JPS6015057B2 - Color photographic image forming method - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for forming a color photographic image using a color photographic light-sensitive material, and more specifically, the present invention relates to a method for forming a color photographic image using a color photographic light-sensitive material, and more specifically, an active site-substituted 2-equivalent alpha acylacetamide yellow coupler is added in an amount of 15 mol % per 1 mol of sound-sensitive silver halide. A multilayer color photographic material having a blue-sensitive emulsion layer containing sound-sensitive silver halide in an amount in the range of ~30 mol % and in a range of 1 to 9 parts of silver per 100 c is used;・
The present invention relates to a method of forming color photographic images of excellent quality by processing with a developer containing an N'-disubstituted paraphenylene diane developer. Generally, in order to process a silver halide color photographic light-sensitive material to form a color photographic image, the light-sensitive material is imagewise exposed,
Developing with a color photographic developer containing an aromatic primary amine color developer, reducing silver halide to silver and oxidizing the developer at the same time, bonding the oxidation product of the developer and the coupler, The method used is to form an image-wise dye that corresponds to the distribution of developed silver. The color image forming method described above includes, for example, exposing a silver halide color photographic material containing a non-diffusible coupler in a pattern, processing it with a color photographic developer, and then desilvering and fixing it to form a color negative image. There is an internal development method in which the silver halide color photographic light-sensitive material is imagewise exposed, black and white first development is performed, and then the remaining silver halide emulsion is uniformly exposed to form an internal or external development method. There is a method in which a reverse color photographic image is formed by processing with a formula color photographic developer, followed by desilvering and fixing, and the above method can also be applied to a multicolor reflective photographic material in which a color photographic emulsion layer is provided on an opaque support. Printing using a film with a color negative image formed by
Methods include 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 are exposed to light and form a latent image are effectively converted into silver and dye. It is not converted,
A considerable amount of the silver halide that has formed the latent image is not effectively utilized and is dissolved in the fixing solution and discarded. If silver halide grains were effectively converted into silver and dyes without wastage, it would be possible to create excellent color images with higher contrast, and the amount of silver would be reduced, making it possible to make thin films of photosensitive materials. Therefore, many advantages can be obtained, such as rapid development processing and the ability to obtain color images with high scale image power. These advantages have become more strongly desired in recent years as automatic processors have been used to rapidly process large quantities. In response to these demands, the conventional p-
A p-phenylenediamine developer has been disclosed which can more efficiently form reduced silver when developing silver halide on which a harbor image has been formed, compared to a phenylenediamine developer. Namely, Samurai Seki No. 50-131526 and Samurai Kao No. 131526
This is described in the specification of No. 11 Kyoku No. 567. In addition, in any of the various color image forming methods described above, beta-ketoacetoacetic acid esters and beta-diketones are conventionally used as yellow-forming couplers that provide a yellow band having absorption in the wavelength range of about 400 to 500 millimicrons. ,N・N
'-malondiamides and alpha-acylacetamides have been used. Among these, alpha acylacetamides have been widely used in the field of color photography as good yellow-forming couplers. However, alpha acylacetamides have many drawbacks both as couplers and as images formed by yellow dyes derived therefrom, and have by no means been satisfactory. In other words, alpha acylacetamides require 4 equivalents of silver halide per molecule as an oxidizing agent to convert into azomethine dyes, and the amount of dye produced is approximately 20,000 somo.
Since it only has a maximum molecular absorbance of about 1/1/cm of skin, it was necessary to use a photographic emulsion containing a large amount of silver halide in order to obtain the absorbance for blue light required for color photography. Additionally, 4-equivalent type yellow-forming couplers generally have low coupling activity with P-phenylenediamine type developers, and therefore a large amount of coupler is required to obtain high density images. On the other hand, incorporating a large amount of silver halide and a large amount of coupler into a light-sensitive material increases the coating thickness of the blue-sensitive emulsion layer, which delays the color development of other layers and makes it difficult to develop quickly. make it difficult or,
This increases the scattering of light in the emulsion, which in turn causes a deterioration in the performance of the light-sensitive material, such as a decrease in its ability to store sharp images. Moreover, the low coupling reaction activity mentioned above not only makes it impossible to obtain a sufficiently high amount of color-forming system, but also delays the development of silver halide and makes rapid development difficult. In order to eliminate these drawbacks of the 4-equivalent type alpha acylacetamide yellow-forming coupler, color photographic materials containing this coupler were modified from conventional p-
JP-A-50-131526 discloses that development can be performed using the above-mentioned more active developer instead of the phenylenediamine developer.
It is stated in the No. It is true that the developer described in the above-mentioned publication or specification has much better permeability and adsorption to the silver halide emulsion layer than the conventional p-phenylenediamine developer, and has a high color development speed. Further, when the latent silver halide image obtained by imagewise exposure of a silver halide photographic light-sensitive material is color developed, reduced silver can be efficiently formed, and there is an advantage that no wasted silver halide is left behind. be. Furthermore, when a port image is color developed, the ratio of the density of the developed silver to the density of the dye simultaneously formed is greater than that obtained with conventional developers. Therefore, although it is true that the drawbacks of yellow-forming couplers of alpha acetamides are considerably improved, the effect cannot be said to be sufficient. On the other hand, in order to improve the above-mentioned drawbacks of 4-equivalent alpha acylacetamide yellow-forming couplers, US Pat. Kaisho 48-294
Publication No. 32, Publication No. 48-66834, Publication No. 49-10
Publication No. 736, Publication No. 47-26133, Publication No. 50-2
No. 8834, No. 48-57829, No. 48-
No. 69866, Tokkan Sho 45-24068, Samurai Kai No. 45-37425, Tokkō 49-129538, Tokkō 50-13041, and U.S. Patent No. 341
Specification No. 9391, Specification No. 3311476, Specification No. 28
It has been proposed to use a so-called 2-equivalent coupler, which is an active point substituted coupler in which one of the active hydrogen atoms is substituted with a leaving group, as described in the specification of No. 01171 and the like. Active point substitution couplers require only two equivalents of silver halide as an oxidizing agent to form one molecule of dye, and therefore can reduce the amount of silver halide contained in a light-sensitive material. Furthermore, since the coupling rate of the p-phenylene zamine developer with the oxidation product is fast, the amount of coupler can be reduced. Therefore, the use of a 2-equivalent alpha acylacetamide yellow-forming coupler reduces the coating thickness of the blue-sensitive emulsion layer, which in turn improves image sharpness by reducing light scattering in the light-sensitive material and improves its suitability for high-temperature rapid processing. It can also be improved. However, 2-equivalent alpha acylacetamide yellow-forming couplers have the serious drawback of being susceptible to considerable yellow fog during development, which is a major hindrance to the use of these couplers in light-sensitive materials. This fact indicates that color photographic materials containing a 2-equivalent alpha acylacetamide yellow-forming coupler,
When developing with the more active developer described above, it is more magnified and becomes a greater obstacle. In other words, the yellow fog becomes very large and causes desilvering failure, and as a result, excellent images with high contrast cannot be obtained, high-resolution color images cannot be obtained, and furthermore, rapid image processing is extremely difficult. It becomes. Accordingly, an object of the present invention is first to provide a color photographic image forming method with high contrast and improved color reproducibility. A second object of the present invention is to provide a color photographic image forming method which is extremely suitable for rapid color development processing using a fixing bleaching solution containing both a weak oxidizing agent and a silver complex forming agent. Furthermore, thirdly, there is a color photographic image forming method in which penzyl alcohol, which has been contained in a color photographic developer but is undesirable because it causes pollution, can be reduced or removed without causing any problems. is to provide. The above objects, and other objects which will become apparent below, are to have a sonic silver halide emulsion layer on a support containing a 2-equivalent alpha acylacetamide yellow-forming coupler, and the sonic silver halide emulsion layer has a 100 c. A color photographic light-sensitive material containing 1 to 14 to 9 blue-sensitive silver halide per mole and 15 to 30 mole % of the 2-equivalent alpha-acylacetamide yellow-forming coupler per mole of the sound-sensitive silver halide. After exposing the bride, develop with a developer containing a compound represented by the following general formula [1] or a salt thereof,
This is achieved by a color photographic image forming method characterized by forming a color photographic image in response to the imagewise exposure. General formula [1] [wherein, R is the formula -(R60)m-(R?○)n-R8
(In the formula, R6 and R7 each represent a substituted or unsubstituted chain alkylene group having 1 to 6 carbon atoms, and R8 is a hydrogen atom, a substituted or unsubstituted aryl group, an aralkyl group, or a carbon atom number 1 represents an alkyl group of 6 to 6, 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 when the sum of m and n is 1, R6 and R7 are It is a linear alkylene group having 1 to 6 carbon atoms having a substituent.), where R2 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or the above R, R3, R4 and R5 each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a hydroxy group, an alkoxy group, a sulfonamide group, an alkylsulfonamide group, an acylamido group. represents a group, an amine/group or a mono- or dialkylamino group. ] Hereinafter, the present invention will be explained in more detail. The silver halide color photographic light-sensitive material used in the present invention has a blue-sensitive emulsion layer containing sound-sensitive silver halide in a range of 9 parts per 100 to 9 parts 14 parts on a support; The sensitive emulsion layer contains a 2-equivalent alpha acylacetamide yellow-forming coupler in the range of 15 to 30 mole percent per mole of blue-sensitive silver halide. If the content range of the coupler and silver halide in the sound-sensitive emulsion layer is changed, and if a developer other than the compound represented by the general formula [1] and a yellow-forming coupler other than the 2-equivalent alpha acylacetamide yellow-forming coupler are used, When performing any one of the uses, as will be clear from the following description,
Therefore, the purpose of the present invention cannot be achieved. Two-equivalent alpha acylacetamide yellow-forming couplers that can be used in the present invention include compounds represented by the following general formula [b]. General formula [B] In the formula, R [1 represents a substituted or unsubstituted aliphatic hydrocarbon group, aryl group or heterocyclic group, and R [1 represents a substituted or unsubstituted aryl group or heterocyclic group]. where Z represents a coupling-off group. general formula

Among the 2-equivalent alpha acylacetamide yellow-forming couplers represented by [0], those having the formula

In [0], R■ is a substituted or unsubstituted phenyl group, and substituents for the phenyl group include a halogen atom, an amino group, an acylamino group, a trifluoromethyl group, a sulfonamide group, a ureido group, Preferred examples include an alkyl group, an alkoxy group, an aryloxy group, a carpoxy group, an alkoxycarbonyl group, a carbamyl group, a sulfo group, a sulfamoyl group, and an imide group. Further, as mentioned above, alpha acylacetanilide type two-equivalent couplers exhibit more preferable effects in the present invention, and among these, bivallylacetanilide type and penzoylacetanilide type couplers are preferable.
For example, the active point 1○-allyl substituted as described in U.S. Pat. No. 3,408,194; the active point 1○-acyl substituted as described in U.S. Pat. No. 3,447,928;
The active point substituted with a hydantoin compound as described in No. 29432; the active point substituted with a urazole compound as described in Hakamakai No. 48-66834; the active point substituted with a succinimide compound as described in Japanese Patent Publication No. 49-13576; The active point substituted with a monooximide compound as described in JP-A-50-28834; the active point substituted with a pyridazone compound as described in JP-A-49-10736; the active point substituted with fluorine as described in British Patent No. 94449 things;
The active point substituted with chlorine or bromine as described in British Patent No. 780507: The active point substituted with 1○-sulfonyl as described in British Patent No. 1092506; Tokuseki Sho 5
1-3631 publication with active point substitution; Tokuseki Sho 5
Active point substituted as described in JP-A No. 0-65231; active point substituted as described in Tokusei No. 50-34232; active point substituted as described in JP-A-50-117423;
These include those in which the active site is substituted as described in Tokoseki No. 51-50734. Among these, the particularly preferred one is the one disclosed in Japanese Patent Application Laid-Open No.
-29432 publication, US Pat.
This is the one described in Publication No. 6834. Representative examples of compounds among the 2-equivalent alpha acylacetamide yellow-forming couplers used in the present invention are shown below. The 2-equivalent alpha acylacetamide yellow-forming couplers used in the present invention are, for example, West German Publication No. 2057941, West German Publication No. 2163812, Japanese Patent Application Publication No. 47-26133, Japanese Patent Application Publication No. 48-29432, and U.S. Patent No. 32771.
Specification No. 33, Specification No. 3408194, Specification No. 3447
Specification No. 928, Japanese Unexamined Patent Publication No. 48-66834, No. 4
No. 8-6 Road No. 35, No. 48-94432, No. 4
No. 9-1229, No. 49-10736, No. 5
No. 0-134232, No. 50-65231, No. 50-117423, No. 51-3631,
It can be synthesized according to the method described in Japanese Patent Publication No. 51-50734. The 2-equivalent alpha acylacetamide yellow-forming coupler is contained in the light-sensitive silver halide emulsion layer, either alone or in combination of two or more, and in some cases, in combination with a 4-equivalent yellow-forming coupler. As mentioned above, the content is 15 to 30 mol% per mol of blue-sensitive silver halide, and the content is carried out according to a conventional method. For example, as described in U.S. Pat. No. 2,322,027, the coupler can be dissolved in a high-boiling solvent, or as described in U.S. Pat. It can also be used by minutely dispersing it into fine particles and then mixing it, and in these methods of dispersion, it is also preferred 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 by the method described in US Pat. No. 2,801,171 or Tokuka Sho 44-76273. Particularly preferred among the applicable solvents are dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, triphenyl phosphate, tricresyl phosphate, diethyl laurylamide, dibutyl lauryl amide, benzyl phthalate, and high boiling point solvents. Monophenyl-P-t-butylphenyl phosphate, phenoxyethanol, diethylene glycol monophenyl ether, dimethoxyethyl phthalate, hexamethylphosphoramide, as well as U.S. Pat.
Examples include high-boiling organic solvents that are immiscible with water and are described in Japanese Patent Publication No. 48-2906. Examples of low boiling point solvents include methyl isobutyl ketone, 8-ethoxyethyl acetate, methoxy triglycol acetate, acetone, methyl acetone, methanol, ethanol, acetonitrile, dioxane,
Dimethylformamide, dimethyl sulfoxide, ethyl acetate, butyl acetate, inpropyl acetate, butanol, chloroform, cyclohexane, cyclohexanol, fluorinated alcohol, etc. can be mentioned, and these low boiling point solvents can be used in place of high boiling point solvents. 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 possible to use the Fischer type, that is, by dissolving it in an alkaline solution. It is also possible to add one to the same layer by a dispersion method and the other by a Fischer type method. The silver halide color photographic light-sensitive material according to the present invention preferably has three light-sensitive silver halide emulsion layers having different photosensitive regions on a support. One example of such a color photographic light-sensitive material includes a red-sensitive silver halide emulsion layer containing a cyan color-forming coupler, a green-sensitive silver halide emulsion layer containing a magenta color-forming coupler, 2. It consists of a sound-sensitive emulsion layer containing an equivalent alpha-acylacetamide yellow-forming coupler, and may further include non-photosensitive auxiliary layers such as a surface protective layer and an intermediate layer, if necessary. As the silver halide in the light-sensitive silver halide emulsion layer of the silver halide photographic light-sensitive material according to the present invention, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, silver chloride, etc. can be used. Any of those used in silver halide photographic emulsions are included. These silver halides may be paper grains or fine grains, and can be prepared by any known method. U.S. Patent No. 2,592,250,
No. 3276877, French Patent No. 1557289, US Patent No. 3317322, No. 2222264, No. 33200
69 3271157, 3206313, 3367
778 3447927, 2996382, 218
4013, 2541472, 3501307, 2
56378 Futoshi 2456953 Futoshi 2861885 Specifications of British Patent 723019, French Patent 1520821, etc., "Journal of Photographic Science (J. Photo. Sci), Vol. 12, No. 5 (9)
, October issue), 196 Butsute, pp. 242-251 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 silver halide emulsion used in the present invention, but those without removal 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 polyvinyl acetate, such as British Patent 523661, West German Patent 2255711-2046682, US Patent 3341
Aqueous polymers such as those described in 332 et al.
Gelatin derivatives (e.g., phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in U.S. Pat. , methacrylic acid, methacrylic acid ester, and other polymerizable monomers with ethylene groups are graft-polymerized onto gelatin), and these hydrophilic colloids form photographic materials that do not contain silver halide. It is also advantageously used to create layers, such as filter layers, protective layers, intermediate layers, etc. The silver halide emulsion used in the silver halide photographic material of the present invention can be sensitized with various chemical sensitizers. Sensitizers include activated gelatin, sulfuric acid sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate), selenium sensitizers (N/N-dimethylselenourea, selenourea), reduction Sensitizers (triethylenetetramine, stannic chloride), noble metal sensitizers such as gold sensitizers, (potassium chlorooleite, 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 palladium, platinum, and iridium salt sensitizers (ammonium chloroparadate,
Potassium chloroplatate, sodium chloroparadite), etc. can be used alone or in appropriate combinations. 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 an appropriate sensitizing dye 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 sensitizing dyes that can be advantageously used in the present invention include the following. That is, useful sensitizing dyes generally include cyanine, merocyanine, and hemicyanine. -methine dyes and styryl dyes such as dacyanine, oxonol, and hemioxonol. More specifically, the sensitizing dyes described in the following patents or literature are effective. US Patent (hereinafter referred to as US) 1846301, US1846302
, USI939201, USI990507,
US2072908, US2112140, US
2165338, US2213995, US22
69234, US2270378, US244
2710, US2454629, US24937
48, US2503776, US2519001
, US2666761, US2739149
, US2739964, US2945763, British Patent (hereinafter referred to as BP) 424559 BP4 Spot 42 BP450
99 pieces BP505979 West German patent (hereinafter referred to as DP), 9
29 Female DP2049967, Special Publication Showa 43-1025
1, Special Publication No. 43-10252, No. 21 of Special Publication No. 43-1,
Tokuko Sho 44-132753 Tokuko Sho 45-27672, Tokuko Sho 45-2767 Toku Tokuko Sho 45-27674, Tokko Sho 4
5-2767 Tsubaki Kosho 46-18100 Special Kosho 46-1
8108 Samurai Koryaku 47-8741, Hakama Kosho 47-2357
4 Samurai Dukes 1974-37443 Henchmen 1977-7893 “The Theory of the Photographic Process” by Rimies/James, 3rd edition (#196) “Cyanindies and Related Compounds” by Harmer (196 Buddha King). Among these patents or documents, US2218995
, US2503776, US2945763
, DP929080, DP2049967, Special Publication Showa 43
113821, Special Publication No. 44-32753, Special Publication No. 46-18108, Special Publication No. 47-8741, Special Publication No. 47-37
The sensitizing dye described in 443 Hakama Sekisho 48-78930 is particularly effective in the present invention. In the silver halide photographic light-sensitive material of the present invention, useful couplers to be contained in the green- or red-sensitive silver halide emulsion layer include pyrazolone-based magenta couplers, or phenolic or naphthol couplers. Examples include cyan couplers,
In combination with these couplers, it is also possible to use azo-type colored couplers, osazone-type compounds, development-diffusible dye-releasing couplers, etc. for auto-masking. Magenta couplers that can be used in the present invention include pyrazolone, pyrazolotriazole, pyr, 'linobenimidazole, and indazolone compounds. US31272 is a pyrazolone magenta coupler.
69, US2600788, US3519429
, US3419391, US3062653, BP
I142553, DP216277 & Special public service 1977-2
9639, described in Japanese Patent Publication No. 48-27930, and as a pyrazolotriazole magenta coupler, DP1810464, Belgian patent (hereinafter referred to as BELG) 7
92525, and US30614 as a pyrazolinobenimidazole magenta coupler.
As the indazolone magenta coupler, those described in BELG 769116 are used. Others, Tokukan Sho 49-1111631, 4
9-129538, 49-74027, 49-74
028 49-122335, 50-13041,
50-i59336, 50-60233, 51-3233, 51-26541, 51-36$8DP
Those described in No. 3364 and No. 211018 can also be effectively used in the present invention. These can be synthesized according to the descriptions in each publication or specification. Particularly preferred magenta couplers in the present invention include Japanese Patent Publication No. 48-2
7930, 3 described in US3127269
-Anilinopyrazolone magenta couplers.
Useful cyan couplers that can be used in the present invention include, for example, US2423730, US280
1171, US2895826, BELG779512
Phenol compounds described in US2474293, BP
Active point -○-aryl substituted naphthol compound described in I084480, JP-A-47-4480, JP-A-47-3
7425, Japanese Patent Publication No. 50-10135, Japanese Patent Publication No. 50-25
228, Tokuseki Sho 50-11203 & Tokuseki Sho 50-120
334, JP-A-50-117422, JP-A-50-13
0441, 51-6551, and DP129201. These can be synthesized according to the descriptions in each publication or specification. Next, typical examples of useful magenta or cyan couplers that can be used in the present invention are listed. Magenta coupler The yellow coupler, magenta coupler or cyan coupler used in the present invention is generally contained in the tone-sensitive, green-sensitive or red-sensitive emulsion layer at about 0.1 to 5.0 mmol/c. Each emulsion layer may contain two or more identically forming couplers. A conventional method may be used to make it contain. As a colored magenta coupler, a compound in which the active site of a colorless magenta coupler is substituted with arylazo or heteroarylazo is used, such as US3005.
712, US2 group 36 females, US2801171, BP9
37621, and the compounds described in Tokukan Sho 44-8433 are used. As a colored cyan coupler, active point aryl a
US30348 group of zo substitution, US2521908, BP
1255111, the compound described in Toku Iso Sho 46-55665, and furthermore, the compound described in Toku Iso Sho 48-5782 Kumochi Gan Sho 48-6 Job 6
0 machigao floor 49-16057, special application 1977-25388,
Masking couplers of the type described in Tsubakiisosho 49-37160 and BPI 084480, which react with the oxidized developer and cause the dye to flow out into the processing chamber, can also be used. In order to incorporate these couplers as well as the couplers represented by the above general formula used in the present invention into a silver halide color photographic light-sensitive material, various known techniques used for couplers can be applied. . In the present invention, various photographic additives can be contained in the light-sensitive emulsion layer or the adjacent layer. For example, as a hardening agent, commonly used photographic hardening agents such as aldehyde type, aziridine type, [for example, P
B Report 19921, US Patent (hereinafter referred to as US) 295
0197, US2964404, US2983611
, US Pat.
95), epoxy systems (e.g. US 304
7394, West German Patent (hereinafter referred to as DP) 1085663, British Patent (hereinafter referred to as BP) 1033518 Patent Publication No. 1987-3549
5), vinyl sulfones (e.g. BP Report 19920, DPIIOO942, BP1251)
091, Tokken Showa 45-54236, Tokkan Showa 48-110
996, Patent Application No. 48-115745, US353964
4, those described in US 3490911), acryloyl type (e.g. Tokusho 48-27949, US 36407)
20), carbodiimides (e.g. US
2938892, those described in Tokuko Sho 46-38715, Toku Iso Sho 49-15095), maleimides (for example, U
S2992109 as described in US3232763)
, acetylene type (e.g. those described in DP2130483), methanesulfonic acid ester type (e.g. US2130483),
726162, US2816125), mucohalogen acid type (e.g., US3110597, described in Japanese Patent Application No. 48-30948), polymer type (e.g., US30 Gifu 27, BP22061, BPI0)
49083, BP1202052, BP12303 Hiroshi), triazine type (for example, US32 Iso7
75, Tokuseki Sho 48-108497), etc., but particularly as hardening agents that can obtain more desirable effects in the present invention, US 2726162, Hakama-gaoka 48-30948 BP Report 19 Group 1, Special Kosho 4
6-4 Mesatoshi, special application 108497, 1973, special application 1977-
54236, Patent Application 1972-110996, Special Publication 1977-
115745PB Report 1992 Special Face Showa 48-27
949, Tsubaki Gansho 49-15090 BP 1251091, and when used in combination with these hardeners, a good hardener that has particularly good color purity and granularity and can withstand high-temperature rapid processing can be mentioned. A silver halide color photographic light-sensitive material can be obtained. 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 to the coating solution immediately before coating using a device such as that described in US 3,286,992. A means of continuously mixing the material into the coating liquid may also be used. The silver halide color photographic light-sensitive material of 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, and ultraviolet absorbers. agent, latent image stabilizer, formalin resistance improver, image stabilizer, photobrightener, antistain agent,
Lubricants, sequestering agents, surfactants, mordants,
Antistatic agent, color clouding prevention agent, thickener, gelatin plasticizer,
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. As the development accelerator, pendyl alcohol and boroxyshetylene compounds can be used, and these compounds are effective even when added to the processing bath. US as a stabilizer
2444677, US2716062, US3
512982, DPI189 spots 0, DP205862
6, DP2118411, Special Publication No. 43-4133, US
3342596, Special Publication No. 47-4417, OP2149
789, Special Publication No. 39-2825, Special Patent Application No. 45-7770
Compounds described in 72 can be used. Particularly preferred compounds include 5,6-trimethylene-7-hydroxy-S triazolo(1,51a) pyrimidine, 5,6-tetramethylene-7-hydroxy-S triazolo(1,51a) pyrimidiso, and 5-methyl-7-hydroxy-S triazolo. (1.5-a) pyrimidine,
7-Hydroxy-S-triazolo(1,5-a)pyrimidine, 5-methyl-6-bromo-7-hydroxy-S-
triazolo(1,5-a) pyrimidine, gallate ester (e.g. isoamyl gallate, dodicyl gallate,
propyl gallate, sodium gallate), mercaptans (1-phenyl-5-captotetrazole, 2
-mercaptobenzthiazole), benztriazoles (5-mercaptobenztriazole, 4-methylbenztriazole), benzimidazoles (6-nitrobenzimidazole), and the like. As a UV absorber, Hakama Kosho 48-76 Special Publication Show 48-5490 Special Publication Sho 4
8-41572, Special Publication No. 48-30492, Special Publication No. 1977
-31255, US3253921, BP309349
Among them, single use of ultraviolet absorbers such as Tinuvin PS, Tinuvin 320, Tinuvin 326, Tinuvin 327, and Tinuvin 328 manufactured by Ciba Geigy, or a combination thereof is effective.
As a latent image stabilizer, DP2217153, DP2217
In addition to the sulfur-containing amino acid compounds described in 895, JP-A-49-1
4120, and the nitrogen-containing heterocyclic compounds described in JP-A No. 49-29835 can be used. As a formalin resistance improver, BELG801533, patent application 1984-134
036, those described in Japanese Patent Publication No. 46-34675 can be used, and among them, BELG801533, which is a combination of a vinyl sulfone hardening agent and an acyclic urea derivative, and the one described in Japanese Patent Application No. 134036-1988 are effective. . Examples of image stabilizers include chroman compounds described in US Pat. No. 3,432,300, chroman and coumaran compounds described in US Pat.
Bisphenol compounds described in Japanese Patent Publication No. 31625-31625, phosphite ester compounds described in Japanese Patent Publication No. 48-32728, and the like can be used. Among them, Special Public Service No. 48-3125
6. Compounds described in Japanese Patent Publication No. 48-31625 are effective, such as 6,8-butylidenebis(2-t-butyl-4-methylphenol), 4,4-methylenebis(2-t-butyl-4-methylphenol),
-6-di-t-phthylphenol), 2,2-dimethyl-4,4'-dihydroxy-5,5'-di-t-butyl-diphenyl sulfide, and the like. As the photobleaching agent, for example, compounds described in Japanese Patent Publication No. 34-7127 can be used. As anti-stain agents, US2732300, US3700453, US
236021 and above, compounds described in US2728659 can be used, among which compounds described in US2732300
, US2360210, such as 2-methyl-5-hexadecyl-hydroquinone, 2-methyl-5-Sec-octadecyl-hydroquinone, 2.5
Compounds such as -G-t-octyl-hydroquinone or a combination thereof are effective. As a lubricant, wax, higher fatty acid glyceride,
Higher alcohol esters of higher fatty acids (e.g. US3
121060), etc. can be used.
Metal ion sealants include ethylenediaminetetraacetic acid or DPI160302, DPI170777, D
Compounds described in PI187132, US3236652, Japanese Patent Application No. 48-45113 and Tsubakiisosho No. 48-52094 can be used, and among them, those described in Samurai No. 48-45113 and Japanese Patent Application No. 48-52094 are effective. Surfactants include anionic, cationic, and nonionic types as coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and materials for controlling various physical properties of photosensitive materials. Alternatively, various species of both sexes can be used. For example BP548532, BP1216
389, US3026202, US351429
3, Special Publication No. 44-26580, Special Publication No. 43-17922
, Special Publication No. 43-17920 Special Publication No. 40-370 Special Publication No. 43-13166, Special Publication No. 43-43130, No. 4 Special Publication No. 43
8-20785, Special Seki Sho 47-18338, Special Application Sho 47
-89630, FP2025688 BELG7734
The activators listed above are effective, but particularly preferred are sodium-alkyl sulfosuccinates (for example, sodium-di-2-ethylhexyl sulfosuccinate or sodium-amyludecyl sulfosuccinate). , sodium alkylbenzenesulfonate (e.g. sodium dodecylbenzenesulfonate, etc.)
, anionic active agents such as sodium alkylnaphthalene sulfonate (for example, sodium triisopropylnaphthalene sulfonate, etc.) or saponin, polyethylene glycol, alkyl phenoxy polyethylene glycol, alkyl phenoxy polyglycidol, sucrose fatty acid ester, organosiloxane. Nonionic surfactants such as boron SR manufactured by Shin-Etsu Chemical Co., Ltd., L-70 L-52 manufactured by Union Carbide Co., etc., or sodium alkylphenoxy polyethylene glycol sulfonates (such as Sodium-pt-octylphenoxypolyethylene glycol sulfonate, etc.)
N-alkyl-N・N-dipolyoxyethylene-N-ruboxymethyl-betaine (for example, N-lauryl-N
- Amphoteric activators such as N-dipolyoxyethylene-N-carboxymethyl-petaine, etc.), and nonionic, anionic, cationic, and betaine-type activators with a fluorine-containing alkyl group (for example, 3M's FC- 134FC-17
2, etc.), and these active agents can be used alone or in combination as disclosed in Samurai Publication No. 48-101118. As a mordant, US2882150DP211
N-guanylhydrazone type compound described in 3381, U
S2548564, US3444138, BP7865
92, quaternary onium salt compounds described in Japanese Patent Publication No. 43-10254, US2675316, BP1221195, B
Tertiary amine compounds or quaternary onium salt compounds described in PI221131 can be used, among which DP21
13381, US2548564 are effective. As an antistatic agent, Japanese Patent Publication No. 46-24159,
Special Publication No. 46-39312, Special Publication No. 48-43809, Special Publication No. 49-4853, Special Publication No. 49-64, Special Publication No. 47-
8742, JP 48-43130, JP 48-89
979 Special Seki Sho 48-90391, Unexamined Patent Publication Sho 48-2078
5. Japanese Patent Publication No. 47-133627, Special Kansai No. 47-11564
1, the compounds described in US2882157, US2979535 can be used, among them, JP-A-4818
9979, Tokuko Sho 48-90391, Tokuko Sho 46-24
159 Tokusekki Sho 47-33627, such as diacetyl cellulose, styrene-perfluoroalkyl sodium maleate copolymer, reaction product of styrene-maleic anhydride copolymer and P-aminobenzenesulfonic acid Alkaline salts, P-xylidene dichloride and N
・Polyadducts of N・N'・N'-tetramethyltrimethylenediamine are effective. Polymers containing vinylpyrrolidone monomer (
(e.g. compounds described in BPI 052487), polymers containing pinyloxazolidinone monomers (e.g. BP
Compounds described in I070688), polymers containing vinylimidazole monomers (for example, compounds described in BP1880976), and the like can be used. As matting agents, those described in BP 1221 I0, such as polymethyl methacrylate, polystyrene, and US 29921
The alkali-soluble polymer described in 01 (for example, methacrylic acid-methyl methacrylate copolymer) is effective. It is also possible to use colloidal silicon oxide. Also, as a latex to be added to improve the organoleptic properties, US295 technique spot 4 FP1395 mouse 4 special public show 48
Copolymers of acrylic esters, vinyl esters, etc. described in 143125 and other monomers having ethylene groups can be used. As a gelatin plasticizer, glycerin or US2960404, Japanese Patent Publication No. 43-493
9 Special Publication No. 45-15462, No. 9 Special Publication No. 48-63715,
Compounds described in DPI904604, BELG762833, etc. can be used. As thickeners, styrene-sodium maleate copolymer, alkyl vinyl ether-maleic acid copolymer and US376741 are used.
0, BELG558143 can be used. The silver halide photographic light-sensitive material of the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer, and an irradiation layer. The dye is contained. As such dyes, dyes such as cyanine, merocyaniso, styryl, benzylidene, cinnamylidene, oxanol, azo, anthraquinone, and triphenylmethane are typically used. Dyes that can be effectively used in the present invention include US1884035 and US215.
0695, US2172262, US2241239
, US2298731, US2298733,
US2322006, US2527583, U
S2011696, US2622082, US2
091579, US2739888, US286
5752, US2956879 US3247127,
Samurai Publication 28-5731, Special Publication No. 31-5920, Special Publication No. 31-10578, Special Publication No. 39-22069, Special Publication No. 43-Sho.
-113168, BP396646, BP446583,
BP506385, BP515998, BP64612
5, those described in BPI128113. Among them, US1884035, US2865752, US2
956879, Special Publication No. 39-22069 Special Publication No. 43-1
3168 and BP506385 are effective. The silver halide photographic material of the present invention is produced by coating a support with a silver halide emulsion layer and other constituent layers containing the various photographic additives as described above, if necessary. Ru. Advantageously used supports include, for example, rose paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate,
Examples include polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc., and these supports are appropriately selected depending on the intended use of the silver halide photographic light-sensitive material. These supports are subjected to undercoat processing if necessary. Typical undercoat materials include copolymers of vinyl chloride or vinylidene chloride, copolymers of vinyl alcohol esters, copolymers of acrylic acid or methacrylic acid esters, copolymers containing unsaturated carboxylic acids, copolymers of gene species such as butadiene, acetal copolymers,
Copolymers of unsaturated carboxylic acid anhydrides such as maleic anhydride, especially copolymers with vinyl alcohol esters such as vinyl acetate or styrene, or ring-opened products thereof with water, alcohols or amines, such as nitrocellulose, diacetyl There are cellulose derivatives such as cellulose, compounds containing epoxy groups, gelatin or gelatin modified products, and polyolefin copolymers. 3564, Special Public Service 1977-
14185, Special Publication No. 47-35458, Special Publication No. 47-3
5459, JP-A-47-37921, JP-A-47-14
274 Japanese Patent Publication No. 48-2472 Japanese Patent Publication No. 48-33672
, JP-A-48-8997. These undercoating materials can be used alone or in combination as necessary. It is also possible to mix it with gelatin or polyols, as described in Japanese Patent Publication No. 48-43122, Japanese Patent Publication No. 48-24270, Japanese Patent Publication No. 48-26124, etc. Furthermore, it is also possible to use monohydric or polyhydric phenols, their halogen-substituted products, crosslinking agents (hardeners), metal oxides, etc. (for example, Tokusekki Sho 48-23862, Tokkan Sho 47-592). When actually undercoating the support,
The above materials may be used alone, but a layer consisting of the above material, a mixed layer of gelatin and the above material, and a gelatin layer may be applied in this order, or one layer of the former two may be removed and gelatin applied thereon. A method of applying layers is used, and if necessary, the number of layers can be increased to perform multilayer coating, and any method can be used depending on the purpose. Furthermore, as described in Tokkyo Tokusei No. 48-89731, No. 48-85120, No. 48-93672, No. 47-19824, etc., corona discharge, glow discharge, and other electronic It is also possible to perform treatments such as impact treatment, fire treatment, surface roughening, ultraviolet irradiation, etc. singly 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 subjected to white exposure or processed in a solution containing a fogging agent, and then color developed with an alkaline developer containing a developer. There are no particular restrictions on the processing method, and any processing method can be applied, but typical examples include:
After color development as described in US 3,582,322,
A method in which a bleach-fixing process is performed, followed by water washing and stabilization treatment if necessary, and a method in which bleaching and fixing are performed separately after color development as described in US Pat. No. 910002, and further water washing and stabilization treatment are performed if necessary. I can give things away. There are also known methods of processing low-silver light-sensitive materials using amplifier agents such as hydrogen peroxide and cobalt mirror salts, 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 temperatures in special cases. When performing high temperature treatment, for example, US
3,342,596 may also be performed. Furthermore, depending on the type of processing agent used, auxiliary cases such as various neutralization cases may be required in some cases, and these auxiliary cases can be used as necessary. Practical examples of these treatments include Eastman Kodak's Flexicolor Chemicals, Three Chemicals, and M-4 (old M-4) treatments. The present invention exhibits sufficient effects when these treatments are applied, but it also exhibits sufficient effects when these treatments are modified and improved. Various methods can be applied to transport the photosensitive material during processing.
Along with this, various types of processing equipment are used. For example, there are various methods such as the hanger method, cine method, roller conveyance method, and versatile method, as well as special methods such as the
, US3189452, Mochiko Showa 46-409 female, US3
The silver halide photographic light-sensitive material of the present invention may also include a method in which the light-sensitive material is coated or sprayed with a processing liquid instead of being immersed in a processing solution, as described in Japanese Patent Application No. 607277. It is effectively used to process. In addition, methods have been developed to reuse processing liquids and to recover chemicals that are important in terms of pollution or resources, such as developers and heavy metal silver, and some processing equipment is equipped with these devices. It can also be processed using Now, in the present invention, the color developing solution has the general formula [1
] Contains the compound shown. In the compound represented by the general formula [1], R. Ha-(R6
0) represents a group represented by m-(R70)n-R8. Here, R6 and R7 are substituted or unsubstituted carbon atoms of 1 to 6
represents a straight-chain alkylene group. Examples of substituents that may substitute one or more hydrogen atoms in the alkylene group include methyl group, ethyl group, propyl group, isopropyl group,
Alkyl groups such as butyl group, t-butyl group, nonyl group, aryl group such as phenyl group, naphthyl group, etc., aralkyl group such as penzyl group in which one or more hydrogens of the above alkyl group are replaced with the above aryl group. , methoxy group,
Typical examples include alkyloxy groups such as ethoxy groups, benzyloxy groups, octyloxy groups, aryloxy groups such as phenoxy groups, halogen atoms, etc. Substituents such as halogen-substituted alkyl groups may have one or more hydrogen atoms further substituted with other substituents. R8 represents a hydrogen atom, a substituted or substituted 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, R6 and R7 are linear alkylene groups having 1 to 6 carbon atoms and having a substituent as described above. Also, general formula [
1], R2 represents a hydrogen atom, a substituted or unsubstituted aryl group, an aralkyl group, an alkyl group having 1 to 6 carbon atoms, or a group represented by R above. Examples of substituents for aryl groups, aralkyl groups, and alkyl groups include hydroxy groups, substituted or unsubstituted amino groups,
Typical examples include alkoxy groups, acylamido groups, carbamyl groups, aryloxy groups, and alkylsulfosamide groups. Further, in the formula, R3, R4 and R5 each represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, such as a hydroxyalkyl group, an acylamidoalkyl group, an alkylsulfonamidalkyl group, a substituted or < represents a substituted alkyl group such as a substituted aminoalkyl group, an alkoxy group, an amino group, a mono- or dialkylamino group, a srunamide group, an alkylsulfonamide group, or an acylamide group. When R4 or R5 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 [1] have been described in detail above, but among these, the compound represented by the following general formula [m] exhibits more preferable effects in the present invention. General formula [m] In the formula, R2 represents a hydrogen atom or a substituted or substituted alkyl group, aryl group, or aralkyl group, and R3
, R4 and R5 are each a hydrogen atom, a halogen atom,
Substituted or unsubstituted alkyl group, hydroxy group, alkoxy group, sulfonamide group, alkylsulfonamide group, acylamido group "represents an amino group or a mono- or dialkylamino group, and R6 and R7 each have 1 to 6 carbon atoms. represents a substituted or unsubstituted alkylene group, R8 represents a substituted or unsubstituted aryl group, aralkyl group, or an alkyl group having 1 to 6 carbon atoms, and p and q
is an integer greater than or equal to 0, and the sum of p and q is greater than or equal to 2, and even more preferably, the sum of p and q is greater than or equal to 3. Next, typical examples of the compound represented by the general formula [1] will be given. Note that the above compounds may be used, for example, sulfuric acid, hydrochloric acid, phosphoric acid,
Salts made with oxalic acid, alkylbenzenesulfonic acids, benzenesulfonic acids, naphthalenesulfonic acids, alkylsulfonic acids, and other organic or inorganic acids can also be effectively used in the present invention in the same way as the above-mentioned exemplified compounds. In order to synthesize the color developer represented by the general formula [1] according to the present invention, for example, N-alkylaniline, N-alkyl-3-alkylaniline, N-alkyl-3-alkoxyaniline, N-alkyl -3-alkylsulfonamide aniline, N-alkyl-3-acylamidoaniline, N-alkyl-3-hydroxyaniline, N-alkyl-3-acylamidoalkylaniline, N-alkyl-3-hydro. Monoalkyl N- such as xyalkylaniline or N-alkyl-3-alkylsulfonamide alkylaniline
Substituted anilines can be obtained and used, in which case these monoalkyl N-substituted anilines and e.g.
-halogen-2-methoxychetane, 1-halogen-2-(2-methoxyethoxy)ethane, 1-halogen-1-methyl-2-methoxy-etaso, 1-halogen-2-(
1-Methyl-2-methoxyethoxy)ethane 1-halogen-2-[2-(2-methoxyethoxy)ethoxy]ethane and other ■-halides are reacted to form the corresponding N.N.
- For example, firstly, alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, tetraethylene glycol, and dibropylene glycol or their monoalkyl ethers are synthesized with paratoluenesulfonic acid halide. to synthesize the corresponding p-toluenesulfonic acid ester, and then reacted with the monoalkyl N-monosubstituted aniline to synthesize the corresponding p-toluenesulfonic acid ester.
- N-disubstituted aniline can be synthesized and used. Other N·N-disubstituted anilines can also be synthesized in the same manner. Also, 3-alkylaniline, 3-alkoxyaniline, 3-alkylsulfonamideaniline, 3-acylamideaniline, 3-hydroxyaniline, 3-hydroxyalkylaniline, 3-alkylsulfonamidealkylaniline, 3-acylamidealkylaniline N.N-disubstituted anilines can also be synthesized and used by reacting anilines such as the above with the Yamaichi halide or p-toluenesulfonic acid ester. To synthesize the color photographic developer used in the present invention from the N·N-disubstituted aniline, first, a diazonium compound obtained by diazotizing a fake or unsubstituted aniline is synthesized with the N·N-disubstituted aniline. to synthesize an azo dye, and then hydrogenate this using a catalyst such as palladium-carbon or nickel to synthesize the corresponding p-phenylenediamine compound, or first, the N.N-disubstituted The corresponding p-phenylenediamine compound can be synthesized by nitrosating aniline and then reducing it. Regarding the synthesis method of the compound represented by the general formula [1],
For details, see the specification of No. 50-157315. The p-phenylenediamine compound thus obtained can be used as a color photographic developer in the image forming method of the present invention, and furthermore, it can be combined with an organic acid or an inorganic acid to form a salt. It can also be used in the present invention. To synthesize the salt-formed developer, the p-phenylenediamine compound and a required amount of, for example, 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 such as an acid or an inorganic acid to precipitate crystals of a salt of the corresponding p-phenylenediamine compound. The color photographic developer used in the present invention can be used as a free base of p-phenylenediamine compounds or as a salt with an organic or inorganic acid, such as hydrochloride, sulfate, phosphate, oxalate. , alkylbenzene sulfonate, benzene disulfonate, alkyl sulfonate or naphthalene disulfonate. 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 in alkaline aqueous solutions and development action, particularly hydrochlorides, sulfates, and alkylsulfonic acids. Salts, p-toluenesulfonate and the like are preferred from the viewpoint of solubility. In order to prepare the color photographic developer of the present invention, the amount of the developer, that is, the compound represented by the above general formula [1], is from 0.001 to 100% per developer.
A range of 0.02 mol, particularly a range of 0.002 to 0.01 mol, is preferred. Examples of additives other than the developer in the developer include alkali metal chlorides, alkali metal bromides, alkali metal iodides, alkali metal sulfites, alkali metal sulfates, alkali metal carbonates, alkali metal hydroxides, Alkali metal metaborate, alkali metal phosphate, ethylenediamine, citradinic acid, other antifoggants such as 5-nitrobenzimidazoles, development aids such as 1-phenyl-3-pyrazolidone, benzyl alcohol, developer stabilization Examples of the agent include diethylhydroxyamine, dihydroxyacetone, glycolaldehyde, glyceraldehyde, dihydroxymaleic acid, and sodium hexametaphosphate.
Next, as typical internal color photographic developers, there are the following, for example. [Color photographic developer] Penzyl alcohol 0-12'
Alkali metal hexametaphosphate 0-3 Ta-Alkali metal phosphate, 12LO IO-60 Ta-Alkali metal bromide 0-5 Ta-Alkali metal iodide (0.1% solution) 0-15 Color photographic developer 0.001- 0.02 mole ethylenediamine sulfate 0-20 tacytrazic acid
0-5 Tadioctanediol
Add 0 to 5 tad of water and finish, e.g. with alkali metal hydroxide or alkali metal carbonate, etc. to adjust the pH.
is adjusted to 10.0 to 14.0. In the present invention, even if penzyl alcohol, which is undesirable in terms of pollution, is removed, it can be used satisfactorily. As bleaching agents, dichromates, red blood salts, permanganates, iron chlorides, halogens, persulfuric acid, hydrogen peroxide or aminopolycarboxylic acid metal salts, such as DP86660
Iron salts, trinitroacetic acid iron salts, or iron tartrate salts of EDTA (ethylenediaminetetraacetic acid) as described in No. 5, cobalt salts as described in DP95447 and BP777 line 5, etc. can be used. In addition, examples of quinone-based bleaches include US2507
183, US2529981; as nitroso compounds, for example, US2705201
Copper key salts include, for example, BP7.
74194, Special Public Service No. 35-1147 & BPI032024
The halogen acid compounds listed in
For example, US3264107, Special Publication No. 41-11068
These bleaching agents can also be used effectively. The fixing agent may be a known fixing agent such as thiosulfate or thiocyanate, or US27480, for example.
For example, thioether polycarboxylic acids are described in Tokukan Sho 47-330. For example, a bissulfonyl alkane fixing agent may be used. Various other bleaching or fixing accelerators can also be used effectively. These accelerators are often used especially for bleach-fixing agents, and typical examples include polyethylene oxide, thiourea, mercapto, amine, onium, and selenium. BP746567
, Special Public Service 18500BPII Shigebura 42, Special Public Service 45
Ichiiso 30 Tsubaki Kimiaki 46-550 DP2139401, Hakama Sekisho 46-28 and special Sekisho 47-7324 JP 47-73
The following are particularly effective. In addition, in order to create the actual treatment liquid using these chemicals, various auxiliary chemicals are required, such as phosphoric acid, acetic acid, citric acid, tartaric acid, boric acid, and their alkali metal salts or ammonium salts for wind adjustment. Salt etc. are used. 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 1 Sample '11 2-equivalent type yellow-forming coupler of exemplified compound (Y-2) 8.
Dibutyl phthalate 4 and ethyl acetate 12
The mixture was heated and dissolved in 50% gelatin solution containing sodium alkylbenzenesulfonate and added to emulsify and disperse. This emulsified dispersion was added to 100 u of a blue-sensitive silver chlorobromide emulsion and spread on a polyethylene laminated paper colored with Ti02 with a silver content of 2/100 and a coupler content of 9/100 of 2.5.
It was applied so that it looked like this. Sample t21 Exemplary Compound (Y-
Heat and dissolve 6.6 parts of the coupler in 2) in 3.3 parts of dibutyl phthalate and 10 parts of ethyl acetate, and prepare 5% gelatin solution containing sodium alkylbenzenesulfonate.
In addition to 'emulsification and dispersion. This emulsified dispersion was added to the blue-sensitive silver chlorobromide emulsion lo0' and coated on polyethylene laminated paper colored with Ti02 so that the amount of silver was 4 blocks/100 and the amount of coupler was 4.4 blocks/100 blocks. did. Sample [3} Silver amount is 18/100, coupler amount is 21 female/10
All other coatings were applied in the same manner as sample [1]. Sample [4 - For comparison, the 4-equivalent type yellow coupler Q-pivaloyl-2'-chloro-51 described in U.S. Pat.
Q-(2,4-ditertiaryamylphenoxy)butyramide] 6.09% of acetanilide was dissolved in 3.0% of dibutyl phthalate and 9.0% of ethyl acetate to form a 5% solution containing sodium alkylbenzenesulfonate. It was added to 50 ml of gelatin solution and emulsified and dispersed. This emulsified dispersion was added to 100 w' of blue-sensitive chlorobromide emulsion and T
P/100 ground with a silver content of 12, c/10 with a coupler content of 13.2 on polyethylene laminated paper colored i02.
It was applied so that it became 0. Sample (5) For comparison, coupler 5 used in sample 41 was heated and dissolved in 2.5 parts of dibutyl phthalate and 7.5 parts of ethyl acetate, and emulsified and dispersed in the same manner as sample '4-. 9/100 with a quantity of 4, a coupler with a quantity of 34/10
It was applied so that it became 0. These samples were subjected to wedge exposure using a conventional method, and then processed using a developer according to the present invention using the following exemplified compounds.
B-, 'q, ■, for comparison, processed with 5 types of developer using the following developer, and then processed with the following bleach-fix solution and stabilizing solution to produce a 2-color image. A sample with [Processing process] 31℃ Processing time Color image 3 minutes 3 minutes Existing sand bleach fixing
1 minute 3 Tochi sand washing
2 minutes 0 seconds stabilization 1
Minutes 0 seconds [Color photographic developer] Penzyl alcohol 5.0
Sodium xametaphosphate 3.00
Anhydrous sodium sulfite 1.85
Sodium bromide 1.40 Potassium bromide 0.50 Talon acid (Na2 & 07.1 female 20) 39.1M
The following color photographic developer was added with 0.01 mol of water and finished overnight, and then adjusted to pHIO. with sodium hydroxide.
Adjusted to 3. [Developer for color photography] Imager ■ p-Toluenesulfonate developer for Exemplified Compound (D-5) [B} p-Toluenesulfonate developer for Exemplary Compound (D-2) [q p-Toluenesulfonate developer for Exemplified Compound (D-20) ■ p-Toluenesulfonate developer for Exemplary Compound (D-7) N-ethyl-N-[2-methoxyethyl]-3-methyl-4- Aminoaniline sulfate [bleach-fix solution] Ethylenediaminetetraacetate iron ammonium 61.0 ethylenediaminetetraacetate mono-2-ammonium 5.0
Ammonium thiosulfate 124.5 Sodium metabisulfite 13.3 Sodium bisulfate 2.7 Water was added, and the pH was adjusted to 6.5. [Stable iQ night] Glacial acetic acid (trihydrate)
Add 20 parts of '800 parts of pure water' and add 3 parts of sodium acetate.
After adjusting the temperature to -3.5 to 4.0 using water salt, it was finished. The yellow color density of these samples was measured using a PD-7R densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.), and the photographic performance obtained is shown in Table 1. Table 1 As is clear from Table 1, blue-sensitive emulsions with a large amount of silver and
Compared to the color image forming method in which the photographic light-sensitive material of sample '4--, which uses a 4-equivalent yellow coupler, is processed with a color developing solution, a method using a low-silver tone-sensitive emulsion and a 2-equivalent type yellow coupler according to the present invention is used. The photographic light-sensitive material of sample m was mixed with a developer,
It can be clearly seen that the dish processing method is an extremely superior color image forming method with significantly higher sensitivity and maximum density. Furthermore, even when Sample 2, which uses a blue-sensitive emulsion with a low silver content and a 4-equivalent yellow coupler, is processed with color developer A used in the present invention, the color image formation method is extremely poor in both sensitivity and maximum density. I understand it well. Furthermore, a sample lake using a high-silver sonic emulsion and a 2-equivalent type yellow coupler was mixed with color developers A, B, C,
In the color photographic image forming method using D and E,
It is clear that the fog is large and it is unusable. Therefore, the amount of silver in the sound-sensitive emulsion layer is 9/100* of 1 to 14, and the 2-equivalent yellow-forming coupler contained in combination therewith is 15 to 14.
30 mol%/mole of silver halide, the developer is of the general formula shown above [
Very good results can be obtained only by the present invention, which is realized by containing the compound shown in 1) and by selecting these three requirements. Note that the sensitivity is expressed as a relative value with respect to the sensitivity of sample {4' treated with color developer E, which is 100. Example 2 After providing an antihalation layer and a gelatin layer thereon on a triacetate film support, the above exemplified cyan coupler C-1 was contained in an amount of 12 mol % per mol of silver halide, and silver iodide was contained in an amount of 6 mol. A red-sensitive silver iodobromide emulsion containing 100% red-sensitive silver iodobromide was coated so that 16 females per 100% were coated. Next, a gelatin layer and a green-sensitive silver iodobromide emulsion containing 10 mol % of the above-mentioned exemplified magenta coupler M-1 per 1 mol of silver halide were coated on this at a ratio of 17 to 9 per 100 areas, and further on this. A yellow filter layer was applied. Then, on top of this, a tone-sensitive silver iodobromide emulsion containing 15 mol % of a 2-equivalent type yellow-forming coupler of exemplified compound Y-14 per mol of silver halide was added at 10 parts per 100.
A silver halide color photographic film for reversal (Sample 6) was prepared by coating the film to form a fence and then coating it with a protective layer. As a comparative sample, Comparative Sample-7 was prepared in the same manner except that the following 4-equivalent type yellow-forming coupler described in Japanese Patent Publication No. 19031/1984 was used in place of Exemplified Compound Y-14. After this color photographic film was subjected to wedge exposure in a conventional manner, the following processing steps were carried out using the following developer solutions F, G and 1 using the developer according to the present invention and developer '1' using a comparative developer. Processed with four types of developer. [Processing process] 38qo processing time 1st
Developing stopped for 3 minutes
0 minutes 3 minutes water washing 1 minute color development 4 minutes stop
0 minutes 3 female wash
1 minute bleach, 1 minute 3 chest wash
Fixed for 1 minute 1
Powder washing for 3 minutes and stabilization for 2 minutes
0 min 3 sand [color photographic developer] sodium tetrapolyphosphate 5.0 tabenzyl alcohol 4.5 sodium sulfite (anhydrous) 7.5 trisodium talate (12k salt) 36.0 potassium taiodide ( 0.1% aqueous solution) 90.0 [Sodium bromide (anhydrous) 0.9# Sodium hydroxide 3.25 Tacitradinic acid 1.5 Taethylenediamine
3.3' tertiary butylaminoborane 0.07 ml Color photographic developer 0.02 mol I sawed with water,
The pH was adjusted to 11.65. [Developer for color photography] Developer (F) Exemplary compound (D
-6) p-toluenesulfonate developer (G) p-toluenesulfonate developer (G) for exemplified compound (D-4)
H) p-Toluenesulfonate developer (1) N-ethyl-N-(2-methylsulfonamidoethyl)-3-methyl-4-aminoaniline sulfate Table 2 of Exemplified Compound (D-7) According to the present invention It can be seen that such color photographic image forming methods are superior to conventional processing methods. Example 3 Sample [1' Blue-sensitive material containing 25 mol % of a 2-equivalent type yellow-forming coupler of exemplary compound Y-7 per mol of silver halide and 4 mol % of silver iodide on a triacetate film support. Sample (2) was prepared by applying a silver iodobromide emulsion at a dose of 7/9 per 100 streams. In addition, as a comparative sample, the following 4-equivalent type yellow-forming coupler was used instead of Exemplified Compound Y-7, and a comparative sample [9] was prepared.
1 was created. After exposing this sample, in the following processing steps, a developer (J) and a developer (K) using the developer used in the present invention below, a developer (L) using the developer for comparison below, and a bleach solution below. Three types of development were performed using a fixer solution and a stabilizing solution. [Processing process] 3800 Processing time Color development 3 minutes 15 seconds Bleaching
6 minutes 3 jobs, wash
1/3 sand set 6
3 minutes, water washing, 3 minutes sand stabilization
1 minute 3 night sand [Developer for color photography] Anhydrous sodium sulfite 0.1
4-hydroxyamine 1/2 sulfate 1.
98 sulfuric acid 0.74
Anhydrous sodium carbonate 28.85
Anhydrous sodium bicarbonate 3.46 Anhydrous potassium sulfite 5.10 Potassium bromide 1.16 Sodium chloride 0.14 Trilotriacetic acid trisodium salt (monohydrate) 1.20 Potassium hydroxide 1.48 The following color photographic developer was prepared by adding 0.01 mol of water. [Developer for color photography] Developer (J) p-toluenesulfonate developer of exemplified compound (D-5) (K) sulfate developer of exemplified compound (D-20) (L) N-ethyl -N-(2-Hydroxyethyl)-3-methyl-4-aminoaniline sulfate The yellow color image density of the color image obtained by the above processing was measured using a PD-7R densitometer. Table 3 shows the photographic performance. In addition, the sensitivity is 1 for sample ■ treated with comparative developer G.
00 and expressed as a relative value to this value. As is clear from Table 3, it is clearly understood that the color photographic image forming method according to the present invention is significantly superior even when the developer does not contain penzyl alcohol.

Claims (1)

[Scope of Claims] 1 A blue-sensitive silver halide emulsion layer containing a 2-equivalent alpha acylacetamide yellow-forming coupler is provided on a support, and the blue-sensitive emulsion layer has a concentration of 1 mg/100 cm^2.
After imagewise exposure of a color photographic light-sensitive material containing 14 mg of blue-sensitive silver halide and 15 mol % to 30 mol % of the 2-equivalent alpha acylacetamide yellow-forming coupler per 1 mol of the blue-sensitive silver halide, the following general Formula [I]
A method for forming a color photographic image, which comprises developing with a developer containing a compound represented by the formula or a salt thereof, and forming a color photographic image in response to the imagewise exposure. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is the formula -(R_6O)m-(R_7O)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, a substituted or unsubstituted aryl group, an aralkyl group, or a carbon atom number 1 represents an alkyl group of 6 to 6, 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 when the sum of m and n is 1, R_6 and R_7 are It is a straight chain alkylene group having 1 to 6 carbon atoms having a substituent.), where R_2 is 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 each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a hydroxy group, an alkoxy group, a sulfonamide group, an alkylsulfonamide group, an acylamido group , represents an amino group or a mono- or dialkylamino group. ]