JPS5842046A - Formation of color photographic image - Google Patents

Abstract

PURPOSE:To obtain a yellow dye image high in developed color density and superior in storgae stability, etc. without requiring use of a developer contg. benzyl alcohol having a problem in environmetnal pollution, by using a psecified 2-equivalent coupler for forming a yellow dye. CONSTITUTION:A silver halide color photographic material contains a 2-euqivalent coupler for forming a yellow dey, having general formulaIin which Q is alkyl or aryl; Y is halogen or alkoxy; R is alkyl or phenyl-substituted alkyl; A is halogen, alkyl, alkoxy, alkylthio, or alkylsulfonyl; and X is a group releasable on coupling; embodied in formulae II and III. An intended color photographic image is obtained by imagewise exposing this material and processing it in presence of an aromatic primary amine developing agent such as 4-amino- N,N-diethylaniline.

Description

[Detailed description of the invention]

This invention relates to a method for forming color photographic images, and more particularly to a method for forming color photographic images 116 using novel yellow dye-forming couplers. Furthermore, it has good solubility, dispersion stability, and spectral absorption characteristics, and in particular, has a fast dye formation rate in a color development processing solution that excludes benzyl alcohol, has a high color density, and has good field storage stability. It relates to a method for forming yellow dye images in the presence of an excellent new yellow coupler. Subtractive color photography is a process in which an aromatic primary amine color developing agent is used to form an exposed halogen dye. The oxidation product of the color developing agent produced from K by reducing the silver oxide particles and the yellow color;
Color images are formed by oxidative coupling of couplers forming cyan and magenta dyes in silver halide emulsions. In these cases, as a yellow coupler for forming a yellow dye, a compound having an open-chain active methylene group is generally used, and as a magenta coupler for forming a magenta dye, a pyrazolone type, pyrazolinobenzimidazole type, Compounds such as indazolone-based compounds are used, and compounds having phenol, nut, and hydroxyl groups are used as uncouplers for forming cyan dyes. Each coupler is dissolved in a substantially water-insoluble high-boiling organic solvent or in combination with an auxiliary solvent as necessary,
It is added to the silver halide emulsion or dissolved in an aqueous alkaline solution and added to the emulsion. The former is an oil droplet dispersion method5, and the latter is an alkali dispersion method, but in general, the former has better light resistance, heat resistance, moisture resistance, granularity,
It is said to be excellent in terms of color sharpness, etc. The basic properties required of each coupler include not only the ability to simply form a dye, but also high solubility in high-boiling organic solvents or alkalis, as well as dispersibility and stability in silver halide photographic emulsions. The dye formed by the pigment should be resistant to light, heat, moisture, etc., have good spectral absorption characteristics, good transparency, and high color density. i obtained
It can be seen that YTG1 has various properties such as the fact that it has a bright color.Furthermore, in recent years, from the standpoint of depollution, the removal of benzyl alcohol added to the coloring YTG1 treatment liquid has been taken up as a major interlayer. It's been getting worse. However, in general, when using a color developing processing solution that does not contain benzyl alcohol, the color development properties of the coupler added to the silver halide photographic process, that is, the rate of dye formation and the maximum color density, decrease. be. This tendency is particularly evident in yellow couplers. Therefore, in this yellow coupler, its coloring properties are based on benzyl alcohol. It is strongly desired that this problem not occur, and along with the improvement of the above-mentioned image storability, research has been carried out to improve this. However, among the conventionally known yellow couplers, a coupler that satisfies all of the above-mentioned required properties has not yet been found. For example, JP-A-50-876
'50 publication discloses that alkylsulfonamide, aralkylsulfonamide,
having a benzenesulfonamide, alkoxybenzenesulfonamide or alkarylsulfonamide bond;
Yellow couplers in which one hydrogen atom at the active site is replaced with an aryloxy group have been described, but these yellow couplers still have poor coupling reactivity in a color development processing solution that excludes benzyl alcohol. In the specification of JP-A No. 50-123342, it is found that: a methanesulfinamide or toluenesulfonamide bond is present at the 5-position of α-bivalylacetanilide.
L, 2. Unsubstituted active site four-equivalent yellow couplers having chlorine atoms at the chlorine and 4-positions are described, but these couplers are so-called external type couplers that are used by dissolving them in a liquid solution. On the other hand, the yellow coupler of the present invention is a two-equivalent yellow coupler that has a group at the active site that can be dissociated upon coupling, and when used in a hacegenated chain emulsion, i.e., used as a -inner coupler. It is different from the external four-equivalent yellow coupler described in JP-A-50-123342 in that it exhibits remarkable effects. Also, JP-A No. 52-11!5219 and JP-A No. 54-
Publication No. 48541 describes a yellow coupler having an alkylsulfonamide or phenoxyalkylsulfonamide bond at the 5-position of α-7 sylacetanilide, and a heterocycle substituted at the active site via the nitrogen atom of the heterocycle. However, these couplers still do not have sufficient color development properties in color development processes that exclude benzyl alcohol. Furthermore, @Kokai No. 55-147-340 discloses a yellow coupler containing an alkoxyalkyl sulfonamide group at the non-coupling position of the α-7 syl acetanilide yellow coupler.
ra is listed. It has been reported that these yellow couplers introduced an ether bond into the hydrophobic alkyl group of the alkylsulfonamide group to increase hydrophilicity, and as a result, the coupling activity of the yellow couplers was improved. As is clear from the examples, the color development is still highly dependent on benzyl alcohol, and yellow couplers containing alkoxyalkyl sulfonamide groups have the disadvantage of having a low melting point and becoming oily, making purification in large-scale synthesis difficult. . The first objective of the present invention is to achieve sufficient coupling reactivity even in a system using a color developing solution without the addition of benzyl alcohol! An object of the present invention is to provide a novel yellow coupler having the following properties and an image forming method using the dye. A second object of the present invention is to provide a novel yellow coupler which has excellent storage stability, that is, heat resistance, light resistance, and humidity resistance of the obtained dye image, and a method for forming the dye Lii acid. A third object of the present invention is to provide a novel yellow coupler that has excellent solubility in alkali and high-boiling organic solvents, dispersibility in silver halide color photographic emulsions, and stability, and a method for forming a dye image using the yellow coupler. There's K things to do. A fourth object of the present invention is to provide a silver halide color photographic material suitable for high-temperature rapid processing by using a novel yellow coupler. As a result of various studies, the present inventors have discovered that a silver hesigenide color photographic light-sensitive material which has been exposed to Iki image in the presence of a yellow coupler represented by the general formula below, can be used as an aromatic primary atom developer. It has been found that the above objects are achieved by processing in the presence of a pigment to form a dye image. In the formula, Q represents an alkyl group or an aryl group. The alkyl group may have a substituent, and is a hammer-shaped or scissor-shaped alkyl group; particularly preferably, 1- is a phenyl group, which may have a substituent. The substituent introduced into the above alkyl group is a halogen atom (e.g., fluorine,
chlorine, bromine, wax, etc.), alkoxy (e.g., methoxy, ethoxy, n-dodecyloxy) wL-hexadecyloxy, n-octadecyloxy, etc.), aryloxy (e.g., phenoxy, etc.), alkylthio (e.g., methylthio, n- butylthio, etc.), arylthio (for example, phenylthio), alkylsulfonyl (for example, methanesulfonyl, n-butanesulfonyl), and arylsulfonyl (for example, benzenesulfonyl). Examples of substituents for the above aryl group include the same substituents as for the alkyl group, but also alkyl (e.g. methyl, ethyl, t-butyl, etc.), acylamino (e.g. eva α-(2, Examples include 4-di-t-amylphenoxy)acylamino, etc.) groups. Y represents a halogen atom (eg, fluorine, chlorine, bromine, etc.) or alkoxy (eg, methoxy, ethoxy, n-dodecyloxy, n-octadecyloxy). R
represents alkyl or alkyl substituted with a phenyl group. Alkyl is straight-chain or branched alkyl, and examples thereof include methyl, n-butyl, n-octyl, 2-ethylhexyl, n-dodecyl, neetradecyl, n-hexadecyl, n-octadecyl, and the like. Alkyl substituted with phenyl group is, for example, benzyl,
phenethyl, etc., and the phenyl group may have a substituent. Examples of this substituent include alkoxy (for example, methoxy, !lt'cutyloxy, 'tl-dodecyloxy, etc.), acylamino (for example, h-tetradecanamide, etc.), sulfonylamino (for example, methanesulfonic acid, n - Examples include dodecanesulfonyl (do, etc.), halogen atoms (e.g., fluorine, chlorine, etc.), nido, hydroxy, and acyloxy. , alkyl (e.g. methyl, ethyl, 1-propyl, fu-octyl, n-
dodecyl, etc.), alkoxy (e.g., methoxy, ethoxy, benzyloxy, 1.-dodecyloxy, n-hexadecyloxy, etc.), alkylthio (e.g., methylthio, ethylthio, n-dodecylthio, cyclohexylthio, benzylthio), or alkylsulfonyl (for example,
(methanesulfonyl, ethanesulfonyl, n-butanesulfonyl, dodecanesulfonyl, etc.). The yellow coupler of the general formula, which represents a K11l releasable group upon XFi coupling, is a so-called two-unit coupler. Specific examples of coupling-off groups include, for example, a herogen atom (e.g., chlorine, bromine, fluorine, etc.), -8-
11 groups (B is an alkyl group, aryl, hetero *111)
, represents a group of nonmetallic atoms necessary to form a 5- to 6-membered ring in an acyloxy group or aryloxy. ), and more specific examples include U.S. Patent No. 2,728. j
ss No. 3,277゜155, No. 3,227,55
No. 4, No. 3,447,928, No. 3,408,194
No., West German Publication No. 725,892, Tokukowa No. 49-1266
No. 2, No. 48-25933, No. 49-13576,
No. 54-10862, No. 54-10863, No. 54
No.-12338, No. 55-34933, JP-A No. 51-
No. 3631, No. 48-29432, No. 48-668
No. 34, No. 48-66835, No. 48-94432, No. 47-26133, No. 48-73147, No. 5
No. 0-6341, No. 50-158329, No. 50
-65231, 50-104026, 51-1
No. 02636, No. 4G-1229, No. 49-1073
No. 6, No. 50-28834, No. 50-34232,
No. 5゜-117423, No. 51-50734, No. 51-50734, No. 51-50734, No.
No. 51-260311, No. 52-150631, No. 4
No. 7-37736, No. 54-63826, No. 54-7
No. 3826, No. 52-35634, No. 51-1433
19, etc. are useful.In the explanation of the divalent coupler that forms the yellow dye according to 1jIK from this publication, for convenience, for example, alkyl group refers to unsubstituted alkyl and substituent group. The term "alkyl" simply means unsubstituted alkyl. The coupler represented by the above general formula is benzene 114KR80mMM of the anilide moiety of α-acylacetanilide.
- (R is the same as above) and a substituent represented by M (A is the same as above), and the coupler is a divalent coupler. It is believed that this is why various good properties were obtained.Next, typical examples of the couplers of the present invention will be given.The couplers of the present invention used in the present invention are as follows: Not determined. Exemplary coupler l I5r Typical synthesis examples of the couplers of the present invention are shown below.0 Synthesis example, (Exemplary coupler 1) Synthesis of -1,3,4-)lyasolicinyl))-2,4-dichloro-5-<--hexadecanesulfonamido)acetanilide. α-Bivalyl α-(1-(3-benzyl-4-phenyl-2,5-dioxo-1,3,4-triaziridinyl)J-2,4-dic4-5-alphonyl sloride 3
．． 4 g was dissolved in pyridine 30111 and reacted at room temperature. After the reaction was completed, the reaction mixture was poured into 1 l-HOjK and extracted with ethyl acetate. The extract was washed with water, dried, and concentrated to obtain a brown oil. This product was treated with activated carbon and then crystallized from ethyl acetate-n-hexane to obtain a white powder of 6.1N. Confirmed from structural MMRK. Actual elemental analysis value 61.60% 6.891g 8.18%
8.30% 3.74% In order to produce an octap silver hehenide color photographic light-sensitive material, the couplers of the present invention may be used alone or in combination of two or more. Good too. The coupler of the present invention can be used in both internal and external color photographic materials, but particularly good results can be obtained when it is incorporated into a silver halide emulsion. When these couplers of the present invention are used as an internal silver halide color photographic light-sensitive material, a solution or dispersion of these couplers is mixed with a silver halide emulsion. Although the timing of its addition is arbitrary, it is usually preferable to add it to the emulsion after the second ripening is completed. The coupler of the present invention is contained in the silver octagenide emulsion at least 1 type, and the content is usually 1 912 silver oxide.
0.07 to 0.7 mol per mol, preferably 0.1 to 0
．． 4 moles of the couplers of the present invention include dibutyl 7-thalerate, dioctyl phthalate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate 7)%
High boiling point water-immiscible organic solvents such as N,w-diethyl laurylamide, carp, Ken-diethyl laurylamide, N,N-dibutyl laurylamide, low boiling point organic solvents such as ethyl acetate, butyl acetate, or methanol, ethanol. , acetone, dioxane, tetrahydrofuran, etc. or high-boiling water-immiscible organic solvents and/or low-boiling and/or water-soluble organic solvents. added. It is advantageous to use surfactants to help finely disperse the coupler solution or dispersion in the hydrophilic colloid used in the photographic emulsion. After the coupler is dissolved in a suitable organic solvent, it is mixed with an aqueous gelatin solution containing a surfactant, and then emulsified and dispersed in a high-speed rotary mixer or colloid mill, and then added directly to the silver halide emulsion, or directly added to the silver halide emulsion, or After setting the emulsified dispersion, it may be chopped, and after removing the low boiling point organic solvent by means of a water washing section, it may be added to the silver halide emulsion. Further, the alkali-soluble coupler can also be added by the so-called Fischer dispersion method. The silver halide color photographic light-sensitive material using the yellow coupler according to the present invention may contain other yellow couplers,
Specifically, a combination of a benzoylacetanilide type yellow coupler, a pivaloylacetanilide type yellow coupler, and a 2-equivalent yellow coupler in which the carbon atom at the coupling position is substituted with a substituent that can be separated during the coupling reaction is used. It's okay. The halogenated, silver color photographic light-sensitive material applied to the present invention may contain other couplers together with the yellow coupler of the present invention to form a multicolor image (magenta, which can be used in combination). Examples of the coupler include compounds of the big four, pyrazolotriazole, pyrazolinopenlydazole, and indasilone types.As the colored magenta coupler, the active site of the colorless magenta coupler is substituted with arylazo or A heteroarylazo-substituted compound is used. Examples of cyan couplers include phenol or naphthol sin forms, and colored cyan couplers include colorless cyan couplers in which an arylazo-substituted phenoxy group is directly or via an alkoxy group. In addition, for the purpose of improving the sharpness, graininess, etc. of one-color images, compounds in which the coupling position of KWl is changed can be mentioned. ) Alternatively, it is also possible to use other development inhibitor-releasing ASS substances that do not form dyes upon reaction with the sanated form of the developing agent.These may be used alone or in combination of two or more. The yellow coupler company of the present invention, Japanese Patent Publication No. 49-2658.
Publication No. 5, Regular Patent No. 3,486,890,
``Re5search'' Research Disclosure
Dlsalogure) 12044, 128401
% can be used in the dye image forming method described in 1. That is, the yellow coupler of the present invention and the aromatic primary alkali developing agent are contained in a co-Km optical material, and after imagewise exposure,
By treating with an alkali bath, a black and white solution, or by heating, it is possible to obtain a dye with uniform gradation. The silver halide color photographic light-sensitive material line to which this WRK is applied is basically composed of a support and a light-sensitive emulsion layer.
Depending on the type of silver halide color photographic light-sensitive material, auxiliary layers such as a subbing layer, an intermediate layer, a single filter layer, an anti-halesic acid layer, an anti-curl layer, a backing layer, and a holding layer may be appropriately combined and layered. In addition, the photosensitive layer itself may be a relatively sensitive silver halide-containing layer that has been color sensitized to the same wavelength range or a different wavelength range. A layer containing a silver halide having a low sensitivity may be superimposed. The emulsion layer containing the coupler of the invention, other emulsion layers, or other auxiliary layers may contain reducing agents or antioxidants, such as sulfites (sodium sulfite, potassium sulfite, etc.), bisulfites (sodium bisulfite, bisulfite, etc.). -potassium, etc.), hydroxylamines (human, xylamine, -methylhydroxylamine, i-phenylhydroxylamine, etc.), sulfinetlll [(sodium phenylsulfinate, etc.), hydrazine 1 m (N111'-dimethylhydrazine, etc.) Hemorrhoids), reductones @ (ascorbic acid moiety), aromatic hydrocarbons that appease one or more hydroxyl groups 1! (P-amine phenol, gallic acid, catechol,
It is preferable to use compounds such as bitetragallol, resorcinol, 2.3-1 hydrosynapthalene, etc., in order to fully exhibit the effects of the present invention. In order to further increase the stability of the dye-image formed,
Alkyl-substituted hydroquinones and alkoxy derivatives thereof, bishydroquinones, polymeric hydroquinones, etc. may be contained singly or in combination in the emulsion layer containing the coupler of the present invention or in a layer adjacent thereto. . Additionally, alkoxy or acyloxy derivatives of Kp-alkoxyphenol/I/@, 6-diVmanol, 6,62-dihydroxy-2,2'-subtetrachroman and the like can be used as well. The silver halide color photographic light-sensitive material according to the present WAK contains benzotriazoles as K ultraviolet IIWk absorbers in its constituent layers (e.g., protective layer, intermediate layer, emulsion layer, back layer, etc.).
It may also contain triazines, pen, Schiff-enone type compounds, or acryloacrylate trilv type compounds. In order to create a silver halide color photographic light-sensitive material, silver halide is dispersed in a suitable protective colloid (dispersed to constitute a photosensitive layer, the photosensitive layer and other auxiliary layers such as an intermediate layer, a protective layer, a filter layer, etc.). The protective colloid used in the layer structure is generally alkali-treated gelatin, as well as acid-treated gelatin, derivative gelatin, co-, loid albumin, co-, luulose derivatives, and synthetic resins such as polyvinyl, alcohol, and polyvinylpyridone. These may be used alone or in combination.The silver halide color photographic light-sensitive material of the present invention is produced on a support that has good flatness and exhibits little dimensional change during the manufacturing process or processing. In this case, the support may be a plastic film, plastic laminate paper, baryta paper, synthetic paper, or even a hard material such as a glass plate, metal, or ceramic. These supports are subjected to surface treatments such as various hydrophilic treatments in order to improve adhesion with the photographic emulsion layer.
For example, treatments such as graining treatment, square discharge treatment, undercoating treatment, and setting treatment are performed. is usually a port silver salt (e.g. 1
1112#I*) solution and a water-soluble hep-gen salt (eg, potassium bromide) solution are mixed in the presence of a water-soluble polymer solution such as gelatin. This /%0 silver genide includes silver chloride, silver bromide, silver iodide,
Any silver halide used in conventional silver halide color photographic light-sensitive materials can be used, such as silver chlorobromide, silver iodobromide, and silver chloroiodobromide. These silver halide emulsions are prepared according to known conventional methods (eg, single or double jet method, controlled double jet method, etc.). Furthermore, two or more types of silver oxide photographic emulsions formed separately may be mixed. Even if the crystal structure of silver halide grains is uniform inside, there are also those with a layered structure with different inside and outside, so-called converged carbon grains, Lippmann emulsions, and covered grains. It may be an emulsion or one that has been optically or chemically fogged before expansion. Further, either a type in which the latent image is mainly formed on the surface or an internal type in which the latent image is formed inside the particle may be used. These can be prepared by various methods such as the ammonia method, neutral method, and acid method, which are recommended by Photo Emulsion Company. Further, the type of silver halide, the content and mixing ratio of silver halide, average grain size, size distribution, etc. are appropriately selected depending on the type and use of the photographic light-sensitive material. The above silver halide emulsion can be sensitized with a chemical sensitizer. The chemical sensitizer is a noble metal sensitizer (potassium aurithiocyanate, ammonium cloparadate,
Potassium Opplatinate, etc.), sulfur sensitizers (allylthiocarno (mido, thiourea, cystine hemorrhoids), selenium sensitizers (active and inactive selenium compounds*), and reduction sensitizers (stannic salts, polyamines, etc.) ) Silver halide emulsions can be chemically sensitized using these sensitizers alone or in combination as appropriate. If necessary, spectral sensitization, superchromic sensitization, and sensitization can be performed by using cyanine dyes such as cyanine, mepcyanine, and carbocyanine alone or in combination, or by combining them with styryl dyes, etc. These color sensitization techniques have been known for a long time, and the selection of the combination of dyes depends on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the silver chloride color photographic light-sensitive material. 〇The above silver halide emulsion Ka, Kl-phenyl- 5-mercaptotetrazole, 3-methylbenzothiazole, 4-
Heterocyclic compounds such as hydroxy-6-'methyl-1.3.3m and 7-titrazaindene, mercapto compounds, and various compounds containing metal salts can be added. Emulsion hardening is carried out according to conventional methods. The hardeners used are conventional photographic hardeners, such as formaldehyde, glyoxal, aldehydes such as glutaraldehyde, derivatives thereof such as acetals or sodium bisulfite adducts, and methanesulfonic acid esters. compounds, mucochloric acid, mucohapgen a+ compounds, epoxy compounds, aziridine compounds, active halogen compounds, maleic acid compounds,
Active vinyl compounds, carbonimide compounds, iso1
Inorganic hardeners such as xazole compounds, U-metallic compounds, tyrol compounds, isocyanate compounds, and chromium ammonium and zirconium sulfate can be mentioned. A surfactant may be added to the above-mentioned silver halide emulsion singly or in combination. They are auxiliary agents, emulsifying and dispersing agents,
These surfactants are used for sensitization, improvement of photographic properties, antistatic properties, anti-adhesion, etc. These surfactants include natural surfactants such as saponin, alkylene oxide type, glycerin type,
7-ion surfactants such as glycidol thread, higher Al2
Killuan compounds, quaternary ammonium salts, pyridine,
Other complex**1 cationic surfactants such as phosphonium or sulfoniums, anionic surfactants containing acidic groups such as carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid groups, phosphate ester groups, amino l! Formation of the color photographic material of the present invention can be performed using various forms of photosensitive materials. It can be realized in One of the companies, branch ``A layer of silver halide emulsion containing a diffusion-resistant coupler on top of the special holiday''
A photosensitive material having aromatic λ1. This is a method in which a water-insoluble or diffusion-resistant dye is left in the emulsion layer by applying an alkaline developer containing an additive. An aromatic photosensitive material having a silver halide emulsion layer combined with a diffusion-resistant coupler on top
An alkaline developer 111 containing an ih developing agent is treated with -t' to make it soluble in an aqueous medium to produce an i-dispersible dye, which is transferred to a recipient layer made of another hydrophilic colloid. That is, it is a diffusion transfer color type. The silver halide color photographic light-sensitive material of the present invention includes all kinds of silver halide color photographic light-sensitive materials such as color negative films, color positive films, color reflective films, and color papers. One embodiment of the silver oxide color photographic light-sensitive material of the present invention includes a blue-sensitive silver oxide emulsion layer containing a yellow coupler, a magenta cuboid, an edge-sensitive silver oxide emulsion layer containing a yellow coupler, and a silver oxide emulsion layer containing a yellow coupler. A red-sensitive silver halide emulsion layer containing an emulsion layer and a cyan coupler was deposited 1i on a support.
There is a silver tetragenide color photographic light-sensitive material that is multi-layered and multicolored. As the blue-sensitive silver halide emulsion, the 11IIsI-type 11 silver halide emulsion, and the red-sensitive silver halide emulsion in such a light-sensitive material, publicly known ones can be used as appropriate. The silver halide color photographic light-sensitive material according to the present invention can obtain color WG1 by the commonly used color development method.The basic steps in the negative-positive method are color development, bleaching, and fixing steps. The basic steps in the reversal process include development with a first developer, followed by white exposure or treatment with a bath containing a capri agent, color development, bleaching,
Includes each fixing process. Each of these basic steps may be carried out independently, but it may also be carried out in a single process using a treatment liquid having two or more of these functions. For example, a one-bath color processing method containing a color developing agent, a ferric bleaching component and a thiosulfate fixing component, or a one-bath bleaching method containing an ethylenediaminetetraacetate iron (2) anchor ring bleaching component and a thiosulfate fixing component. There are fixing methods, etc. Also, each step can be divided into two or more times as necessary, or a combination of color development, first fixing, and bleach-fixing can be performed. In addition, the developing process 11IK is a must for the above! Depending on the situation, various steps such as a pre-hardening bath, a neutralization bath, an image stabilization bath, and water washing are combined. Although the processing temperature may be less than 18°C,
It is often above ℃. Particularly commonly used is 20℃~
It is in the range of 60°C. Rapid processing f1MK11 about 30℃~6
0℃ remains. Note that it is not necessary that the set temperature for each step in the series of processing be the same. The color developing solution is an alkaline aqueous solution containing a developing agent and having a pli of 8 or more, preferably 9 to 12. The above-mentioned developing agent refers to a compound having a -71 group on an aromatic ring and having the ability to develop exposed silver halide, or a precursor for forming such a compound. Preferred are p-phenylene diamines, such as 4-amino-M, N-diethyl, diline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-biethyl-beta -Hydroxyethylaniline, 3-methyl-4-γ-I-ethyl-U-β-hydroxyethylaniline, 3-methyl-4-amino-N-:L f
A/-Ken-β-methanesulfonade ethylaniline 3-methyl-4-amino-U-ethyl-U-β-methoxyethylaniline, 3-β-methanesulfonadoethyl-4-amino-11,M -diethylaniline, 3-
Methoxy-4-amino-ethyl-momi-, β-human tetraxyethylaniline, 3-methoxy-4-amino-ken-
Ethyl-do-β-methoxyethylaniline, 3-acedo-4-amino-v1w-diethylaniline, 4-
Amino-L w-dimethylaniline, 1-ethyl-biβ-[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aryonoaniline, y-ethyl-bi-β-[β-methoxyethoxy ]Ethyl-3-methyl-
4-aminoaniline and these clays, such as sulfur @ clay,
Hydrochloride, sulfite, p□ -toluenesulfo/I! It's a viper, etc. Add various additives to the color developing solution as needed'0
Main examples include alkaline agents (e.g. alkali metal and ammonium hydroxides, carbonates, arm salts, etc.), pH l
1f/lj or buffers (e.g. ms and l14m groups such as acetic acid, boric acid, salts thereof, etc.), development accelerators (e.g. pyridium compounds, cationic compounds, potassium nitric acid, sodium i*aI, polyethylene Glycol-coated metals and their derivatives, nonionic compounds such as polythioethers, polymer compounds with sulfide esters, organic compounds such as pyridine, ethanolamine, benzyl alcohol, hydrazine, etc.), anti-fogging agents (such as alkali bromides, alkali iodides, nitrobenzimidazoles, mercaptobenzoic dazoles, 5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole, compounds for rapid processing liquids, thiosulfonyl compounds, phenazine bioxides, benzothiazolium derivatives, etc.), stain or sludge inhibitors, multilayer effect promoters, preservatives (
Examples include sulfite, oxysulfite, hydroxylamine loamate, form sulfide, alkanol anion sulfite adduct, etc.). A silver halide color photographic light-sensitive material containing the coupler of the present invention can be subjected to color development processing without impairing its practicality even in the presence of a competing coupler such as citradinic acid. The silver halide color photographic light-sensitive material according to the present invention can be bleached and processed in a conventional manner after color development. This treatment may be performed simultaneously with fixing or separately. This processing solution can also be used as a bleach-fixing bath by adding a fixing agent if necessary. Various compounds are used as bleaching agents, among which Red 11! Polyvalent metal compounds such as LjJI; heavy acid; iron (2), cobalt (2), both values), especially complex salts of these polyvalent metal cations and organic acids, such as ethylenecyanotetraacetic acid. Aminopolycals such as nitritriacetic acid, cyanolobanoltetraacetic acid, 7m% citric acid ≧ tartaric acid, metal anchor rings and excesses such as malic acid (e.g. alkyl peracids, persulfates, permanganates, peroxides) Commonly used are water chloride), hypochlorous acid S (for example, chlorine, bromine, salicy powder, etc.) alone or in appropriate combinations. Furthermore, various additives including a bleaching accelerator can be added to this treatment solution. Typical examples of internal color developing solutions include those having the following composition. [Color developer composition] - Potassium bromide 1.o9 Potassium hydroxide 0.55II Add water to make II. The coupler of the present invention contained in the color emulsion used in the present invention reacts with the oxidation product of the color developing agent produced when silver halide is developed with such a color developing solution to form a yellow dye. do. After such color development processing, conventional photographic processing is carried out, such as a stop solution containing an organic acid, a stop fix solution containing an organic acid and a fixing component such as hypo or ammonium thiosulfate, or a fixing component such as hypo or ammonium thiosulfate. fixer containing;
A bleaching solution mainly containing a ferric salt of an aminopolycarboxylic acid and an alkali halide;
Treatments selected from treatments such as treatment with a bleach-fix solution containing a fixing component such as iron oxide and wart or ammonium thiosulfate, other processing solutions such as stabilizing solutions, washing with water, and drying may be carried out in an appropriate combination. The INK couplers of the present invention can also be used in color light-sensitive materials with a low silver content, where the amount of silver halide in the emulsion is one to one hundredth of that of ordinary color light-sensitive materials. can. In this way, for a color photosensitive material with a reduced amount of silver halide, a development processing method in which the developed silver produced by color development is subjected to four generation bleaching, and then color development is performed again to increase the amount of produced phosphorus; A sufficient color ms can be obtained by applying a development method using color intensification using peroxide, cobalt complex salt, or sodium chlorite. Next, a typical example of a color development process in which the present invention can be used to process internal color negative light-sensitive materials will be shown. [Processing process] Processing process (33°C) Processing time Color development Km 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixation 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Stabilization 1 minute 30 seconds Above treatment Engineering! The composition of each treatment solution that can be used in
For example, as follows. [Color developer composition] 4-amino-3-methyl-ethyl-yami-(β-hydroxyethyl)-aniline sulfuric acid, @
4.8g anhydrous sodium sulfite
, 0.11hydrovxylamine, 4 sulfate
1.98 F sulfuric acid 0.74 ■ Anhydrous potassium carbonate 28.851 Anhydrous potassium bicarbonate 3.46 N Anhydrous potassium sulfite ゛ 5.1 ON Potassium bromide
1.16N sodium chloride
To 0.1, add triloacetic acid, trisodium salt (monohydrate), 1.201 potassium hydroxide, 1.48 N water to make 11. [Bleaching solution composition] [Fixing solution composition] [Stabilizing solution composition] Next, typical examples of variations of the color development process in which the present invention can be used for processing internal color positive light-sensitive materials will be shown. [Processing process] Processing process (30°C) Processing time Color development g1 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Water washing 2 minutes Stabilization 1 minute The composition of each treatment salt solution that can be used in the above treatment process is as follows:
For example, as follows. [Color developer composition (1)] (Color developer composition (ri)) The above color developer (1) ti is a color developer composition excluding benzyl alcohol, and color developer (2) is:
This is a conventional color developer composition containing conventional benzyl alcohol. When the present invention is used to process internal color positive light-sensitive materials, any of the above color developing solutions (1) and (2) can be used, but from the viewpoint of pollution prevention, it is particularly desirable to use the above color developing solution (1). Rarely, in the present invention 111j, good photographic properties can be obtained by using this desirable color developing solution (1). However, the embodiments of the present invention are not limited by K. Examples (1) Couplers of the present invention as shown in Table 1 below (indicated by the numbers of specific examples in ltI) and comparative coupler (A) below.
,(B),01
- and heated to 60°C to completely dissolve. This solution was mixed with 200 d of a 10% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and 200 ml of an aqueous gelatin solution and emulsified using a cotetrahydric solution to prepare a dispersion of each coupler. This coupler dispersion was then added to a 500 F gelatin-silver chlorobromide (containing 20 mole percent silver bromide) emulsion, coated on polyethylene-coated paper and dried to obtain 10 types with stable coatings. 8. Q silver halide color photographic light-sensitive materials (sample numbers [1] to (16)) were obtained. The obtained 10 kinds of silver halide color photographic light-sensitive materials were wedged according to a conventional method. After the exposure, as a specific example, color development gIv is carried out according to the above-mentioned color development treatment process for internal color positives.
As a result, a yellow-colored Il image was obtained. Note that the color developing solution is one to which benzyl alcohol is added [the above color developing solution (
The experiment was carried out on two types of compositions: 2)] and one without addition [the color developing solution (1) 1]. Photographic properties were measured for each of the obtained samples. The results are shown in Table 1. Note that the sensitivity in the table is expressed as a relative value when the sensitivity in the benzyl alcohol-added system of Sample 7 using the comparative coupler [Gen] is set as 100. Comparison coupler (8 (B), (0)
and [The structure of gong is as shown below. Comparison "1-Illusion."
7′-1”). (Comparison coupler described in the above-mentioned Japanese Patent Application Laid-Open No. 11521915219)

[0] 1 Comparative coupler LD (described in IE No. 54-48541) l As is clear from Table 1, the sample processed by the image forming method of the present invention has favorable spectral absorption characteristics. ,Also,
In the color-forming liquid system without the addition of benzyl alcohol, the maximum density of the obtained color image was that of the comparative couplers (A) and C.
], [d), and LD). Example (2) Samples 11 to 20 of 10 kinds of photosensitive materials for forming yellow colored images were obtained in the same manner as in Example (1) above, and the light resistance, heat resistance,
We investigated moisture resistance. The light resistance in the table shows the results obtained using a xenon fade meter.
! :Residual concentration after 200 hours exposure vs. concentration before exposure 10
Expressed as 0. In addition, the humidity resistance is 50℃, relative humidity 8
The residual concentration after storage for 2 hours under 0% conditions was expressed with the concentration before the test as 100. Furthermore, the heat resistance was expressed as the residual concentration after storage for 2 days at 77° C., with the concentration before the test being 100. As is clear from Table 2, the exemplary couplers according to the present invention have light resistance, heat resistance, and moisture resistance equivalent to those of the comparative couplers [Xun, (B), [0], and (D). Example (3) Exemplary couplers (1) and (n
), (劫, (1) Also, the comparative coupler [A], (9
) and comparative couplers (K), (?)1 having the following structures:
0Ii, dibutyl (7 thale) 2-5111 and 201 J of ethyl acetate were added to this mixture, and the mixture was heated to 60° C. to completely dissolve. This solution was mixed with 5d of a 10≦aqueous solution of alkanol 1 and 20G of an aqueous solution of gelatin 5, and:!
A coupler dispersion was prepared by emulsification using a pidomill. Next, this dispersion was added to 5009 high-sensitivity negative gelatin silver iodobromide emulsion (containing 6.0 mol% silver iodide), coated on a cellulose acetate film base, and dried to form a stable coating layer. /% silver halide photographic materials Samples 21 to 28 were obtained. This silver 10ogenide photographic light-sensitive material was exposed in the same manner as in Example (1), and color development was carried out according to the color development process for internal color negatives described above to obtain a yellow color image. Photographic characteristics of the obtained yellow colored image were measured. The results are shown in Table 3. As is clear from Table 3, the sample using the coupler of the present invention had a thicker maximum density (0) Also, the sample according to the present invention produced a yellow negative image with excellent transparency.0 Comparison Coupler (IC) l (Described in JP-A No. 54-99433) Agent
Kuwabara - Beauty

Claims (1)

[Scope of Claims] In the presence of a two-equivalent coupler that forms a yellow dye represented by the following general formula, a silver halide color photographic light-sensitive material that has been illuminated with wmii is treated with an aromatic primary amine color developing agent. 1. A method for forming a color photographic image, characterized by processing in the presence of a color photographic image. General formula (wherein, q represents an alkyl group or an aryl group, Y represents a halogen atom or alkoxy, R represents an alkyl or phenyl-substituted alkyl group, and M represents a \rogen atom, alkyl, alkoxy, alkylthio, or alkyl) sulfonyl, X represents a group that can be separated during coupling 0)