e.g., those described in US 3110597, Samurai Iso Akimo-30 Group 8), polymeric systems (e.g., US 30 Gikaku No. 27, BP 822061, BPI 049 Female No. 3). ,BP12
02052, BP1230354),
For example, triazine-based hardeners (for example, those described in US Pat. No. 3,288,775, Tokushi Sho 48-1 Guo 48-309 mother number, BP report 19921, special public service number 46-4
08 Madara No., Samurai IsoSho 48-108497, Mochigao Sho 45-
Nezumi No. 236, Tokuiso Sho 45-110996, Tokuiso Nariyakuichi No. 115745, PB Report No. 19920, Machigao Sho 4
No. 8-27, Samurai Warabi Sho 49-15096, BP12
51091, and when used in combination with these hardeners, the color purity and graininess are particularly good.
Moreover, it is possible to obtain a silver halide color photographic light-sensitive material having a good hardening agent that can withstand rapid high-temperature processing. In addition, in order to apply these hardeners to silver halide color photographic light-sensitive materials, they may be added and mixed into the coating solution in advance, or they may be added and mixed in the coating solution in advance, or by using an apparatus such as that described in US Pat. No. 3,286,992. It is also possible to use a means of continuously mixing it into the coating liquid immediately before coating. The silver halide color photographic light-sensitive material used in the present invention contains various photographic additives commonly used in the silver halide emulsion layer or auxiliary layer, such as tone adjusters, development accelerators, stabilizers, Ultraviolet absorbers, latent image stabilizers, formalin resistance improvers, image stabilizers, optical brighteners, antistaining agents, lubricants, sequestering agents, surfactants, mordants, antistatic agents, color clouding prevention agents, Thickeners, gelatin plasticizers, latex, matting agents, etc. can be contained. As the tone adjusting agent, metals of group 8 (for example, rhodium, ruthenium), cadmium, thallium, etc. can be used. Penzyl alcohol and polyoxyethylene compounds can be used as development accelerators, and these compounds are effective even when added to the processing bath. US as a stabilizer
No. 2444677, US2716062, US351
2 spots No. 2, DPI 189 spots No. 0, DP 20 spots No. 626,
DP211 Masu No. 11, Samurai Kosho 46-4133, US3
No. 342596, Samurai Kosho 47-144175, DP21
Compounds described in No. 4978y, Hakama Kosho No. 39-2825, and Hakama Kaosho No. 45-777072 can be used. A particularly preferred compound is 5,6-trimethylene-7-hydroxy-s-triazolo(1,5-
a) pyrimidine, 5,6-tetra〆0thylene-7-hydroxy-s-triazolo(1,5-a)pyrimidine,
5-methyl-7-hydroxy-striazolo(1,
5-a) Pyrimidine, 7-hydroxyl-s-triazolo(1,5-a)pyrimidine, 5-methyl-6-methyl-7-hydroxyl-s-triazolo(1,5-a)pyrimidine, gallic acid ester ( For example, isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercaptans (1-phenyl-5-captotetrazole, 2-mercaptobenzthiazole), benztriazole (5-brombenztriazole, 4-methylbenztriazole), triazole), benzimidazoles (6-nitrobennimidazole), and the like. As ultraviolet absorbers, Tokoku No. 48-1763, Tokko No. 48-5496, Tokko No. 48-41572, Tokko No. 48-30492, Tokko No. 48-31255,
Compounds described in US Pat.
It is effective to use UV absorbers such as Tinuvin 327, Tinuvin 32*, alone or in combination. As a latent image stabilizer, in addition to the sulfur-containing amino acid compounds described in DP Matsu No. 17153 and DP 217895, Hakama Kaisho No. 49-1412,
Nitrogen-containing, heterocyclic compounds described in Samurai Seki Sho 49-2 Shigarori No. 5 can be used. Examples of formalin resistance improvers include BELG801533, Hakama Akisho 48-1 Reverse 036,
Those described in Hakamako No. 46-34675 can be used, and among them, BEUG 801533, which combines a vinyl sulfone hardening agent and an acyclic urea derivative, and the one described in Tokuka Sho 48-1134036 are effective. be. As image stabilizers, chroman compounds described in US Pat. No. 3,432,300, chroman and coumaran compounds as described in US Pat. The phosphite ester compounds described in No. 1 can be used. Among them, Hakama Kosho 4
Compounds described in No. 8-31256 and Hakama Kosho No. 48-131625 are effective, such as 6,6'-butylidenebis(2-t-butyl-4-methylpheno-3), 4,
4'-methylenebis(2,6-di-t-butylphenol), 2,2-dimethyl-4,4'-dihydroxy-5
, 5'-di-t-butyl-diphenyl sulfide. As the fluorescent bleaching agent, for example, the compound described in No. 4 of Jikosho I-7127 can be used.As the lubricant, wax, glyceride of higher fatty acid, higher alcohol ester of higher fatty acid (for example, US
312106 and No. 1), etc. can be used. As the metal ion sequestering agent, ethylenediaminetetraacetic acid or the compounds described in DPI No. 160302, DPI 170777, DPI 187132, US 3236652, Machigao No. 48-45113, Hakamawaki No. 48-52094 can be used, Among them, the samurai face in 1974.
The ones described in No. 5113 and Samurai Fujisho No. 48-52094 are effective. Surfactants include coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and materials used to control various physical properties of photosensitive materials, including anionic, cationic, and nonionic agents. A variety of types or bisexual types can be used. For example BP54853
No. 2, BP1216389, US3026202,
US3514293, Samurai Kosho 44-26580, Tokuko Sho 43-179 Matsu, Tokusho 43-17926, Mochiko Sho 40-376, Tokko Sho 43-13166, Hakama Kosho 43-4313, Tokukansho No. 48-20785, Tokubatsu Sho 47-183 Iku No., Hakamahi Sho No. 47-8963, F
The activators described in P2025688, BELG773459, etc. are effective, but particularly preferred are sodium-alkyl sulfosuccinates (e.g. sodium-di-2-ethylhexyl sulfosuccinate or sodium-alumidecyl sulfosuccinate). etc.), anionic active agents such as sodium alkylbenzenesulfonate (e.g., sodium dodecylbenzenesulfonate, etc.), sodium alkylnaphthalenesulfonate (e.g., sodium triisopropylnaphthalenesulfonate), or saponin, polyethylene glycol, alkylfeed/thousandy polyethylene glycol. nonionic surfactants containing polyol, alkylphenoxy polyglycidol, sucrose fatty acid ester, and organosiloxane (for example, Poron SR manufactured by Shin-Etsu Chemical Co., Ltd., L-76 manufactured by Union Carbide Co., Ltd.
N-alkyl-N,N-dipolyoxyethylene- N-carboxymethyl-betaine (e.g. N-lauryl-N,N-dipolyoxyethylene-N-carboxymethyl-betaine, etc.)
There are amphoteric surfactants such as, and nonionic, anionic, cationic, and betaine type surfactants having a fluorine-containing alkyl group (for example, FC-134 and FC-172 manufactured by 3M), and these surfactants can be used alone. It can be used in
Furthermore, as disclosed in Hakama Seki No. 48-101118, several types can be used in combination with silk. As a mordant, US2 Iso No. 2156, DP2113381
N-guanyl hydrazone compounds described in US25
No. 48564, US34441, TaBP78659
No. 2, quaternary onium salt compounds described in Japanese Patent Publication No. 43-10254, tertiary amine compounds or quaternary onium salt compounds described in US Pat.
The compound described in P2113 paper No. 1 and US2548564 is effective for Z. As an antistatic agent, JP-KOKU 1973
No. 4159, Special Publication No. 39312, Special Publication No. 1977-
4380 shout number, Hakama Kosho 49-48 ball number, Tokuko Sho 49-6
No. 4, Special Publication No. 47-8742, Special Publication No. 48-4313
No. 0, JP-A No. 48-89979, Tokusei No. 48-903
No. 91, Hakama Kaisho 48-20785, Toku Z Kaisho 4713
No. 3627, Higan No. 115641, US 2 spot 2
Compounds described in No. 157, US 2979 Ball No. 5 can be used, among them, Mochikai No. 48-89979, Japanese Patent Application Kokai No. 48-90391, Hakama Kosho No. 46-2415y,
Those described in Hakamakai No. 47-33627, such as diacetylcellulose, styrene-perfluoroalkyl sodium maleate copolymer, reaction product of styrene-maleic anhydride copolymer and p-aminobenzenesulfosic acid Alkali salt, p-xylidene dichloride and N,N
, N',N'-tetramethyltrimethylenediamine polyadducts are effective. As agents for preventing color turbidity (preventing poor desilvering), polymers containing pinylpyridone monomers (for example, compounds described in BPI 052487), polymers containing vinyloxazolidinone monomers (for example, BPI
Compounds described in No. 070 No. 5), polymers containing pinylimidazole monomers (for example, compounds described in BPI No. 0976), and the like can be used. As matting agents, those described in BP1221, such as polymethyl methacrylate, polystyrene and U.
The alkali-soluble polymer described in S2992101 (
For example, monomethyl methacrylate copolymer is effective. It is also possible to use colloidal silicon oxide. In addition, the latexes added to improve the pus properties include US295 Technique No. 4 and FP139.
Copolymerization of acrylic esters, vinyl esters, etc., and other ethylene group-containing monomers as described in No. 5 I No. 4, Samurai Ko Kakemo-43125, etc. can be used. Glycerin or US296 as a gelatin plasticizer
No. 0404, Special Publication No. 43-4939, Publication of Tsubaki No. 45-1
No. 5462, Mochikai No. 48-63715, DPI904
Compounds described in No. 604 and BELG 762833 can be used. As thickeners, styrene-sodium maleate copolymers, alkyl vinyl ether-maleic acid copolymers, and US Pat. No. 3,767,410, B
Compounds described in ELG5 Spot No. 143 can be used. The silver halide photographic light-sensitive material used in the present invention can be provided with a filter layer, an antihalation layer, and an auxiliary layer for the irradiation layer. The dye is contained. As such dyes, dyes such as cyanine, merocyanine, styryl, benzylidene, cinnamylidene, oxanol, azo, anthraquinone, and triphalmethaso are typically used. Dyes that can be effectively used in the present invention include USI Shigeru No. 035 and US2150.
No. 695, US2172262, US2241239
No., US2298731, US2298733, U
S23 Matsu No. 006, US2527 Spot No. 3, US2011
No. 696, US2622082, US2091579
No., US273, Shigeru No., US2865752, US2
No. 956879, U63247127, Special Publication No. 28-5731, Hakama Kosho 31-ta 5 Madarabi No., Samurai Kosho 31-1
No. 0578, Hakama Koukai 39 Ichimono No. 069, Tokuko Sho 43-1
No. 3168, BP396646, BP446 Spot No. 3,
BP506 Paper No. 5, BP5159 Group No., BP64612
No. 5 and BPI No. 128113. Among them, US 1884035, US 2865752, OUS 295 Suji 79, Hakama Kosho 39-22069,
The ones listed in 131-131 of the Fin Kosho and BP506 Total No. 5 are valid. In the silver halide photographic material used in the present invention, a silver halide emulsion layer containing various photographic additives as described above and other constituent layers are coated on a support, if necessary. Manufactured by. Advantageously used supports include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate/cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate,
There are polyamide films, polycarbonate films, polystyrene films, etc., and these supports are appropriately selected depending on the intended use of the silver halide photographic material. These supports are subjected to undercoat processing if necessary. Typical undercoat materials include copolymers of vinyl chloride or vinylidene chloride, polymers of vinyl alcohol esters, copolymers of acrylic acid or methacrylate esters, copolymers containing unsaturated carboxylic acids, Copolymers of gens such as butadiene, copolymers of acetals,
Copolymers of unsaturated carboxylic acid anhydrides such as maleic anhydride, especially copolymers with vinyl acetate alcohol esters or styrene, or their complexes with water, alcohols, or amines, such as nitrocellulose, diacetylcellulose, etc. cellulose derivatives, compounds containing eboxy groups, gelatin or gelatin modified products, polyolefin copolymers, etc.
144 private number, special public number 1124 dollar number 1971, samurai public number 1999
No. 65, Special Publication No. 1973-3564, Special Publication No. 1971-141
No. 85, Special Publication No. 471354, Special Publication No. 4713, Special Publication No. 5
No. y, Tokukan Sho 47-37921, Tokukan Sho 47-142
No. 74, Tokuseki Sho 48-124723, Barrel opening Sho 48-93
No. 672, Mochikai No. 48-89979, etc. These undercoating materials can be used alone or in combination as necessary. Also, special public service 48-4312
No. 2, Special Publication No. 48-2427, Tsubaki Kai-Sho 48-261
It is also possible to use gelatin or polyols in combination as described in No. 24. Furthermore, it is also possible to use monohydric or polyhydric phenols, halogen-substituted products thereof, crosslinking agents (hardening agents), metal oxides, etc. (for example, JP-A-48-2
Madara No. 62, Samurai Kaisho 47-15). When actually undercoating the support, the above material may be used alone, but a layer consisting of the undercoating material, a mixed layer of gelatin and the above material, and a gelatin layer may be applied in this order, or one of the former two may be used. A method is used in which one layer is removed and a gelatin layer is applied thereon, and if necessary, layers can be added to perform multilayer coating, and either method can be used depending on the purpose. For example, Tokkan Sho 48-89731, Samurai Sho 48-85
No. 126, JP-A No. 93672, Hakama Kaisho 47-1 Madara No. 24, etc., the surface of the support is subjected to corona discharge, glow discharge, other electronic impact, flame treatment, and dregs formation. It is also possible to perform treatments such as , ultraviolet irradiation, etc. alone or in combination with each other, and it is also possible to perform these surface treatments in combination with the above-mentioned material processing.
In the present invention, the above-mentioned silver halide photographic material is subjected to color development after exposure. In the reversal method, the image is first developed with a black-and-white negative developer, then exposed to white light or treated with a solution containing a capri agent, and then color developed with an alkaline developer containing a color developing agent. There are no particular restrictions on the processing method, and any processing method can be applied; for example, a representative example is a bleach-fixing process after color development as described in US 3 Spot No. 232, followed by washing with water if necessary. Stabilization method and US
After color development, bleaching and fixing are carried out separately, as described in No. T910002, and further water washing and stabilization treatment are carried out as necessary. Furthermore, methods are known in which light-sensitive materials with a low silver content are processed using a polishing agent such as hydrogen peroxide or cobalt salt, and these methods can also be used for processing. In addition, these treatments may be carried out at high temperatures in order to perform them quickly, or may be carried out at room temperature or lower in special cases. When carrying out the high temperature treatment, a pre-hardening treatment can also be carried out, for example as described in US Pat. No. 3,342,596. Also, depending on the type of processing agent used, auxiliary cases such as various neutralization cases may be necessary in some cases.
These auxiliary cases can be used as appropriate.
Practical examples of these treatments include Eastman Kodak's Flexicolor Chemicals, Three Chemicals, and ME-4 treatments. The present invention exhibits sufficient effects when these treatments are applied, but it also exhibits sufficient effects when these treatments are modified or improved. Various methods can be used to transport the photosensitive material during processing, and various types of processing equipment are used accordingly. For example, hanger method, cine method, roller conveyance method,
There are various methods such as Parsamatu method, and special methods such as Mochiko Sho 35-11 Mura No. 5, Hakama Kosho 36-16 Shoku No. 9, US 3
18th Place No. 52, Special Publication No. 46-40908, US 360
The method of coating or spraying a processing liquid onto a photosensitive material, instead of soaking the photosensitive material into a processing liquid, as described in No. 7277, etc., is also applicable to the present invention. It is effectively used in processing photographic materials. In addition, methods have been developed to reuse processing liquids, and to recover chemicals that are important in terms of pollution and resources, such as developers and heavy metal silver. Processing can also be carried out using these as appropriate. In the present invention, the color developing solution contains a compound represented by the general formula [W] shown above. In the compound represented by the general formula [Hada], R'1- in the formula represents a group represented by 1(,R'610)m1(R'710)n1R'81. R[6} and R'7'' represent a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms. Examples of substituents that may substitute one or more hydrogens of the alkylene group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, nonyl group, etc. Aryl groups such as phenyl groups and naphthyl groups,
Aralkyl groups such as penzyl groups in which one or more hydrogens of the above alkyl groups are substituted with the above aryl groups, alkyloxy groups such as methoxy groups, ethoxy groups, benzyloxy groups, octyloxy groups, etc., phenoxy groups, etc. Typical examples include aryloxy groups, halogen atoms, etc.; however, one or more hydrogen atoms may be further substituted with another substituent, such as a halogen-substituted alkyl group. Further, R'81 represents a hydrogen atom, a substituted or unsubstituted aryl group, an aralkyl group, or an alkyl group having 1 to 6 carbon atoms. m and n are each an integer of 0 or more, and the sum of m and n is an integer of 1 or more. However, when the sum of m and n is 1, R
[6} and R are straight-chain alkylene groups having 1 to 6 carbon atoms and having the above-mentioned substituents. In the general formula [blood], R'21 represents a hydrogen atom, an unsubstituted or unsubstituted aryl group, an aralkyl group, an alkyl group having 1 to 6 carbon atoms, or a group represented by R1' above. Examples of substituents for aryl groups, aralkyl groups, and alkyl groups include hydroxy groups, substituted or unsubstituted ami/groups,
Typical examples include alkoxy groups, acylamido groups, carbamyl groups, aryloxy groups, and alkylsulfonamide groups. Furthermore, in the formula, R'3', R
'4} and R'5' are each a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms,
For example, a hydroxyalkyl group, an acylamidoalkyl group, an alkylsulfonamidoalkyl group, a substituted alkyl group such as a pupil or an unsubstituted aminoalkyl group, an alkoxy group, an amino group, a mono- or dialkylamino group,
Represents a sulfonamide group, an alkylsulfonamide group, or an acylamide group. When R'4' or R'51 is an alkyl group having 1 to 6 carbon atoms, it is extremely useful as a color developing agent in the present invention. The compounds represented by the general formula [blood] have been described in detail above, but among these, the compound represented by the following general formula [W] exhibits a more preferable effect in the present invention. General formula [W] In the formula, R■ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or an aralkyl group; R'6} and R'7
} each represents a substituted or unsubstituted straight mirror alkylene group having 1 to 6 carbon atoms, R represents a substituted or unsubstituted aryl group, aralkyl group, or alkyl group having 1 to 6 carbon atoms, p and q is an integer greater than or equal to 0, and p
The sum of p and q is 2 or more, and even more preferably the sum of p and q is 3 or more. Next, typical examples of the compound represented by the general formula [skin] will be given. In addition, salts of the above compounds with, for example, sulfuric acid, hydrochloric acid, phosphoric acid, oxalic acid, alkylbenzenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, alkylsulfonic acid, and other organic or inorganic acids may also be used in the same manner as the above-mentioned exemplified compounds. can be effectively used in the present invention. In order to synthesize the color developer represented by the above general formula [skin] according to the present invention, for example, N-alkylaniline, N-alkyl-3-alkylaniline, N-alkyl-3-alkoxyaniline, N- Alkyl-3-alkyl-3-acylamidoaniline, N-alkyl-3-acylamidoaniline, N-alkyl-3-hydroxyaniline, N-alkyl-3-acylamidoalkylaniline, N-alkyl-3-hydroxyalkylaniline or N-alkyl-3-alkyl Monoalkyl N-substituted anilines such as sulfonamide alkylanilines are available and used, in which case these mono/alkyl N-substituted anilines are combined with, for example, 1-halogen-2-methoxychetane, 1-halogen-2- (2-methoxyethoxy)ethane, 1-halogen-1-methyl-2-methoxyethane, 1-halogen-2-(1-methyl-2-methoxyethoxy)ethane 1-halogen-2-[2-(2-methoxyethoxy)ethoxy] The corresponding N,N-disubstituted aniline can be synthesized by reacting with a -halide such as ethane, or, for example, first ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, tetraethylene glycol, dipropylene glycol, etc. The alkylene glycols or monoalkyl ethers thereof are reacted with p-toluenesulfonic acid halide to synthesize the corresponding p-toluenesulfonic acid ester, and then the monoalkyl N-substituted aniline is reacted with this to synthesize the corresponding N-substituted aniline. , N-disubstituted aniline can be synthesized and used. Other N,N-disubstituted anilines can also be synthesized in a similar manner. Also, 3-alkylaniline, 3-alkoxyaniline,
Anilines such as 3-alkylsulfonamide aniline, 3-acylamide aniline, 3-hydroxyaniline, 3-hydroxyalkylaniline, 3-alkylsulfonamide alkylaniline, 3-acylamide alkylaniline, and the above-mentioned -halides or p N,N-disubstituted aniline can also be synthesized and used by reacting it with -toluenesulfonic acid ester. In order to synthesize the color photographic developer used in the present invention from the N,N-disubstituted aniline, first, a diazonium compound obtained by diazotizing substituted or unsubstituted aniline is added to the N,N-disubstituted aniline. Coupling is performed to synthesize an azo dye, which is then hydrogenated using a catalyst such as palladium-carbon or nickel to synthesize the corresponding p-phenylenediamine compound, or first the N,N-disubstituted aniline Nito. The corresponding p-phenylenediamine-based compound can be synthesized by converting the p-phenylene diamine into a compound, followed by reduction. The method for synthesizing the compound represented by the general formula [Hada] is detailed in the specifications of Tokuto No. 50-117246 and Tokuto No. 50-157315. The p-phenylenediamine compound thus obtained can be used as a color photographic developer for the image forming method of the present invention, and furthermore, a salt obtained by binding an organic acid or an inorganic acid to the p-phenylenediamine compound can be used as a color photographic developer for the image forming method of the present invention. It can also be used in inventions. To synthesize the salt-formed developer, the p-phenylenediamine compound and a necessary amount of hydrochloric acid, sulfuric acid, oxalic acid, phosphoric acid, alkylbenzenesulfonic acid, benzenesulfonic acid, alkylsulfonic acid, or naphthalenedisulfonic acid are combined. It is sufficient to cause a mixed reaction with an organic acid or an inorganic acid such as, for example, to precipitate crystals of a salt of the corresponding p-phenylenediamine compound. The color photographic developer used in the present invention is a free base of a p-phenylenediamine compound or a salt with an organic or inorganic acid, such as hydrochloride, sulfate, phosphate, oxalic acid. Salts, alkylbenzenesulfonates, benzenesulfonates, alkylsulfonates, naphthalene disulfonates, and the like are used. Although some free bases are stable, in general, salts with the above-mentioned organic acids or inorganic acids are preferred from the viewpoint of solubility of alkaline aqueous solutions and development action, and in particular, hydrochlorides, sulfates, and alkylsulfonic acids. Salts such as p-toluenesulfonate are preferred from the viewpoint of solubility. In order to prepare the color photographic developer of the present invention, the developer, that is, the compound represented by the above general formula [skin], should be added at 0.001 1/day of the developer.
A range of 0.02 to 0.02 mol, particularly a range of 0.002 to 0.01 mol, is preferred. Additives other than the developer to the developer include, for example, alkali metal chlorides, alkali metal bromides, alkali metal compounds, alkali metal sulfites, alkali metal sulfates,
Alkali metal carbonates, alkali metal hydroxides, alkali metal metapolates, alkali metal phosphates, ethylenediamine, citradinic acid, other antifoggants such as 6-nitrobenzimidazole, development aids such as 1-phenyl-3 Examples of stabilizers for developer include diethylhydroxyamine, dihydroxyacetone, glycolaldehyde, glyceraldehyde, dihydroxymaleic acid, and sodium hexametaphosphate.
Bleaching agents include dichromates, red blood salts, permanganate, iron chloride, halogens, persulfuric acid, hydrogen peroxide or aminopolycarboxylic acid metal salts, such as EDTA (ethylenediaminetetra) as described in DP866605. Cobalt salts such as iron mirror salts of acetic acid), iron trinitroacetic acid salts, iron tartrate salts, and those described in DP954475 and BP777635 can be used. In addition, an example of a quinone-based bleach is US2507.
No. 183, US 2,529,981; examples of nitroso compounds include US 27,052;
For example, BP774194, Samurai Kouka No. 35-11478, BPI
Examples of the halogen acid compounds described in No. 032024 include those described in US 32 I No. 107 and Tsubaki Kosho 4.
There are bleaching agents such as those described in No. 1-110 Iso, and these bleaching agents can also be used effectively. Examples of the fixing agent include known fixing agents such as thiosulfates and thiocyanates; for example, thioether polycarboxylic acids described in US Pat. A bissulfonyl alkane fixing agent or the like is used. In addition, various bleaching or fixing accelerators can be effectively used. These accelerators are often used particularly in bleach-fixing, and representative examples include polyethylene oxide, thiourea, mercapto, amine, onium, and selenium accelerators, such as BP746567.
No., Samurai Kosho No. 45-18506, BPII No. 38842,
Special Publication No. 45-1 No. 36, Special Publication No. 46-556, DP2
Particularly effective are those described in Japanese Patent Application Laid-Open No. 139401, Japanese Patent Application Laid-open No. 46-28-P, Chikai No. 47-7324, and Chikai No. 47-7325. Furthermore, using these chemicals,
In preparing the actual treatment solution, various auxiliary chemicals are used, such as phosphoric acid, acetic acid, citric acid, tartaric acid, boric acid, and their alkali metal salts or ammonium salts for bait adjustment. In addition, developers usually contain antioxidants, development accelerators, etc., and in the present invention, various processing steps using these various chemicals are effectively used. be able to. Next, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited thereby. Example ○} Preparation of dispersant (1). - Exemplary compound (Y-1) as a forming coupler: 50% of dibutyl phthalate, 100% of ethyl acetate.
The mixture was heated and dissolved, added to a 10% gelatin solution 600ml containing 60% sodium dodecyl bezenesulfonate, and emulsified and dispersed in a colloid mill. '2) Preparation of dispersion (0) Dispersion (1) using (Y-7), dibutyl phthalate 63, and ethyl acetate 126 in place of exemplary compound (Y-1) as yellow-forming couplers. Prepared in the same manner. Preparation of '31 dispersion (m) In place of exemplified compound (Y-1) as a yellow-forming coupler (Y-9), 50 mg of dibutyl phthalate [,
Prepared similarly to dispersion (1) using ethyl acetate loo'. Preparation of 4' dispersion (N) In place of exemplified compound (Y-1) as a yellow-forming coupler (Y-14), dibutyl phthalate 70 [
, ethyl acetate 140' in the same manner as dispersion (1). ■ Preparation of dispersion (V) Exemplary compound (M-1) 60 as a magenta-forming coupler
In the evening, dibutyl phthalate 60 [, ethyl acetate 1
Dispersion (1) was prepared similarly using 20'. '6} Preparation of dispersion (W) Exemplary compound (M-15) 6 as magenta coupler-forming coupler
3rd evening, 63 dibutyl phthalate products, 1 ethyl acetate product
26' was prepared in the same machine as dispersion (1). Preparation of dispersion (skin) of Exemplary compound (M-11) as a magenta-forming coupler Funayu, dibutyl phthalate Satoshi's [, ethyl acetate 13]
Dispersion (1) was prepared using 6'. ■ Preparation of dispersion (W) Exemplary compound (M-3) 55 as a magenta-forming coupler
Evening, dibutyl phthalate 55 [, ethyl acetate 1
Dispersion (1) was prepared similarly using 10'. [Preparation of 9' dispersion (K) Exemplary compound (M-9) 55 as magenta-forming coupler
55% of dibutyl phthalate, 1% of ethyl acetate
Dispersion (1) was prepared in the same machine using 10 skins. 00 Preparation of Dispersion (X) Dispersion (X) was prepared in the same manner as Dispersion (1) using Exemplified Compound (C-1) 43, Tricles phosphate 43 Z, and Ethyl acetate 860' as cyanogen-forming couplers. (11) Preparation of dispersion (phantom) Prepared in the same manner as dispersion (1) using exemplified compound (C-7) 55, tricresyl phosphate 55, and ethyl acetate 110 as cyanogen-forming couplers. did. (12) Preparation of dispersion (fine) Dispersion (1) was prepared in the same manner as exemplified compound (C-10) as a cyan-forming coupler, using tricresyl phosphate 44 and ethyl acetate. (13 Preparation of dispersion (1) Exemplary compound (S-2) 80% dibutyl phthalate
The mixture was heated and dissolved in 160 g of ethyl acetate, added to 1,000 g of a 10% aqueous gelatin solution containing 10 g of sodium dodecylbenzenesulfonate, and emulsified and dispersed in a colloid mill. (Preparation of 1-core dispersion 'B') Preparation of exemplified compound (S-7) in place of exemplified compound (S-2) was carried out in the same manner as for the dispersion base. (IQ Preparation of dispersion [C') (S-11) was prepared in the same manner as the dispersion using 20 minutes instead of (S-2). (16) Preparation of dispersion plate Example compound (S-16) instead of (S-2) (17) Preparation of dispersion leg Prepared in the same manner as dispersion W using (S-19) in place of exemplified compound (S-2). . River Dispersion (1) (D) (Town) (N) (Wind) (K) (Fox), Dispersion Song [CI Blood and Blue Sensitive Silver Chlorobromide Emulsion 100
0', a green-sensitive silver chlorobromide emulsion loo0', and a red-sensitive silver chlorobromide emulsion loo0' were coated on a paper support laminated with polyethylene to obtain samples as shown in Table 1 below. . The pitch layer was adjusted to have a silver content of 1 c, the green sensitive layer was adjusted to 10 m, the red sensitive layer was adjusted to 5 m, and the barrier layer had a dry film thickness of 1 micron. Samples a, b, c, d, e, For f and g, a barrier layer with a thickness of 1 micron was provided using 10% gelatin. Table 1 This sample was subjected to wedge exposure in the usual manner through blue, green and red filters, respectively, and was then treated with a developer according to the invention using the following exemplified compounds.
B--Developer using the following developer for comparison [CI] A sample having a color image was prepared by processing with three types of developer and then processing with the following bleach-fixing and stabilizing solution. [Processing process] 31℃ Processing time Color development 3 minutes 3 nights Bleach fixing
1 minute 3 seconds washing
2 minutes 0 seconds stabilization 1 minute 0 seconds [Color photographic developer] Penzyl alcohol 5.0 Z
Sodium hexamethacrylate 3.00 Anhydrous sodium sulfite 1.859 Sodium bromide IJ
Um 1.40 potassium bromide
0.50 Yusa sand (N also KO7, 1 Misaki 20) 39.10 ta The following color photographic developer 0.01 mol of water was added and finished for one night, and the PHI was adjusted to 0.3 with sodium hydroxide. [Developer for color photography] Developer style p-toluenesulfonate developer of exemplified compound (D-2) 'B- p-toluenesulfonate developer of exemplified compound (D-5) {C' N-ethyl-[2-(
Methylsulfonamido)ethyl]-13-methyl-4-aminoaniline sulfate [bleach-fix solution] Iron ammonium ethylenediaminetetraacetate 61. M ethylenediaminetetraacetic acid--bivalent ammonium
0.5 ammonium thiosulfate
124.5 Sodium metabisulfite
13.3 Sodium bisulfate
Added 2.7 liters of water, finished with a saw, and adjusted the solution to 6.5. [Stabilizing liquid] Glacial acetic acid (trihydrate) 2
After adding 800 g of pure water and adjusting the pH to 3.5-4.0 using sodium acetate trihydrate, the mixture was finished with a sawdust. The yellow, magenta and cyan silver concentrations of these samples were measured using a PD-7R thermometer (manufactured by Konishiroku Photo Industry Co., Ltd.), and the photographic performance obtained is shown in Table 2. Table 2 As is clear from Table 2, {B} of the color developing solution of the present invention
Samples processed with '' have low fog density and high image density, whereas samples processed with '' in the comparative developer cause a decrease in peak density and sensitivity. This result shows that the present invention is an extremely excellent image forming method. The sensitivity is expressed as a relative value with respect to the value of sample 'd{e-(g) treated with color developer 'C', which is set to 100. Table 3 By combining as shown in Table 3, blue-sensitive silver iodobromide emulsion LOOO0' is used as a blue-sensitive emulsion, green-sensitive silver iodobromide emulsion 1000' is used as a green-sensitive emulsion, and red-sensitive silver iodobromide emulsion is used as a red-sensitive emulsion. Emulsion loo0', dispersion (m) as coupler (W
) (V) (of) (K) (X) (phantom) and dispersions as barrier layers, respectively, on triacetate-based supports using the dispersion, wind {B'[C}■, with a silver content of 10 female/100 The barrier layer was applied so that the dry film thickness was 1 micron. Further, a barrier layer was applied to h, i, j, k, 1, m, and n using 10% gelatin so that the dry film thickness was 1 micron. This sample was processed in the following processing steps using the developer ○ used in the present invention and the developer E using the developer for comparison shown below.
Various types of development were performed. [Processing process] Total °C Processing time Color development 3 minutes 19 Sand bleaching
6 minutes 3 misaki washing
1/3 sand set 6/3
Thigh washing 1/3 sand stabilization
1 minute lake view [Developer for color photography] Anhydrous sodium sulfite 0.14 tahydroxyamine 1'2 sulfate 1. Spotted sulfuric acid
0.74 anhydrous potassium carbonate
288.5 ta anhydrous potassium bicarbonate
3.46 ta anhydrous potassium sulfite
5.10 Potassium bromide 1.1
6T Sodium Chloride 0.14Tanitrilotriacetic acid trisodium salt (monohydrate)
1.2M potassium hydroxide
1.48 ta The following color photographic developer
0.01 mol water was added and the mixture was polished in step 1. [Developer for color photography] Developer ■ Exemplified compound (D-2) p-toluenesulfonate developer [9 Exemplified compound (D-6) sulfate developer [F' N-Ethyl-N-(2 -Hydroxyethyl)-3-methyl-4-aminoaniline sulfate Table 4 From the results in Table 4, the sample treated with comparative developer 'F)
h) (i) (m) shows that the maximum density and sensitivity are reduced, whereas the image forming method according to the present invention has a low capri density and high image density and sensitivity. It is clear that this method is much superior to the subordinate method. Table 5 Multilayer color photosensitive materials were obtained in which one to six layers were coated from the support side using the combinations shown in Table 5. However, the support used was paper laminated with polyethylene, and the first layer contained a sound-sensitive silver chloride emulsion 1000/2, the third layer a green-sensitive silver chlorobromide emulsion loo0', and the fifth layer a red-sensitive salt emulsion. Using silver bromide emulsion loo0', the amount of silver is lo
The coating was applied so that the dry film thickness of the second, fourth and sixth barrier layers was 1 micron. Also, each barrier layer of sample o was similarly coated using gelatin. In Table 5, the numerical values for the 2nd, 4th, and 6th layers are the contents of the compounds represented by the general formulas [1] to [W] in the barrier layer. This sample was subjected to three-color separation exposure in a conventional manner, treated with the developer described below, and then treated with the bleach-fix solution and stabilizing solution described below to prepare a sample having a color image. [Processing process] 3100 Processing time Color development 3 minutes Inkstone sand bleach fixing 1 minute Sand washing
2 minutes 0 seconds stabilization 1
Minutes 0 seconds [Color photographic developer] Penzyl alcohol 5.0 Sodium hexametaphosphate 3.00 Anhydrous sodium sulfite 1.85 Sodium bromide
1.40 Potassium bromide
0.50 ta shelf sand (N & 07.1 Cape 20
) 39.10 N-ethyl-N-[2-(methylsulfonamido)ethyl]-3-methyl-4-aminoaniline sulfate Add 0.01 mol of water, finish with 1 sawn, and add sodium hydroxide. Spot 10.3
Adjusted to. [Bleach-fix solution] Iron ammonium ethylenediaminetetraacetate 61.0% Ethylenediaminetetraacetate-2-ammonium
5.0 ammonium tathiosulfate
124.5 Sodium metabisulfite
13.3 Sodium bisulfate
Add 2.7 liters of water and finish overnight to bring the pH to 6.5.
Adjusted to. [Stabilizing solution] Add 20% of glacial acetic acid (trihydrate) and 800% pure water, and adjust the pH using sodium acetate trihydrate.
After adjusting it to 3.5 to 4.0, I finished one. Three color densities of these samples were measured using a PD-7R densitometer manufactured by Konishi Rokumuroshin Kogyo Co., Ltd. Table 6 From Table 6, general formula [1]

[0][m][W]Compared with sample o which does not have the compound shown by [V] or [town] in the barrier layer, samples p, q, r, s, containing the compound
At t, the color temperature color almost disappears, and it is clearly seen that the image forming method according to the present invention is very superior.

Claims (1)

[Scope of Claims] 1. Supports a red-sensitive silver halide emulsion layer containing a cyan-forming coupler, a green-sensitive silver halide emulsion layer containing a magenta-forming coupler, and a blue-sensitive silver halide emulsion layer containing a yellow-forming coupler. having the following general formulas [I], [II], [III], [IV], [V] on the body and in contact with at least one surface of at least one silver halide emulsion layer.
] or a developing solution containing a compound represented by the following general formula [VII] or a salt thereof by imagewise exposing a silver halide color photographic material having a non-photosensitive barrier layer containing the compound represented by [VI]. 1. A method for forming a color photographic image, comprising: developing the photographic material with a color photographic material, and forming a color photographic image corresponding to the imagewise exposure. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Q represents a group of nonmetallic atoms necessary to form a hydrocarbon ring or a heterocycle, X represents a hydrogen atom or a halogen atom, Y represents a group that, when the sulfur atom of the thioether bond is separated, forms a compound with the sulfur atom that has a development inhibiting effect.) General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Formula (wherein, R_1 represents a substituted or unsubstituted aliphatic hydrocarbon group, aryl group, or heterocyclic residue, and X and Y each have the same meaning as in general formula [I].) General formula [III] ▲ Formula , chemical formulas, tables, etc.▼ [In the formula, A and A' each represent a hydrogen atom or a group whose bond with oxygen is cleaved under alkaline conditions, and B, C, and D each represent a hydrogen atom or a substituted or unsubstituted group. Alkyl group, aryl group, amino group or heterocyclic residue, halogen atom, hydroxyl group, group represented by the formula -S-Y (
Y has the same meaning as in general formula [I]. ), or a group represented by the formula -O-W (W represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic residue).
), C and D may be condensed with each other to form a carbon ring, and Y has the same meaning as in general formula [I].
] General formula [IV] ▲ Numerical formulas, chemical formulas, tables, etc. ), A and A' have the same meanings as in general formula [III]. ] General formula [V] ▲ Numerical formulas, chemical formulas, tables, etc. or represents a phenoxy group, and R_6 represents a substituted or unsubstituted aryl group.) General formula [VI] ▲ Numerical formula, chemical formula, table, etc. are available ▼ In the formula, R_7 represents an aliphatic residue, and R_8 represents a hydrogen atom. , halogen atom, substituted or unsubstituted alkyl group,
Aryl group or heterocyclic residue, formula -O-W (however,
W represents a substituted or unsubstituted alkyl group, aryl group, heterocyclic residue, or acyl group. ), groups represented by the formula -COV (where V represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic residue), groups represented by the formula ▲ mathematical formulas, chemical formulas, tables, etc. ▼ ( However, R_9 and R_1_0 each represent a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, or heterocyclic residue. ) or a group represented by the formula -S-V, Q' represents a nonmetallic atomic group necessary to form a 5- or 6-membered heterocycle, and r is 0. or an integer of 1, An■ represents an anion, and Y has the same meaning as in general formula [I]. ] General formula [VII] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R(1) is the formula -(R(6)O)m-(R(7)
)O)n-R(8) (wherein R(6) and R(7) each represent a substituted or unsubstituted linear alkylene group having 1 to 6 carbon atoms, and R(8) is a hydrogen atom Or, it represents a substituted or unsubstituted aryl group, aralkyl group, or alkyl group having 1 to 6 carbon atoms, m and n are each an integer of 0 or more, and the sum of m and n is an integer of 1 or more. However, when the sum of m and n is 1, R (6) and R (7) are straight chain alkylene groups having a substituent and having 1 to 6 carbon atoms. (2) represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a group represented by R(1) above, R(3), R(4
) and R(5) are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
It represents a hydroxyl group, an alkoxy group, a sulfonamide group, an alkylsulfonamide group, an acylamide group, an amino group, or a mono- or dialkylamino group. ]