JPH0389339A - Method for processing silver halide color photograhic sensitive material - Google Patents

Abstract

PURPOSE:To obtain stable photograhic characteristics without imapairing rapidity by inocrporating silver halide particles having >=90mol% silver chloride content into a silver halide emulsion, forming an arom. primary amine color developing agent of a specific color developing agent and specifying the amt. of the replenishing liquid of a color devloping agent to <=120ml/m<2>. CONSTITUTION:The silver halide particles having at least 90mol% silver chloride content is incorporated into the silver halide emulsion at the time of subjecting the silver halide color photographic sensitive material having silver halide emulsion layers on a base to imagewise exposing, then developing the same with the color developing soln. contg. the arom. primary amine color developing agent and continuously processing while replenishing the replenishing liquid thereof. Further, the arom. primary amine color developing agent is formed of the color developing agent expressed by formula I and the amt. of the replenishing liquid for the color developing agent is specified to <=120ml/m<2>. In the formula I, R<1> denotes a hydrogen atom or methyl group; X denotes a sulfate, hydrochloride or P-toluene sulfonate. The replenishing amt. of the color developing soln. is drastically decreased in this way without impairing the rapidity of the processing and the stable photographic characteristics are obtd.

Description

[Detailed description of the invention]

[Business use I? ] The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically to a silver halide color photographic light-sensitive material that can form a stable t1 color photographic image in an am manner even if the amount of replenishment is extremely changed. Regarding the lAl1 method. [Background of the Invention 1] Generally, when processing a silver halide color photographic light-sensitive material (hereinafter referred to as a photographic material), in order to keep the composition of the color-forming IJi image solution constant and maintain photographic performance, a fixed amount per unit area of the photographic material is used. The developer replenisher is replenished. The composition of the developer changes due to photographic processing, and the photographic performance also changes. For example, the m degree of the color developing agent is consumed and reduced by the reaction, and the concentration of the inhibitory halide is eluted from the photographic material by the reaction and increases. Therefore, the activity of current *i will change and become inactive if nothing is done. As a method for preventing such inactivation, for example, German Patent Application No. 2,007,459, 2,00
No. 7,457 and No. 2,717,674, U.S. Pat.
US-A) No. 3,647,461, No. 3, 647.4
62M and No. 4,186,007 and European Patent Application Publication (εP-A) No. 00029722j! It is stated in These methods are called replenishment methods and are performed by replenishing the replenisher. The substances consumed in the development process are maintained at the desired concentration by the addition of such replenishers, and at the same time the amount lost from the developer bath is reduced in order to prevent undesirable halide accumulation in the developer solution. A larger volume of replenisher is added. In this case, the concentration of halide in the replenisher is low, and although recent efforts have been made to reduce the amount of replenishment by using replenishers that do not contain any halides, this still results in a relatively large amount of overflow fluid. is bringing. Another method is to reduce the replenishment amount by removing the halide concentration from the developer by specific means,
In some cases, a method is often used in which the halides in the overflow liquid are removed, the missing components are supplemented, and the overflow liquid is used again as a replenisher, thereby reducing the overflow liquid. The former has the disadvantage that the halide concentration increases and development is inhibited, so it is necessary to perform a high activation treatment to eliminate the inhibitory effect, and furthermore, the amount of liquid to be discharged is relatively large. The latter uses an ion exchange tower or an electrodialysis tower, and is generally expensive. Another drawback is that maintenance work is extremely complicated, such as requiring analytical operations to keep the developing composition constant. Therefore, a low replenishment system (LR system), which can easily reduce replenishment, is generally employed especially in minilabs and the like. However, the disadvantage of this system is that bromide accumulates in fairly high concentrations, and as a result, high temperature treatments are used to overcome its inhibitory effect, as mentioned above. In this case, the effect of evaporation cannot be ignored and the toxic components are am
As the amount of water increases, the disadvantage that the liquid becomes easily oxidized also appears. As a method to solve the drawbacks of these methods,
No. 70552, Mei-III, a photographic material consisting of a very high silver halide silver chloride content is processed with a replenishment amount so low that it does not overflow even when replenished, so that the elution of bromide ions is reduced, and as a result, bromide ions are A treatment method has been proposed that does not require high-temperature treatment because the ions do not have a high concentration. This method has been well known for a long time, and since bromide has a much greater inhibitory effect on development than chloride, this method makes it easier for chloride ions, which have a smaller inhibitory effect, to dissolve into the developer solution. It's not new, but
Low replenishment processing can be achieved without high temperature processing. However, according to research conducted by the present inventors, as the ratio of silver chloride in photographic materials increases, the performance of conventional developing solutions cannot be maintained, resulting in lower color density and problems with aging of color developing solutions. The drawbacks are that the gradation changes significantly over time, and even the slight change in the preservative sulfite 11 due to air oxidation changes the photographic performance. It was found that this method could not be put to practical use as it was. To solve these problems, Japanese Patent Application Laid-Open No. 63-106655
The publication discloses that the above-mentioned problem can be solved by substantially not containing hydroxylamine, using a hydroxylamine derivative as a substitute compound, and further adding chloride at a certain concentration. However, the above technology has the problem that the photographic properties are not stable during continuous processing or when processing in large amounts and small amounts because the hydroxyl derivative itself has a certain degree of development inhibitory effect, although it is not as strong as hydroxylamine. It turns out that. Furthermore, the inventors have found that uneven development is more likely to occur when the color developer replenishment amount is lowered and continuous IA development is performed, and that the type of automatic processor, for example, the conveyance speed, is more likely to occur. Large machines with a speed of 10m or more per minute and 1m to 3m per minute
It was also discovered that the developing performance was different from that of the small-sized machine used in the Koni Lab. In order to solve these problems, the present inventors conducted intensive studies and found that a certain specific aromatic primary color developing agent was used to solve the problem of low replenishment using a high concentration silver chloride emulsion. It turns out that the problem can be solved by using In other words, silver chloride emulsions are more easily developed by reducing agents than conventional silver chloride emulsions and silver bromide emulsions, so it is necessary to exclude reducing agents from color developing solutions as much as possible. The preservatives used are used for the purpose of preventing oxidation of the color developing agent, and most of them are reducing substances such as sulfites, hydroxylamine, and derivatives thereof. Therefore, when a high-concentration silver chloride emulsion is used, the above-mentioned problems are thought to occur because the storage stability, developability, and processing stability of the color developing solution are in a trade-off relationship. Regarding development unevenness, it is thought that because high silver chloride emulsions have good developability, the bleaching after color development or the stopping effect in the bleach-fix solution is small, so that uneven development tends to occur, but the explanation is not clear. Furthermore, it is thought that the problem of different developability due to the feeding speed of the automatic developing machine suggests that the developability is not sufficient when low replenishment is performed. The above are facts and predictions obtained based on the research results of the present inventors, but in order to achieve low replenishment using a high concentration silver chloride emulsion, it is necessary to combine a certain color developing agent. It was completely unexpected for the present inventors to be able to obtain stable photographic characteristics without impairing the speed of the process. [Object of the Invention] Therefore, the first object of the present invention It is an object of the present invention to provide a method that can significantly reduce the amount of replenishment of a color developing solution without impairing the speed of processing.A second object of the present invention is to improve photographic properties, especially development unevenness even during continuous processing. The object of the present invention is to provide a development processing method that is difficult to develop and is stable.An object of the present invention is to provide a development IA processing method that can stably obtain photographic properties with less variation in developability due to differences in the type of automatic processing machine, etc. [Structure of the Invention] The above object of the present invention is to (1) imagewise expose a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support; A method in which development is performed with a color developer containing a group primary amine color developing agent, and continuous processing is performed while replenishing the color developer with a replenisher, wherein the silver halide emulsion has a silver chloride content of at least 90 mol%. wherein the aromatic primary amine color developing agent is a color developing agent represented by the general formula [I], and the amount of replenisher of the color developing solution is 120 tail 7 m'' or less. IA method for silver halide color photographic light-sensitive materials, characterized by or represents P-toluenesulfonate,
(2) Claim 1, wherein the support of the silver halide color photographic light-sensitive material is a reflective support.
A method for processing a silver halide color photographic light-sensitive material as described in . (3) The silver halide color photograph according to claim 1 or 2, characterized in that the color developing solution contains at least 3 x 10-' moles of chloride per 1°C of the color developing solution. IAI of photosensitive materials! Method. (4) A method for processing a silver halide color photographic light-sensitive material according to claims 1 to 3, wherein the color developing solution does not substantially contain sulfate. (5) IA of the silver halide color photographic light-sensitive material according to claims 1 to 4, wherein the color developing solution does not substantially contain hydroxyl.
Processing method (6) A method for processing a silver halide color photographic material according to any one of claims 1 to 5, characterized in that the color developing solution does not substantially contain benzyl alcohol. (7) The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 6, wherein the color development IA processing time is 30 seconds or less. (8) The silver halide color photographic light-sensitive material has the general formula [
This was achieved by the method for processing a silver halide color photographic light-sensitive material according to claims 1 to 's7, characterized in that it contains a magenta coupler represented by M]. General Formula [M] [In the formula, 2 represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a vine group that is released upon reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a substituent.] The present invention will be described in detail below. The color developer of the present invention contains a compound represented by the general formula [11], but specifically, the compound represented by the general formula [N] is a known compound and is used for general color negative film. It is used as a color developing agent. Furthermore, regarding the combination of the compound represented by the formula [I] and a high concentration silver chloride emulsion, JP-A-63-1706
Publication No. 42 discloses a fog prevention technology during continuous processing using a combination with a hydrazine derivative.
JP-A No. 64-59352 describes that the water washing time can be shortened by combining with the membrane swelling degree, and EP-330442 describes a color development method for color vapor with the aim of reducing the amount of waste liquid. Techniques have been disclosed in which the overflow of the solution is used as a color development replenisher for color negatives, but in either case, the processing stability is unstable when the replenishment level is low, and uneven development is likely to occur. There is no disclosure that the above problem can be solved by using a specific color developing agent. - To explain in more detail about the compound of formula [1], the compound represented by general formula [I] is usually hydrochloride, sulfate p-
It is used in the form of salts such as toluene sulfonate. The color developing agent used in the present invention is usually a color developer I.
It is preferable to use it in a range of 1 Xl0-' to 2 x 10-' moles per A, but more preferably a range of 5 X10-' to 2 X10-' moles per 1A of color developer. The above color developing agents may be used alone or in combination of two or more. Examples of the color developing agents that can be used in combination include N,N-diethyl-p-phenylene cyanide, 4-amino-3-methylN-ethyl- N-(β-methanesulfonayodoethyl)aniline may be mentioned, but the effect of the present invention is preferably more pronounced when used alone.Additionally, if desired, black and white developer main ingredients such as phenidone, 4
-Hydroxymethyl-4-methyl-1-pheny, Ru 3
- May be used in combination with pyrazolidone, metol, etc. The replenishment amount of the color developer in the present invention is 120+aJZ
However, with the conventional technology, the above-mentioned problem occurs and the replenishment amount of the zero color developing solution, which was difficult to achieve for the first time with the present invention, is as low as 11 for a color photographic light-sensitive material. 30 N120+++J! per unit, preferably 40 to 100 I11°C. 30mf/+*”
In the case of squid, the amount of replenishment of the color developing solution is less than the amount carried out by the photosensitive material, which is unrealistic, and at 120a+i or more, the above-mentioned problem hardly occurs. °In carrying out the processing method of the present invention, from the viewpoints of low pollution, low cost, and stabilization of color negative processing, part or all of the color developer used in the present invention is used as a color development replenisher for color negative film processing. In other words, by using a high-concentration silver chloride color developing solution for color paper, stable speed can be obtained even without benzyl alcohol. are substantially the same except for Moreover, bromide can be made free by reducing the amount of color negative film replenishment, making the above-mentioned possible. In carrying out the present invention, it is preferable to use the overflow N- of the color developer for color paper, and also use the overflow of the color developer for color paper as a color developer replenisher for color negative film. In this case, materials such as sulfite, hydroxyl base salt, color developing agent, etc. that are normally used in the color negative film 2 may be used as a replenisher. It is preferable that the color developing solution of the present invention does not substantially contain sulfite ions, in order to achieve the effects of the present invention, particularly in preventing fluctuations in photographic properties during continuous processing. This means 1.0Xl per color developer IJZ.
It is preferably not more than 0-" moles, preferably not more than 5 x 10-3 moles. Particularly preferably, it does not contain sulfite ions at all. The color developing solution of the present invention uses an organic preservative other than hydroxylamine. As mentioned above, organic preservatives significantly affect processing characteristics due to their reducing properties, but with the structure of the present invention, even if organic preservatives other than hydroxylamine are contained, the effects of the present invention are not achieved at all. Not only does it not disappear, but it is also effective against uneven development. The organic preservatives used in the present invention include hydroxylamine derivatives (excluding hydroxylamine, the same applies hereinafter), hydroxamic acids, hydrazines, hydrazidoes, and fluorocarbons. , saccharides, monoamines, cyano-based chains, boria-based chains, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and fused ring-based chains are particularly effective organic storage compounds. Regarding the preferred spring preservative, its formula and specific compounds are listed below, but the present invention is not limited thereto.Additionally, the following compounds may be added to the color developing solution. The amount is: 0.005 mol/i to 0.5 mol/i, preferably 0
．． 03 mol/l SO, 1 mo41z/JL (F) It is desirable to add it so that it is 0 degrees. The following are preferable as the hydroxyl-containing conductor. General Formula (A) In the formula, R11 and R12 are a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic M! G
R11 and R12 cannot both be hydrogen atoms, and may be bonded together to form a heterocycle with the N atom.The ring structure of the heterocycle is ° , 5~
B-membered ring T, carbon atom. Hydrogen atoms, halogen atoms, oxygen atoms, i! Elementary atoms. It is composed of sulfur atoms, etc., and may be mh or unsaturated. It is preferable that R11 and R12 are an alkyl group or an alkenyl group, and the number of carbon atoms is preferably 1 to 10, preferably 4.
．． Examples of the gi-containing heterocycle formed by connecting R11 and FL12 in which y is 1 to 5 include a piperidyl group, a pyrrolysilyl group, an N-furkylpiperazyl group, an intolinyl group, and a benzyl group. Triazole groups etc. can be used. Examples of substituents for R11 and R12 include a hydroxy group, an alkoxy group, an alkyl or asolsulfonyl group, an amide group, a carboxy group, a cyano group, a sulfo group, a nitro group, and an acrylic group. Compound v11 Example-1 C2)1. -7-02) 1゜i1 -2 C8,QC2H,-11-02H4-OCR3-3 C2H5QC2H4-7-CH2-CH-CH211 4H -5 -7- The following are preferred as hydrazine cultivation and hydrazide knowledge . General formula CB) In the formula, R2', rt'', and R2al; represent water, et-substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, and R24 is hydroxyl group, hydroxyl group, or substituted It represents an alkyl group, an aryl group, a hetero JO group, an alkoxy group, an aryloxy group, a carbamoyl group, or an akuno group. The heterocyclic group is a 5- to 6-membered ring, c. H, Consists of O, N, S and halogen. Can be either saturated or unsaturated.
iv, and n is 0 or l. Especially n++ao
, R represents a group selected from an alkyl group, an aryl group, and a hetero Ig group, and R23 and R24 may form a heterocyclic ring. In the -Allt formula (m), R21 , R22, and R23 are preferably hydrogen atoms or Ct to C10 alkyl groups, and most preferably '1.yeR'' and R22 are hydrogen atoms. In the general formula (m), R24 is an alkyl convex , aryl 15,
Preferably, it is an alkoxy group, a carbamoyl group, or a main group.4. ) is preferably an alkyl group or a substituted alkyl group, and the substitution of alkyl T, which is inappropriate here, 25
is a carboxyl group, a sulfo group, a nitro group, an akuno group, or a cisphono group. X21 is -co- or -8o2-
Preferably. -Co- is also green. (Compound example) -1 -2 -10 1111□Question--4C1 Blind 2 Yoto 71! IQ, llN1
12 liver coNll. -4 3-12 -6 MHlIIIcOcONI(lIIIzgo2osj
B>Cn. -17 -18 11112NMC82C112COOH13-19 13-z. s++, oc! H9coon The following cyanates are preferred. - Formula [C] [wherein R"R" R33i and R" are water 1 [
R represents a divalent organic group, specifically an alkylene group, an arylene group, an aralkylene group, or a heterocyclic group. . R$1 R$2, FL33oJ:HR''4Tocy-CSpecially dihydrogen R, an alkyl group is preferable, and R3s is particularly preferably an alkylene group. -1 -2 (IOC11□C11□+-MCII □CH214+c
H2CH20H)Z-3 H-4)1214CI(ZCH211-(-(:12C112
0)1)2-5 82M CII□ClICl2NH2 Heavy H -6- 7- -9 - 1 0 -1 H The following are preferable as the compressed anions. General formula [0]

[In the formula, X represents a trivalent atomic group necessary to complete the synthesis, R", Ro is an alkylene group, an arylene group,
Represents an alkynylene group and an aralkylene group. Here R4
1. R42 may be the same or different. I D-l-2 The following Alkadrua compounds are preferable. - Formula [E] (In the formula, Rr+ is a hydroxyalkyl group having 12 to 6 carbon atoms, R5, 2 and Rra are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a hydroxyalkyl group having 2 to 6 carbon atoms. , pencil group or wax' and 2' of formula ~6 each have a hydrogen atom and a carbon number of 1
-6 alkyl group or a hydroxyalkyl group having 2 to 6 carbon atoms. ) Preferred specific examples of the compound represented by formula [E] above are as follows. (E-1) Ethanolamine, (E-2) Jetanolamine, (E-3) Triethanolamine, (E-4>Di-isopropanolamine, (E-5)2
-Methylaminoethanol, (E-6>2-ethylaminoethanol, (E-end) 2-dimethylreadannoethanol, (E-8) 2-diethylaminoethanol, (
E-9) 1-diethylamino-2-propanol, (E-10) 3-diethylamino-1-propanol, (E-11) 3-dimethylamino-1-propanol, (E-12) Isopropylamine Ethanol, (E-1
3) 3-Amino-1-propatol, (E-14)
2-Aro-2-methyl-1,3-propanediol, (・E-15) Ethylenediaminetetraisopropanol (E-16) Benzyljetanolamine (E-17)
2-Ayono 2-(human also xymethyl)-,1,3-propanediol. In the color developing solution in the present invention, chloride is added to the color developing solution I.
Containing 3 x 10-'' moles or more per JZ has the effect of the present invention, especially a remarkable improvement effect on processing stability when low replenishment is performed. 1. It is also effective against slight development unevenness. It is necessary that bromide is not substantially contained in the replenisher solution or the tank solution.In other words, the presence of bromide has a large development suppressing effect and the effects of the present invention can be obtained.Chloride ions are used in color development. The amount of bromide is 3 x 10-2 mol or more per liquid 11, preferably 4 x 10-' mol to 5 mol or less, preferably 5.0
xlO-' mole or less. The chloride referred to in the present invention is
Any compound may be used as long as it releases chloride ions in the color developing solution. Specific compounds include potassium chloride,
Examples include sodium chloride, lithium chloride, magnesium chloride, and the like. Examples of bromides include potassium bromide, sodium bromide, lithium bromide, and the like. Complexing agents for water softening, preservatives, development accelerators, competitive couplers, fogging agents, auxiliary yAmAm gold compound adhesives
, can be carried out in the presence of a regulatory agent; Research Disclosure
re) 17544.December 1978, Section
ndtlstrlal Oppotun+t+es
Ltd, ), HOleWell HaVant, mouth aushire, published by Grent3 ritaine, and Ullmann's Enzyklovedi der Technissien Hemi (U IIa+ansEnzyklpu
die der technique CI+e
mle), 4th edition, volume 18, 1979, especially pages 451, 452, and 463 to 4r35. Appropriate developer compositions can be found in Grant Haist.
, Modern Photographic Processing (M
odernPhotoaraplNe Process
ino), John Wiley & Sons (J
ohn W 1ley and 3ans), 19
73, Vol. 1 and 2. In the present invention, when a manganese salt or a cerium salt is used in combination with the color developing TA image solution of the present invention, the antioxidant performance of the color developer is further improved, and the decline in color development during storage over time is also improved. Since it also has other effects, it is more preferably used in the present invention. Manganese salts and cerium salts according to the present invention refer to compounds that release manganese ions or cerium ions when dissolved in a developer, and are preferably used as listed below, but are not limited to these. . Manganese chloride Manganese sulfate Manganese sulfite Manganese bromide Manganese phosphate Manganese nitrate Manganese permancanate Potassium acetate Manganese sulfate Manganese citrate Manganese ethylene diamine Tetra vinegar Manganese sulfate Cerium v141! Cerium Cerium chloride Cerium carbonate Cerium phosphate Cerium acetate Cerium citrate Cerium oxalate These manganese salts and cerium salts should be used in the form of ions (manganese ions and cerium ions) in the range of 0.1 mg to 100 mg per color development liquid 11. is preferable, more preferably 0.3-g to 201
When the color developer 1III solution according to the present invention contains a compound represented by the following formula [B-II to CB-IV], the objective effect of the present invention can be achieved. Better performance and even more color development
It is more preferably used in the present invention because it has the effect of reducing the 1° bleaching edge burr that occurs when bleaching or bleach-fixing is carried out immediately afterwards. General formula [B-I] - Numerical formula [B-I [] ) (In the formula, R++, R+2, Rye and R14 are each a hydrogen atom, a halogen atom, a sulfonic acid group, and a carbon atom number of 1
~7 alkyl group, OR+s. Also, R1
5, Rls, RI7 and R16 each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, R
When +2 represents 10H or a hydrogen atom, R++ represents a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -0R15. The alkyl groups represented by R1+, R+2, R13 and R14 include those having substituents, such as methyl group, ethyl group, 1so-propyl group, n-propyl group, [-butyl group, n-butyl group, hydroxymethyl group. The alkyl group represented by R+5, Rye, RI7 and R+8 has the same meaning as above, and further includes an octyl group. Furthermore, the phenyl groups represented by R11, R12, Rye and R1to include phenyl group, 2-hydroxyphenyl group,
Examples include 4-aminophenyl group. Typical examples of the chelating agent of the present invention are listed below, but the invention is not limited thereto. (B-I-1) 4-isopropyl-1,2-dihydroxybenzene CB-I-2) 1.2-dihydroxybenzene-3,5-disulfonic acid (B-I-3) 1.2.3-tri Hydroxybenzene-5-carboxylic acid (B-■-4) 1.2.3-trihydroxybenzene-5-carboxymethyl ester (B-I-5) 1.2.3-trihydroxybenzene-5- 5-tert-butyl-1,2,3-trihydroxybenzene (B-I-7) 1,2-dihydroxybenzene-3,4,6-trisulfonic acid ( 8-II-1> 2.3-dihydroxynaphthalene-6-sulfonic acid (B-It-2) 2.3.8-trihydroxynaphthalene-6-sulfonic acid (B-II-3) 2.3-dihydroxy Naphthalene-6-carboxylic acid (B-II-4) 2.3-dihydroxy-8-isopropyl-naphthalene (B-n-5) 2.3-dihydroxy-8-chloro-naphthalene-6-
Among the above-mentioned sulfonic acid compounds, 1,2-dihydroxybenzene-3 is particularly preferably used in the present invention.
, 5-disulfonic acid, and can also be used as alkali metal salts such as sodium salts and potassium salts. In the present invention, the formula [B-11 and [B-I[
] The compound represented by is 5 mg to 2 per 111 color developing solutions.
Can be used in the range of 0a, preferably 1011
Good results are obtained by adding between 10 g and 10 g, more preferably between 2.1 g and 3 g. General formula [B-1111 General formula [B-TV] (-In the formula [B-1 [1] and [8-IVI], is an alkylene group, a cycloalkylene group, a phenylene group, -L
a-0-La 0-La- or -Ls-Z-Ls-
represents. Here Z is N-LIO-R40, -N-L+
+ -N -L 12- R41L 12- R41L
1 to Lt3 each represent an alkylene group. R33~R
43 is a hydrogen atom, a hydroxyl group, a carbonyl group (
(including its salts) or a phosphonic acid group (including its salts). However, at least two of R33 to R36 are carboxylic U groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least two of R37 to R39 are carboxylic acid groups (including salts thereof). (including its salts) or a phosphonic acid group (including its salts). ) In the above-mentioned formulas [B-1111 and [B-IV], the alkylene group, cycloalkylene group, and phenylene group represented by 1, and the alkylene groups represented by 1 to L+a include those having a substituent. Next, preferred specific examples of the compounds represented by these formulas [8-1[[] and [a-IV] are listed below. [Exemplary Compounds] [B-111-1] Ethylenediaminetetraacetic acid [8-m-21 Diethylenetriaminepentaacetic acid [8-111-3] Ethylenediamine-N-(β-hydroxyethyl)-N
, N' , N' -Triacetic acid [B-111-4] Propylene diamine tetraacetic acid [B-111-5] Triethylenetetraminehexaacetic acid [B-111-6] Cyclohexanediaminetetraacetic acid [B-111-7] 1.2-diaminopropane-tetraacetic acid [B-1[[-8] 1.3-diaminopropan-2-ol-tetraacetic acid [B-11[-91 Ethyl ether cyanotetraacetic acid [B-1[[ -101 Glycol ether diamine tetraacetic acid [B-1[[-
11] Ethylenediaminetetrapropionic acid [B-11-121 Phenylenetetraacetic acid CB-111-13] Ethylenediaminetetraacetic acid disodium salt [8-II
I-14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [8-111-15] Ethylenediaminetetraacetic acid tetrasodium salt [, B-III-16] Diethylenetriaminepentaacetic acid pentasodium salt [8-III-17] Ethylene diamine N-N-(β-hydroxyethyl)-N
,N',N'-Triacetic acid sodium salt [B-1[1-18] Propylenediaminetetraacetic acid sodium salt [8-11
-191 Ethylenediaminetetramethylenephosphonate [8-II
I-20] Cyclohexanethiaminetetrawit sodium salt [B-1-211 Diethylenetriaminepentamethylenephosphonic acid CB-11 [-223 Cyclohexanediaminetetramethylenephosphonic acid [B-IV-1 with trilotriacetic acid] [B-rV-21 Iminodiacetic acid [B-IV-3 and trilotribrobionic acid [B-IV-4] Nitrilotrimethylenephosphonic acid [B-IV-51 Iminodimethylenephosphonic acid [8-rV-6] Nitrilotriacetic acid bale trisodium salt [ Among the compounds represented by the general formula [B-1111 or [B-IVI], compounds particularly preferably used in the present invention include [B-III-11, [8-111-2], [B
-III-5], [8-111-81゜[8-III-
191, [B-IV-11, [B-IV-4] and CB
-IV-71. Furthermore, these − formula [B
-1] or [B-IVI] is preferably used in an amount of 0.1 to 20111 per liter of color developing solution, and particularly preferably used in an amount of 0.3 to 5 g from the viewpoint of the purpose of the present invention. It will be done. The compounds represented by formulas [B-I] to [B-IVI] may be used alone or in combination; Other chelating agents such as phosphonocarboxylic acids such as phosphonobutane-1,2,4-tricarboxylate, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid may be used in combination. In the present invention, the color development is preferably less than that according to the present invention. General formula [1[[] In the formula, Xl, X2, Y+ and 'UY2jt are each a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy I! (e.g. methoxy, ethoxy, methoxyethoxy, etc.), aryloxy groups (e.g. phenoxy, p
-sulfophenoxy etc.>, alkyl groups (e.g. methyl, ethyl etc.), aryl groups (e.g. phenyl, methoxyphenyl etc.), amino groups, alkylamino groups (e.g. methylamino, ethylamino, propylamino), dimethylamino, cyclo Xylamino, β-hydroxyethylamino, di(β-hydroxyethyl)amino, β-sulfoethyl-amino, N-(β-sulfoethyl)-N'-methylamino, N-(β-hydroxyethyl-1N'-methylamino) etc.), arylamino group ((5'l is anilino, O-1-El-sulfoanilino, O-p-riOOanilino, O-■-p-toluidino, O-1-D-
1M, which represents carboxyanilino, O-1-D-hydroxyanilino, sulfonaphthyla, O-1-E) -aminoanilino, o-m-a-anilino, etc., is water 113? represents sodium, potassium, ammonium or lithium. Specifically, JP-A-63-106655 (A'-1) to (A
'-14) can be mentioned. - These triazylstilbene type brighteners are preferably used in an amount of 0.2 to 6 g, particularly preferably 0.4 to 3 g, per 1 color developer used in the present invention. The preferred phenomenon liquid of the present invention preferably does not substantially contain benzyl alcohol. Here, "substantially free" means that benzyl alcohol is 2d/J! Benzyl alcohol, which is most preferably not contained at all in the present invention, has extremely low solubility and in the process of the present invention, in which the amount of replenishment is extremely small, the liquid tends to condense, so the photographic material due to oil precipitation This causes extremely troublesome problems such as adhesion failure and formation of tar due to oxidation of the active ingredient. Further, by using a high-concentration silver chloride emulsion, benzyl alcohol is substantially unnecessary, and benzyl alcohol is also unnecessary since it is used as a replenisher for a color developing solution for a color negative film. In the present invention, color development IA is preferably carried out at a bath temperature in the range of 20°C to 80°C, more preferably in the range of 30°C to 60°C, from the viewpoint of prevention of tar generation and processing stability. It is preferable. The pH of the color developer is generally 8 or higher, preferably 9.
．． It is 5 or more and 10.5 or less, and if it is 1000 or more, development fog and development unevenness tend to occur, which is not preferable. From the viewpoint of rapidity, the color development processing time in the present invention is 6.
Within 0 seconds, preferably within 45 seconds, particularly preferably within 30 seconds, and in an embodiment of the present invention, within 30 seconds is preferred. In particular, the effect is remarkable in terms of development process stability and prevention of uneven development. In the present invention, after color development processing, a treatment with fixing ability i* is used! i! X treatment, but a process that has the fixing ability]l
! If the solution is a fixer, it is preceded by a bleaching process. As the bleaching agent used in the bleaching solution or the clean fixing solution used in the bleaching process, a trusted metal n salt is used, and the metal complex salt is made of gold R produced by Genga.
It has the effect of oxidizing m and converting it into silver halide and at the same time coloring the uncolored part of the coloring agent, and its composition is Akunobolicarpon or 1i! , metal ions such as iron, cobalt, copper, etc. are coordinated with organic acids such as citric acid. The most preferred compound used to form such a metal complex salt is polycarboxylic acid or aminopolycarboxylic acid. 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. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Dihyroxyethylglycine Citric acid (or tartaric acid) [9] Ethyl ether diamine tetraacetic acid [10] Glycol ether diamine tetraacetic acid [11] Ethylene diamine tetrabrobionic acid [121]
Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt' [14] Ethylenediaminetetraacetic acid tetra(I~limethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriamine pentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β-oxyethyl)
-N, N', N' - Lamb triacetate [19] Sodium nitriloacetate [20] Sodium cyclohexanediaminetetraacetate The bleaching solution used contains a metal complex salt of the above-mentioned acid as a bleaching agent. It can also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide. D I-1tl Iji81 such as magoljic acid salts, kansei salts, itamishio salts, disaster acid salts, Shinzaki salts, etc. It is known that 31Tl such as 1'L r 11) can be added as needed. Furthermore, fixed! 4P & 7! Liquid 11, ammonium nitrite, potassium FAIllite, thorium nitrite, meta! 11 nitrous & IM ammonium, metam potassium sulfite, fi') 1lil [l1QA11sl-+)
UmtLcQ! lff1M Salt/PI11 Kai, lff!
914 class ■ agent consisting of various salts such as sand, sodium hydroxide, potassium hydroxide, sthorium carbonate, υZII potassium, s1-lium m carbonate, potassium carbonate, acetic acid, sthium acetate, ammonium hydroxide, etc. may be used alone or in combination of two or more. Bleach window @Wl<bath)% When cleaning the area while replenishing a light trapping agent, add 1 thiosei salt and 1 diosyan salt to the bleaching solution (1). U may be made to contain Sunshio Sen, or these salts may be added to 1 g of cough solution and collected in the purification bath.Especially, when thiocyanate is used, it is rapid. In the present invention, in order to increase the activity of the bleaching solution or bleach-fixing solution, air may be blown into the bleaching bath or bleach-fixing bath and in the storage tank of the bleach replenisher or bleach-fixing solution, if desired. Alternatively, oxygen may be blown in, or a suitable thickening agent such as hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate. Therefore, a bleach-fix solution is preferably used, and when a high-silver chloride photosensitive material is used as in the present invention and bleach-fix processing is performed immediately after color development, uneven development tends to occur.The structure of the present invention prevents uneven development. However, by using the bleach-fix solution in the pH range of 3.0 to 6.8, preferably in the range of 4.0 to 6.5, not only can uneven development be more effectively solved, but the silver bleaching speed can no longer be reached. This effect is particularly evident when the pH of the bleach-fix solution is between 4.5 and 6.
Good when 0. Furthermore, by adding a halide to the bleach-fix solution, uneven development and desilvering properties are also improved. A preferable amount of addition is 0.1 mol or more, particularly preferably 0.2 mol or more and 2.0 mol or less per bleach-fixing@iJZ to obtain good results. In the treatment of the present invention, silver may be recovered by known methods from treatment solutions containing soluble silver complexes such as washing or washing substitute stabilizing solutions, fixing solutions and bleach-fixing solutions. 2,299.667), precipitation method (No. 2,299.667), precipitation method (No.
Special ran number OH52-73037, German patent 2.33
1,220), ion exchange method (Japanese Patent Application Laid-Open No. 1711-1982)
No. 4, Akita Patent No. 2,548,237) and metal substitution method (British Patent No. 1,353,805) can be effectively used. In the processing method of the present invention, after color development, bleaching and fixing (or bleach-fixing), stabilizing treatment may be performed without washing with water, or washing with water may be performed followed by stabilizing processing. In addition to the above steps, known auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water may be added as necessary. A typical example of a preferred treatment method includes the following steps. (1) Color development → bleach fixing → washing with water (2) Color development TAI! -4 Bleach and fix → Wash with a small amount of water → Wash with water (3
) Color development → bleach fixing → water washing → stabilization (4) color development → bleach fixing → stable (5) color development → bleach fixing → first stable → second stable (6) color development → water washing (or stabilization) → bleach fixing →Washing with water (
(7) Color development → stop → bleach-fix → water washing (or stable) (8) color development → bleach → water washing → fixing → water washing → stable (9) color development → bleaching → fixing → water washing → stable (10) Color development → bleaching → small amount of water washing → fixing → first stable → second stable (11) color development → bleaching → small amount of water washing → fixing → small amount of water washing →
Washing with water → Stable (12) Color development → Washing with a small amount of water → Bleaching → Washing with a little melon → Fixation →
A small amount of water washing→Water washing→Stabilization (13) Color development→Stop→Bleaching→Small amount of water washing→Fixing→Small amount of water washing→Water washing→Stabilization Among these steps, steps (4) and (5) are particularly preferably used. Another preferred embodiment of the processing method of the present invention is a method in which part or all of the overflow solution of the color developing solution according to the present invention is allowed to flow into the subsequent bleaching solution or bleach-fixing solution. This means that the color developing solution according to the present invention is added to the bleach solution or bleach-fix solution! This is because, by flowing in, the generation of sludge in the bleach solution or bleach-fix solution is suppressed, and surprisingly, the recovery efficiency of silver from the bleach-fix solution is also improved. Furthermore, in addition to the above-mentioned method, when part or all of the overflow liquid of the stabilizing liquid in the subsequent process is poured into the bleach-fixing liquid or the fixing liquid, the above-mentioned effects are particularly well achieved. Specific examples of these embodiments include those shown in FIG. 1, for example. The silver halide grains used in the silver halide emulsion layer of the silver halide color photographic light-sensitive material used in the present invention are as follows:
It is necessary that the silver chloride content is 0 mol% or more, and 10
Although it is preferable that the silver chloride content be close to 0%, it has been found that when the silver chloride content is 90 mol% or more, an effect that is substantially close to 100% silver chloride can be obtained. In particular, when the silver chloride content is 95 mol % or more, the desired effects of the present invention are particularly well achieved. The silver halide emulsion containing the above-mentioned silver halide grains can contain silver bromide and/or silver iodide as a silver halide composition in addition to silver chloride, and in this case, silver bromide is 10 mol %.
The content is more preferably 3 mol %, and when silver iodide is present, it is 1 mol % or less, preferably 0.5 mol % or less. Such silver halide grains containing 90 mol % or more of silver chloride may be used in at least one silver halide emulsion layer, but preferably they are used in all silver halide emulsion layers. . The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [1,0,0] planes to [1,1,1] planes can be used. Furthermore, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered IM structure (core-shell type) with an R award on the inside and outside. Furthermore, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside one grain. In addition, tabular silver halide grains (JP-A-58-1139
No. 34, Tokucho Publication No. 59-170070 rKA) may also be used. It may also be a high silver chloride emulsion in which Br is concentrated in a specific part of the silver halide. Further, the silver halide grains may be obtained by any preparation method such as an acid method, a neutral method, or an ammonia method. Alternatively, for example, seed grains may be produced using an acidic method, and then grown using an ammonia method, which has a fast growth rate, to grow to a predetermined size.When growing silver halide grains, the pat, pAg, etc. in the reaction vessel may be Control 1-roll, and sequentially inject and mix fillet armor ions and halide ions into 11 tR corresponding to the growth of silver halide grains in ml as described in, for example, JP-A No. 54-48521. Preferably, the preparation of the halogenated chain grains described in III is preferably carried out as described above, and contains halogenated chain grains.The product is referred to as a silver halide emulsion in the specification. The silver halide emulsion layer used carries color couplers. These color couplers react with color developer oxidation products to form non-diffusible dyes. The color couplers are advantageously applied in non-diffusive form to the photosensitive layer. The red-sensitive layer may thus contain a non-diffusive color coupler, generally a phenolic or alpha-naphthol coupler, to produce a cyan partial color image, for example. The side layer may contain at least one non-diffusing color coupler, usually a tobirazolone type color coupler, and a pyrazolotriazole to produce, for example, a magenta partial color image. The resulting at least one non-diffusible color coupler, generally a color coupler based on an open-chain ketomethylene group, can be included.The color coupler can be, for example, a 4- or 2-equivalent coupler.In the present invention , especially 2-equivalent couplers are preferred; suitable couplers are disclosed, for example, in the following publications:
Agfa research report (Mittellunglnaug)
dan I'orschLinglaborator
ien der^gfa), Leverkusen/Muncben
, Vol, m, p, 111 (1961) "Color coupler" by W. Bell (W, I'elz)
(Farl+kuppler) ; K. Venkataraman, “The Kekustrion. Synthetic Dice J (Tbe Chemlr)
sry of Syntl+etlc Dyes), Vo
l, 4,: 141-3117, Akadeku Tsuku◆Press (
8 academic I'regs), r the← Theory on the Photographic Process J (
TheTbeory of the Pbotogra
phlc Process), 4th edition, 353-36
2 pages; and Research Disclosure (Ilese
arch Dlsclogur@) No, 17843
, sexy eyes■. In the present invention, as a magenta coupler, the following formula [M
] Couplers are preferred in preventing uneven magenta development.
is used. In the magenta coupler represented by 2, 2 represents a nonmetallic atom necessary to form a nitrogen-containing heterocycle, and the ring formed by 2 may have a substituent. When X reacts with a hydrogen atom or an oxidized product of the coloring agent, ll1l! Represents a group that can be eliminated. Also, R is a hydrogen atom or l! Represents a substituent. There are no particular restrictions on the substituent represented by R, but typical examples include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and alkyl groups; halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido , sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonylroxycarbonyl, and heterocyclic thio groups, as well as spiro compound residues, bridged hydrocarbon compound residues, and the like. The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be straight or branched. The aryl group represented by R is preferably a phenyl group. Examples of the acylamino group represented by R include an arylcarbonylamino group and an arylcarbonylamino group. Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group. Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above. The alkenyl group represented by R includes those having 2 to 32 carbon atoms. The cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be straight or branched. The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred. Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group, etc.; As an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc.; As a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc.; As a sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl group, etc.; 7' syloxy group includes alkylcarbonyloxy group, arylcarbonyloxy group, etc.; carbamoyloxy group includes alkylcarbamoyloxy group; ureido group includes alkylureido group, arylureido group, etc.; sulfamoyl As the amino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; as a heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, a 2-thienyl group, a 2-pyrindinyl group, etc. group, 2-benzothiazolyl group, etc.: As the heterocyclic oxy group, one having a 5- to 7-membered heterocycle is preferable, for example, 3.
4,5.6-tetrahydropyranyl-2-oxy group, 1
-Phenyltetrazole-5-oxy group, etc.; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-penzothiazolylthio group, 2,4-diphenoxy- 1.3.5-triazole-6 monothio group, etc.; As the oxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; as the imide group, succinimide group, 3-heptadecylsuccinimide group, etc. Nispiro compound residues such as yodo group, phthalimide group, and glutarimide group include spO[3.3]hebutane-
1-yl, etc.; as a bridged hydrocarbon compound residue, bicyclo[2. 2, 11 hebutan-1-yl, tricyclo[3. 3,1.13/7]]decan-1-yl7,7-dimethyl-bisicC][2.2.1]hebutan-1-yl and the like. Groups that can be separated by reaction with the precipitate of the coloring agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, aryloxycarbonyl. , alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino, aryloxycarbonylamino, each group such as carboxyl, (R1' has the same meaning as R above, 2' has the same meaning as 2 above, R2' and Ra' do not represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group); , preferably a halogen atom, particularly a chlorine atom. Examples of the nitrogen-containing heterocycle formed by 2 or 2' include a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned. More specifically, what is represented by the general formula CM-11 is represented by, for example, the following formulas [M-I[] to CM-Vll. CM-Ill CM-Ill CM-IV] CM-41 [M-VIE General formula [] In the above formula [M-I11 to [M-V[], R4
~R8 and X have the same meanings as R and X above. Also, preferred among the formulas [M-IF] are those represented by the following formula [M-■]. - Formula [M-■] In the formula, R1, X and zl are R in the general formula [M-4],
It has the same meaning as X and 2. Particularly preferred among the magenta couplers represented by the formulas [M-11 to [, M-VIE] are those represented by the general formula [M-VIE].
The magenta coupler represented by IF has the general formula [M-I
The ring formed by 2 in F and the formula [M-■]
The substituent that the ring formed by zl in may have, as well as those represented by the following formula [M-rX] are preferred. Formula CM-IXI -R' -302-R2 In the formula, R1 represents an alkylene group, and R2 represents an alkyl group, a cycloalkyl group, or an aryl group. The alkylene group represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and does not matter whether the straight chain is bibranched or not. The cycloalkyl group represented by R2 is preferably a 5- to 6-membered one. In addition, when used for positive image formation, the substituent R on the heterocycle
And, the most preferable one as R1 is the following formula CM
-XI. -Formula CM-XI s Rso -C- In the formula, Rs, R1a and Rt+ are each the same as R above. Also, two of the above Rs, R+o and R++, for example, R9
and Rho may be bonded to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R++ may be further bonded to the ring to constitute a bridged hydrocarbon compound residue. Good too. -Iff1 formula CM-Xl is preferably (1
) When at least two of Rs to R+t are alkyl groups, (ii) One of Rs to Ra1, for example R1+, is a hydrogen atom, and the other two, R9 and Rho, bond together with the root carbon atom. When forming cycloalkyl. Furthermore, in (1), it is preferable that two of NR9 to Rat are alkyl groups and the other one is a hydrogen atom or an alkyl group. In addition, when used for negative image formation, the substituent R on the heterocycle
And R1 is most preferably represented by the following formula [M-X
The general formula [M-XI] R12-CH2- is represented by l1, where R12 has the same meaning as R above. Preferred as RI2 is a hydrogen atom or an alkyl group. The following is a representative example of the compound according to the present invention.
3-106655 specification, pages 29 to 34 (includes N011 to N0.77, which are described in the specification).For the general formula [C-I] or [C-11], which is also described on page 34, (Specific exemplary cyan couplers include FIl
(C″-1) to (C′) described in UA specifications, pages 37 to 42
-82), (C"-1') to CC"-coS)), and high-speed yellow couplers described in the same <20 member (as specific examples of cyan couplers,
t(')(Y'-1) ~(Y'-3'
It is preferable to use 1) in combination with the light-sensitive material of the present invention from the viewpoint of the desired effects of the present invention. In the present invention, 1. When a nitrogen-containing heterocyclic mercapto compound is used in combination with the high silver chloride photosensitive material of the present invention, not only does it exhibit the desired effect of 1. This method can be cited as a more preferred embodiment in Akira Kizawa because it has the additional effect of minimizing the effect on photographic performance that occurs when the white fixer is mixed in. Specific examples of these nitrogen-containing heterocyclic mercapto compounds include CI''-1) to (I'-117) described in JP-A-63-106655, 42-45μ. Silver nitride emulsions having a chain content of 90 mol % or more can be 11!1 processed by conventional methods (for example, constant material or (; single or double inflow with rapid acceleration). While adjusting the pAg. 1ll according to double inflow method 1
l! Particularly preferred is the method No. 21: Research Institute No. 17643, Section I and II 9.
Light. Emulsions can be chemically sensitized. Reducing agents can also be used as chemical sensitizers, with sulfur-containing compounds such as ally-inthiocyanate, allylthiourea or osulfuate being particularly preferred; they are described, for example, in Belgian patents 493.41i4 and 56 (1,687
Silver compounds such as those described in No.
7,323, such as diethylenetriazine or atomylsulfinic acid derivatives. Noble metals and precious metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable sensitizers. This chemical sensitizer is used in Zeitschrift 1 to Ver-Bissenschaftrift Photography 4 (Z
, ”R55s, Photo,) 413.65~72
(1951) by Earl Koslovsky (nJosio)
vsky); Also, the above Research Disclosure Share No. 1764, Section ■
See also: The emulsions can be sensitized by optically known methods, for example using common polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like:・Kum Hammer (1', M', JI
as+ar)'s "The Cyan+ne Dye
s and relaLad Compounds)
(1964) Ullmann's Hekui (formerly 1st layer anns E
nzyklpadle derLecl+n1Scbe
n 1eiie) 4th edition, volume 18, page 431 and the following, and the above Research Disclosure No. 17
04 Ko, Sexy Gun 1v Sanho. Conventional fog inhibitors and stabilizers can be used in the emulsion. Azaindene is a particularly suitable stabilizer,
Tetra- and penta-azaindene are preferred, especially those substituted with a hydroxyl group or an atom group. Compounds of this type are described, for example, in the paper by Bier (Olrr). Zeitschrift Fair Bissenschaftliche Photography (Z, Wlsi, Pboto)
47.1952, p. 2-58. and the above-mentioned Research Disclosure No. 17643, Section 1. The components of the photosensitive material can be incorporated by conventional known methods; for example, U.S. Pat. No. 2,322,027;
2,533,514, 68EI, 271
No. 3.7 [i4, 3:16 and No. 1, 7 [i5
．． [See No. 197. Components 1 of the photosensitive material, such as couplers and UV absorbers, can also be contained in the form of charged latex;
Akita Patent Release No. 2,541,274 and European Special Vinegar J11rl14. ! No. 121, the components can also be immobilized in the light-sensitive material as polymers; e.g.
National Patent Application Publication No. 2,044,992, US l! I Patent No. 370,952 and No. 4,0 (see No. 10,211). Ordinary supports can be used as supports for photosensitive materials!
For example, cellulose esters such as cellulose acetate supports and polyester supports may be used.
Paper supports are also suitable and these can be coated, for example, with polyolefins, in particular polyethylene or vopropylene; see in this regard Research Disclosure No. 1704, supra, section VVI. In the present invention, if the photosensitive material is a photosensitive material that is processed by a so-called internal development method in which a coupler is combined with the photosensitive material, color vapor, color negative film, color positive film, color reversal film for
Although it can be applied to any photosensitive material such as a color reversal film for movies, a color reversal film for TV, and a reversal color vapor, it is most preferably applied to color vapor. [Example 1] The present invention will be explained in more detail with reference to Examples below, but the implementation of the present invention is not limited to these examples. Example 1 The following layers were formed on a polyethylene coated paper support. were arranged side by side sequentially from the support side to produce an Il&light material. In addition, polyethylene foot paper has an average molecular weight of 10
0,000. Density 0.95 (+) po! J! Chin 2 (toll weight part and average molecular weight 2,000.@ degree 0.8
8.5% by weight of anatase-type titanium oxide was added to a mixture of 20 parts by weight of polyethylene, and a coated layer with a thickness of 0.035 am was formed on the surface of high-quality paper weighing 165 g/III' using an extrusion coating method. is made of polyethylene with a thickness of 0.040a+m.
The one provided with N was used. After the polyethylene-coated surface of the support was pretreated by corona discharge. The following layers were applied in sequence. First Calendar: A blue-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 0.5 mol% of bromide. Sensitized with 2.4XtO-4 mol (using isopropyl alcohol as a solvent),
Contains 200 g/rrt of 2,5-di-1-butylhydroquinone dissolved and dispersed in dibutyl phthalate and 2.3X 10-1 mol of [Y-11] of the following structure per mol of silver halide as a yellow coupler, A amount 20
Sheet octylhydroquinone 30067m'' dissolved and dispersed in Nidibutyl 7 tallate, 2-(2'~Human 1:I4L Sea 3) as an ultraviolet absorber. ',5'-G1
-, butylphenyl)benzotriazole, 2-(2'
-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chloro-benzotriazole and 2-(2'- Hydroxy-3', 5'
-di-1-butylphenyl)-5-chloro-benztriazole compound (1:1:l:1) 2
Contains 00mg/rn'< Gelatin 18 in Latin Calendar
00mg10i'. S3m = chlorobromide II containing 0.5 mol% silver bromide! In the green-sensitive silver halide emulsion layer consisting of an emulsion, the emulsion is halogenated #! Gelatin per mole 380. was sensitized using 2JXIO-4 moles of a sensitizing dye (S-2) having the following structure per mole of silver halide, and dissolved in a solvent consisting of dibutyl phthalate and tricresyl phosphate (2). 2,5-di-1-butylhydrosequinone and [M-1] of the following structure as a magenta coupler per 1 mole of silver halide
．． 5X1G, -1 mole content, silver amount 2oov g/m
In addition, as an antioxidant, 2,2.4-)rifthyl-8-teuryloxy-7
-0.30 mol of tooctylchroman was added per mol of coupler. 255 g/m' of fractionated di-1-octylhydroquinone dissolved in 4th dioctyl phthalate and UV. 2-(2'-hydroxy-3', 5" as a line absorber)
-butylphenyl)benzotriazole, 2
-(2,'-hydroxy-6°-L-butylphenyl)
Benzotriazole, 2-(2'-hydroxy-3'
-t-butyl-5'-methylphenyl)-5'-chloro-benzotriazole and 2-(2''-hydroxy-3
',5'-di-t-butylphenyl)-5-chloro-
A mixture of benzotriazoles (2:4.5=,
5: Z) 400ag/m' is a gold medal gelatin calendar, coated to give gelatin 1800mg/ITI''. 5th calendar: Silver chlorobromide containing 0.4 mol% silver bromide. A tA-separated silver halide emulsion layer consisting of an emulsion containing 420. of gelatin per mole of silver halide, and 2.2Xto-i mole of a sensitizing dye having the following structure (≦-3) per mole of 1R halide. 2,5-di-L-butylhydroquinone sensitized using dibutyl phthalate and dispersed in dibutyl phthalate.
g/rn” and the cyan coupler, [C-
It contains 3.5 x 10-1 moles of 11/\silver halide and is coated in a silver amount of 2'3cy++sg/rn'. 6th Calendar: It is a gelatin calendar, and gelatin is m-blooded to be 1300H/rn'. The silver halide emulsion used in each light-sensitive emulsion layer (1st, 3.5 layers) is described in Japanese Patent Publication No. 46-7772 as a film agent using bis(vinylsulfonylmethyl)ether (gelatin tg).
12ml/ml) and saponin as a coating aid. Sensitizing Dye C5-Z] Sensitizing Dye C5-3"J ['+'-+1 I σeH. After exposing the color paper produced by the above method, the following processing steps and processing are performed using a processing solution. Processing process!!
2) Bleach fixing 35℃ t&0 3o seconds 0)
Drying 80℃~80℃ [JiaIl image tank liquid] Diethylene glycol Potassium bromide Potassium chloride M Potassium sulfate (SO% solution) 30 seconds 5g 0.01g 2.36 0.5mi Diethylhydroxylamitriethanolamine Potassium carbonate Diethylenetriamine: fL Nan' acetate (85%) Thorium salt 5.0g 10.0g 0g 2.0s Fluorescent brightener (Keicol PK-Cane manufactured by Nippon Soda Co., Ltd.) 2.0g Add water to make 1i, potassium hydroxide or 1* The pH was adjusted to 10.15 with sulfuric acid. [Color development replenisher] Diethylene glycol 17g Potassium chloride 3.0g Potassium sulfite (50% solution) σ, 5 Furumi diethylhydroxylamine (85%) 7.0g Trietasolamine 10-0g Potassium carbonate
30゜ethylenetri7minepentaacetic acid sodium salt 2.0g Fluorescent brightener (Nippon Soda Co., Ltd. Keikol PK-Come) 2-
5g of water was added to make the solution 11, and potassium hydroxide or sulfuric acid was added to make the solution 10.40. [Bleach-fix tank solution and replenisher] Ammonium thiosulfate (70% solution) 100, osJl 5-amino/-1,3,←thiadiazole-2-thiol TiAmmonium sulfate (40% solution) pHr, 0 with aqueous ammonia or glacial acetic acid Add water to bring the total volume to 11. [Stable tank fluid and replenishment fluid 1 0.5g 27.5tafL II! ! 2-methyl-4-inchazolin-3-one (+-0
13,000 Nopal SFP (manufactured by Ciba Geigy) 0
．． 3g Nitrilotriacetic acid ◆Trisodium salt 1.5g
Make 1 layer with water and add ptt with ammonia water and 50% sulfuric acid.
7.5. Continuous processing was carried out until the above photosensitive material was replenished to three times the tank capacity of the color developing solution. However, the processing amount per day is 0.
．． It was set as 075 rounds. The sensitometric characteristics at the end and start are shown in blue, green,
The maximum density and minimum density of red were measured using PDA-65 (manufactured by Konica Corporation) and the amount of change in reflection density was measured. In addition, development unevenness was visually observed using the following evaluation criteria. The results are shown in Table-1. No uneven development was observed in the O'N light area. △ 〃 Occurrence is slightly observed. × 〃 Significant occurrence. The occurrence of X X n is considerably observed. H2 Hx cut: I'! ! f) tq (2-) 'Ea! 9+l (1) Is /, -+t <9.
)ii'l b tz :/”L9-1t, r l-
”u 4 shi+va(nts9ζ), A-2, A-!
, B-IO2β-no4, B-zot go-noe-
1, I;)-1S @・r<'23.17 (1
"t" Lft b! ,-”'OA'7tb7p nLl
Town Ld'ri SSde 03 = k4) c 1"ζk. Mukai C3 cheap! Iruri (3) Takushi voice Shirosu 0fi=10,000...7, M-1/) Hole'sol: l Possible e/shitsu Are Kugler X/iI"'! '#
f's/C'/k'fj;j'l-s t4
cf'J 5 f 77=. F-''' , /'l'-F!3 IL″h;f
tq f'F/lf, 7. bt: 7J3r'yr-Old Vertical T2゜'t'''!'F-Uranus 11 苧1 (Jino t; shown. -2-6 Mourning (L) Example (4) Example (1) The silver halide emulsions of the first, third, and fifth layers were made as shown in Table (3), and after photoprinting, they were subjected to rerunning processing using an automatic processor according to the following processing steps.Processing process Temperature Time Replenishment amount (Sensitive material 1rn2
Color development 36.5°C 35 seconds White fixing described in Table (3) 35°C 35 seconds 54 raft
Stable 30℃ 60 seconds 20OaIL drying
60'C~80℃ 1 minute 30 seconds *34 stabilization tanks!
It is a counter current. The composition of the treatment liquid used is as follows. [Color development tank W,] Potassium bromide 0.018
Potassium chloride 3.0g Potassium sulfite 0.5mA Color developing agent Listed in Table (3) Diethylhydroxylamine (85%) B -19 -1 Triethanolamine Potassium carbonate Ethylene cyano Tetrakis methylene Phosphonic acid Sodium water Finished to 1 ft. Potassium hydroxide pH was adjusted to 10.5. [Color development replenisher] Potassium chloride Potassium sulfite Color developing agent Diethylhydroxylamine-19 -1 Triethanolamine Potassium carbonate Ethylenediamine Tetrakis methylene phosphonic acid sodium salt 3.0 g 0.511 Listed in Table (3) (85%) 5. 0 g 5.0 g 7.0 g 10.0 g 0 g Rum salt z, o g 3.0 g with rum or sulfuric acid 3.0 g 5.0 g 10.0 g 0 g 2.0 g IJZ with water Finish pH with potassium hydroxide or sulfuric acid
Adjusted to 10.40. [Bleach-fixing tank solution] Ethylene shea-tetraacetic acid ferric ammonium dihydrate 1i0.0g Ethylene-thia-based tetraacetic acid 3.0g Ammonium thiosulfate (70!¥ solution) ICl0. O
tall ammonium sulfite (4ON solution)
27.51sll ammonium bromide
30g ammonium nitrate
30g 5-ano 1.3.4 thiadiazole-2-
Thiol 0.5g Aqueous ammonia is adjusted to pH 5.50 with glacial acetic acid, and water is added to bring the total volume to 1ft. [Bleach-fixing replenisher] Ethylene sia-based tetraacetic acid 3J2 Iron ammonium dihydrate 70.0 g Ethylene sia-based tetraacetic acid 3゜0 g Ammonium bromide 30 g Ammonium nitrate 30 g Ammonium thiosulfate (70% solution) 120 g 5-Ayono 1,3 .4-thiazole-2-thiol 0.5 g ammonium sulfite (40%) tI solution 30 mj2 Adjust the pH to 5.0 with aqueous ammonia or glacial acetic acid, and add water to make the total amount IJZ. [Stabilizer tank liquid and replenisher] Ion exchange water (2 pp each of calcium and magnesium
m or less) For running processing, the above color developing tank solution, bleach-fixing tank solution, and stabilizing tank solution were placed in an automatic processor, and the above color developing solution was replenished every 3 minutes while processing the color paper sample. The process was carried out while replenishing the solution, bleach-fixing replenisher, and washing alternative stable replenisher through a metering pump. Note that the running processing amount per day is 0.0SR. When the amount of color developer replenisher added to the color developer tank liquid becomes three times the capacity of the color developer tank, the maximum color density is measured through a wedge-exposed check sample, and the maximum color density is measured at the start of running processing. The activity of the developer and the running stability were evaluated by calculating the relative value with the maximum color density of 100 as 100. The results are shown in Table-3. However, in Table 3, since almost the same results were obtained with the yellow, magenta, and cyan dyes, the magenta dye is listed as the representative characteristic. Furthermore, in Table 4, the evaluation of development unevenness was evaluated at a replenishment amount of 80mj.
2/m2, the method of Example (1) was more closely observed. As is clear from Table 3, by using a high-concentration silver chloride emulsion, even if the amount of replenisher changes, the running fluctuation is smaller than that of conventional high-concentration silver bromide, especially when silver chloride is 90 mol%.
It can be seen that the effect is large in the above cases. However, when low replenishment is used, running fluctuations are large when the developing agent of the present invention is used with a high concentration silver chloride emulsion, and when low replenishment is used, running fluctuations are small when using the developing agent of the present invention. I understand. In particular, the amount of replenishment fluid is shown in Table 4.
As is clearer, it can be seen that uneven development is effectively prevented by using the color developing solution main agent of the present invention. It is also clear from Table 4 that uneven development is more likely to occur when the silver chloride content is high. Therefore, it is clear from this example that only by the structure of the present invention, processing stability is good even when low replenishment is performed without impairing speed, and development unevenness is less likely to occur. Example (5) Trii, third layer and fifth layer of the photosensitive material of Example (4)
The same evaluation as in Example (4) was carried out by adding 0.3@H of heterocyclic mercapto compounds 1'-24, 41, 60, 65, 79, 84 and 87 per inch of photosensitive material to the layer. Good results were obtained regarding processing stability. Example (6) In Example (4), the color development IA process time table-5 was changed as shown in Table 5, and the replenishment amount of the color developer was increased to 80 m ,e/
As I11' (bleach fixing, stable replenishment amount is additional example (4)
) The same evaluation as in Example (4) was performed. The results are shown in Table-5. As is clear from Table 5, the running process fluctuations become larger as the replenishment level becomes lower and the color development processing time becomes faster. It can be seen that the fluctuations are small.Furthermore, since the processing fluctuations are small due to differences in color development processing time, it is expected that the processing fluctuations due to differences between automatic development types will also be small.Example (7) Example (4) The pH of the bleach-fix solution was adjusted to 5.0 to 7.
By setting it to 0, some development unevenness occurred. This means that even if there is uneven development, it will be affected by the pH of the bleach-fix solution, and at low pH.
H indicates that uneven development is less likely to occur. Further, when ammonium bromide was removed from the bleach-fix solution at pH 5.0, color development with slightly uneven development was observed. This suggests that ammonium bromide is effective against uneven development. Example 8 In Example 4, the chloride concentration Δ in the color developer was shown in Table (6
), and the same evaluation as in Example 4 was performed. However, the method of Experiment No. 4-10 was used. The results are shown in Table (6). Mugiko 6) As is clear from Table (6), the chloride concentration is 3X10
It can be seen that running fluctuations due to differences in the amount of replenisher decrease at -2 mol/fL or more. Example 9 The color developing solution subjected to the running process in Example 4 (Experiment No.
4-10 and the amount of replenishment fluid is 80mj! /m"), the following results were obtained. [Color developer composition (1)] Potassium bromide 0.005g
Potassium chloride 4.2g Potassium sulfite (50% solution) 0 Color developing agent (
I-1) 5.0g diethylhydroxylamine (85%) 3.5g B-193.5g D-15.5g Triethanol 10.0g Potassium carbonate 30 gPH
10,14 Add the following compounds to the above running liquid to adjust the pH
A replenisher for color negative film was prepared by adjusting the concentration to 10 and 10. Addition liquid JZ Hydroxylua main sulfate 4.0 g Potassium sulfite (50% solution) 3. [1mft
Color developing agent (1-1) 2.5 g Using the above-mentioned replenisher for color negative film, a running process was performed using the photographed film according to the following processing steps and composition. IA processing process processing time Processing temperature Color development 3 minutes 15 seconds 38℃ Bleaching 45 seconds 38℃ constant
Arrival 1 minute 30 seconds 38℃ stable
50 seconds 38℃ drying 1 minute 4
0 DEG C. to 70 DEG C. (The amount of replenishment is the value per 1-unit of photosensitive material.) However, the fixing process was carried out using a two-bath force scale system, and the stabilization process was carried out using a three-bath force scale system. The composition of the color developing solution used is as follows. Replenishment amount 760 m 310 mj2 620 mu 860 valL Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide
1.2mg hydroxylamine sulfate 2.5g sodium chloride
0.6g 4-A-β-methyl-N-ethyl-N-(β-hydroxylethyl) aniline sulfate 4.5g diethylenetriaminepentaacetic acid 3.0g potassium hydroxide
Add 1.2 g of water to make one layer, and adjust to pH 10.8 using potassium hydroxide or 20% sulfuric acid.
Adjust to. The composition of the bleaching solution used is as follows. 1.3-Propylenediaminetetraacetic acid ferric ammonium 150g Ethylene diaminetetraacetic acid disodium 10g Glacial acetic acid Add 40n+J2 water to bring the temperature to 1°C, and adjust the pH using ammonia water or glacial acetic acid.
Adjust as appropriate so that it becomes 4.5. The composition of the bleach replenisher used is as follows. 1.3-ferric ammonium tetraacetate 180 g Ethylenecyanatetetraacetic acid disodium 2 g ammonium bromide 178 g glacial acetic acid
Add 50mJZ water and tJ
2, and then adjust the pH to 3. using aqueous ammonia or glacial acetic acid.
Adjust to 5. The compositions of the fixing solution and fixing auxiliary solution used are as follows. Ammonium thiosulfate 180 g Ammonium thiocyanate 120 g Anhydrous sodium bisulfite 12 g Sodium metabisulfite 2.5 g Ethylene sia-based ditrithium acetate o, s g Add water to 1°C, and add acetic acid and ammonia water to p
Adjust to H6.5. The compositions of the stabilizer and stable replenisher used are as follows. Formaldehyde (37% solution) 2mj25-
Chloro-2-methyl-4-isothiazolin-3-one 0.05g Triton pH7,0
Adjusted to. The photosensitive material used for running was Konica G
GX-400, GX-3200, 5HR-H, Reala,
5HG-400, 5HG-200, 5HR-11160
0% Gold-100, x Lid-25, VR-10
Using a mixture of 00 and Gold-1800, running was performed until the color developer replenisher was replenished to three times the capacity of the color developer tank, and wedge exposure was performed at the start and end of the run. The above-mentioned photosensitive material was processed and the change in maximum density and minimum density was measured. As a result of the measurement, there was almost no change in the maximum and minimum concentrations at the start and end of running. This makes it possible to use it as a color developer replenisher for color negative film even when processing for color paper requires low replenishment.Moreover, the amount of waste liquid is significantly reduced, which has a significant effect on lowering pollution and lowering costs. Admitted. [Effects of the Invention] As explained above, the present invention provides a silver halide color that does not impair speed even when the amount of replenishment of a color developing solution is significantly reduced, and the photographic characteristics of the obtained image can always be stably supplied. We can provide a method for processing photographic materials.
. Procedural amendment (method) % formula % 1. Indication of the case 1999 Patent Application No. 228992 2. Name of the invention Relationship with the case

Claims (8)

[Claims] (1) After imagewise exposing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, it is developed with a color developing solution containing an aromatic primary amine color developing agent. , in the method of continuous processing while replenishing the color developer replenisher, the silver halide emulsion contains silver halide grains having a silver chloride content of at least 90 mol %, and the aromatic primary amine The color developing agent is a color developing agent represented by the general formula [I],
A method for processing a silver halide color photographic light-sensitive material, characterized in that the amount of replenisher for the color developing solution is 120 ml/m^2 or less. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 represents a hydrogen atom or a methyl group, and
represents sulfate, hydrochloride or P-toluenesulfonate. ] (2) Claim 1, characterized in that the support of the silver halide color photographic light-sensitive material is a reflective support.
A method for processing a silver halide color photographic light-sensitive material as described in . (3) The halogenated compound according to claim 1 or 2, wherein the color developer contains at least 3 x 10^-^2 moles of chloride per 1 liter of the color developer. Processing method for silver color photographic materials. (4) The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 3, wherein the color developing solution contains substantially no sulfate. (5) A method for processing a silver halide color photographic material according to any one of claims 1 to 4, wherein the color developing solution does not substantially contain hydroxylamine. (6) A method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 5, wherein the color developing solution does not substantially contain benzyl alcohol. (7) A method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 6, wherein the color development processing time is 30 seconds or less. (8) The silver halide color photographic light-sensitive material has the general formula [
8. A method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 7, characterized in that it contains a magenta coupler represented by M]. General formula [M] ▲ Numerical formulas, chemical formulas, tables, etc. It may have. ] X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a substituent.