JPH0339736A - Color image forming method - Google Patents

Abstract

PURPOSE:To rapidly form a color image having high max. color density and low min. density with improved developability by using a high silver chloride color photographic sensitive material. CONSTITUTION:A silver halide color photographic sensitive material having a silver halide emulsion contg. >=80mol% silver chloride in at least one layer and hardened with a hardening agent represented by formula I is processed with a color developing agent having <=3X10<-3>mol/l concn. of sulfite ions and 3.5X10<-2>-1.5X10<-1>mol/l concn. of Cl ions. In the formula I, each of R1 and R2 is H, alkyl, aralkyl or arom. and n is 0 or 1. A color photograph having high max. color density and low min. density is rapidly obtd. with superior develpability.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a color image forming method using a silver halide color photographic light-sensitive material. More specifically, the present invention relates to a color image forming method using a silver halide color photographic light-sensitive material. This invention relates to a color image forming method that performs development processing with excellent silver properties. (Prior Art) In recent years, in the photographic processing of color photographic materials, it has been desired to shorten the processing time due to the shortening of the finishing delivery time and the reduction of laboratory work. Common methods for shortening the time of each treatment step include increasing the temperature and increasing the amount of replenishment, but many other methods have been proposed, such as strengthening stirring or adding various accelerators. In particular, for the purpose of speeding up color development and/or reducing the amount of replenishment, color photographic materials containing silver chloride emulsion in place of the conventionally widely used silver bromide thread emulsion or silver iodide emulsion are processed. For example, if a method is known,
International Publication No. WO87104534 describes a method for rapidly processing a silver chloride color photographic material with a color developer substantially free of sulfite ions and benzyl alcohol. However, it has been found that when a so-called high silver chloride color light-sensitive material with a high silver chloride content is developed using the above method, the minimum density (Dmin) after processing is high and the white background is stained. did. Furthermore, it has been found that when a high-silver chloride color photographic light-sensitive material is rapidly desilvered, desilvering failure occurs. As described above, in rapid processing using high-silver chloride color photographic light-sensitive materials, white backgrounds are affected due to an increase in the minimum density (Dmin) accompanying development processing, the occurrence of so-called staining, and the occurrence of desilvering defects during desilvering processing. It has become clear that there is a serious practical problem of significant contamination. JP-A-58-95345 and JP-A-59232 are methods for suppressing the increase in minimum density (especially fog) that occurs during development processing in rapid processing methods using high silver chloride color photographic materials.
No. 342 proposes a method of using an organic antifoggant. However, its fog prevention effect is insufficient;
Moreover, it has been found that the problem of poor desilvering due to rapid desilvering treatment is further increased. Furthermore, JP-A-61-70552 discloses a method for reducing developer replenishment by using a high-silver chloride color photographic light-sensitive material and adding a replenishing amount in an amount that does not cause overflow into the developing bath during development. JP-A-63-106655 discloses that, for the purpose of stabilizing the processing, a high-silver chloride color photographic light-sensitive material is developed with a color developing solution containing a hydroxyamine compound and chloride at a predetermined concentration or higher. A method is disclosed. However, these methods were found to cause an increase in staining and poor desilvering due to the development process described above, and were not practical. (Problem to be solved by the invention!) Therefore, the first object of the present invention is to use a high-silver chloride color photographic light-sensitive material to develop quickly, have a high maximum color density, a low minimum density, and improve developability. An object of the present invention is to provide a color image forming method. A second object of the present invention is to provide a color image forming method that uses a high silver chloride color photographic light-sensitive material and has a small amount of residual silver and excellent desilvering properties. (Means for Solving the Problems) An object of the present invention is to provide a silver halide color photographic material,
A method of processing with a color developer containing at least one type of aromatic primary amine color developing agent, in which at least one layer contains a silver halide emulsion containing 80 mol% or more of silver chloride, and A silver halide color photographic light-sensitive material hardened with at least one hardening agent represented by formula (I) has a sulfite ion concentration of 3X10-'
mol/l or less, chloride ion concentration is 3.5X10-”~
This was achieved by a color imaging process characterized by processing with a color developer of 1.5 x 10-' mol/i. General formula (1) % formula % Chlorine ion is well known as one of the antifogging agents, but its effect is small and even when used in large quantities, it cannot completely prevent the increase in fog; This had the negative effect of delaying development and lowering the maximum density.Also, when high-silver chloride photosensitive materials were processed with a developer solution containing sulfite ions, color development deteriorated significantly due to the silver halide dissolving action of sulfite ions. However, there was no evidence that fogging was suppressed simply by processing with a developer that does not contain sulfite ions.Furthermore, high silver chloride color photosensitive materials hardened with vinyl sulfone hardeners A method for obtaining color photographs by processing with a color developing solution is described in Japanese Patent Application Laid-Open No. 59-23234.
No. 2, No. 62-250437 and No. 62-253147
However, processing with the color developing solution specifically disclosed in these specifications was insufficient to achieve the object of the present invention. However, when using a high silver chloride photosensitive material using a hardening agent represented by general formula (I), chloride ions are 3.5X10 to 1.5X10
-'mol/l concentration and sulfite ion concentration 3X
The fact that processing with a developer of 10-' mol/Il or less results in a lower minimum concentration, less residual IT, and significantly improved developability and desilvering performance is unexpected and truly surprising. Met. This effect is particularly remarkable when a two-equivalent funol-based cyan coupler, a two-equivalent pyrazoloazole-based magenta coupler, and an N-eliminating pivaloylacetanilide-based yellow coupler are used as couplers contained in the color sensitive material. The compound represented by the general formula ([) used in the present invention will be explained in more detail. R3 and R2 are each a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (e.g. methyl, ethyl)
, an aralkyl group having 6 to 20 carbon atoms (e.g. benzyl, phenethyl), an aromatic group having 5 to 20 carbon atoms (e.g. phenyl, naphthyl, pyridyl), and these groups may be further substituted. Examples of groups include sulfonic acid groups, hydroxyl groups, carboxyl groups, and the like. Particularly preferred as R1, R1 is a hydrogen atom. n represents 0 or l, with O being particularly preferred. Examples of hardeners using the general formula (expressed visually) used in the present invention are listed below, but the present invention is not limited thereto. 1) CL = CH5O! clItsOtcH=cHt■ 2) CHz=CI(SOzC)ItOCHtSOiCHHz I-3) CHz=CH3OtCHSOxCHsCH. CH. 4) CHz-CHSOtCHSOxCI=CH*tHs H ■-6) C) Ix=CH5OxCH5 (hcH=cHzC1l. SukoNa 1-11) CHz=CH3OxCIISO□CH= CH! ■ 12) CH*=CH3OxCH5OtCH=CH*-Formula (■
It is preferable to select the optimum amount of the compound expressed by the m class of the compound example, the type of gelatin, etc.
-' mole is appropriate, preferably 5 x l〇-3 to 40
X10-' mole. In the present invention, the hardener may be added to the coating solution in advance, or may be mixed with the coating solution immediately before coating. Furthermore, in the present invention, the hardening agent may be added to all of the photographic layers (for example, a light-sensitive emulsion layer, an intermediate layer, a surface protection layer, a filter layer, etc.) coated on the support, or may be added to any layer ( −
It may be added to a layer or a plurality of layers). The chloride ion concentration of the color developer in the present invention is 3.5
X10-" to 1.5X10-' mol/2, preferably 4 x 10-2 to 1.OX 10-1 mol/l. If the chloride ion concentration is more than 1.5X10-' mol/l, 3.5
If it is less than ``mol/I!'', the minimum concentration and residual silver amount will be high;
The effects of the present invention cannot be sufficiently obtained. Here, chlorine ions may be added directly to the color developer, or may be eluted from the photosensitive material in the developer. When added directly to the color developer, sodium chloride, potassium chloride, etc. are used as chloride ion supply substances. ,Ammonium chloride,
Examples include di-nokel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred are sodium chloride and potassium chloride. It may also be supplied as a counter ion to a fluorescent brightener added to the developer.When eluted from the photosensitive material in the developer, it may be supplied from the silver chloride emulsion, or it may be supplied from the optical brightener. You may. In the present invention, the sulfite ion concentration of the color developer is
The content of sulfite ions is not more than 3 X 10-' mol/l, preferably O to 1.5 X 10-' mol/l, and most preferably contains no sulfite ions at all. If it is 3XlO-' to 1Xl or more, staining, especially fogging, will increase significantly, derailment will also worsen, and the object of the present invention will not be satisfied.
It is more preferable to contain 0-3 mol/E of bromide ion in terms of stability and derailment. In the presence of bromine ions at a concentration of 1X10-' mol/l or more, the object of the present invention cannot be achieved in terms of development progress and a decrease in maximum density, but 3x10-5-I
The fact that the presence of a trace amount of bromine ions such as 10-":ent/1. eliminates the above-mentioned drawbacks and further improves stain and derailment properties was unexpected and surprising. In the present invention, color development Bromine ions present in the solution may be added directly or eluted from the color photographic light-sensitive material.The color photographic light-sensitive material of the present invention has a blue-sensitive silver halide emulsion layer, a green It can be constructed by coating at least one sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer.In general color photographic paper, these layers are coated on a support in the above order. However, a different order may be used, and an infrared-sensitive silver halide emulsion layer may be used in place of at least one of the above-mentioned emulsion layers. These include a silver halide emulsion sensitive to each wavelength range, and dyes that are complementary colors to the light to which they are exposed - yellow for blue, magenta for green, and cyan for red.
By containing a so-called color coupler that forms a color, subtractive color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above. Those consisting of the following can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol%.
Hereinafter, the halogen composition of the emulsion, which is preferably 0.2 mol% or less, may be different or equal between the grains, but when using an emulsion having the same halogen composition between the grains, each grain It is easy to make the properties homogeneous. Regarding the distribution of halogen inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grains, and grains with a core inside the silver halide grains and those surrounding it. Particles with a so-called layered structure in which the halogen composition differs between the shell (-layer or multiple layers), or a structure having seven non-layered parts with different halogen compositions inside or on the particle surface (if present on the particle surface, Particles having a structure in which parts of different compositions are joined on the edges, corners, or surfaces of the particles can be appropriately selected and used. In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When silver halide grains have the above-mentioned structure, even if the boundaries between parts with different halogen compositions are clear boundaries, the boundaries may be unclear due to the formation of mixed crystals due to compositional differences. It is also possible to actively have continuous structural changes. Furthermore, so-called high-silver chloride emulsions having a high silver chloride content are preferably used in light-sensitive materials suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more,
More preferably 95 mol% or more. Such a high silver chloride emulsion preferably has a structure in which the silver bromide localized layer is inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above.The halogen composition of the localized layer is The silver bromide content is preferably at least 10 mol %, more preferably more than 20 mol %, and these localized layers are inside the grain, on the edges, corners or surfaces of the grain surface. However, one preferred example is one in which part of the corner of the particle is epitaxially grown. On the other hand, in order to minimize the decrease in sensitivity when a photosensitive material is subjected to pressure, even in a high silver chloride emulsion with a silver chloride content of 90 mol% or more, grains with a uniform structure with a small distribution of halogen composition within the grains are used. It is also preferable to use It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of development processing solution trapped. In such cases, the silver chloride content is 98 mol% to 10
Emulsions of almost pure silver chloride, such as 0 mol %, are also preferably used. Average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken)
is 0. t μ to 2 μ is preferable. In addition, the particle size distribution of these particles is preferably a so-called monodisperse one with a coefficient of variation (the difference in particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less. For the purpose of obtaining FJ! 'Wrapping is also preferably done. The shape of silver halide grains contained in photographic emulsions is regular (cubic, tetradecahedral, or octahedral).
lar) those with crystal shapes, those with irregular crystal shapes such as spherical, plate-like, etc.
Alternatively, a composite form of these can be used. In addition, it may be composed of a mixture of particles having various crystal forms. Among these, in the present invention, particles having the above-mentioned regular crystal form account for 50% or more, preferably 70% or more, and more preferably 90% or more. % or more. In addition to these, the average aspect ratio (yen equivalent diameter/
Emulsions in which the projected area of tabular grains having a thickness of 5 or more, preferably 8 or more, exceeds 50% of the total grains can also be preferably used. The silver chlorobromide emulsion used in the present invention is P, Glafkid
Chimie et Ph1sique Pho by es
tographique (PaulMon Le 1
Publishing, 1967), G., F., Duffin, P.
hoLo-graphic Es+ulsion Ch
esistry (published by Focal Press, 19
66), V. L., Zelikman et a.
Written by t1king and Coating Photo
graphic Es+uldion (Focal
Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble Wagen's salt may be any method such as the one-sided mixing method, the simultaneous mixing method, or a combination thereof. It is also possible to use a method in which zero particles are formed in an atmosphere containing excess silver ions (so-called back mixing method). A method of keeping the pag constant in the liquid phase in which silver halide is produced as one type of simultaneous mixing method,
That is, the so-called Chondral double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention in the form of emulsion grains or in the process of physical ripening. Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and krillam, or iron, which is a group II element,
Examples include salts or complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies widely depending on the purpose, but is preferably from 10@-9 to 10@4 mol relative to silver halide. The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization. Regarding the chemical sensitization method, sulfur sensitization typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction sensitization can be used alone or in combination. Regarding compounds used for chemical sensitization, see the lower right column on page 18 of the specification of JP-A-62-215272.
Those described in the upper right column of page 22 are preferably used. Spectral sensitization is performed for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. This is preferably carried out by adding an absorbing dye - a spectral sensitizing dye. Examples of the spectral sensitizing dye used in this case include 11 by F. M. Llarmer.
eterocyclic compoundsCyan
ine dies and related comp
ounds (John Wiley & 5ons (
(New York, London), 1964). Examples of specific compounds and spectral sensitization methods are described in the above-mentioned JP-A-62
22nd right upper column to 38th of the specification of the publication No.-215272
Those described on page 1 are preferably used. The silver halide emulsion used in the present invention has the following properties:
Alternatively, various compounds or their precursors can be added for the purpose of stabilizing photographic performance. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-62-215272 mentioned above are preferably used. The emulsion used in the present invention is either a so-called surface latent image type emulsion in which a latent image is formed mainly on the grain surface, or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Also good. Yellow couplers, magenta couplers, and cyan couplers which develop yellow, magenta, and cyan colors, respectively, by coupling with oxidized products of aromatic amine color developing agents are commonly used in color light-sensitive materials. The cyan coupler, magenta coupler and yellow coupler preferably used in the present invention have the following formulas (C-1), (C-11), <M-1), (M-11).
and (Y). General formula (C-1) 11 General formula (C-n) H 2 General formula (M-i) General formula (M-n) bc”-Otori general formula (Y) General formula (C-1) and ( In C-11), R3,
R2 and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, R1, R3 and each represent a hydrogen atom, halogen atom, aliphatic group, aromatic group or acylamino group, R3 together with R8 Y may represent a group of nonmetallic atoms forming a nitrogen-containing 5- or 6-membered ring;
, Yt represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent, and n represents 0 or l. R3 in general formula (C-■) is preferably an aliphatic group, such as methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, phenyl group. Examples include a chinamethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group, and a methoxymethyl group. Preferred examples of the cyan coupler represented by the formula ((, -1) or ((, -II)) are as follows. In the general formula (C-1), R is preferably an aryl group,
A heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, it is an aryl group substituted with a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group. - When R2 and R2 do not form a ring in formula (C-1), R2 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R] is preferably a hydrogen atom. In the general formula (C-■), R4 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group. In general formula (C-11), R1 preferably has 2 to 2 carbon atoms.
It is a methyl group having 15 alkyl groups and a substituent having 1 or more carbon atoms, and the substituents are preferably a ruthio group, an alkylthio group, an azilamino group, an aryloxy group, or an alkyloxy group. In the general formula (C-■), R1 is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms. In the general formula (C-■), R & is preferably a hydrogen ring,
Preferred Yl and Y2 in general formulas (C-1) and (C-n), which are halogen atoms, particularly preferably chlorine atoms and fluorine atoms, are hydrogen atoms, halogen atoms, alkoxy groups, aryloxy groups, and acyloxy groups, respectively. , is a sulfonamide group. -i In formula (M-1), R1 and R9 represent an aryl group, R1 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group,
Y represents a hydrogen atom or a leaving group. Aryl group (preferably phenyl group) of R1 and R1
The permissible substituents ta for substituent Rt are the same as the substituents permissible for substituent Rt, and when there are two or more substituents, they may be the same or different; R, is preferably a hydrogen atom. , an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Preferred Y3 is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, for example as described in U.S. Pat.
Particularly preferred are sulfur atom dissociative types such as those described in No. 51,897 and International Publication No. W08B104795. In the general formula (M-n), R1 represents a hydrogen atom or a substituent, Y4 represents a hydrogen atom or a leaving group, and a halogen atom or an arylthio group is particularly preferred. ZaSZ
b and Zc are methine, substituted methine, =N- or -N)
I-, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. When the Zb-Zc bond is a carbon-carbon double bond, R4 or Y, including when it is part of an aromatic ring. When forming a multimer with two or more positions, Za. When zb or Zc is a substituted methine, this includes the case where the substituted methine forms a multimer with two or more positions. Among the pyrazoloazole couplers represented by the formula (M-It), imidazo (1, 2-b) Preferred are pyrazoles,
Pyrazolo (1
,5-b)(1,2,4)) riazoles are particularly preferred. In addition, a branched alkyl group as described in JP-A No. 61-65245 is directly connected to the 2.3 or 6-position of the pyrazolotriazole ring, and the pyrazolotriazole coupler 1 is described in JP-A-61-65246. pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent Publication No. 226. It is preferred to use pyrazolotriazole couplers having an alkoxy or aryloxy group at the 6-position, such as those described in No. 849 and No. 294,785. In the general formula (Y), Ro represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group,
RIg represents a hydrogen atom, a halogen atom, or an alkoxy group, A represents -N) ICORl 3, provided that R
13 and Ro each represent an alkyl group, aryl group, or acyl group e Y% represents a leaving group * Il+i and R
13. The substituents for Rt4 are the same as the substituents allowed for R1, and the leaving group Ys is preferably one that leaves at either an oxygen atom or a nitrogen atom; Particularly preferred are molds. General formula (C-1), (C-11), (M-1), (M-
Specific examples of couplers represented by If) and (Y) are listed below. (C-1) Shi2 (C-2) Shi1 (C-3) Shi1 (C-4) H (C-5) (C-6) CyoHl Shi1 (C-7) (C- 8) zHs (C-9) (C-10) (C-12) H (C-13) (C-14) (C-15) (C-16) C,U. (C-17) (C-18) (C-19) Eye 1 (C-20) (C-21) (C-22) υshi■3 (M-1) I Shil (M-2) I Shi2 (M-3) r# CM-6) Shil (M-7) (M-8) t (Y-1) (Y-2) (Y-3) υ11 (Y-4) (Y -5) (Y-6) (Y-7) (Y-8) (Y-9) The couplers represented by formulas (C-1,) to (Y) above are halogenated The silver emulsion layer usually contains 0.1 to 1.0 mol, preferably 0.1 to 0.5 mol, per mol of silver halide. In the present invention, in order to add the coupler to the photosensitive layer, various known techniques can be applied.Usually, the coupler can be added by an oil-in-water dispersion method known as an oil protection method. After dissolving, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. (or water or gelatin water in coupler solution containing surfactant)
A dispersion of oil droplets in water may be obtained by adding a liquid to the solution and carrying out phase inversion. Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
The low-boiling organic solvent may be removed by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion. As a dispersion medium for such couplers, the dielectric constant (25°C
)2-20. It is preferable to use a high boiling point organic solvent and/or a water-insoluble polymer compound having a refractive index (25° C.) of 1.5 to 1.7. As the high boiling point organic solvent, preferably used are high boiling point organic solvents represented by the following general formulas (A) to (E). General formula (A) General formula (B) -COO--2 General formula (E) H, -0-W (wherein 1, W2 and WY are respectively substituted or unsubstituted alkyl groups, cyclo Represents an alkyl group, alkenyl group, aryl group or heterocyclic group, -4 is w, O
N, or S-W, where n is an integer from 1 to 5, and when n is 2 or more, 4 may be the same or different from each other, - In formula (E), h and 6 may form a fused ring). The high boiling point organic solvent that can be used in the present invention also has a melting point of 100°C or less and a boiling point of 140
Compounds that are immiscible with water at temperatures above ℃ and can be used as long as they are good solvents for couplers. The melting point of the high-boiling organic solvent is preferably 80°C or lower. The boiling point of the high boiling point solvent is preferably 160°C or higher, more preferably 170°C or higher. For details on these high boiling point organic solvents, please refer to JP-A-62
-215272 Publication Specification, page 137, lower right column ~ 14
It is written in the upper right column of page 4. These couplers can also be impregnated into Rhodapul latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling EL T8 media described above, or can be made into water-insoluble and R-containing polymers. ? It can be dissolved in a medium-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. W088100723 are used, and acrylamide-based polymers are particularly preferred from the viewpoint of color image stabilization. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and the phenolic properties of these compounds, *silylation of acid groups , alkylated ether or ester derivatives are representative examples. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used. Specific examples of organic antifade agents are described in the following patent specifications: Hydroquinones are disclosed in U.S. Patent No. 2,360,290;
2.418.613, 2,700.453, 2.701.197, 2,728.659
No. 2,732,300, No. 2,735,76
No. 5, No. 3,982.944, No. 4,430.4
25, British Patent No. 1,363,921, U.S. Patent No. 2.710.801, U.S. Patent No. 2,816.028, etc. U.S. Patent No. 3,432,30
No. 0, No. 3.573.050, No. 3,574.6
No. 27, No. 3.6! js. No. 909, No. 3.764,337, JP-A No. 1983-1
No. 52225, etc., and spiroindanes are covered by US Patent No. 4.
, 360,589; P-alkoxyphenols are disclosed in U.S. Pat. No. 2.735.765;
No. 66.975, JP-A-59-10539, JP-A-Sho 5
No. 7-19765, etc., and hindered phenols are disclosed in U.S. Patent No. 3,700,455 and JP-A-52-7222.
No. 4, U.S. Patent No. 4,228.235, Special Publication No. 1982-6
No. 623, etc., gallic acid derivatives, methylenedioxybenzenes, and aminophenols are each patented in U.S. Patent No. 3.
, 457.079, U.S. Pat.
3, British Patent No. 1.326.889, British Patent No. 1,35
No. 4,313, No. 1.410,846, Special Publication No. 1973
-1420, JP-A-58-114036, JP-A No. 59
-53846, 59-78344, etc., gold R
The complex is described in U.S. Pat. Nos. 4,050,938 and 4,24.
1°155, British Patent No. 2,027,731(A), and the like. These compounds usually have a ratio of 5 to 10 to the corresponding color coupler.
The objective can be achieved by co-emulsifying 0% of the coupler with the coupler and adding it to the photosensitive layer. In order to prevent cyan dye images from deteriorating due to heat and especially light, ultraviolet absorbers are added to the cyan coloring layer and the adjacent layers on both sides.
It is more effective to introduce As the ultraviolet absorber, a benzotriazole compound substituted with an aryl group (for example, U.S. Pat. No. 3.533.7) is used.
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314.794, U.S. Pat. No. 3,352.
681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat. No. 3,705°805 and 3,707,395). ), butadiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxydole compounds (for example, as described in U.S. Pat. No. 3,406,070, U.S. Pat. 271,307) can be used. Ultraviolet absorbing couplers (for example, α-naphthol cyan dye-forming couplers), ultraviolet absorbing polymers, and the like may be used, and these ultraviolet absorbers may be mordanted in specific layers. Among these, benzotriazole compounds substituted with the aforementioned aryl group are preferred. In addition to the couplers described above, it is particularly preferable to use the following compounds, particularly the combination with pyrazoloazole couplers. That is, the compound (F) that chemically bonds with the aromatic agonist developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or the compound (F) remaining after color development processing. For example, after treatment, a compound (G) that chemically bonds with the oxidized aromatic amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent the occurrence of staining and other side effects due to the formation of coloring dyes due to the reaction between the color developing agent remaining in the film or its oxidized product and the coupler during storage. A preferred compound (F) has a second-order reaction rate constant kg (in trioctyl phosphate at 80°C) with p-aningine of 1. Oj! /mol-see-IX
It is a compound that reacts in the range of 10-' (!/sol・sec. The second-order reaction rate constant can be measured by the method described in JP-A-63-158545. If k! is from this range If k2 is too large, the compound itself becomes unstable and may react with gelatin or water and decompose.On the other hand, if k2 is smaller than this range, it will react slowly with the remaining aromatic amine developing agent, resulting in residual In some cases, it may not be possible to prevent the side effects of aromatic amine developing agents. A more preferable compound (F) can be represented by the following formula (F) or (Fll). General formula ( FI) R+ (A)-X General formula (Fn) R-CyoY In the formula, R1 and Rz each represent an aliphatic group, an aromatic group, or a heterocyclic group, and n represents 1 or O. A represents a group that reacts with an aromatic amine developer to form a chemical bond, X represents a group that reacts with the aromatic amine developer and leaves, B represents a hydrogen atom, an aliphatic group, Aromatic groups, heterocyclic groups, acyl groups, or sulfonyl groups,
and Y represents a group that promotes addition of an aromatic amine developing agent to the compound of general formula (Fn), where R
+ and X, Y and Itt or B may be bonded to each other to form a cyclic structure. Among the methods of chemically bonding with the residual aromatic amine developing agent, the representative ones are the exchange reaction and the addition reaction. -i For specific examples of compounds represented by formula (Fri, (Fll)), see JP-A-63-158545 and JP-A No. 62-2.
83338, European Patent Publication No. 298321, European Patent Publication No. 277
Those described in specifications such as No. 589 are preferred. On the other hand, a more preferable compound (G) that chemically bonds with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inactive and colorless compound is shown below - Formula (Gl ). General formula (Gl) -Z In the formula, R represents an aliphatic group, aromatic group or heterocyclic group, Z is a nucleophilic group, or a nucleophilic group that is decomposed in the photosensitive material to release a nucleophilic group. The compound represented by formula (Gl), which represents a group where Z is Pearson's nucleophilic nCht value (
R.G., Pearson+ et al., J.
An+. Chew, Soc, fl, 319 (1968
)) is preferably 5 or more, or a group derived therefrom. -8 For specific examples of the compound represented by formula (Gl), see European Patent Publication No. 255722, Japanese Patent Application Laid-Open No. 1430-1983
No. 48, No. 62-229145, patent application No. 63-136
No. 724, No. 62-214681, European Patent Publication 29
Those described in No. 8321, No. 277589, etc. are preferred. Further, details of the combination of the above-mentioned compound (G) and compound (F) are described in European Patent Publication No. 277589. The photosensitive material produced using the present invention contains water-soluble dyes or dyes that become water-soluble through photographic processing as filter dyes in the hydrophilic colloid layer, or for various purposes such as preventing irradiation and Halley's irradiation. Such dyes which may be used include oxonol dyes, hemioxonol dyes, styryl dyes, melon dyes, anine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. In the present invention, the gelatin may be lime-treated or acid-treated. Details of the gelatin manufacturing method can be found in Arthur Vuis, The Macromolecular History of Gelatin ( Published by Academic Press, 1964). As the support used in the present invention, transparent films such as cellulose nitrate film and polyethylene terephthalate, which are usually used in photographic light-sensitive materials, and reflective supports can be used. For the purpose of the present invention, reflective supports are used. More preferably, the "reflective support" used in the present invention refers to one that enhances reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Such a reflective support includes: A support coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, etc., or a support using a hydrophobic resin containing a light-reflecting substance dispersed therein. Examples include baryta paper, polyethylene-coated paper, polypropylene-based paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyethylene terephthalate, cellulose triacetate, or cellulose nitrate. There are polyester films, polyamide films, polycarbonate films, polystyrene films, vinyl chloride resins, etc. Other reflective supports include specular reflective or second W
#, a support with a diffusely reflective metal surface can be used. The metal surface has a spectral reflectance of 0.0 in the visible wavelength range.
5 or more is better, and the metal surface is roughened or gold,
*It is best to use powder to make it diffusely reflective.The metal used is aluminum, tin, aluminum, magnesium, or its alloys, and the surface is a metal plate or metal foil obtained by rolling, vapor deposition, or plating. , or the surface of a metal "1fIN". Among these, it is preferable to provide a layer of water-resistant resin, especially a thermoplastic resin, on the metal surface, which is preferably obtained by vapor-depositing the metal on another substrate. It is preferable to provide an antistatic layer on the side opposite to the metal surface of the support of the present invention.For details of such a support, see, for example, JP-A No. 61-210.
No. 346, No. 63-24247, No. 63-24251
No. 63-24255, etc. These supports can be appropriately selected depending on the purpose of use. As a light-reflecting substance, it is best to sufficiently mix and coat a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with two layers.
It is preferable to use one treated with ~tetrahydric alcohol. The occupied area ratio (%) of white pigment fine particles per defined unit area is calculated by dividing the observed area into adjacent unit areas of 6-x6μ and projecting onto the unit area. It can be determined by measuring the occupied area ratio (C%) (R1) of the fine particles. The coefficient of variation of the occupied area ratio (%) is the ratio s of the standard deviation S of R to the average value (R) of R
/R can be obtained. The number (n) of target unit areas is preferably 6 or more, and therefore the coefficient of variation S/π can be determined by. In the present invention, the coefficient of variation of the occupied area ratio (%) of pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. When O,OS or less, the dispersibility of the particles is substantially "uniform". It can be said that. The color photographic material of the present invention is preferably subjected to color development, bleach-fixing, and water-washing treatment (or stabilization treatment). Bleaching and fixing may be performed separately instead of in one bath as described above. . The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto. D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotriene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)a≧no]aniline D-52-methyl-4-[N-ethyl-N-(β-nihydroxyethyl)aξno]aniline D-64-amino-13-methyl-N -ethyl-N-(
β-(methanesulfonamido)ethyl]-aniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonade ξ-do D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3 -Methyl-N-ethyl-N-methoxyethylaniline D-1o 4-amino-3-methyl-N-ethyl-N
-β-ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-(β-(
Methanesulfonamido)ethyl)-aniline (exemplified compound β-6). In addition, the amount of the aromatic amine developing agent, which may be a salt such as sulfate, hydrochloride, sulfite, or p-toluenesulfonate, with these p-phenylenediamine derivatives is determined by the amount used in the development process. Preferably about 0.1g to about 20g per liquid 11
1 and more preferably from about 0.5 g to about 10 g. In carrying out the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol. Here, "substantially free" means preferably 2d/2 or less,
More preferably, the benzyl alcohol concentration is 0.5-/ffi or less, and most preferably, it contains no benzyl alcohol at all. The developer used in the present invention preferably does not contain substantially sulfite ions, and more preferably does not substantially contain hydroxylamine. This is because hydroxylamine acts as a preservative for visual fluids. This is because, in addition to its function, it itself has silver development activity, and fluctuations in the concentration of hydroxylamine are thought to have a large effect on photographic properties. As used herein, "substantially no hydroxylamine is contained" preferably means a hydroxylamine concentration of s, ox to-ff mol/l or less, and most preferably no hydroxylamine at all. It is more preferable that the developer used in the present invention contains an organic preservative instead of the hydroxylamine or arsenite ion. The term "organic preservative" as used herein refers to any organic compound that is added to the processing solution for color photographic materials to reduce the rate of deterioration of aromatic primary amine color developing agents. It is an organic compound that has the function of preventing oxidation by air, etc. Among them, droxylamine derivatives (excluding hydroxylamine, the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy Ketones, α-aminoketones,
Particularly effective organic preservatives include mM, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and fused amines. These are JP-A-6
No. 3-4235, No. 63-30845, No. 63-21
No. 647, No. 63-44655, No. 63-53551
No. 63-43140, No. 63-56654, No. 63-58346, No. 63-43138, No. 63-
No. 146041, No. 63-44657, No. 63-44
656, U.S. Pat. No. 3.615', 503, U.S. Pat.
．． 494,903, JP-A-52-143020, JP-B-48-30496, etc. Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acid described in No. 180588, JP-A-54-3
Alkanolamines described in No. 532, JP-A No. 5 (i-
Polyethyleneimines described in US Pat. No. 94349, aromatic polyhydroxy compounds described in US Pat. No. 3,746.544, etc. may be contained as necessary. In particular, it is preferable to add Ti alkanolamines such as triethanolamine, dialkylhydroxyluenes such as diethylhydroxylamine, hydrazine derivatives, or aromatic polyhydroxy compounds. Among the above-mentioned organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred.
It is described in No. 5270, No. 63-9713, No. 63-9714, No. 63-11300, etc. Further, it is more preferable to use the above-mentioned hydroxylamine derivative or hydrazine derivative in combination with amines in terms of improving the stability of the color developer and, in turn, improving the stability during continuous processing. The amines mentioned above include cyclic amines such as those described in JP-A No. 63-239447.

[nya JP-A-63-12
Examples include amines such as those described in Japanese Patent Application No. 8340, and other amines such as those described in Japanese Patent Application No. 63-9713 and No. 63-11300. The color developer used in the present invention is preferably p11
9 to 12, more preferably 9 to 11.0, and the color developer may contain other known developer component compounds. In order to maintain the above ρ11, it is preferable to use various buffering agents. Examples of the buffering agents include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N -Dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3゜4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2
-Methyl-1°3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are soluble, pl+
Excellent buffering capacity in the high pH range of 9.0 or higher,
It has the advantages of not having any adverse effect on photographic performance (fogging, etc.) even when added to the developer, and being inexpensive.
11 Using 7FII Ila c 17 Main 1
．． These! Examples of street agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium O-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (5
-sodium sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds. The amount of the buffer added to the color developer is 0.1 mol/l.
It is preferable that it is more than 0.1 mol/l-0.
Particularly preferred is 4 mol/2. In addition, various caloric acid agents can be used in the color developer to prevent precipitation of calcium and magnesium, or to improve the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Ethylenecyagontetraacetic acid, N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N',N'-
Tetramethylene sulfonic acid, transsilohexanecyamine tetranodic acid, 1,2-diaminopropanetetraacetic acid, glycol ethercyamine tetranodic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2
,4-)licarboxylic acid, ]-hydroxyethylidene-1
, 1-diphosphonic acid, N. Examples include N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid. Two or more of these chelating agents may be used in combination, if necessary. These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer.
! It is about 0.1g to 10g per serving. Any development accelerator can be added to the color developer if necessary. As the developer polarizing agent, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 3B-7826, No. 44-1
No. 2380, No. 45-9019 and U.S. Patent No. 3,8
Thioether compounds represented in No. 13,247 etc.
p-phenylenediamine compounds disclosed in JP-A-52-49829 and JP-A-50-15554;
Quaternary ammonium salts shown in Japanese Patent Publication No. 0-137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 56-156826 and Japanese Patent Publication No. 52-43429, etc., U.S. Patent No. 2゜49
4, No. 903, No. 3.128.182, No. 4,23
No. 0,796, No. 3,253.919, Special Publication No. 1977-
No. 11431, U.S. Patent No. 2,482,546, U.S. Pat.
, 596,926 and 3,582,346, etc., Japanese Patent Publication No. 37-16088, 4
No. 2-25201, U.S. Pat. No. 3,128,183,
Polyalkylene oxides shown in Japanese Patent Publications No. 41-11431, No. 42-23883, U.S. Pat. be able to. In the present invention, any antifoggant can be added if necessary. As the anti-fogging agent, alkali metal alloys such as sodium chloride, potassium bromide and potassium iodide, genides and organic anti-fogging agents can be used. Examples of organic antifoggants include hensitriazole, 6-
Nidrobenzimiguzole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Typical examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzicameridazole, indazole, hydroxyazaindolizine, and adenine. It is preferable that the color developer that can be applied to the present invention contains a fluorescent brightener.
-Diamino-2,2'-disulfostilbene compounds are preferred, and the amount added is preferably 0 to 5 g/It, preferably 0.
It is 1g to 471. Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary. The processing temperature of the color phenomenon liquid that can be applied to the present invention is 20~
50"C, preferably 30 to 40°C. Processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. The replenishment amount is preferably small, but
00me is suitable, preferably 50 to 300-, more preferably 60In1 to 200+111! S is most preferably 60d to 150d. Next, a desilvering process that can be applied to the present invention will be explained. The desilvering step may generally include any process such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, or a bleach-fixing step. The bleaching solution, bleach-fixing solution, and fixing solution that can be applied to the present invention will be explained below. As the bleaching agent used in the bleach or bleach-fix solution, any bleaching agent can be used, but especially iron (
Organic complex salts of f[[) (e.g. ethylenediaminetetraacetic acid,
complex salts with aminobolicarboxylic acids such as diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; hydrogen peroxide, etc. is preferred. Among these, organic complex salts of iron (I [ Examples of acids or organic phosphonic acids or their salts include ethylenediaminetetraacetic acid,
Examples include diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methylinodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, etc. . These compounds may be sodium, potassium, thium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaξnopropanetetraacetic acid, methylyξnoni Iron (ilI) if salt of acetic acid is preferred because it has a high bleaching edge. These ferric ion complex salts may be used in the form of complex salts, such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. It may be used in excess of the amount that is formed.
Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/l, preferably 0.05 to 0.50 mol/Il. Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. Specification No. 812, JP-A-53-95
Publication No. 630, Research Disclosure No. 1712
No. 9 (July 1978 issue), compounds having a mercapto group or disulfide bond, and Japanese Patent Publication No. 45-85
No. 06, JP-A-52-20832, JP-A No. 53-3273
Thiourea compounds described in No. 5 and US Pat. No. 3,706,561, or halides such as iodine and bromide ions are preferred because they have excellent bleaching properties. In addition, the bleaching solution or bleach-fixing solution that can be applied to the present invention contains bromides (for example, potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg, potassium chloride, sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide) can be included. If necessary, one type with p■ buffering capacity with borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, and loxylic acid. The above inorganic acids, organic acids, alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added. The fixing agent used in the bleach-fixing solution or fixing solution is a known fixing agent, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid. , 3,6-dithia-1,8-octanediol and other water-soluble halogenated Ti solubilizers such as thioureas and thioureas.
A species or a mixture of two or more kinds can be used. In addition, a special bleach-fixing solution consisting of a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used.In the present invention, thiosulfate Particularly preferred is the use of ammonium thiosulfate salt, the amount of fixing agent per le is:
Preferably 0.3 to 2 mol, more preferably 0.5 to 1 mol
．． It is in the range of 0 mol. pH of bleach-fix solution or fix solution
Region I is preferably 3 to 1O, and particularly preferably 5 to 9. Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol. Bleach-fix solutions and fixing solutions contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives.
, metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately 0.02 to 0.02 in terms of sulfite ion.
0.05 mol/j! The content is preferably 0.04 to 0.40 mol/l, and more preferably 0.04 to 0.40 mol/l. Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added. Furthermore, buffering agents, optical brighteners, chelating agents, antifoaming agents, antifungal agents, etc. may be added as necessary. After desilvering treatment such as fixing or bleach-fixing, washing with water and/or stabilization treatment is generally performed. The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set. Among these, the relationship between the number of flushing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motorcycle Picture and Television Engineers (Jour
na of the 5oeiety of
Motion Picture and Te
1evi-sion Engineers) Volume 64,
It can be obtained by the method described in p., 248-253 (May 1955 issue). Generally, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4. According to the multistage countercurrent method, the amount of washing water can be greatly reduced, for example, to 0.52 to 12 or less per tnt of photosensitive material, and the effect of the present invention is remarkable. As the time increases, problems arise such as bacteria propagating and resulting floating matter adhering to the photosensitive material. As a solution to such problems, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Also, JP-A-57-8
Isothiazolone compounds and thiabendazoles described in No. 542, chlorine-based disinfectants such as chlorinated sodium incyanurate described in No. 1461-120145, JP-A-61
- Benzotriazole, copper ion, etc. described in No. 267761, Hiroshi Horiguchi, Chemistry of antibacterial and anti-mildew J (1986), Sankyo Publishing, Society of Sanitary Technology [r Sterilization, sterilization, and anti-mildew technology of microorganisms] (1982) Industrial It is also possible to use the disinfectants described in "Encyclopedia of Antibacterial and Antifungal Agents J (1986)," edited by the Japan Society of Antibacterial and Mildew Prevention and Prevention. A chelating agent such as EDTA can be used as a softening agent.It is also possible to perform the treatment directly with a stabilizing solution following the water washing process described above, or without going through the water washing process.The stabilizing solution has an image stabilizing function. For example, an aldehyde compound such as formalin, or a membrane suitable for dye stabilization is added.
) Buffers for preparing I and ammonium compounds can be mentioned. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used. In addition, surfactants, optical brighteners, and hardeners may be added.In the processing of photosensitive materials according to the present invention, when stabilization is directly preceded without a water-washing step, Japanese Patent Application Laid-Open No. 57
-8543, 58-14834, 60-220
All known methods described in No. 345 and the like can be used. In addition, it is also a preferred embodiment to use chelating agents such as l-hydroxyethylidene-1,1 diphosphonic acid and ethylenecyamine tetramethylene phosphonic acid, and magnesium and bismuth compounds. A so-called rinsing solution is also used as a washing solution or stabilizing solution used after desilvering treatment. The preferred pH of the water washing step or stabilization step is 4-10, more preferably 5-8. The temperature can be set in various ways depending on the use and characteristics of the photosensitive material, but generally it is between 15 and 45 degrees.
C. Preferably 6 hours at 20 to 40°C can be set arbitrarily, but shorter times are preferable from the viewpoint of reducing processing time.
Preferably 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to
It is 1 minute and 30 seconds. The smaller the amount of replenishment, the better from the viewpoints of running costs, discharge fitting, ease of handling, and the like. The specific preferred amount of light is 0.5 to 50 times the amount brought in from the front bath per unit area of the photosensitive material, preferably 3
It is 40 times to 40 times. or 12 or less per photosensitive material,
Preferably it is 500 yards or less. Further, replenishment may be performed continuously or intermittently. The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is reducing the amount of waste liquid by using a multi-stage counter-current system to allow the overflow of the washing water to flow into the bleach-fixing bath, which is a pre-bath, and replenishing the bleach-fixing bath with Concentrated Solution 11. Example 1 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows. No.-N! ! ! Fabric liquid preparation Yellow coupler (ExY) 19.1 g, color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cp
d-7) Add and dissolve 27.2cc of ethyl acetate and 8.2g of solvent (Solv-1) to 0.7g, and dissolve this solution in 9c of 10% sodium dodecylbenzenesulfonate.
The mixture was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing c. On the other hand, chlorobromide emulsion (cubic, average grain size 0.
A 3:7 mixture of 88- and 0.70-
1 molar ratio) 6 The coefficient of variation of the particle size distribution is 0.08 and 0.
．． 10. Each emulsion contains 0.2 mol% of silver bromide locally on the grain surface) and the blue-sensitive sensitizing dye shown below! ! ! 2.0X10- for large size emulsions per mole, respectively.
'molar addition, and for small size emulsions, 2 molar additions each.
．． After adding 1 mole of 5×1 (1"), sulfur sensitization was performed to make a product manufactured by UA. The above emulsified dispersion and this emulsion were mixed and dissolved to obtain the composition shown below, and a first coating solution was prepared as follows. The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer.The following spectral sensitizing dyes were used in each layer.Blue-sensitive emulsion layer ( green-sensitive emulsion layer (2.0 x 10-' mol each for large size emulsions and 2.5 x 10-' mol each for small size emulsions) per mole of silver halide) , 4.0XlO-' moles for large size emulsions and 5.6 for small size emulsions.
X10-' moles) and (per mole of silver halide, for large size emulsions ?, 0XIO-S moles and for small size emulsions 1
．． 0x10-S mol) red-sensitive emulsion layer (0.9x10-' mol for large size emulsions and 1.1x10-' mol for small-sized emulsions per 1N mole of halide) in the red-sensitive emulsion layer For halogenated 1
In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer in an amount of 2.6 x 10-" moles per 11 moles. 80.5 x 10-' mol, ?, 7 x 10-' mol, per 1 mol of i
2.5 X 10-' moles were added. Also, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,? -tetrazaindene per 1M mol of each halogenated lXl0
-'mol and 2X10-'mol were added. The following dyes were added to the emulsion layer to prevent irradiation. and (II Structure) The composition of each layer is shown below. The numbers are the coating amount (g/po). Silver halide emulsion 1 represents the coating amount in terms of silver. Support polyethylene laminate Contains a white pigment and a blue dye (ulmarine blue)] First [(Blue Sensation N) Silver chlorobromide emulsion gelatin yellow coupler (ExY) Color image stabilizer (Cpd-1) Solvent (Solv-1) Color image Stabilizer (Cpd-7) Second layer (color mixing prevention layer) Gelatin color mixing prevention agent (cpd-5) Solvent (Solv-1) (TiOg) 0.30 1.86 0.82 0.19 0.35 0. 06 0.99 0.08 0.16 Silver chlorobromide emulsion (cubic, 1:3 mixture of one with an average grain size of 0.55 m and one with an average grain size of 0.39- (Ag molar ratio) 0 grains, child size The coefficient of variation of the distribution is 0, lO and 0.08
, each emulsion contained 8 mol% of AgBr O locally on the grain surface) 0.12 Gelatin
1.24 magenta coupler (EXM
) 0.20 color image stabilizer (Cpd-2
) 0.03 color image stabilizer (Cpd
-3) 0.15 color image stabilizer (C
pd-4) 0.02 color image stabilizer (Cpd-9) 0.02 solvent (
Solv-2) 0.40 Fourth layer (UV absorption N) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture prevention agent (Cpd-5) 0.05
Silver chlorobromide emulsion (cubic, 1:4 mixture (Ag molar ratio) of one with an average grain size of 0.5 gm and one with an average grain size of 0.45 μm. The coefficient of variation of the grain size distribution is 0.09 and 0.11,
Each emulsion contained 0.6 mol% of AgBr locally on a part of the grain surface) Gelatin cyan coupler (ExC) Color image stabilizer (Cpd-6) Color image stabilizer (Cpd-7) Color image stabilizer (Cpd-8) Solvent (Solv-6) Sixth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-5) 0.23 1.34 0.32 0.17 0. 40 0.04 0.15 0.53 0.16 0.02 Gelatin l, Acrylic modified copolymer of 33 polyvinyl alcohol (denaturation degree 17
%) 0.17 liquid paraffin 0.03 (Y to ε) 1: ■ Mixture (molar ratio) with yellow coupler (ExM) 1: 1 (R compound (molar ratio)) of magenta coupler ([1xC) Cyan coupler 1?-C, I+, and C, I+. A mixture of 2:4:4 by weight, respectively (Cpd 1) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) ) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixture inhibitor H (Cpd-6) 2:4:4 mixture of color image stabilizer (weight ratio) (Cpd-7) Color image stabilizer + CHt-C1l) ii- No. C0NIIC4Hq(t) Average molecular weight 60.000 (Cpd-8) Color image stabilizer 0■ <Cpd-9) Color image stabilizer (tlV-1) Ultraviolet absorber 4 :2:4 mixture (weight ratio) (Solv l) Solvent (Solv-2) 2:1 mixture (volume ratio) of solvent (Solv-4) Solvent (Sol Sea 5) Container C00CsHI? (CIIzL COOCall+v (Solv-6) solvent The sample obtained in the above manner was designated as A.Next, the same procedure was carried out except that the hardening agent l-1) used for sample A was changed as follows. Samples B, C, D, and Snake were prepared. Sample B 12) Sample Cl-6) Sample D Formaldehyde sample E Dimethylol urea Samples A, B, C%D, E were heated at 40°C7 immediately after application.
It was stored in an atmosphere of 0% RH for 16 hours. The amount of hardening agent added to each of Samples B, C, D, and E was adjusted so that the swelling thickness at that time was approximately the same as that of Sample A. The hardener of the present invention was added by mixing with the coating solution immediately before coating, and formaldehyde and dimethylol urea were added to the coating solution in advance. In order to investigate the photographic performance of these coated samples, the following experiment was conducted. First, using a sensitometer (FWH model manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200K) on the coated sample,
Provided gradation exposure for sensitometry. The exposure at this time was carried out at an exposure time of 1/1O second and an exposure amount of 250 CMS. The above sample was processed using the following processing steps and the following processing composition. However, the composition of the color developer was changed as shown in Table 1. ILIJ ■ Toyota color development 38°C 45 seconds bleach fixing 30-36°C 45 seconds rinse ■ 30-37°C 30 seconds rinse ■
Rinse for 30 seconds at 30-37°C Dry for 30 seconds at 30-37"C
The precepts for the treatment solution at 70-80°C for 60 seconds are as follows. Imperial Niasataka Tosui 800
I11゜Ethylene ξ - N, N, N, N. Tetramethylene phosphone fil 3. Og dimethylhydroxykylamine 0.03 mol Sodium chloride See Table 1 Potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl 4-aminoaniline sulfate Triethanolamine Fluorescent brightener (4, 4'-diaminostilbene type) Add sodium sulfite water to pH (25℃) Ammonium thiosulfate (70%) Sodium sulfite ethylenecyaminetetraacetic acid (I[[) Ammonium ethylenediaminetetraacetic acid disodium odor Ammonium chloride glacial acetic acid 5g g 10.0g 2.0g Refer to Table 1 000d 10.05 00ae oo- 7g 5g g 0g g Add water to tooOdpH (2
5℃) 5.40115 (tank fluid and refill fluid are the same) Ion exchange water (3 ppm each of calcium and magnesium
Below) In the above sensitometry, the minimum density (Dmin) of blue (B), green (G), red (R) and the maximum density (Dmax) of blue (B) were measured using a Macbeth density needle, and the results were are shown in Table 1. At the same time, the light-sensitive material was uniformly exposed so as to obtain 90% developed silver based on the coated iml, and then processed, and the developed silver amount and residual silver amount were measured using fluorescent X-rays. First! Shown in the table. According to Table 1, samples A, B using the hardener of the present invention,
In C, the maximum density is high, the minimum density is very low, and the amount of residual silver is also small, as seen from experiment Ncl~6 using the process of the present invention. In particular, in the present invention, the effect is remarkable when the sulfite ion concentration in the developer is 3.0XlO-''mol/l or less and the chloride ion concentration is 4XlO-2-IXIO''mol/l. Recognize. In addition, as a hardening agent, I3, I-4 according to other inventions
, l-11 and l-12 can also provide similar effects. Example 2 Using the wipes A and D of Example 1, the developer and desilvering properties were tested in the same manner as in Example 1. The composition and treatment steps of each treatment liquid are as follows. However, the chlorine ion concentration and bromide ion concentration in the color developer were adjusted as shown in Table 2. "Dokoro" HiL Ni, Masutomo K plate color development 38℃ 45 seconds bleach fixing 3
0 to 36°C 45 seconds 30 seconds 30 seconds 30 seconds 60 seconds Rinse ■ Rinse ■ Rinse ■ Drying - Li dihydrogen water Ethylenediamine - N, N, N Tetramethylenephosphonate diethyl hydroxylamine Sodium chloride Potassium bromide Potassium carbonate N-ethyl-N-(β-methanesulfonade ξdoethyl)-3-methyl 4-aminoaniline sulfate triethanolamine optical brightener (4,4' tilbene type) Add water to pH (25°C) N. Diaminos 30-37°C 30-37°C 3″0-37°C 70-80°C 00d 3,0g O,03mol See Table 2 See Table 2 5g 5°0g 10°0g 2,0g 000d 10.05 Returning King Ji Oto Rainbow Liquid.Water 400
dAmmonium thiosulfate (70%) 100dSodium sulfite 17gEthylenethiagontetraacetate iron (I
Add 9g water
1000dpH (2'5°C)
5.40fl (tank fluid and replenishment fluid are the same) Ion exchange water (calcium, magnesium each 3ρp-
Below) The above color developer is applied to the aperture ratio (contact area with air (C1
1")/volume (ell-")) 0,020-, and aged at room temperature for 1 month, with a minimum of 4% before and after aging.
Example 1: Maximum concentration and residual silver amount after change in degree and time
Measurements were made in the same manner as above, and the results are shown in Table 2. According to Table 2, as can be seen from experiments t4a14-19 using the treatment of the present invention in sample A using the hardener of the present invention, the minimum density difference of the color developer before and after aging is very small. , the maximum density was high and the developability was improved. Furthermore, the amount of residual silver is small and the desilvering property is improved. Among the present invention, it is found that it is particularly preferable in terms of preventing staining and reducing the amount of residual silver when the color developer solution contains 4×bromine ions in an amount of 5×10 −′ to 4×10 −′ mol/l. Example 3 Samples E~ were prepared in the same manner as Sample ASD of Example 1, except that the halogen &l1tc of the emulsion was changed as shown in Table 3. As in Example 1, the amount of hardener added to Sample JSK was adjusted so that the swollen film thickness was approximately the same as Sample E. Sensitometric iAn light was applied to these coated samples in the same manner as in Example 1. The above sample was processed using the following processing steps and the following processing &[l] using an automatic paper processing machine. The composition of each treatment liquid is as follows. Genritsu 2gen-image amount water 800
methylenediamine-N,N,N,N. - Tetramethylenephosphonic acid 3.0g Organic preservative below 0.03sol Sodium chloride 3.0g Potassium carbonate
25g N~ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5,0g triethanolamine IO,0g optical brightener (4,
4'-Diaminostilhene type) Add sodium sulfite water to pH (25°C) 2.0 g See Table 4 000d 10.05 Ammonium hydrothiosulfate (70%) Sodium mononitite ethylenediaminetetraacetic acid (III) Ammonium ethylenediaminetetraacetic acid (III) Add disodium acetate ammonium bromide glacial acetic acid water and pH (25℃) Yunogome Yogi (tank liquid and replenisher liquid are the same) 00m 100yd. 7g 5g g 0g g 000d 5,40 Ion exchange water (calcium, magnesium each app-
Below) Maximum density of blue (B) (f) of the above sensitometry
wax), the minimum concentration (Dsin) was measured using a Macbeth densitometer, and the results are shown in Table 4. At the same time, the light-sensitive material was uniformly exposed so as to obtain developed silver of 90% of the coated silver amount, and then processed, and the developed silver amount and residual silver amount were measured using fluorescent X-rays. are shown in Table 4. According to Table 4, experiments using the treatment of the present invention were carried out in samples E-G using the CIl content and hardener of the present invention. 4
As can be seen from A25 to A28, the maximum density is high and the minimum density is low, showing good photographic performance, and furthermore, the amount of residual silver is small, and no desilvering failure is observed. It can be seen that among the samples of the present invention, the highest concentration of F is particularly preferable for samples with a Cl content of 95 mol% or more. (Effects of the Invention) According to the color image forming method of the present invention, a color photograph can be quickly obtained which has a high maximum color density, a low minimum density, and has excellent desilvering properties.

Claims (4)

[Claims] (1) A method of forming a color image by processing a silver halide color photographic light-sensitive material with a color developer containing at least one aromatic primary amine color developing agent, in which the content of silver chloride is 80 mol% or more. A silver halide color photographic light-sensitive material having at least one layer containing a silver halide emulsion and hardened with at least one kind of hardening agent represented by the following general formula (I) is prepared with a sulfite ion concentration. is less than 3×10^-^3 mol/l, and the chloride ion concentration is 3. A color image forming method characterized by processing using a color developer having a concentration of 5 x 10^-^2 to 1.5 x 10^-^1 mol/l. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 each represent a hydrogen atom, an alkyl group, an aralkyl group, or an aromatic group. n represents 0 or 1. (2) The color image forming method according to claim (1), wherein the silver halide color photographic light-sensitive material contains an N-leaving pivaloylacetanilide yellow coupler. (3) Claim (3) characterized in that the silver halide color photographic light-sensitive material contains a two-equivalent phenolic cyan coupler, a pyrazoloazole magenta coupler, and an N-eliminating pivaloylacetanilide yellow coupler.
2) Color image forming method described above. (4) Claim (4) characterized in that the color developer contains a hydroxylamine derivative or a hydrazine derivative.
1) The color image forming method described above.