JPH02139546A - Color developing solution for silver halide color photographic sensitive material, processing agent kit containing the color developing solution and kit set - Google Patents

Abstract

PURPOSE:To enable rapid processing independently of environmental conditions and to stabilize photographic performance by using a developing soln. contg. a specified color developing agent but not contg. hydroxylamine. CONSTITUTION:A color developing soln. contg. a p-phenylenediamine compd. (A) having a water soluble group by >=1.3X10<-2> mol per 1l developing soln. but not practically contg. hydroxylamine (B) is used. A compd. represented by the formula may be used as the component A and a hydroxylamine compd. such as HO-N-(C2H5)2 may be added as a preservative. When a color developer kit is produced, a kit part contg. the component A by 200-600g/l is used and a kit part contg. the component B is not preferably used.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a color developer, a color developer kit, and a processing agent kit set for rapid processing of silver halide color photographic light-sensitive materials (hereinafter sometimes simply referred to as light-sensitive materials). The present invention relates to a color developer, a color developer kit, and a processing agent kit set for rapid processing of photosensitive materials, which enable rapid processing and obtain stable photographic performance regardless of changes in the environment during processing. [Background of the Invention] In general, in order to obtain a color image by processing an imagewise exposed light-sensitive material, the generated metallic silver is desilvered after the color development process, and then washed with water, stabilized or stabilized as an alternative to water washing, etc. A processing step is provided. However, photosensitive materials are either subjected to running processing in an automatic processing machine installed in a photo lab, or as part of an effort to improve service to users, they are processed and returned to users on the same day they are received. Recently, it has become necessary to return the item within a few hours of receiving it. Furthermore, in fields such as the press, where it is necessary to convey new news to readers as quickly as possible, reducing the processing time by one minute or one second holds the key to meeting the manuscript deadline. Therefore, there is a strong desire for the development of rapid processing technology. Furthermore, in the press, rather than processing in a laboratory, it is often the case that the images are developed on site and sent to the head office by electronic means. The current situation is that the process takes a long time and is controlled. Therefore, due to long-term development, the temperature changes, the development level changes, and the quality becomes unstable, and stable quality can only be maintained by an experienced person.The development process takes too long and the immediacy of the news is lacking. was there. On the other hand, as a rapid processing technology, improvement of silver halide composition (for example, silver halide fine graining technology as described in JP-A-51-77223, JP-A-58-18142 and JP-B-Sho 56-18939) technology for reducing silver bromide of silver halide as described), use of additives (for example, JP-A-56-6
The technique of adding l-aryl-3-pyrazolidone having a specific structure as described in No. 4339 to a silver halide color photographic light-sensitive material, and the technique of adding l-aryl-3-pyrazolidone having a specific structure as described in JP-A-57-144547 and JP-A-57-144547
No. 8-50534, No. 58-50535, No. 58-5
A technique of adding l-arylpyrazolidones as described in No. 0536 into a silver halide color photographic light-sensitive material),
Technology using fast-reactive couplers (e.g. Japanese Patent Publication No. 51-1
No. 0783, JP-A-50-123342, JP-A No. 51-1
No. 02636, a technique using a fast-reacting yellow coupler), a technique for thinning layers for photographic structure (for example, a technique using a fast-reacting yellow coupler described in
0-204992)
etc., and furthermore, processing liquid stirring technology (for example, patent application 1986).
1-23334), a technique using a development accelerator, a technique for reducing the concentration of halogen ions, especially bromide ions, etc. are known. However, the reality is that even with these conventional rapid processing techniques, the above-mentioned problems cannot be solved. [Object of the Invention] The first object of the present invention is to provide a color developer for photosensitive materials, a color developer processing agent kit, and a processing agent kit set, which allow rapid processing regardless of the environmental conditions during development processing. That's true. A second object is to provide a color developer for photosensitive materials, a color developer processing agent kit, and a processing agent kit set, which enable stable processing regardless of the environmental conditions during development processing. A third object is to provide a hobby processing agent kit and a kit set that allow rapid processing using a simple method. [Structure of the Invention] The present inventor has made extensive studies to achieve the above object, and as a result, has arrived at the present invention. That is, the color developing solution for silver halide color photographic light-sensitive materials according to the present invention contains at least 1.3 p-phenylenediamine compounds having a water-soluble group per lfL of the color developing solution.
It is characterized by containing 2 moles of X 10 and substantially no hydroxylamine.
□Also, the color developer kit for silver halide color photographic light-sensitive materials contains at least 200 to 6
00 g/ffi and substantially no hydroxylamine-containing kitvat. Furthermore, the processing agent kit set for silver halide color photographic light-sensitive materials is characterized by comprising the color developer kit for silver halide color photographic light-sensitive materials and the bleach-fixing agent kit for silver halide color photographic light-sensitive materials. The present invention will be explained in detail below. In the color developing solution used in the present invention, instead of hydroxylamine, which is conventionally used as a preservative, - formula [I]
The compound represented by (hereinafter also referred to as the preservative of the present invention) is preferably used from the viewpoint of rapidity. General formula [I] This is not a specification. Further, R2 and R2 may form a ring. In general formula [I], R1 and R2 each represent an alkyl group or a hydrogen atom that is not a hydrogen atom, or
The alkyl groups represented by R1 and R2 may be the same or different, and each is preferably an alkyl group having 1 to 3 carbon atoms. The alkyl groups of Rt and R2 include those having substituents, and R1 and R2 may be combined to form a ring, for example, a heterocyclic ring such as piperidine or morpholine. -Specific compounds of the hydroxylamine compound represented by formula [I] are disclosed in U.S. Patent Nos. 3,287,125 and 3
, No. 293,034 and No. 3,287,124, etc., and particularly preferred specific exemplary compounds are shown below. In the following blank formulas, Ro and R2 each represent an alkyl group or a hydrogen atom. However, both Rt and R3 are hydrogen atoms at the same time.These compounds of the present invention are usually free amines, hydrochlorides, sulfates, p-toluenesulfonates, oxalates, phosphates,
It is used in the form of acetate, etc. The concentration of the compound represented by the general formula [I] of the present invention in the color developing solution is usually 0.2 g/liter to 50 g/fL, preferably 0.5 g/u to 0.0 g/l, more preferably Ig
/l~15g/view. The compound represented by the general formula [I] of the present invention can be used in place of hydroxylamine sulfate, which has been widely used as a preservative in color developing solutions for conventional silver halide color photographic light-sensitive materials. Among the compounds of the present invention, for example, N,N-diethylhydroxylamine is known to be used as a preservative for black and white developing agents in color developing solutions to which black and white developing agents are added. In the so-called external color development method, in which color photographic materials are developed by the reversal method using a color developing solution containing
-22198)). In the present invention, "substantially free of hydroxylamine" means less than 1 g/L; This means that the content is 0.5 g/l or less, and more preferably not at all. Furthermore, what is hydroxylamine here? Chemical formula: NH, which is usually used as a preservative for color developing solutions.
It means the compound represented by 2OH, and does not include the compound represented by the formula CI], that is, a hydroxylamine derivative. The color developer used in the present invention preferably has a sulfite concentration of 4 x 10-'3 mol or less per color developer, more preferably 2 x 10-' to 0 mol per color developer. When the concentration of sulfite in the solution is high, it is much more susceptible to this effect than conventionally used emulsions containing high silver bromide, causing a significant decrease in concentration. Examples of the sulfite used in the present invention include sodium sulfite, potassium sulfite, N bisulfite, sodium acid, potassium bisulfite, and the like. The p-phenylenediamine compound of the present invention has at least one water-soluble group on the amino group or benzene nucleus of the p-phenylenediamine compound, and specific water-soluble groups include: -(CH2). -CLOD, -(CHz)--NH3Ot-(Cu2)n-CL, -
(CL), -0-((:ff2), -(:It,,4C
82CH20) ncemH2m+r (l and n each represent an integer of 0 or more), -COOII group, -
Preferred examples include 3O3H group. Specific examples of color developing agents preferably used in the present invention are shown below. [Exemplary color developing agent] ff1 NU. NH1 NH. Nut NH. NHl NH. Nut Nut NH. Nut NH! N.H. N.H. Among the color developing agents exemplified above, preferred for use in the present invention are exemplification Nos., (B-1), (B-2), and (B-1).
-3), (B-4), (B-6), (B-7) and (
B-15), particularly preferably N
o, (B-1). The color developing agents mentioned above are usually used in the form of salts such as salts, sulfates, and p-toluenesulfonates. The p-phenylenediamine compound having a water-soluble group used in the present invention is 1.3X 10 per color developer ti.
-" must be at least 1.5X molar, preferably 1.5X
The range is from 10-" to 1.OX 10-' mole, more preferably from 1.7X to-" to 7. Ox 10-
2 moles, most preferably 1.8 x 10
-2 to 5.0 x 1 O-2 moles. The color developer of the present invention may contain the following developer components in addition to the above components. As an alkaline agent, for example, sodium hydroxide. Potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc. can be used alone or in combination to achieve the above effects, i.e., no precipitation and pH stabilization effect. Can be used together within the range that maintains this. In addition, disodium hydrogen phosphate, dipotassium hydrogen phosphate, and sodium bicarbonate are added for purposes such as pharmaceutical necessity or to increase ionic strength. Various salts such as potassium bicarbonate, borates, etc. can be used. Furthermore, inorganic and organic antifoggants can be added as necessary. Furthermore, a development accelerator can also be used if necessary. As a development accelerator, U.S. Patent No. 2.648,6
No. 04, No. 3,671,247, Special Publication No. 44-950
Various pyridinium compounds as typified by Publication No. 3, other cationic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate, and U.S. Pat.
, No. 533,990, No. 2.531,832, No. 2,
950,970, 2,577.127, and nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc., as described in Japanese Patent Publication No. 44-9504, and organic solvents and organic compounds as described in Japanese Patent Publication No. 44-9509. Includes amines, ethanolamine, ethylenediamine, jetanolamine, triethanolamine, etc. In addition to phenethyl alcohol described in US Pat. No. 2,304,925, acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, and amines may be mentioned. Benzyl alcohol is not preferred for use in the present invention;
In addition, regarding the poorly soluble organic solvent represented by the above-mentioned phenethyl alcohol, it is preferable to eliminate its use in order to efficiently achieve the object of the present invention. Therefore, tar is likely to be generated especially during running processing using a low replenishment method, and the generation of such tar may adhere to the vapor photosensitive material to be processed, resulting in a serious failure that significantly impairs its commercial value. In addition, since poorly soluble organic solvents have poor solubility in water, not only is it troublesome that a stirring device is required to prepare the color developing solution itself, but even with the use of such a stirring device, the dissolution rate is poor. from. There is also a limit to the development accelerating effect. In addition, poorly soluble organic solvents reduce the biochemical oxygen demand (
Benzyl It is preferable to reduce or eliminate the amount of not only alcohol but also other poorly soluble organic solvents used. Furthermore, the color developing solution of the present invention may contain ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and others as required.
The compounds described in each publication can be used as an organic solvent to increase the solubility of the developing agent. Additionally, auxiliary developers may be used with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminophenol hexulfate (methol).
, phenidone, N,N'-diethyl-p-aminophenol salt m salt, N,N,N',N'-tetramethyl-p-
Phenylenecyamine hydrochloride etc. are known, and the amount added is usually 0.01g to 1. Og/i is preferred. Furthermore, other anti-stain agents and anti-sludge agents 1
Various additives such as interlayer effect promoters can be used. Furthermore, various chelating agents may be added to the color developer and color developer processing agent kit of the present invention, such as diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, ethylenediaminetetramethylenephosphonic acid, and tripolyphosphoric acid. , hexametaphosphoric acid, -hydroxyethylidene 1,1-diphosphonic acid, etc. may be added. Each component of the above-mentioned color developing solution can be adjusted by sequentially adding and stirring to a certain amount of water. In this case, components with low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, a plurality of components that can coexist stably are prepared in advance in a small container as a concentrated aqueous solution or in a solid state, and then added to water and stirred to prepare the color developing solution of the present invention. You can get it. In the present invention, the above color developing solution can be used in any pH range, and from the viewpoint of rapid processing, pH 9.5 to 13.0 is required.
pH is preferably 9.8 to 1, more preferably pH 9.8 to 1.
Used in 2.0. In the present invention - starting with the bath treatment. It is also possible to use various other processing methods, such as a spray method in which the processing solution is atomized, a web method in which contact is made with a carrier impregnated with the processing solution, or a development method using a viscous processing solution. , the processing steps essentially include color development, bleach-fixing, and washing with water (including stabilization treatment as an alternative to washing with water).
It is preferable that the process consists of the following steps. The processing agent kit set according to the present invention includes a color development processing agent and/or a processing agent having fixing ability, or a washing substitute stabilizer as a set, and one color development processing agent is a color development processing agent and a processing agent having fixing ability. The former processing agent contains the color developing agent at a concentration of 1.5x 10-2 mol or more and substantially does not contain hydroxylamine, and if necessary, the processing agent contains the chelate. It contains additives such as agents. The processing agent may be separated into two or more parts liquids, or may be in any form such as powder or paste, and of course may have a concentration that can be used as is. Concentrated (liquid) used after dilution
It may be of. However, in the present invention, it is preferable that all of the processing agent be in the form of powder or granules. This is from the viewpoint of ease of handling and portability. On the other hand, in the latter explanatory text 1, as shown in FIG.
There is also an indication that the processing temperature can be set arbitrarily, such as "The processing temperature of the color developing solution can be set arbitrarily for this processing. Please decide the time according to the processing temperature based on the club below." 3, and a graph or table 4 showing the relationship between color developer temperature and time is displayed. The explanatory text does not need to be displayed on one sheet of paper; it may be displayed on two or more sheets of paper, or it may be displayed on a magnetic tape, disk, optical disk, or other recording medium. good. Note that the explanatory text 1 may be attached to the processing agent container in the form of a tag or affixed in the form of a label. In the present invention, it is preferable to provide a bleach-fixing step immediately after the color development treatment step in view of speed and achieving the effects of the present invention. The bleaching agent that can be used in the bleach-fix solution used in the present invention is not limited, but metal complex salts of organic acids are preferred. The complex salt is a polycarboxylic acid, an aminopolycarboxylic acid, or an organic acid such as oxalic acid or citric acid.
It is coordinated with metal ions such as copper. The most preferred organic acid used to form such a metal complex salt of an organic acid is an aminopolycarboxylic acid. These aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. [1l ethylenediaminetetraacetic acid [2] diethylenetriaminepentaacetic acid "3"
Ethylenediamine-N-(β-oxyethyl)-N,N
”,N”-Triacetic acid [4] 1.3-Propylenediaminetetraacetic acid [5
] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid

[71
Iminodiacetic acid [8] 1,2-propylenediaminetetraacetic acid [9]
] Ethyl ether cyamine tetraacetic acid [101
Glycol ether diamine detraacetic acid [1l] Ethylenediaminetetrapropionic acid [12] Ethylenecyaminetetraacetic acid ammonium [13J Ethylenediaminetetraacetic acid disodium salt [14] Ethylenecyaminetetraacetic acid tetra(trimethylammonium) salt [I51 Ethylenecyaminetetra Tetrasodium acetate salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β-oxyethyl)-N,N'',I'm''-triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [ 191 Nitriloacetic acid sodium salt 201 Cyclohexanediaminetetraacetic acid sodium salt These bleaching agents are used in amounts of 5 to 450 g/l, more preferably 20 to 250 g/l. The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fix solution consisting of an ethylenecyaminetetraacetate iron (m) acetic acid bleach and a large amount of a halide eJ such as ammonium bromide other than the silver halide fixing agent, and furthermore an ethylenediaminetetraacetate iron (m) III
) A special bleach-fix solution having a composition consisting of a combination of an acetic acid bleach and a large amount of a halide such as ammonium bromide can be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can. The silver halide fixing agent contained in the bleach-fixing solution includes compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. thiosulfates, potassium thiocyanate, sodium thiocyanate. Typical examples include thiocyanate salts such as ammonium thiocyanate, thioureas, thioethers, and the like. These fixing agents are used in amounts of 5 g/l or more, within the soluble range, or generally from 70 g/l to 250 g/l. The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH buffering agents such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. Also hydroxylamine,
Preservatives such as hydrazine and bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitro alcohols and nitrates, organic solvents such as methanol, dimethylsulfamide, and dimethylsulfoxide, etc., as appropriate. It can be made to contain. Examples of the bleach-fixing solution used in the present invention include JP-A No. 46-280, JP-A No. 8506-8506, JP-A No. 46556, Belky Patent No. 770,910, JP-A No. 8836-8836, JP-A No. 5
No. 3-9854, JP-A-54-71634 and JP-A No. 49
Various bleaching accelerators described in Japanese Patent No. 42349 and the like can be added. The pH of the bleach-fix solution is used at 4.0 or higher, but generally it is used at pH 4.0 or higher and pi (9.5 or lower), preferably at pH 4.5 or higher and pH 8.5 or lower. The most preferable pH is 5.0 or higher, 8.5
Processed below. The treatment temperature is 80'C or less, preferably 55C or less, to suppress evaporation and the like. The bleach-fixing treatment time is preferably 3 seconds to 120 seconds, more preferably 5 seconds to 60 seconds, and most preferably 10 seconds to 30 seconds. In the present invention, water washing treatment is performed following the color development and bleach-fixing steps, and the water washing treatment or processing is performed with a replenishing amount of 0.1 to 50 times the amount of prebath brought in per unit area of the photosensitive material. It is preferable for the effects of the present invention, particularly for the stabilization of dye images, when the dye is used. Hereinafter, preferred embodiments of the water washing treatment will be described. Compounds preferably used in the washing solution include chelating agents having a chelate stability constant of 8 or more with respect to iron ions, and these are preferably used to achieve the object of the present invention. Here, the chelate stability constants are L, G, 5illen
・A.E. Martell, “5tabil”
ity (:instants of Metali
on Complexes, The Chemi
cal 5ociety. London (1964), Chabere, S.
K-A, E. Martell, “Organic S.
equestering Agents, Wi
ley (1959) and others. Examples of chelating agents having a chelate stability constant of 8 or more for iron ions that are preferably used in the washing solution include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. Note that the above-mentioned iron ion refers to ferric ion (Fe 3 +
) means. Specific examples of compounds of chelating agents having a chelate stability constant of 8 or more with ferric ions include, but are not limited to, the following compounds, including ethylenediamine diorthohydroxyphenylacetic acid. , diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenecyaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenecyaminenipropionacetic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid , transcyclohexanecyaminetetraacetic acid, glycolneedlediaminetetraacetic acid, ethylenecidiaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, l-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonethane-2- Carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate, tetrapolyline and sodium hexametaphosphate, particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,
1-diphosphonic acid, among others, 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used. The usage amount of the above chelating agent is 0.01 to 1fL of washing liquid.
It is preferably 50 g, more preferably in the range of 0.05 to 20 g. Further, ammonium compounds are particularly preferred as compounds to be added to the washing liquid. These are supplied by ammonium salts of various inorganic compounds, and specific examples include ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, and ammonium acetate. Further, in the present invention, a washing liquid treated with an ion exchange resin may be used. The pH of the washing liquid that can be applied to the present invention is 5.5 to 100.
It is in the range of 0. As the pH adjusting agent that can be contained in the washing liquid that can be applied to the present invention, any commonly known alkaline agents or acid agents can be used. The processing temperature of the water washing treatment is preferably 15°C to 60°C,
More preferably, the temperature is in the range of 20°C to 45°C. Furthermore, from the viewpoint of effectively achieving the object of the present invention, it is preferable that the treatment time be as short as possible. The time is preferably 5 seconds to 60 seconds, most preferably 5 seconds to 50 seconds, and in the case of a multiple tank washing process, it is preferable that the front tank is processed for a short time and the rear tank is processed for a long time. In particular, it is desirable to carry out the treatment sequentially for 20% to 50% longer treatment time than in the previous tank. As for the method of supplying the washing liquid in the washing process which can be applied to the present invention, when a multi-tank countercurrent system is used, it is preferable to supply the washing liquid to the rear bath and overflow to the front bath. Of course, it can also be treated in a single tank. The above compounds can be added as a concentrated liquid to the washing tank, or
Alternatively, there are various methods such as adding the above-mentioned compounds and other additives to the washing liquid supplied to the washing tank and using this as a supply liquid for the washing replenisher. The amount of washing water in the washing step of the present invention is preferably 0.1 to 50 times, particularly preferably 0.5 to 30 times, the amount of prebath (bleach-fixing solution) brought in per unit surface of the photosensitive material. However, in the present invention, a batch, disposable method is preferred. The number of washing tanks in the washing treatment applicable to the present invention is preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. The silver halide grains used in the silver halide color photographic light-sensitive material applied to the present invention contain at least 80% silver chloride.
Silver halide grains containing mol % or more are preferred, more preferably 90 mol % or more, particularly preferably 97 mol %.
It contains the above. The silver halide emulsion containing the above-mentioned silver halide grains may contain silver bromide and/or silver iodide as a silver halide composition in addition to silver chloride. In this case, the silver bromide content is 20 mol% or less, It is preferably 10 mol% or less, more preferably 3 mol%, and when silver iodide is present, it is 1 mol% or less, preferably 0.5 mol% or less. Silver chloride 8 like this
Silver halide grains containing 0 mol % or more may be applied to at least one silver halide emulsion layer, or preferably to all silver halide emulsion layers. The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [1,0,03 planes to [Ll,I] planes can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-shell type) in which the inside and outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. In addition, tabular silver halide grains (JP-A-58-1139
No. 34 and Japanese Patent Application No. 170070/1983) may also be used. Further, the silver halide grains may be obtained by any preparation method such as an acid method, a neutral method, or an ammonia method. Alternatively, for example, seed particles may be prepared using an acid method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, 9H, pAg, etc. in the reaction vessel are controlled, and the amount of silver ions commensurate with the growth rate of silver halide grains is controlled, for example, as described in JP-A-54-48521. It is preferable to implant and mix the and halide ions sequentially and simultaneously. Preferably, the silver halide grains are prepared as described above. A composition containing the silver halide grains is referred to as a silver halide emulsion in Muming Shu. In the present invention, the color developer kit refers to a component assembled as a composition in which one or more components of a color developer are dissolved or mixed, and each component is called a kit part. In the present invention, all of the kits are in powder form (or powder or granule).
These are preferably used from the viewpoint of ease of handling and transportation. This point of view is particularly important in the news and amateur markets. In the present invention, silver halide color photographic materials include color vapor, color negative film, color positive film, and color reversal for slides, if the light-sensitive material contains a coupler and is processed by the so-called internal development method. It can be applied to any silver halide color photographic material such as film, color reversal film for movies, color reversal film for TV, color reversal paper, etc. [Effects of the Invention] According to the present invention, there is provided a color developer for light-sensitive materials, a color developer processing agent kit, and a processing agent that enable rapid processing regardless of the environmental conditions during processing and provide stable photographic performance. We can provide drug kit sets. Furthermore, it is possible to provide a hobby processing agent kit set that allows rapid processing using a simple method. [Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited to these. Example 1 A photosensitive material was prepared by sequentially coating the following layers on a polyethylene coated paper support from the support side. Note that polyethylene coated paper has an average molecular weight of 10
7.0% by weight of 7-natase type titanium oxide was added to a mixture of 200 parts by weight of polyethylene with an average molecular weight of 0,000 and a density of 0.95 and 20 parts by weight of polyethylene with an average molecular weight of 2,000 and a density of O and aO, and extrusion coating was performed. By method, the surface of high-quality paper with a weight of 180g/rn' and a thickness of 0.03
A 5 mm thick coating layer was formed, and a 0.040 ma+ thick coating layer made only of polyethylene was provided on the back side. After the polyethylene-coated surface of the support was pretreated by corona discharge. The following layers were applied in sequence. First layer: A blue-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 0.5 mol % of silver bromide. The emulsion contains 340 g of gelatin per mol of silver halide, and the following per mol of silver halide Sensitized using 2.5X10-4 moles of the sensitizing dye [In[] (using isopropyl alcohol as solvent) and dissolved and dispersed in dibutyl phthalate, 2,5-
Contains 200 mg/rn' of di-t-butylhydroquinone and [Y-1] of the following structure as a yellow coupler, OX 10-1 mole per mole of silver halide, silver amount 2
It is applied at a concentration of 90 mg/rn'. 2nd layer 290 mg/m" of di-tert-octylhydroquinone dissolved and dispersed in dibutyl phthalate. 2-(2'-hydroxy-3",
5' di-t-butylphenyl)benzotriazole, 2
-(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-
dobutyl-5'-methylphenyl)-5-chlorobenzotriazole and 2-(2'-hydroxy-3',5
'-di-t-butylphenyl)-5-chloro-benzotriazole mixture (1:l:l:l)
Gelatin 1 in the gelatin layer containing 220 mg/ln'
l]Ohg/m'. Third layer: A green-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 0.4 mol% of silver bromide, the emulsion containing 420 g of gelatin per mol of silver halide, and the following per mol of silver halide: A sensitizing dye of the structure [I] was sensitized using 2.5X 10-4 mol of 2,5-di-
1. t-butylhydroquinone and [M-1] having the following structure as a magenta coupler per mol of silver halide.
It contains 8X 10-1 moles and is coated to give a silver content of 210 mg/ni'. In addition, as an antioxidant, 2
,2.4-)dimethyl-6-lauryloxy-7-t-
0.30 mol of octylchroman was added per mol of coupler. 4th layer 30 mg/m' of di-t-octylhydroquinone dissolved and dispersed in dioctyl phthalate and 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole as an ultraviolet absorber , 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-1-butyl-5'
-methylphenyl)-5''-chloro-benzotriazole and 2-(2'-hydroxy-3',5'-di-
t-Butylphenyl)-5-chloro-benzotriazole mixture (2: 1.5: 1.5: 2) 45
The gelatin layer contains 0 mg/m', and gelatin 1
It is coated at a concentration of 900 mg/m'. Fifth layer: a red-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 0.3 mol % of silver bromide, the emulsion containing 480 g of gelatin per mol of silver halide; Sensitizing dye [II] having the following structure: 2,5-di-t-butylhydroquinone 150+* sensitized using 2.5X10-5 mol and dissolved and dispersed in dibutyl slate
g/rn' and cyan coupler, [C-
1] per mole of silver halide, and was coated to give a silver amount of 29 Gmg/rn'. 6th layer: This is a gelatin layer, coated with gelatin at a concentration of 800 mg/m''. The silver halide emulsion used in each photosensitive emulsion layer (1st, 3.5th layer) is a Japanese Patent Publication No. 46- They were prepared by the method described in Japanese Patent No. 7772, chemically sensitized using sodium thiosulfate pentahydrate, and 4-hydroxyloxy-6- as a stabilizer.
Methyl-1,3,la,? - Tetrazaindene (2.5 g per mole of silver halide), bis(vinylsulfonylmethyl)ether as hardener (1 g per Ig of gelatin)
kg) and saponin as a coating aid. Sensitizing dye [II Sensitizing dye [1l] Sensitizing dye [II[] [Y-1] m17 [M-1] n Q EC-1 The color vapor produced by the above method is subjected to the processing step of the exposure method After processing using the processing solution. Processing steps (1) Color development (2) Bleach-fixing (3) Washing with water (4) Drying [Color developer] Potassium carbonate Potassium bromide Potassium chloride Potassium sulfite (55% solution) Exemplary compound (B-1) Hydroxylamine System compound treatment temperature 30 to 35°C 35°C 30°C 60 to 80°C Triethanolamine Benzyl alcohol Cyethylene triamine Pentaacetic acid Treatment time 40 seconds 40 seconds 40 seconds 30 seconds 0g ll1g g 0.7 III Described in Table 1 ( (listed in Table 1) g 10g g g Fluorescent brightener (manufactured by Chihakaigyi Co., Ltd., Chippanol MSP) g Add water to complete the solution, and sterilize with potassium hydroxide or sulfuric acid.
Adjusted to H10,15. [Bleach-fix solution] Diethylenetriaminepentaacetic acid ferric ammonium salt 60.0g Diethylenetriaminepentaacetic acid 3.0g Thiois ammonium (70% solution) IOo, 0n
15-amino-1,3,4-thiadiazole-2-thiol 0.5g ammonium sulfite (40% solution) 27.5tnl Adjust the pH to 6.50 with aqueous ammonia or glacial acetic acid and add water to bring the total volume to 1l. . [Washing liquid] Orthophenylphenol 1.0g 5-chloro-2-methyl-4-isothiazolin-3-one
0.02g 2-methyl-4-inchazolin-3-one 0.02g ethylene glycol 1.0g 2-methyl-4-inchazolin-3-one
0.01g ■-Hydroxyethylidene-1.1-diphosphonic acid (fi[]% aqueous solution) IQgB
iC sentence, (45% aqueous solution) 2.0gM
g504th7H□O' 0.2gpvp (polyvinylpyrrolidone) 1.0g ammonia water (
25% aqueous solution) 2.5g nitrilotriacetic acid trisodium salt Adjust to 1M with 1.5g water, and adjust to pH 8.0 with aqueous ammonia and sulfuric acid. However, after the color developer was stored for 3 days, the color development process was performed at temperatures of 30°C and 35°C. At this time, the density difference in the reflection flue density at the highest density part of the treated color vapor (the value obtained by subtracting the density at 30°C from the density at 35°C) was determined using a densitometer. Furthermore, the reflection clean density of the unexposed area at 35°C was determined. The results are summarized in Table 1 below. From Table 1 below, the color developing agent of the present invention 1.3 x 10-2
It can be seen that the effects of the present invention can be effectively achieved when the amount of hydroxylamine is used in the amount of mol/liter or more and does not contain hydroxylamine. Furthermore, when using the compound represented by formula [I],
It can be seen that the effects of the present invention are more effectively achieved. Example 2 A similar experiment was conducted by changing the color developing agent (B-1) in the color developing solution used in Experiment No. 1-3 of Example 1 to those listed in Table 2 below. The results are summarized in Table 2 below. From Table 2 above, it can be seen that the effects of the present invention are achieved only when the color developing agent according to the present invention is used. Example 3 The following color developer kit (liquid) was prepared using the color developer used in Example 1. When it was used as a color developing solution in Example 1, it could be processed without any problems. Example 4 Alkali-cleavable water-soluble salt of pencil alcohol (()→
CH20COOK) was synthesized by the method described in US Pat. No. 4,414,307, and the following color developer kit (powder) for color vapor was prepared. For the 100-mon kit, stir 85 liters of warm water at around 40°C and then add A Bart. Stir until there is no oily substance floating on the surface of the water (be careful not to leave any solvent in the container). Next, add part B and stir until complete ζa (E/'!).When used as a color developing solution in Example 1, it was processed without any problems.Example 5 Bleach-fix kit as shown below and Example 3 or 4
A processing agent kit set was created by combining the color developer kit and instructions in one box. [Bleach-fix kit] (Powder) (1-sentence kit) When used as a bleach-fix solution in Example 1, it was processed without problems.

[Brief explanation of the drawing]

FIG. 1 is a front view showing an example of the explanatory text of the processing agent kit set according to the present invention.

Claims (1)

[Claims] 1. At least 1.3 x 10^-^2 of p-phenylenediamine compound having a water-soluble group per liter of color developer.
1. A color developing solution for silver halide color photographic light-sensitive materials, which contains molar amount of hydroxylamine and substantially no hydroxylamine. 2. A silver halide having a kit part containing at least 200 to 600 g/l of the p-phenylenediamine compound having a water-soluble group, and substantially no kit part containing hydroxylamine. Color developer kit for color photographic materials. 3. When using the color developer kit for silver halide color photographic light-sensitive materials according to claim 2, the p-phenylenediamine compound having a water-soluble group is substantially at least 1.3 x 10^-^2 1. A color developer kit for a silver halide color photographic light-sensitive material, characterized in that it has an explanatory text instructing the concentration to be mol/l. 4. A processing agent for silver halide color photographic light-sensitive materials, comprising the color developer kit for silver halide color photographic light-sensitive materials and the bleach-fixer kit for silver halide color photographic light-sensitive materials according to claim 2 above. kit set. 5. A color developer kit for silver halide color photographic light-sensitive materials, characterized in that the developer kit for the color developer for silver halide color photographic light-sensitive materials according to claim 1 is entirely in powder form.