JPH02149844A - Method for processing silver halide color photographic sensitive material and color developing agent composition - Google Patents

Abstract

PURPOSE:To obtain a color image having improved tone and improved preservability of picture by constituting a silver halide color photographic sensitive material having a photographic emulsion layer having a specified dry film thickness and a specified degree of swelling and incorporating a specified color developing agent into a color developer. CONSTITUTION:A dry film thickness of a photographic emulsion layer of a silver halide color photographic sensitive material is regulated to <=17mum, and a degree of swelling of the photographic emulsion layer is regulated to <=3.5. A color developer contains >=7.0X10<-3>mole/liter color developing agent expressed by the formula I. In the formula, R1 is a (substituted) 1-4C alkyl group; n is an integer 1-4; HX is HCl, H2SO4, p-toluene sulfonic acid, HNO3 or H3PO4. Thus, a color image having superior tone and preservability of picture is obtd.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for processing a silver halide color photographic material (hereinafter referred to as "photosensitive material" or "color photosensitive material, as appropriate") and a color developing agent composition. The present invention relates to a method for processing a silver halide color photographic material that has excellent storage stability and can be rapidly processed, and a color developing agent composition. [Prior Art] Processing of photosensitive materials basically consists of two steps: color development and desilvering, and desilvering consists of bleaching and fixing steps or bleach-fixing steps. In addition to this, rinsing treatment, stabilization treatment, etc. are added as additional treatment steps. In color development, the exposed silver halide is reduced to silver, and at the same time the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. During this process, the halogen ions produced by the silver halide field dissolve and accumulate in the developer solution. Additionally, components such as inhibitors contained in the silver halide photographic light-sensitive material are also eluted into the color developing solution and accumulated. In the desilvering step, silver produced by development is bleached with an oxidizing agent, and then all silver salts are removed from the photographic material as soluble silver salts with a fixing agent. A one-bath bleach-fixing method is also known in which the bleaching step and the fixing step are carried out simultaneously. In recent years, simplifying, speeding up, and reducing pollution in the processing of color photosensitive materials has become an important issue, but at the same time, methods for faithfully reproducing printing materials and objects have also become important. Especially in the field of printing plate making, continuous tone image irregularities such as reversal film, color negative film, color paper, etc.
A large amount of plate-making film is used to separate the colors in the process of creating a printing plate consisting of images made up of halftone dots. Since synthesis is performed, the work becomes complicated and mistakes are likely to occur. For this reason, a preliminary check collectively called "proofreading" is performed, but the hue of the color image generated from the coupler on the color paper used is quite different from the hue of the color image obtained by printing, and it is difficult to faithfully reproduce the printing material. , a desirable color tone is required. Also, preferred color tones are required for color printing materials as well as proofing of printing materials. For this reason, conventional methods for changing the color tone of color photosensitive materials have been proposed in Japanese Patent Application Laid-open No. 54-119922 and Japanese Patent Publication No. 48-327.
27 and JP-A-81-28!348, etc., or the method of changing the high Buddha point solvent, or JP-A-61-28!
948 and No. 81-47957, etc., methods of changing the color tone by using couplers have been proposed, but neither method can be said to have a desirable color tone, and is particularly insufficient as a color image for proofreading. Ta. The inventors of the present invention have considered the current situation and have made extensive studies, and as a result have been able to obtain a preferable color tone by using a specific N-hydroxyalkyl-substituted paraphenylenediamine derivative as a color developing agent. However, it has been found that the use of certain N-hydroxyalkyl-substituted paraphenylenediamine derivatives has the drawback of increased image storage stability, particularly photobleaching and stain density. Therefore, an object of the present invention is to provide a processing method and color development method for a silver halide color photographic light-sensitive material that has good color tone, image storage stability, particularly low photobleaching and stain density increase, and is suitable for rapid processing. An object of the present invention is to provide a developer composition. [Means for Solving the Problems] In order to achieve the above object, the inventors of the present invention have made extensive studies and have arrived at the present invention. That is, the method for processing a silver halide color photographic light-sensitive material according to the present invention is a method for processing a silver halide color photographic light-sensitive material in which the silver halide color photographic light-sensitive material is subjected to color development treatment and then immediately subjected to bleach-fixing treatment. The dry film thickness of the photographic emulsion layer of the silver halide color photographic light-sensitive material is 17 mm or less, the degree of swelling of the photographic emulsion layer is 3.5 or less, and the color developing solution has the following general formula (1). At least 7. OX 10-3 mol/l
It is characterized by containing. General formula (I) R1 is an alkyl group having 1 to 4 carbon atoms which may have a substituent, and n is an integer of 1 to 4. HX is salt. The present invention will be explained in more detail below. The color developing agent used in the present invention is: It is an N-hydroxyalkylparaphenylenediamine compound represented by the following general formula (I). General formula CI) R1 is an alkyl group having 1 to 4 carbon atoms which may have a substituent, and n is an integer of 1 to 4. HX represents hydrochloric acid, sulfuric acid, halertoluenesulfonic acid, nitric acid or phosphoric acid. The color developing agent represented by the general formula (1) is #Kaikai81-
No. 281740, No. 11-275837 and No. 8l
-2H14e etc., the color developing agent of the present invention is 4-amino-3-methyltoethyl-N-(
Unlike the β-hydroxyethyl)-aniline salt, the 3-position is not substituted with alkyl. Therefore, the tone and image storage stability of the color dye image exhibit the desired effects of the present invention. Specific compounds are illustrated below, but the present invention is not limited to these exemplified compounds. [Exemplary Compounds] Hydrochloric acid, sulfuric acid, and p-)luenesulfonic acid of the compounds (1) to (5) above are particularly preferred. Among these exemplified compounds, (1), (2), (
3) and (4) are preferably used, especially (2) and (3).
) is preferably used. The color developing agent of the present invention contains 7, (rX
It is necessary to contain Io-3 mole or more from the viewpoint of color tone and quickness. 7. When OX is less than 10-3 mol/l, the color tone is not sufficient and the speed is also low. Preferably 8. OX 10 bow ~1. OX 1CI-2 mol/cross, particularly preferably 1. OX 10.2-5. OX
It is 10-2 mol/dante. In the present invention, color developing agents other than those of the present invention may be used in combination. The dry film thickness of the photographic emulsion layer of the silver halide color photographic light-sensitive material used in the present invention is +7 pm or less. When the dry film thickness of the photographic emulsion layer exceeds lagm, image storage stability tends to deteriorate. This is probably because one color developing agent tends to remain in the emulsion. Furthermore, it is not preferable from the viewpoint of speed. The dry film thickness of the photographic emulsion layer is preferably 15 gm or less, particularly preferably 13 μm or less. The term "photographic emulsion layer" as used herein refers to a group of laminated wood-philic colloid layers that include at least one photosensitive silver halide emulsion layer and are mutually water-permeable with this layer. A back layer on the opposite side of the photosensitive silver halide emulsion layer is not included. The degree of swelling of the photographic emulsion layer used in the present invention is 3.5.
It is necessary that the following is true. Preferably 1.5-3
．． 6, particularly preferably 2.0 to 3.2. The term "degree of swelling" as used herein refers to the value obtained by dividing the thickness of the photographic emulsion layer by the thickness of the dry layer after immersing the photosensitive material in distilled water at 33° C. for 2 minutes. If the degree of swelling of the photographic emulsion layer exceeds 3.5, the effects of the present invention on image storage stability and speed cannot be obtained, and if it is too low, for example, 1.5 or less, the same as above applies. 1 Image storability and speed become insufficient. Another problem is that adhesive properties are likely to deteriorate. Any method may be used to achieve the degree of swelling within the scope of the present invention, but generally it can be adjusted by adjusting the amount and type of gelatin, the amount and type of hardener, and the drying conditions during coating. can. Gelatin is usually used in the photographic emulsion layer, but high molecular weight polymers, gelatin derivatives, etc. can also be used. The processing step in the present invention is to perform a bleach-fixing treatment immediately after the color development treatment, but after the bleach-fixing step, it is preferable to perform an anhydrous washing stabilization treatment in order to achieve the effects of the present invention. In the case of a water washing treatment, Rather, there is a problem in that image storage performance deteriorates. The specific processing steps will be shown below. (i) Color development → bleach fixing → washing → drying (11) color development → bleach fixing → waterless washing stability → drying (iii) color development →
Bleach-fixing → washing or rinsing → water-free washing stability → drying (i-ma) black and white development → water-washing → color development → bleach-fixing → water-free washing stability → drying (ma) black-and-white development → water washing → color development → bleach-fixing → water washing → water-free washing Stable→drying Among the above treatment steps, (ii) is particularly preferred. Next, the color developer composition of the present invention will be explained. The color developing agent composition of the present invention uses, in addition to the color developing agent represented by general formula (1), a commonly used color developing agent, such as CD-2, CD-3, CD-4, CD-6, etc. in combination. In addition, the following components may be included. Examples of alkaline agents include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, silicates, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc. alone or in combination. Can be used. In addition, various salts such as disodium wood phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium carbonate, and borates are added for the purpose of compounding or to increase ionic strength. can be used. Additionally, inorganic and organic antifoggants can be added as necessary. Yet again. A development accelerator can also be used if necessary. As a development accelerator, U.S. Patent No. 2.848,8
No. 04, No. 3,871,247, Special Publication No. 44-850
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.
,533. E1130, No. 2,531,832, No. 2,950,970, No. 2,577.127, and nonionic compounds such as polyethylene glycol and derivatives thereof, polythioethers, etc. described in Japanese Patent Publication No. 44 J504, The organic solvents and organic amines described in Publication No. 44-9509, such as ethanolamine, ethylenediamine, jetanolamine, and triethanolamine, are included. In addition, benzyl alcohol 2 phenethyl alcohol described in U.S. Patent No. 2,304,925 and others,
Examples include acetylene glycol methyl ethyl ketone, cyclohexanone, thioethers, pyridine, and ammonia. Furthermore, if necessary, ethylene glycol, methyl selon, methanol, acetone, dimethylformamide, β-cyclodextrin, and other ingredients may be added.
Organic solvents for increasing the solubility of the developing agent described in the publications No. 78 and No. 44-11509 can be used. Furthermore, auxiliary developers can also be used with the developing agents. As these auxiliary developers. For example, LfN-methyl-p-7 minophenol hexulfate (methol), phenidone, N,N'-diethyl-p-7 minophenol hydrochloride, N,N,N'
, H'-tetramethyl-biphenylenediamine hydrochloride, etc. are known, and the amount added is usually 0.01. ~
] Og/l is preferred; in addition to these, competing couplers, fogging agents, colored couplers, development inhibitor-releasing couplers (so-called DIR couplers), development inhibitor-releasing compounds, etc. may be added as necessary. Can be done. Furthermore, other anti-stain agents, anti-sludge agents,
Various additives such as a multilayer effect accelerator can be used. In addition, the color developer may contain sulfite as a preservative, specifically sodium sulfite, potassium sulfite, sodium bisulfite, potassium orthosulfite, bisulfite adduct of formaldehyde, potassium metabisulfite. etc. In addition, examples of compounds that directly preserve color developing agents include hydroxylamine, JP-A-63-23151, JP-A No. 111.
No. 3-41850, No. 83-431311 and No. 83
Hydroxylamine rust conductor described in JP-A-41852, α-hydroxy aromatic alcohol as described in JP-A-52-7779, hydroxamic acids as described in JP-A-52-27838, α-amino acids as described in JP-A-52-143020. It is preferable to use 7 carbonyl compounds, amino acid derivatives described in JP-A-52-102727, and various preservatives described in JP-A-13-135938. Other preservatives include salicylic acids described in JP-A-59-180588, alkanolamines as described in JP-A-54-3532, polyethyleneimines as described in JP-A-58-94348, JP-A-83 It is preferable to add the alkylene diamines described in No. 204258 and No. 83-239447, and in particular, alkanolamines and alkylene diamines improve the preservation of the color developer and are good for image preservation. The color developing processing agent composition of the present invention includes Japanese Patent Application No. 81-18
It is preferable to add a triazylstilbene fluorescent brightener represented by the general formula [I] described in No. 9315. These triadylstilbene-based brighteners are 1, for example, "Fluorescent Brighteners" published by the Japan Chemical Industry Association (published in August 1976)8.
It can be synthesized by the usual method described on page 1. These triadylstilbene-based brighteners are used in the color developing solution 1 of the present invention. It is preferably used in a range of 0.2 to 20 g per Q, particularly preferably in a range of 0.4 to 10 g. The color developing solution used in the present invention has the following general formula (K-I
), (K-II), and (K-Ill) are preferably included. General formula (K-1) “A-COOM general formula (K-f
l]B POsM* In the formula, A and B each represent a -valent group or atom, and may be an inorganic substance or an organic substance. D represents an aromatic ring or an aromatic ring which may have a substituent, and M represents a hydrogen atom or an alkali metal atom. The general formula CK-1), (K-ff) or [K-! I
The chelating agent represented by t) has the following general formula (K-11/
3 to (+< -X V 3. General formula (K-TV) Mm+Pm, 01e General formula (K-V) Mn, + * Pn, Osn++ 1 General formula CK-■] A, -R, -Z-R, -COOH cycloalkylene group, phenylene group, Rt OR. -Rt OR? OR - or -R? Z R?-, Z is > N -Rt A s or > N-A
i, R3 to Rヮ each represent a substituted or unsubstituted alkylene X group, and Al-As each represents a hydrogen atom, -OH,
-Co. M or -P Os M t, M represents a hydrogen atom or an alkali metal atom, m is an integer of 3 to 6, n is 2
Represents an integer between ~20. General formula (K-■) RsN (C) M represents a hydrogen atom or an alkali metal atom. BIBy as In the formula, R9 to R1 are each a hydrogen atom, OH1 lower alkyl (unsubstituted or as a substituent -OH1-C00M or -
may have P O3M m), B, -B
s is a hydrogen atom, -OH1-C00M, -PO
s(M) or -N(J)t, J is a hydrogen atom, a lower alkyl group, CIF(, OH or -POsll)
, M represents a hydrogen atom or an alkaline metal, and n and h each represent O or 1. General formula (K-X) y K-R,, -P-0-OR,. . In the formula, Rrt and RIs each represent a hydrogen atom, an alkali metal atom, a C3-C11 alkyl group, an 01-CI2 alkenyl group, or a cyclic alkyl group. In the formula, R+4 is a C8-C0 alkyl group, a CI-CI alkoxy group, a Cl-C0 monoargylamino group, C
2-C11 dialkylamino group, amino group, C+"
C! 4 represents an aryloxy group, a C5 to C14 arylamino group, and an amyloxy group; ~Q, each represents -OH, C, ~C14 alkoxy group,
-OM, (M represents a cation), an amino group, a morpholino group, a cyclic amino group, an alkylamino group, a dialkylamino group, an arylamino group, or an argyloxy group. General formula (K-X■) In the formula, R16, R51, RI? and Ro are each hydrogen atom, halogen atom, sulfonic acid group, substituted or unQ+
(2) in Qt represents an unsubstituted phenyl group. RIg, R1゜, RIg
and Rffit each have a hydrogen atom or a carbon atom number of 1~!
8 represents an alkyl group. n represents an integer of 1 to 3. The RIgs may be the same or different. The R port is preferably a sulfonic acid group. In the formula, R13 and Rtt represent a hydrogen atom, a halogen atom, or a sulfo group. General formula (K-XV) represents a salt, W 1 , Z t and Yl each represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group or a salt thereof, an alkoxy group or Represents an alkyl group. Also, 1 is O or 1, R3
is an integer from 1 to 4, and h is! or 2, p is an integer from 0 to 3,
Q+ represents an integer from 0 to 2. Specific examples of the chelating agents represented by the general formulas CI<-rV) to (K-XV) include the following. In the formula, R1 and R3° are each a hydrogen atom, a phosphoric acid group, a carboxylic acid group, -C)-T, C00H1-'CH, PO. ■ (or a salt thereof; X is a hydroxyl group or its [
Exemplary chelating agents] (1) Na4P*O+t (3) u, p, o. (5) NaaPaO4 (2) NaaPsO@ (4) H, P, O,. POJ* oasts 0511w PO,+! . C11, C00I+ PO, I+. PO,)11 Calls -C-COO11 0allt shin! rLJ Ko■den POJ. CIl. PO311°OH (5I) H,03P-C-POjll. 110cN*c! I(O)I)-CLOP (ONg
)-110CII, C11, OP-(Oll). 110cIl*cll* OP (QNa)tCI
1,011 (63) □ I HOCH*C'C11s OP (Off)y80
CH* CHCII* OP (011)*
1+J CtltCIIt-OP (OH)2H,
N-Coo-P-(OK). H-CCoo P (Off) *O O OHOll OH C00I+ C00I+ CIItl'0slb CI1, Po, +1°CH*PO3Nal (+02) In the present invention, general formulas (K-IV), (K-V) [K
-■), (K-■), (K-IX), (K-■] or (
It is more effective to use a chelating agent represented by the general formula [K-■], [K-
(2)] or by using a chelating agent represented by (K-XV). In the present invention, particularly preferred are chelating agents (6) and (7). (14), (19), (31), (44), (81),
The method is to use a chelating agent represented by (82), (90), (94) or (99). Two or more of these chelating agents can be used in combination. The above general formulas (K-1) to (K-In
) The chelating agent represented by any of the above is preferably added in a range of +xio-' mol to 1 mol, more preferably in a range of 2XlO-4 to 1Xl0-' mol, per 1Q of color developer. , more preferably 5X
It can be added in a mole range of IO-' to 5XIO-'. CI1, COO11 The color developing solution of the present invention can be used in any p)I range, but
pHIo is preferably 9 or less, more preferably pos, a to, ? , especially preferably 10. O
Used in N10.6. If the pH exceeds 1009, staining tends to occur and is also unfavorable from the viewpoint of image preservation.
If it is below, the speed will be poor. The processing temperature for color development using the color developer of the present invention is 3.
The temperature is preferably 0°C or higher and 60°C or lower, and the higher the temperature, the more preferable it is because it enables rapid processing in a short time, but there is also the problem that the preservation property tends to deteriorate, so it is more preferably 30°C or higher.
The temperature should preferably be 5°C or lower. Furthermore, the relatively shorter one-color development processing time is, the better the image preservation is, and the more easily the effects of the present invention can be achieved.Therefore, the processing time is preferably 160 seconds or less. More preferably it is 140 seconds or less. After color development using the color developer of the present invention, processing is performed with a bleach-fix solution. As the bleach used in the bleach-fix solution, the organic acid Metal Rust J1 is preferably used, and the metal complex salt is It has the effect of oxidizing the metallic silver produced by the present process and converting it into silver halide, and at the same time coloring the uncolored part of the coloring agent. Its structure is based on organic acids such as aminopolycarboxylic acid, oxalic acid, citric acid, etc. It is made by coordinating metal ions such as iron, cobalt, and copper with acid. The most preferred organic acids used to form such organic acid metal rust salts include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. (11 ethylenediaminetetraacetic acid

[21 Diethylenetriaminepentaacetic acid 13]
Ethylenediamine-N-(β-oxyethyl)-N,N
' , N' ~ Triacetic acid [4] 1,3-propylenediaminetetraacetic acid [5
1 Nitrilotriacetic acid [61 Cyclohexanediaminetetraacetic acid [71 Iminodiacetic acid] [8] Dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyl ether diamine tetraacetic acid [1O]
Glycol ether amine tetraacetic acid 111]
Ethylenediaminetetrapropionic acid [12]; y
Enylenediaminetetraacetic acid [+3] Ethylenediaminetetraacetic acid disodium salt] 14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt (16J Diethylenetriaminepentaacetic acid pentasodium salt [17J Ethylenediamine-N-( β-oxyethyl)-N,N',N''-)-diacetic acid sodium salt [181
1,3-Propylenediamine tetraacetic acid sodium salt [181 nitrilotriacetic acid sodium salt [20] Cyclohexanediamine tetraacetic acid sodium salt Particularly preferred bleaching agents in the present invention are [+1, t2]
. [It is 101. The bleach-fix solution used contains the above-mentioned ammonium metal complexes as bleaching agents, and may also contain various additives, such as alkali halides or ammonium halides, such as potassium bromide, Rehalogenating agents such as sodium bromide, sodium chloride, and ammonium bromide. Metal salts and chelating agents can be included. In addition, p)I buffers such as borates, borage, carbonates, and phosphates, alkylamines, polyethylene oxides, and the like may be added as appropriate. Furthermore, the bleach-fix solution contains 10 sulfurous acids such as ammonium sulfite, potassium sulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, and sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, and sodium carbonate. , potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, and the like. When processing is carried out while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) contains thiosulfate and thiocyanine. & salt or F & salt, etc., or the bleach-fixing replenisher may contain these salts and be replenished into the processing bath. In order to increase the activity of the bleach and bleach-fix solutions, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or a suitable oxidizing agent, e.g. Hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate. The pH of the bleach-fix solution preferably used in the present invention is 3.0.
-8.5 is preferable, and the range of 4.0-8.0 is more preferable. If the pH of the bleach-fix solution exceeds 8.5, it tends to have an adverse effect on image storage, especially staining, and another problem is the occurrence of staining due to a decrease in stopping properties. In the present invention, after bleach-fixing, water washing or waterless washing stabilization processing is performed, and waterless washing stabilization processing is preferred from the viewpoint of improving image storage stability as described above. In the present invention, waterless washing stabilization treatment refers to immediately after treatment with a treatment liquid with fixing ability, a water washing alternative stabilization treatment using a single tank or multiple tank countercurrent system, etc. It may also include treatment steps other than general washing, such as a known washing promotion bath. In the stabilization treatment step of the present invention, the method of bringing the stabilizing solution into contact with the silver halide photosensitive material is preferably by immersing the silver halide photographic material in a bath as in a general processing solution. It may be applied to the emulsion surface of the silver halide photographic light-sensitive material, both sides of the transport leader, and the transport belt using a synthetic mM cloth, or it may be sprayed onto the transport belt.Hereinafter, when using a stabilizing bath by the dipping method I will mainly explain about. It is preferable that the stabilizing liquid contains a chelating agent having a chelate stability constant of 6 or more with respect to iron ions. Examples of the chelating agent having a chelate stability constant of 6 or more for iron ions include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, and the like. Note that the above-mentioned iron ion means ferric ion (Fe 3 .). Specific examples of compounds of chelating agents having a chelate stability constant of 6 or more with the second wheat ion include diethylenetriaminepentaacetic acid and nitrilotriacetic acid. Examples include 1-hydroxyethylidene-1,1-diphosphonic acid. The amount of the above chelating agent used is 0.01 to 11 per 11 stabilizing liquids.
50g, preferably in the range of 0.05-20g. Furthermore, preferred compounds to be added to the stabilizing solution include:
Examples include anti-spill agents, water-soluble metal salts, ammonium compounds, and the like. The above anti-piping agents include hydroxybenzoic acid compounds, phenol compounds, isothiazole compounds,
Pyridine compounds, guanidine compounds, carbamate compounds 1 Morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds, inxazole compounds, propatoolamine compounds, sulfamide compounds, amino acid compounds, and penztriazole Examples include type compounds. Note that methods for reducing magnesium and calcium as described in JP-A-63-70858 and JP-A-83-74059 are also effective for preventing bacteria. Furthermore, as metal salts, Ba, Ca, Ce, G
o, In. La, 14n, old, Pb, Sn, Zn, Ti
, Mg, An, Sr gold g salts, halides, hydroxides, sulfur m salts. It can be supplied as an inorganic salt such as carbonate, phosphate, acetate or as a water-soluble chelating agent. The amount used is IX 10-4 to IX 10-1 mo/L per 11 stabilizers (7)
aili range, preferably 4X 10-4 to 2X
10-2 mol, more preferably 8X 10-4 to IX
It is in the range of 1G-2 moles. In addition to the above compounds, the stabilizing liquid also contains optical brighteners, organic sulfur compounds, onium salts, hardeners, quaternary salts, water droplet prevention agents such as polyethylene oxide derivatives, siloxane derivatives, etc.
p)ltll of boric acid, citric acid, phosphoric acid, butyric acid, or sodium hydroxide, sodium acetate, potassium citrate, etc.
l Conditioner, organic solvents such as methanol, ethanol, and dimethyl sulfoxide, dispersants such as ethylene glycol and polyethylene glycol, and other colors 1! It is optional to add various additives to improve and extend the processing effect, such as l-regulators. The above compounds and other additives can be added to the stabilization tank as a concentrated liquid, or the above compounds and other additives may be added to the stabilizing liquid supplied to the stabilization tank and then stabilized. There are various methods, such as using it as a supply solution for the stabilizing solution, or adding it to the pre-bath of the stabilization treatment process and making it present in the stabilization tank by including it in the silver halide photographic light-sensitive material to be processed. It may be added by such an addition method. As for the method of supplying the stabilizing liquid in the stabilization treatment step, when a multi-tank countercurrent system is used, it is preferable to supply the stabilizing liquid to the rear bath and overflow from the front bath. The amount of stabilizing liquid to be replenished is preferably 3 to 50 times the amount brought in from the previous bath, more preferably 5 to 30 times. The amount of photosensitive material is generally 20 to 100 layers per rn' of photosensitive material. The pH value of the treatment liquid in the stabilizing bath is preferably in the range of pH 3 to 8.5. If the pH exceeds 8.5, the occurrence of staining, image storage stability, and dark fading will be significantly deteriorated. In addition, p
) I can be adjusted using the above-mentioned pH adjusting agent. The treatment temperature during stabilization treatment is 1, for example, 20°C to 50°C.
C., preferably in the range of 25.degree. C. to 40.degree. C., and the treatment time is preferably short from the viewpoint of rapid processing, but usually 10 seconds to 5 minutes, most preferably 15 seconds to 2 minutes. If it is too short, the image storage stability will be greatly reduced, and the length will also be slightly reduced. In the multi-vessel countercurrent system, it is preferable that the first stage be treated in a short time and the latter stage be treated for a long time. In the present invention, washing with water may not be necessary before and after the stabilization treatment, but rinsing with a small amount of water within a short time or surface cleaning with a sponge, stabilization of images, and surface physical properties of silver halide photographic light-sensitive materials. It is optional to provide a treatment tank for adjusting. Examples of agents for stabilizing the image and adjusting the surface properties of the silver halide photographic light-sensitive material include activators such as formalin and its derivatives, siloxane conductors, polyethylene oxide compounds, and quaternary salts. In the present invention, it is optional to provide additional processing steps in addition to the above processing steps. Furthermore, silver may be recovered by a known method not only from the above-mentioned stabilizing solution but also from a processing solution containing a soluble silver complex salt such as a fixing solution or a bleach-fixing solution. In addition, if the above-mentioned stabilization treatment is performed, the washing process is virtually unnecessary, so there is no need for piping equipment for washing.
This has the advantage that the device itself can be easily installed at any location. In addition to these treatments, there is a method in which the development armpit produced by color development is subjected to halogenation bleaching and then color development is performed again, and various intensification treatments (amplification treatments) described in JP-A-58-15483!3 are also available. It may be processed using a developing method that increases the amount of dye produced. Each processing step is usually carried out by immersing the photosensitive material in the processing solution, but other methods are also available, such as a spray method that supplies the processing solution in the form of a spray, or by contacting it with a carrier impregnated with the processing solution. A web method, a method of performing viscous development processing, etc. may be used. Margins Below Next, the silver halide emulsion used in the photosensitive layer of the silver halide color photographic light-sensitive material of the present invention will be described. The silver halide emulsion used in the present invention includes any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. can be used. The composition of silver halide grains may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different, or when the composition inside and outside the grain is different, The composition may change continuously or discontinuously. There is no particular restriction on the particle size of the silver halide grains, but in consideration of other photographic performance such as rapid processability and sensitivity, it is preferably 0.2 to 1.8 lm, more preferably 0.25 lm.
It ranges from 1.2 to 1.2 ru. The particle size distribution of the silver halide grains may be polydisperse or monodisperse. The silver halide emulsion used in the present invention may be obtained by any of the acidic method, neutral method, and ammonia method. The grains may be grown all at once, or after forming seed grains,
The method for producing and growing type 0 particles that may be grown may be the same or different. In addition, the methods for reacting soluble silver salts and soluble halogen salts include forward mixing method and back mixing method. PA method, simultaneous mixing method, combination thereof, etc. may be used. Furthermore, as a form of simultaneous mixing method, PA described in JP-A No. 54-48521 etc.
The g-chondral double jet method can also be used. Furthermore, if necessary, a silver halide solvent such as thioether may be used. Any shape of silver halide grains can be used. The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes. In the process of forming and/or growing silver halide grains, the silver halide emulsion used in the present invention contains cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or MIn, rhodium salt or complex salt, iron Salt or! Metal ions can be added to the interior of the particles and/or on the surface of the particles using salt, and reduction-sensitized nuclei can be added to the interior of the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. can. In the silver halide emulsion used in the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left in the silver halide emulsion. Life Disclosure 17843
It can be carried out based on the method described in No. The silver halide grains used in the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain. The silver halide emulsion used in the present invention can be chemically sensitized by conventional methods. In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensitivity methods and the like can be used alone or in combination. When employing a direct positive image forming silver halide emulsion as the silver halide emulsion, for example, an internal latent image type silver halide emulsion can be used, for example, US Pat.
So-called converted silver halide emulsions according to the conversion method described in No. 50, or U.S. Pat.
[f, 31E1, 3,317,322 and 3,
Silver halide emulsions having internally chemically sensitized silver halide grains as described in U.S. Pat. No. 3,271,157, U.S. Pat. Silver halide emulsions having silver halide grains incorporating polyvalent metal ions as described in US Pat. Silver halide emulsions whose grain surfaces are weakly chemically sensitized, or JP-A Nos. 50-8524, 50-38525, and 53
So-called core-shell type silver halide emulsions produced by the lamination method described in No. 2408 and No. 83-5342,
Others JP-A-52-156814, JP-A No. 55-1275
Silver halide emulsions described in No. 49 and No. 57-79840 can be used. In this case, the internal latent image type silver halide emulsion is preferably one made of laminated grains, and it is particularly preferred that the shell contains at least 20 mol % or more of the silver chloride emulsion. When using internal latent image type silver halide emulsions, the emulsions contain stabilizers that are commonly used, such as compounds with azaindene rings, in order to keep the surface sensitivity as low as possible and to impart lower minimum density and more stable properties. and a heterocyclic compound having a mercapto group. In the case of a surface latent image type silver halide emulsion, it is preferable to contain at least 90 mol % or more of silver chloride from the viewpoint of rapidity and image storage stability. In the silver halide color photographic light-sensitive material of the present invention, the following sensitizing dyes can be used to form at least 3N silver halide emulsion layers having mutually different spectral sensitivities. Useful sensitizing dyes used in blue-sensitive silver halide emulsion layers include, for example, West German Patent No. 9211.080, US Pat. No. 2,231,858, US Pat.
No. 2.503,776, No. 2,518,001,
2,912.32!3, 3,853!35iII
No. 3,872,897, No. 3.4194.217
No. 4,025,349, No. 4,046,572
No., British Patent No. 1,242,588, Special Publication No. 1977-14
Typical examples include those described in No. 030 and No. 52-24844. In addition, useful sensitizing dyes used in green-sensitive silver halide emulsions include 5, for example, U.S. Pat. No. 1.939,201;
No. 2,072,808, No. 2,739,149,
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in 2J45,783 and Fukoku Patent No. 505,979. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat. No. 2,289,234;
No. 2,270,378, No. 2,442,710,
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent No. 2,454,829 and Japanese Patent No. 2,776.280. Furthermore, U.S. Pat. No. 2,213,995,
Green-sensitive silver halide emulsions or red-sensitive silver halide emulsions are prepared using cyanine dyes or composite cyanine dyes such as those described in Patent No. 2,493,748, No. 2,519,001, and West German Patent No. 929,080. It can be advantageously used in emulsions. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is
No. 3-4932, No. 43-4933, No. 43-493
No. 8, No. 44-32753, No. 45-25831,
No. 45-28474, No. 4B-11827, No. 4B
-18107, 47-8741, 47-111
No. 14, No. 47-25379, No. 47-37443, No. 48-28293, No. 48-3840E1, No. 48-38407, No. 48-38408, No. 48-
No. 41204, No. 49-8207, No. 50-4086
No. 2, No. 53-12375, No. 54-34535,
No. 55-1589, JP-A No. 50-33220, No. 5
No. 0-33828, No. 50-3852θ, No. 51-
No. 107127, No. 51-115820, No. 51-1
No. 35528, No. 51-151527, No. 52-23
No. 931, No. 52-51932, No. 52-10491
No. 8, No. 52-104917, No. 52-109!12
No. 5, No. 52-110818, No. 54-80118, No. 5B-25728, No. 57-1483, No. 58
-10753, 58-91445, 58-15
No. 3928, No. 59-114533, No. 511-1
No. 1845. US Pat. No. 59-11H47, US Pat. No. 2.888.545, US Pat. No. 2.977.229, US Pat. No. 3,397,080, US Pat. No. 817,293, No. 3.628,984,
3,886,480, 3. F372,888, F3,879,428, F3,703,377,
It is described in No. 3,7811,301, No. 3,814,809, No. 3,837,882, and No. 4,026,707. Examples of dyes that do not themselves have a spectral sensitizing effect, or substances that do not substantially absorb visible light and exhibit supersensitization, are used with sensitizing dyes, such as aromatic organic acid formaldehyde condensates ( For example, US Patent 3,4
73,510), cadmium salts, azaindene compounds, aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g., those described in U.S. Pat. No. 2,933,390 and U.S. Pat. No. 3,835,721) U.S. Patent Nos. 3,815,813, 3,815,841, 3,817,295, and 3,835,721, etc.
The combinations described in this issue are particularly useful. In addition to the one or more additives mentioned above, commonly used additives can be used in the silver halide color photographic material of the present invention. In addition to the emulsion layer forming an image-bearing layer on the support, the silver halide color photographic light-sensitive material of the present invention may optionally include a filter layer, an intermediate layer, a protective layer, a subbing layer, and a backing layer. Various photographic constituent layers such as anti-halation, anti-halation layer, etc. may be formed. Although any support can be used, representative examples include baryta paper, polyolefin laminated paper such as polyethylene, polyethylene terephthalate film kneaded with white pigment, and the like. The silver halide color photographic light-sensitive material of the present invention has at least three light-sensitive layers having different spectral sensitivities, one layer is a blue-sensitive silver halide emulsion layer, and the other layer is a green-sensitive silver halide emulsion layer formed by a sensitizing dye. A green-sensitive silver halide emulsion layer with maximum sensitivity to red light, and a red-sensitive silver halide emulsion layer with maximum sensitivity to red light with the remaining sensitizing dye. Examples of preferred layer configurations, including combinations of the spectral sensitivities of the above three layers and the hue of the image, are given below, where it is preferable to have spectral sensitivities that do not easily cause color mixture when exposed to light having a spectral distribution. The light-sensitive material of the present invention can be exposed using NTji waves in the spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, and electron beams. Any known light source can be used, such as light emitted from a phosphor excited by X-rays, gamma-rays, alpha-rays, or the like. The silver halide color photographic light-sensitive material of the present invention has a structure having each of blue-sensitive, green-sensitive and red-sensitive color-sensitive layers that ordinary color paper has, and the filter (optical filter) is a three-color separation filter, such as Wratten N.
o, 25. No, 29°No, 58. No, 81.
No, 478. No, 98. No. 98 can be used. When the image forming layer of the light-sensitive material of the present invention is an internal latent image type/\silver halide emulsion layer and a positive image is directly formed using this, the main process is to form an internal latent image type that has not been fogged in advance. It is common to carry out surface development of a silver halide photographic light-sensitive material after subjecting it to a fogging process after image exposure or while subjecting it to a fogging process. The fogging process can be carried out by providing uniform exposure over the entire surface or by using a fogging agent. In this case, the entire surface uniform exposure is preferably carried out by immersing or moistening the image-exposed internal latent image type silver halide photographic light-sensitive material in a developer or other aqueous solution, and then uniformly exposing the entire surface. The light source used here may be any light within the wavelength range to which the internal latent image type silver halide photographic light-sensitive material is sensitive; it may also be irradiated with high-intensity light such as flash light for a short period of time, or It is possible to irradiate weak light for a long time, and the time for uniform exposure over the entire surface depends on the internal H3 image type silver halide photographic light-sensitive material, development processing conditions, and the type of light source used, so that the best positive image can be obtained in the end. can vary widely. Further, a wide range of compounds of class a can be used as the above-mentioned fogging agent, and this fogging agent only needs to be present during development processing, for example, in an internal latent image type silver halide photographic light-sensitive material such as a silver halide emulsion layer. Alternatively, it may be contained in a developing solution or a processing solution prior to development processing, but it is preferably contained in an internal latent image type silver halide photographic light-sensitive material (
Among these, when added to a silver halide emulsion layer, the amount used can be varied over a wide range depending on the purpose. 1 to 1500 mg per mole of s,
Particularly preferably 10 to 1000 mg. In addition, the preferable amount of addition when adding to a processing solution such as a developer is 0.01
~5g/1, particularly preferably 0.08~O, 15g/1
It is i. Such fogging agents include 1, for example, US Pat.
．． 5H,785, 2,588,882 and JP-A-63-23 [103B], or the hydrazides or hydrazone compounds described in U.S. Pat. No. 3,227,552, and Patent 3,81
No. 5,815, No. 3.718,470, No. 3.711
No. 1,494, No. 3,734,738 and No. 3,75
Examples include heterocyclic quaternary nitrogen compounds described in U.S. Pat. These fogging agents can also be used in combination.For example, Research Disclosure
Closura) No. 15162 does not mention the use of non-adsorbent fogging agents in combination with adsorption fogging agents1.
It can also be applied to the present invention. Also, Japanese Patent Publication No. 63-2213652
The nucleation accelerators described in the above are also preferably used in the present invention. Specific examples of useful fogging agents include hydrazine hydrochloride,
Phenylhydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-formyl-2-(4-methylphenyl)hydrazine, 1-acetyl-2-phenylhydrazine, 1-acetyl-2-(4-acetamidophenyl)hydrazine, 1-methylsulfonyl-2-phenylhydrazine, l-benzoyl-2-7enylhydrazine, 1-
Examples include hydrazine compounds such as methylsulfonyl-2-(3-phenylsulfonamidophenyl)hydrazine and formaldehyde phenylhydrazine. Yellow couplers that can be used include closed ketomethylene compounds, active point -0-7 aryl substituted couplers called so-called 2-equivalent type couplers, active point -low acyl substituted couplers, active point hydantoin compounds substituted cab, ra, and active point urazole compounds. Substituted couplers and active point succinimide compound substituted couplers, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -O-sulfonyl substituted couplers, etc. can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Pat. No. 2,875,057, U.S. Pat. , No. 3,725,072, No. 3
．． 8!31,445, West German Patent No. 1.547,888, West German Patent Application No. 2.2111,1117, West German Patent No. 2.28
No. 1,381, No. 2,414,006, British Patent No. 1,425,020, Japanese Patent Publication No. 10783/1983, Japanese Patent Publication No. 28133/1983, No. 48-73147, No. 5
No. l-10263fi, No. 504341, No. 50-1
No. 23342, No. 50-130442, No. 51-21
No. 827, No. 50-87850, No. 52-82424
No. 52-115219, No. 5B-95346, and the like. Particularly preferred yellow couplers for the present invention are yellow couplers 1-1-I-50 represented by the general formula [I] described in Japanese Patent Application No. 146096/1982. By using the above-mentioned yellow coupler, the hue is improved, and in particular, the hue of the color image obtained by printing and the hue of the color image generated from the coupler are extremely similar, so that a desirable color tone can be provided. Magenta couplers that can be used include pyrazolone,
Examples include pyrazolotriazole, pyrazolinobenzimidazole, and indacylon compounds. These magenta couplers are similar to the yellow couplers 4
Specific examples of magenta couplers that can be used include not only equivalent type couplers but also Zmffi type couplers, as described in U.S. Pat. Nos. 2,600,788 and 2,883,8
No. 08, No. 3,0132,853, No. 3,127,2
No. 89, No. 3,311,478, No. 3.418,39
No. 1, No. 3,519,429, No. 3,558,31
No. 9, No. 3,582,322, No. 3,615.5
0fi No. 3,834,908, No. 3,891,4
No. 45, West German Patent No. 1.810,484, West German Patent Application (OLS) 2, No. 408.685. No. 2,417,945, No. 2,418,958, No. 2,424,487, Japanese Patent Publication No. 40-8031, Japanese Patent Publication No. 20828-1982, No. 52-58!322, No. 4
No. 9-129538, No. 49-74027, No. 50-
No. 159338, No. 52-42121, No. 49-74
No. 028, No. 50-60233, No. 51-28541
No. 53-55122, patent application No. 55-110114
Examples include those described in No. 3 and the like. A particularly preferable magenta coupler is disclosed in Japanese Patent Application Laid-open No. 83-108855 (!8510-5), which has good single image storage stability and color tone.
This is a magenta coupler represented by the general formula [M-1] described on page 18). Examples of cyan couplers that can be used include phenolic and naphthol couplers. These cyan couplers are not limited to 4-power I-type couplers like the yellow couplers, but may also be 2-power couplers. Specific examples of cyan couplers that can be used include U.S. Pat. No. 2.38'a, 928; 2,434,2
No. 72, No. 2,474,283, No. 2,521,90
No. 8, No. 2,885,828, No. 3.034,892
No. 3,311.47f1, No. 3,458,31
No. 5, No. 3,478,583, No. 3,583,971
No. 3.591,383, No. 3. ? H, No. 411,
No. 3,772,002, M 3,933,4134, No. 4,004,929, West German patent W1 (OLS)
2.4, No. 830, No. 2,454.3211, JP-A-48-59838, No. 51-2 [1034, No. 1034]
No. 48-5055, No. 51-148827, No. 52-
No. 88824, No. 52-130832, No. 58-95
Examples include those described in Japanese Patent Publication No. 348, Japanese Patent Publication No. 49-11572, and the like. Particularly preferable cyan couplers are the general formulas [C-1] and [C
-2] is a cyan coupler. In the silver halide emulsion layer and other photographic structure T& layers, couplers such as colored magenta or colored cyan couplers, polymer couplers, etc. may be used in combination.For colored magenta or colored cyan couplers, patent application filed in 1983 by the present applicant -193811, and regarding the polymer coupler, there is a patent application filed by JI JI in 1983.
-172151 can be referred to. Although the amount of the above coupler added is not limited, it is preferably lXl0-3 to 5 mol per mol of silver, more preferably l
Xl0-2 to 5 X 10-1 mol. The coupler used in the present invention can be introduced into the photosensitive material by a known method, and the high boiling point solvent can be used, for example, in US Pat.
No. 22,027. Particularly preferable high boiling point solvents are represented by the general formula [II] or [ml (11-1) described in Japanese Patent Application No. 83-148098.
~(m-94) This is a compound shown in the following formula, and is preferable in terms of providing good color tone and image storage stability. The silver halide color photographic light-sensitive material to which the present invention can be applied may contain various other photographic additives. Agents, color stain inhibitors, optical brighteners, one-color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like can be used. Supports for silver halide color photographic light-sensitive materials include reflective supports and transparent supports such as baryta paper and polyethylene-coated paper, and these supports are appropriately selected depending on the intended use of the light-sensitive material. In the photosensitive material to which the present invention can be applied, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and additional layers such as a filter layer, anti-curl layer, protective layer, antihalation layer, etc. They can be used in appropriate combinations as constituent layers. In these constituent layers, wood-philic colloids that can be used in the emulsion layer as described above can be similarly used as a binder, and can also be contained in the emulsion layer as described above. Various photographic additives can be included. AI is used in photosensitive materials to improve so-called sharpness and adjust sensitivity.
Dyes can be used, but stains tend to occur when AI dyes are used, and dyes of the general formula [AI-I], [AI-■], [AI-m] or [ A I IV] This is likely to occur when an AI dye is contained. Therefore, in the present invention, staining is less likely to occur even when the above-mentioned dye is used, and the image storage stability is also slightly improved. The photosensitive material may contain a DIR compound, and in addition to the DIR compound, it may also contain a compound that releases a development inhibitor during development; for example, as described in U.S. Pat. .379,521, West German Patent Application (OLS) No. 2,417,914. JP-A-52-15271, JP-A No. 53-9118, JP-A No. 5
Examples include those described in No. 9-123838 and No. 59-127038. The above DIR compound is a compound capable of releasing a development inhibitor or a development inhibitor precursor by reacting with an oxidized form of a color developing agent, and may be a non-diffusible DIR compound or a diffusible DIR compound. . A typical example of such an IR compound is a DIR coupler in which a group capable of forming a compound having a development inhibiting effect when separated from the active site is introduced into the active site of the coupler. No. 454, US Pat. No. 3,227,554, US Pat. No. 4.0!15,984, US Pat. No. 4,149,888, etc. The above-mentioned DIR coupler has the property that, when subjected to a coupling reaction with an oxidized form of a color developing agent, the coupler core forms a dye while releasing a development inhibitor. Additionally, the present invention is based on U.S. Patent No. 3. [i52,345 No. 3,1328.0
No. 41, No. 3,958.9! No. 33, No. 3,1361.
No. 959, No. 4,052,213, Japanese Unexamined Patent Publication No. 1983-11
No. 0529, No. 54-13333, No. 55-1812
It also includes compounds that release a development inhibitor when subjected to a coupling reaction with an oxidized form of a color developing agent, such as those described in No. 37, but do not form a dye. Furthermore, JP-A-54-145135 and JP-A-56-1
When reacted with oxidized color developing agents such as those described in No. 14948 and No. 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction. Or so-called timing D, which is a compound that releases a development inhibitor through an elimination reaction.
It may also be an IR compound. Also, JP-A-58-180954, JP-A No. 58-18294
Timing DI in which a timing group as described above is bonded to a coupler core that produces a completely diffusible dye when reacted with an oxidized color developing agent described in No. 9.
It may also be an R compound. The light-sensitive materials that can be applied in the present invention include color paper, color reversal paper, color direct positive light-sensitive material, color positive film, and color negative film, but it is preferably applied to color paper and color direct positive light-sensitive material. In the following margin [Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. Example 1 Equimolar amounts of silver nitrate aqueous solution and potassium bromide aqueous solution were simultaneously added to gelatin aqueous solution at 50°C for about 50 minutes by double jet method to obtain cubic silver bromide particles with an average particle size of 0.3 gm. An emulsion was obtained. To this emulsion, a silver nitrate aqueous solution and a sodium chloride/potassium bromide mixed aqueous solution (molar ratio 1:1) were added simultaneously to obtain an average grain size of 0.45 l.
A cubic core/shell type emulsion (EX-1) consisting of a silver bromide core and a silver chlorobromide shell of Lm was prepared. RD-1°RD- suitable for each photosensitive layer of the above emulsion
After spectral sensitization by adding sensitizing dyes No. 2, GO-1, and BD-1, each layer of the formulation shown below was coated to construct a silver halide color photographic material for use as a sample. *Additional amount is based on silver equivalent. RD-1 RD-2 RD-1 RD-1 I-1 I-2 C-1 e C-1 C-2 o-1 S-2 T-1 T-4 A-1 CH1+ Q) O-2 T -2 HA-2 UV-1 UV-2 u Csl(, (t) A-1 2H5 OH2(:00CH-CHCsH odor A-2 First layer to first θ layer on the surface of a support whose both sides are laminated with polyethylene A color photographic paper was produced by coating the paper according to the composition shown in the table above. At this time, 5A-1 and 5A-2 were used as coating aids, and HA-1 and HA-2 were used as hardeners. The degree of swelling was varied as shown in Table 1. The dry film thickness was 12 liters. The internal latent image type direct positive silver halide color photographic photosensitive material No. 4 prepared as above was exposed through wedge exposure. These exposed samples were processed in the following processing steps. Processing steps (processing temperature and processing time) (1) Immersion (coloring lyophilic) 37°0 12 seconds (2)
Fog exposure -1 lux 112 seconds (3) Color development 37℃ 1 minute 35 seconds (4) Bleach fixing 35℃ 45 seconds (5) Stabilization 25-30℃ 1 minute 30 seconds (6) Drying
75-80°C 45 seconds [Color developer] Benzyl alcohol Ge2(SOs)3 Ethylene glycol Potassium sulfite Potassium bromide Sodium chloride Potassium carbonate T-4 Hydroxylamine sulfate Diethylenetriamine Sodium pentaacetate Developing agent Exemplary compound (3) 15 l2 0.015 g 81 sentences 2.5 g 0.6 g 0.2 g 25.0 g 0.1 g 5.0 g 2g 1.5X 10-'Molar optical brightener ( 4,4'-diaminostilbendisulfone i!iS derivative) t,o g Potassium hydroxide 2.0 g Diethylene glycol Add 15 portions of water to make a total of 1 portion, p
Adjust to H10,15. [Bleach-fix solution] Ferric ammonium diethylenetriaminepentaacetate 90 g diethylenetriaminepentaacetic acid 3 g ammonium thiosulfate (70% solution) 180 m ferric ammonium sulfite (40 g
% solution) 27.5 m 3-mercapto-1,2
, 4-) Su7sol 0.15 g Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total amount to 11. [Stabilizing liquid] Ortho phenylphenol 0.3s Potassium sulfite (50% solution) 12M ethylene glycol to gl-hydroxyethylidene-1,1-diphosphonic acid 2.5g Bismuth chloride 0.2g Zinc sulfate 7
Water salt 0.7g Ammonium hydroxide (28% aqueous solution) 2.0g Polyvinylpyrrolidone (K-I7) 0.2g Optical brightener (4,
2 g of 4°-diaminostilbendisulfonic acid derivative) Add water to bring the total amount to IfL, and adjust p)I to 7.5 with ammonium hydroxide or sulfuric acid. Note that the stabilization treatment was performed using a countercurrent method with a two-tank configuration. place! The sample was stored for one week under xenon lamp irradiation, and changes in yellow, magenta, and cyan dye density were measured using a spectral reflection densitometer PDA-85 (manufactured by Konica). The results are shown in Table 1. As is clear from the results in Table 1, it can be seen that when the degree of swelling is 3.5 or less, especially in the range of 1.5 to 3.5, the image preservation property is good, and when it is 4.0 or more, it is rather deteriorated. On the other hand, if the degree of swelling is too low, it tends to deteriorate. Example 2 The dry film thickness of the photosensitive material (1-4) used in Example 1 was varied as shown in Table 2, and the swelling degree was adjusted to Ii1!
! The same evaluation as in Example 1 was performed by adjusting the amount of membrane agent and gelatin. The results are shown in Table 2. As is clear from Table 2, it can be seen that the image storage stability is good when the dry film thickness is 17 gm or less, preferably +5 JLm or less. It can be seen that when the dry film thickness is 19 pm or more, the image preservability deteriorates significantly. Example 3 The silver halide color photographic light-sensitive material used in Example 1 was continuously processed until three times the amount of the color developer tank was replenished. The processing steps are the same as in Example 1, and the replenishment fi
t (per rn' of photosensitive material), tank capacity, and composition of each processing solution are as follows. The amount brought in from the main solution was 35 i/ml. The composition of each treatment liquid is as follows. [Color developer tank liquid] Same as Example 1 [Color developer replenisher] Benzyl alcohol Ge2(Sow)3 Ethylene glycol Potassium sulfite Potassium bromide Sodium chloride Potassium carbonate S? -4 Hydroxylamine sulfate diethylenetriamine sodium pentaacetate 2g Developing agent (exemplary compound (3)) +, ax + o - 2 mol Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0. Diethylene glycol 18.0 g Add water to bring the total amount to 11, and add KOH or H2SO4 to 18.5
m sentence 0.015 g 0 g 2.5 g 0.3 g 0.2 g 25.0 g O, 12 g 5.0 g P) Adjust to 110.35. [Bleach-fixing tank liquid and replenisher] Same as Example 1 [Stabilizing tank liquid and replenisher] After the same running treatment as in Example 1, evaluation was performed in the same manner as in Example 1, and the results were almost the same as in Example 1. I was able to obtain the following results. Example 4 Using sample 1-4 of Example 1, the developer concentration and type of the five color developing solutions were changed as shown in Table 4, and the color tone and image storage stability were evaluated. The color tone was visually observed to determine whether it was suitable as a color proof for the printing process. X: Unsuitable Δ: Fairly good O: Good ■=Very good The results are shown in Table 4. DP-1 As is clear from Table 4, even if the developing agent of the present invention is used, the color tone will be inferior if the amount added is outside the scope of the present invention, and when a developing agent other than the present invention is used, both the color tone and image storage stability will be significantly inferior. I understand that. Example 5 On a paper support laminated on both sides with polyethylene, the following Ja layers were sequentially coated to prepare a negative silver halide color photographic light-sensitive material. A 1-4 As a hardening agent, 2.4-dichloro-6-hydroxy-5-) riazine sodium was added in layer 2, layer 4, and layer 7 in an amount of 0.017 g per 1 g of gelatin, respectively. Added, IJM moisture level 3.0. The dry film thickness was 11 mm. The silver halide color photographic light-sensitive material prepared as described above was exposed and processed in the first processing step. Processing steps (38°C) Color development 2 minutes bleach-fixing 45 seconds stabilization 1 minute 30 seconds drying 60-80°C 45 seconds The color developer, bleach-fix solution and stabilizing solution were the same as in Example 1. Created. After development, changes in yellow density and color tone were evaluated in the same manner as in Example 4. However, regarding image storage stability, in addition to photobleaching, dark fading at 50° C. 75% If) I was also evaluated. The results are shown in Table 5. As is clear from Table 5, by using a yellow coupler and a high boiling point solvent, which are preferable for the present invention, the image storage stability and color tone are good, and this can be said to be a preferable embodiment for carrying out the present invention. In the table, "1" indicates the compound described in Japanese Patent Application No. 1480/1980!30. B5-1 B5-2 Example 6 In Examples 1 and 5, when a water washing bath (flow rate of IOJL/m'') was used instead of the waterless washing stabilizing bath, the photobleaching property deteriorated by about 10 to 20%. Therefore, as an embodiment of the present invention, it is preferable to use an anhydrous washing stabilizing bath. Example 7 In Example 5, the processing liquid and processing steps were the same as in the color photosensitive material (5-1) used in Example 5. The process was carried out in the same manner as in Example 5 except that the pH of the processing solution was changed as shown in Table 6, and the image storage stability and staining immediately after processing were evaluated. C7reenm degree P[]]A-65
(manufactured by Konica). The results are shown in Table 6. As is clear from Table 6, when the pH of the color developing solution is 10.8 or less - 9.8, the bleach-fixing solution has a pH of 8.5 or less, and the anhydrous washing stabilizer has a pH of 8.5 or less, the image storage stability is improved. Both conditions are good, and this can be said to be a preferred embodiment for carrying out the present invention. Example 8 Color tone, speed, maximum yellow density, and image storage stability (photobleaching of yellow density) when the color development processing time was changed as shown in Table 7 in Example 5, and the developing agent was also changed. evaluated. As photosensitive material No. 4, Sample No. 5-1 was used. The results are shown in Table 7. As is clear from Table 7, when the one-color development processing time is 160 seconds or less, image storage stability is improved by using the developing agent of the present invention, and speed is hardly impaired. DP-1, which has excellent speed, has problems with both color tone and image storage stability, but Dr-1, which has excellent single-image storage stability,
It can be seen that 2 has problems with color tone and speed. DP-2 Example 9 When 200 mg of each of the following structures was added per mole of halogenated IR to the first layer, third layer, and 5R, and the same evaluation as in Example 5 was performed, similar results were obtained. Obtained. Example 10 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
0,000, density 0.95 polyethylene 200 parts by weight and average molecular weight 2,000, density 0.80 polyethylene 20! 6.8% by weight of anatase-type titanium oxide was added to the mixture of i part of titanium oxide and coated on the surface of high-quality paper with a weight of 170g/m' to a thickness of 0.035mm using an extrusion coating method.
A +em coating layer was formed, and a coating layer with a thickness of 0.040 mm was provided on the jI side only by polyethylene. The polyethylene-coated surface of this support was pretreated by corona discharge, and then the following layers were sequentially applied. 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 350 g of gelatin per mol of silver halide, and the following per mol of silver halide The sensitizing dye of the structure [I] was sensitized using 2.5X 10-4 mol (using isopropyl alcohol as solvent) and dissolved and dispersed in dibutyl phthalate 2,
200 mg/m' of 5-di-t-butylhydroquinone and [Y-1] of the following structure as a yellow coupler were contained at 2.0xlO-1 mole per mole of silver halide, and applied to give a silver amount of 3oomg/rn'. has been done. 2nd layer Dissolved and dispersed in dibutyl phthalate, monooctylhydroquinone 300g/rn', 2-(2''-hydroxy-3',5'-di-t-
butylphenyl)benzotriazole. 2-(2'-hydroxy-5'-dobutylphenyl)benzotriazole, 2-(2''-hydroxy-3'-
t-butyl-5'-methylphenyl)-5-chloro-benzotriazole and 2-(2'-hydroxy-3',
Mixture of 5'-di-t-butylphenyl)-5-chloro-benzotriazole (1:1:1:1)
Gelatin 1 in sulceratin layer containing 200mg/m'
900 mg/m''. Third layer: A green-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 0.5 mol % of silver bromide, where the emulsion contains 1 mol of silver halide. Sensitized using 2.5X 10-4 moles of sensitizing dye [II] having the following structure per mole of silver halide, containing 450 g of gelatin per mole of silver halide, dissolved in a solvent consisting of dibutyl phthalate and tricresyl phosphate in a ratio of 2:1. 2,5-di-t-butylhydroquinone and magenta coupler [M-1] having the following structure were contained in an amount of 1.5X 10-1 mol per mol of halogenated #1i, and the amount of silver was 230 mg/r.
nj, A I dye was applied at a concentration of 50 mg/m'. In addition, 0130 mol of 2,2.4-trimethyl-8-lauryloxy-7-t-octylchroman was added per 1 mol of coupler as an antioxidant. 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, 2-(2'-hydroxy-5'-dobutylphenyl)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)
It is a gelatin layer containing 500 mg/rn', and gelatin! 900 I1g/m''. Fifth layer: A red-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 0.5 mol% of silver bromide. 2,5-di-t containing 500 g of gelatin per mole and sensitized using 2.5X10-5 moles of a sensitizing dye [m] having the following structure per mole of silver halide, dissolved and dispersed in dibutyl phthalate. -Butylhydroquinone 1501g/r
n' and [C-1] having the following structure as a cyan coupler, containing 3.5×10 moles per mole of silver halide,
The amount of silver is 280 mg/g/m'', and the AI dye is applied to be 40 g/m''. 6th layer: This is the gelatin layer, and the gelatin is applied to be 800 g/rrl. Each The silver halide emulsions used in the light-sensitive emulsion layers (layers 1, 3, and 5) were prepared by the method described in Japanese Patent Publication No. 7772/1983, and each emulsion was prepared using sodium thiosulfate pentahydrate. Chemically sensitized and 4-hydroxy-8- as a stabilizer
Methyl-1,3,3a,? - Tetrazaindene (2.5 g per mole of silver halide), bis(vinylsulfonylmethyl) ether was added as a hardening agent, the 1Ii1 measurement was changed as shown in Table 8, and saponin was further added as a coating aid. Ta. Note that the dry film thickness was 11. Margin sensitizing dye [1] [Y-1] Sensitizing dye [11] [M-1] Sensitizing dye [m] C1! [C-1] After exposing the color paper produced by the above method, it was processed using the following processing steps and processing liquid. Processing steps (1) Color development 35°C 45 seconds (2) Bleach fixing 35°C 45 seconds (
3) *Water washing 30°0 1st tank 30 seconds 2nd tank
30 seconds (4) Drying 60°C to 80°C for 1 minute and 30 seconds This is also called waterless stabilization treatment. [Color development tank liquid] Ethylene glycol 10° Exemplary compound [11-7] 0. :Jg potassium bromide 0.01g potassium chloride 2.3g potassium sulfite (5
0% solution) 0.5g + Illustrated compound (3) of color developing agent DP-1 = I/l (molar ratio)
2, OX 101 mol Diethyl hydroxylamine (85%) 5.0 g Triethanolamine lo, 0 g Triethylenediamine 5.0 g Potassium carbonate 30 g Ethylenediaminetetraacetic acid Lithium acetate ill 2.0 g Fluorescent brightener (P manufactured by Otansha Co., Ltd.
K-Cone) 2.0g of water was added to make a final solution, and the pH was adjusted to 10.10 with potassium hydroxide or sulfuric acid. [Bleach-fixing tank solution] Ferric ammonium ethylenediaminetetraacetate dihydrate 80.0g diethylenetriaminepentaacetate 12-iron ammonium ethylenediaminetetraacetate Ammonium thiosulfate (70% solution) Ammonium sulfite (40% solution) p with aqueous ammonia or glacial acetic acid) Add water with I 5.50 to bring the total volume to 11. [Water tank liquid] Ortho-phenylphenol 5-chloro-2-methyl-4-inthia 80.0g 3.0g 100.0g Adjust to 27.5m 1.0g Zolin-3-one 0.02゜2 −
Methyl-4-inchazolin-3-one 0.02゜ethylene glycol 1.0g 2-year-old cutyl-4-isothiazolin-3-one
0.01゜l-hydroxyethylidene-
1,1-diphosphonic acid (60% aqueous solution) 3.0゜Bi
C sentence 3 (45% aqueous solution) O, [15g
HgSOg・7H20Q, 2g PVP (polyvinylpyrrolidone) 1.0g
Ammonia water (ammonium hydroxide 25% aqueous solution) 2.5゜Nitrilotriacetic acid trisodium salt 1.5g Make one sentence with water, and adjust to pH 7.8 with ammonia water and sulfuric acid. After the silver halide color photosensitive material was optically exposed, it was treated with the above processing solution and evaluated in the same manner as in Example 1. The results are shown in Table 8. As is clear from the results in Table 8, it can be seen that image storage stability is good when the degree of swelling is 3.5 or less, particularly in the range of 1.5 to 3.5. Example 11 In Example 10, the magenta couplers were M-2 to
Replaced each with M-11, cyan coupler was applied for in 1986.
C-1, C-3, C-19, C-30, C in the compound described on pages 76 to 124 of Specification No. -82855
Evaluations were conducted in the same manner as in Example 10, except that CC-58, C-76, or CC-2 or CC-a shown on pages 81 to 85 of the same specification were used. As a result, the photobleaching property was improved by about 10% and the color tone was also at a slightly better level.

Claims (1)

[Scope of Claims] 1. A method for processing a silver halide color photographic light-sensitive material in which the silver halide color photographic light-sensitive material is subjected to color development treatment and then immediately subjected to bleach-fixing treatment, wherein a photographic emulsion of the silver halide color photographic light-sensitive material is provided. The dry film thickness of the layer is 17 μm or less, and the degree of swelling of the photographic emulsion layer is 3.5 or less,
A method for processing a silver halide color photographic material, wherein the color developing solution contains at least 7.0 x 10^-^3 mol/l of a color developing agent represented by the following general formula (I). General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [R_1 is an alkyl group having 1 to 4 carbon atoms that may have a substituent, and n is an integer of 1 to 4. HX is salt. 2. The method for processing a silver halide color photographic material according to claim 1, wherein the color developing solution has a pH of 10.9 or less. 3. The method for processing a silver halide color photographic material according to claim 1 or 2, wherein the processing time of the color development processing is 160 seconds or less. 4. The method for processing a silver halide color photographic material according to claim 1, 2 or 3, wherein the pH of the bleach-fix solution is 3.0 or more and 8.5 or less. 5. The development process comprises a color development process, a bleach-fixing process, and a water-free washing stabilization process, and the pH of the bleach-fix solution and the water-free washing stabilizing solution are each 8.5 or less. A method for processing a silver halide color photographic material according to claim 1, 2 or 3. 6. A halogen-based silver halide color photographic light-sensitive material in which the dry film thickness of the photographic emulsion layer is 17 μm or less and the degree of swelling of the photographic emulsion layer is 3.5 or less is subjected to bleach-fixing treatment immediately after color development treatment. A color developing treatment agent composition used for processing silveride color photographic materials, the composition having the following general formula (
I) of at least 7.0 x 10 color developing agents
A color developing processing agent composition characterized in that it contains ^-^3 mol/l. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [R_1 is an alkyl group having 1 to 4 carbon atoms that may have a substituent, and n is an integer of 1 to 4. HX is salt. 7. The color developer composition according to claim 6, wherein the color developer has a pH of 10.9 or less.