JPH04317055A - Photographic bleach-fix composition and method for processing photographic sensitive material by using same - Google Patents

Abstract

PURPOSE:To reduce bleaching fog and to enhance stability of a processing solution and desilverability by using a combination of thioether having carboxylic and containing substantially no thiosulfate ions and of a bleaching agent high in potential. CONSTITUTION:This photographic bleach-fixing composition contains at least one of the thioether compounds having at least one carboxylic group and containing substantially no thiosulfate ions and at least one of the bleaching agents having an oxidation-reduction potential of <=300mV. It is preferred to use the thioether compound represented by formula: L1-(A-L2)n-B-L3 in which each of L1 and L3, is alkyl, aryl, aralkyl, alkenyl, or a heterocyclic group; L2 is alkylene, arylene, aralkylene, or the like; each of A and B is -S-, -O-, -NR-, or a combination of some of them and an optional group; n is an integer of 1-10; M is H or a counter ion; and R is H, alkyl, aryl, or the like.

Description

[0001] [Field of Industrial Application] The present invention relates to a method for processing silver halide color light-sensitive materials. This invention relates to an excellent method for processing silver halide color photographic materials and a bleach-fixing composition. 2. Description of the Related Art Processing of silver halide color photographic materials generally consists of a color development process and a silver removal process. The silver produced during development is oxidized with a bleaching agent and then dissolved with a fixing agent. As a bleaching agent, a ferric (III) ion complex salt (for example, an aminopolycarboxylic acid-iron (III) complex salt) is mainly used, and as a fixing agent, a thiosulfate is usually used. The bleaching agent and the fixing agent are used in the same bath as a bleach-fixing bath in the processing of color photographic paper, etc. from the viewpoint of speeding up the process. The bleaching agent used here is usually an ethylenediaminetetraacetic acid-iron(III) complex salt. In recent years, in order to further speed up the process, oxidizing agents with higher oxidizing power (higher redox potential) have been used in bleaching baths. However, it is known that bleach fog is large and that there are problems with liquid stability when used in a bleach-fixing bath. The problem with liquid stability is that thiosulfate undergoes oxidative degradation and forms a precipitate. [0003] This problem has become more and more difficult as the replenishment rate has increased in recent years.
In order to prevent the oxidation of thiosulfate, which is particularly problematic,
Sulfite is commonly used as a preservative, but even if an increased amount is added, other problems such as oxidation of sulfite and precipitation of Glauber's salt occur, making it difficult to solve the problem using sulfite. For these reasons, it has been desired to develop a fixing agent that has excellent oxidation stability and excellent fixing properties in place of thiosulfates. However, thiocyanate compounds (especially ammonium salts) have long been used as fixing agents other than thiosulfates.
Thiourea compounds, thioether compounds (e.g. 1,10
-dioxa-4,7-dithiadecane, etc.), but no good compound has been found to date because of insufficient fixing ability or insufficient solubility. On the other hand, a method has been disclosed in which a thioether compound is used in a bleach-fix or fix solution to accelerate the bleach-fix or fix process. Such means include:
For example, Japanese Patent Publication No. 60-24936, Japanese Patent Publication No. 53-374
No. 18, JP-A-62-129855, JP-A-62-1
No. 35834, JP-A-62-136651, JP-A-6
2-136657, JP 62-177556, JP 54-71634, JP 64-21444,
JP 49-16436, U.S. Patent No. 3,241,9
No. 66, U.S. Patent No. 3,716,362, JP-A-2-
No. 44355, etc., but all of these methods are promoting methods in the coexistence of thiosulfate, and such methods cannot serve as a means for improving the liquid stability, which is the objective of the present invention. Further, U.S. Patent No. 2,748,000 discloses the use of a thioether compound included in the present invention as a fixing agent and potassium ferricyanide or quinone as a bleaching agent in a bleach-fixing bath, but desilvering performance is poor. If it is not sufficient, the bleaching fog will increase significantly and it cannot be used as a means for the purpose of the present invention. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a processing method and a bleach-fixing composition including a bleach-fixing bath that causes less bleaching fog and has excellent liquid stability and desilvering properties. It is in. [Means for Solving the Problems] The above object was achieved by the following means. (1) At least one bleaching agent containing substantially no thiosulfate ions, containing at least one thioether compound having at least one carboxylic acid group or a salt thereof as a fixing agent, and having a redox potential of 300 mV or less. 1. A photographic bleach-fixing composition comprising: (2) In a processing method in which a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support is exposed and then subjected to color development and processed with a bleach-fix solution, the bleach-fix solution contains thiosulfuric acid. substantially free of ions,
A silver halide color photograph comprising at least one thioether compound having at least one carboxylic acid group or a salt thereof as a fixing agent and at least one bleaching agent having a redox potential of 300 mV or less. How to process photosensitive materials. Among the above thioether compounds, the following general formula (I) is preferred. General formula (I) L1
-(A-L2)n -B-L3 where L1 and L3
may be the same or different and each represents an alkyl group, aryl group, aralkyl group, alkenyl group, or heterocyclic group, and L2 represents an alkylene group, arylene group, aralkylene group, heterocyclic linking group, or a linking group combining these represents. A and B may be the same or different, and each is -S-, -O-, -NR-, -CO-, -CS-
, -SO2 - or any combination thereof. n represents an integer of 1 to 10. However, at least one of L1 and L3 shall be substituted with a -COOM group. M represents a hydrogen atom or a counter cation,
R represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an alkenyl group. However, at least one of A and B represents -S-. General formula (I) will be explained in detail below. L1 and L3 are substituted or unsubstituted and have 1 carbon number
~10 alkyl groups (e.g., methyl group, ethyl group, propyl group, hexyl group, isopropyl group, carboxyethyl group), substituted or unsubstituted aryl groups having 6 to 12 carbon atoms (e.g., phenyl group, 4-methyl phenyl group,
3-methoxyphenyl group), a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group), or substituted or unsubstituted aralkyl group having 2 to 10 carbon atoms
alkenyl group, (e.g. vinyl group, propenyl group,
1-methylvinyl group) or a substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms (e.g., pyridyl group, furyl group, thienyl group, imidazolyl group), and L2 represents a substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms (for example, pyridyl group, furyl group, thienyl group, imidazolyl group); 10 alkylene groups (
For example, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 1-methylethylene group, 1-hydroxytrimethylene group), substituted or unsubstituted arylene group having 6 to 12 carbon atoms (e.g. phenylene group, naphthylene group), substituted or unsubstituted aralkylene group having 7 to 12 carbon atoms (e.g. 1,2-xylylene group), substituted or unsubstituted heterocyclic linking group having 1 to 10 carbon atoms (e.g. ##STR1## A and B are -S-, -O-, -NR-, -
Represents a group such as CO-, -CS-, -SO2- or any combination thereof; examples of the arbitrary combinations include -CONR1-, -N(R2)CO-, -N(R3)
CON(R4)-, -COO-, -OCO-, -SO2
NR5 −, −N(R6)SO2 −, −CSNR7
, -N(R8)CS-, -N(R9)CSN(R10
)- etc. n represents an integer from 1 to 10. However, L1 and L3
At least one of these is substituted with a -COOM group. M represents a hydrogen atom or a counter cation (e.g., an alkali metal atom such as a sodium atom, a potassium atom, an alkaline earth metal atom such as a magnesium atom or a calcium atom, an ammonium group such as ammonium or triethylammonium, etc.) . R and R1 to R10 are hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms (for example,
methyl group, ethyl group, propyl group, hexyl group, isopropyl group), substituted or unsubstituted aryl group having 6 to 12 carbon atoms (e.g., phenyl group, 4-methylphenyl group, 3-methoxyphenyl group), substituted or Unsubstituted aralkyl group having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group) or substituted or unsubstituted aralkyl group having 2 to 1 carbon atoms
0 alkenyl groups (e.g. vinyl group, propenyl group,
1-methylvinyl group). L1, L2, L3
, R, R1 to R10 each has a substituent,
Examples of the substituents include lower alkyl groups having 1 to 4 carbon atoms (e.g. methyl group, ethyl group), aryl groups having 6 to 10 carbon atoms (e.g. phenyl, 4-methylphenyl group), aralkyl groups having 7 to 10 carbon atoms. group (e.g. benzyl group), alkenyl group having 2 to 4 carbon atoms (e.g. propenyl group), alkoxy group having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group), halogen atom (e.g. chlorine atom, bromine atom), cyano group, nitro group, carboxylic acid group (may be in the form of a salt), hydroxy group, sulfonic acid group, amino group (e.g. unsubstituted amino group, dimethylamino group), ammonium group (e.g. trimethylammonium group) , etc. However, when n is 2 or more, A and L2 may be any combination of the groups listed above. Also, at least one of A and B
1 represents -S-. In general formula (I), preferably L1 and L
3 represents an alkyl group having 1 to 6 carbon atoms substituted with a -COOM group, and L2 represents an alkylene group having 1 to 6 carbon atoms. A and B represent -S-, -O- or -NR-, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 6. In general formula (I),
More preferably A and B represent -S-, and n is 1-3
represents an integer. Specific examples of the compound of general formula (I) of the present invention are shown below, but the compound of the present invention is not limited thereto. [Formula 2] [Formula 3] [Formula 3] [Formula 4] [Formula 5] [Formula 5] The compound represented by the general formula (I) of the present invention is described in the Journal of Organic・Chemistry (J.Org.Chem.) 30, 2867 (1965
), 27, 2846 (1962), Journal of the American Chemical Society (J.Am.C.
hem. Soc. ) 69, 2330 (1947) etc., it can be easily synthesized. Compositions related to the present invention include bleach-fix solutions, replenishers, concentrates, and the like. Moreover, it may be in the form of a kit or in the form of a powder. In the present invention, "substantially not containing thiosulfate ions" specifically means 0.05 mol/liter or less of thiosulfate ions, more preferably 0.0 mol/liter or less.
It means that it is 1 mol/liter or less. It is unexpected that the compound of the present invention was able to function effectively as a fixing agent by substantially not containing thiosulfate, which is commonly used. It was also unexpected that the aforementioned objects could be achieved by using the compounds of the invention in combination with high potential bleaching agents. The amount of the compound of the present invention used in the bleach-fixing bath is such that it can function as a fixing agent, for example 1.times.10@-1 mol/liter or more. It is preferably 1.5 x 10-1 mol/liter or more, more preferably 2 x 10-1 mol/liter or more, and particularly preferably 2 x 10-1 to 3 mol/liter. Here, when the halogen composition of the silver halide emulsion in the photographic material to be processed is AgBrI (I≧1 mol% or more, preferably 3 to 15 mol%), 0.5 to 2 mol/liter is used. It is preferable, and more preferably 1.
2 to 2 mol/liter is preferred. In addition, the halogen composition is AgBr, AgBrCl or high silver chloride (AgCl≧8).
0 mol% or more), it is preferably used at 0.2 to 0.9 mol/liter, more preferably 0.4 to 0.9 mol/liter.
9 mol/liter is preferred. The former is for photosensitive materials that usually have a relatively large amount of coated silver (for example, 2 to 10 g/m2), and the latter is for prints that usually have a relatively small amount of coated silver (for example, 0.4 to 0.9 g/m2). This is the case for photosensitive materials. In recent years, as the trend towards low replenishment has progressed, it has been desired to improve the liquid stability of each processing bath. A problem with the stability of bleach-fix baths and subsequent wash baths is sulfide precipitation resulting from oxidative degradation of the thiosulfate salts used as fixing agents. Problems also occur in the washing bath because the bleach-fix solution is carried into the washing bath during processing. Sulfite is normally used as an antioxidant to prevent this precipitation, but when using low replenishment, simply increasing the amount of sulfite used will cause solubility problems and oxidation of sulfite. Problems such as the formation of Glauber's salt precipitates have made it difficult to solve the problem. The present inventors investigated various fixing agents with excellent oxidation stability to replace thiosulfates, and found that the thioether compound of the present invention has a fixing ability, is stable against oxidation, and is effective at low replenishment amounts. It has been found that no precipitate is formed, and the bleach fog is also smaller than that of thiosulfates, and good results are obtained especially in bleach-fix solutions combined with high-potential oxidizing agents within a range of redox potentials. Next, the bleaching agent used in the present invention will be explained. The bleaching agent used in the present invention has an oxidation-reduction potential of 300 mV or less, and examples thereof include iron (III), cobalt (
III), compounds of polyvalent metals such as chromium (IV) and copper (II), peracids, nitro compounds, etc. are used. Typical bleaching agents include: dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes, etc. may be used. can. Of these, iron ethylenediaminetetraacetate (
III) Aminopolycarboxylic acid iron(I) including complex salts
II) Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. In addition, iron aminopolycarboxylate (II
I) Complex salts are particularly useful. In addition, when considering rapid processing of the bleach-fixing process, in particular, the redox potential is 150 mV or more and 300 mV or less, preferably 200 mV or more and 300 mV or less.
The following so-called high potential oxidizing agents are preferred. [0020] The redox potential of the oxidizing agent in the above is determined by the Transactions of the Faraday Society.
raday Society), Volume 55 (1959)
It is defined by the redox potential measured by the method described in , p. 1312-1313. The redox potential in this case was obtained by the method described above under the condition of pH 6.0. The reason why the potential determined at pH 6.0 is used is that pH around 6.0 is a guideline for the occurrence of bleaching fog. Specific examples of aminopolycarboxylic acid iron (III) complex salts are listed below, but the invention is not limited thereto. In addition, the redox potential in the above definition will be described. In addition, aminopolycarboxylic acid iron (I
II) As the complex salt, salts such as sodium, potassium, and ammonium salts are used, but ammonium salts are preferred because they bleach the fastest. Compound No.

redox potential

(mV vs.NHE, pH=6)II-
1. Iron(III) N-(2-acetamido)iminodiacetate
) Complex salt 180II-2. Methyliminodiacetic acid iron(III) complex salt
200II-3. Iron(III) iminodiacetate complex salt
210
II-4.1,4-butylenediaminotetraacetic acid iron (III
) Complex salt 230II-
5. diethylenethioether diaminetetraacetate iron (III)
) Complex salt 230II-6. Glycol ether diamine tetraacetic acid iron(III) complex salt
240II-7.1,3-Propylenediaminetetraacetic acid iron(III) complex salt
250II-8. Ethylenediaminetetraacetic acid iron(III) complex salt
110II-9. Diethylenetriaminepentaacetic acid iron(III) complex salt
80II-10. trans-1,2-
Iron(III) cyclohexanediaminetetraacetate
80 Complex salt
00
22] The pH of the bleach-fix solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH can be lowered. . The bleaching agent of the present invention is 0.00% per liter of processing solution.
It is effective to contain 0.05 to 1 mole, and more preferably 0.1 to 0.5 mole per liter of treatment liquid. Next, the silver halide color photographic light-sensitive material and the processing method using the same will be described in detail. The silver halide color photographic light-sensitive material of the present invention may be provided with at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support. There are no particular limitations on the number and order of the silver halide emulsion layers and non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. but,
Depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer. between the silver halide photosensitive layers and the uppermost layer;
A non-photosensitive layer such as various intermediate layers may be provided at the bottom layer. The intermediate layer may contain a coupler, a DIR compound, etc., and may also contain a commonly used color mixing inhibitor. A plurality of silver halide emulsion layers constituting each unit photosensitive layer include a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of emulsion layers can be preferably used. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
As described in JP-A Nos. 57-112751, 62-200350, 62-206541, and 62-206543, there is a low-sensitivity emulsion layer on the side away from the support, and a side close to the support. A high-sensitivity emulsion layer may be provided. As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) /high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive layer (RL),
Alternatively, they can be installed in the order of BH/BL/GL/GH/RH/RL, or in the order of BH/BL/GH/GL/RL/RH. Alternatively, as described in Japanese Patent Publication No. 55-34932, the layers may be arranged in the order of blue-sensitive layer/GH/RH/GL/RL from the side farthest from the support. Also, JP-A-56-25738, JP-A No. 62-6393
As described in No. 6, the layers may be arranged in the order of blue-sensitive layer/GL/RL/GH/RH from the side farthest from the support. In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even in the case where the layer is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464, medium-sensitivity emulsion is added from the side remote from the support in the same color-sensitive layer. They may be arranged in the following order: layer/high-speed emulsion layer/low-speed emulsion layer. As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material. When the silver halide color photographic light-sensitive material is a color negative film or a color reversal film, the preferred silver halide contained in the photographic emulsion layer is silver iodobromide, containing about 30 mol% or less of silver iodide; Silver iodochloride or silver iodochlorobromide. Particularly preferred are silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide. When the silver halide color photographic light-sensitive material is color photographic paper, the silver halide contained in the photographic emulsion layer consists of silver chlorobromide or silver chloride, which does not substantially contain silver iodide. can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide/silver chloride emulsion can be used. Although this ratio can vary widely depending on the purpose, those having a silver chloride ratio of 2 mol % or more are preferably used. For light-sensitive materials suitable for rapid processing, so-called high silver chloride emulsions containing a high silver chloride content are preferably used. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, and 9
More preferably 5 mol% or more. For the purpose of reducing the amount of replenishment of the processing solution, an almost pure silver chloride emulsion having a silver chloride content of 98 to 99.9 mol % is also preferably used. The silver halide grains in the photographic emulsion include those having regular crystal shapes such as cubic, octahedral, and tetradecahedral, those having irregular crystal shapes such as spherical and plate shapes, and those having irregular crystal shapes such as spherical and plate shapes. It may be one having crystal defects such as crystal planes, or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion. Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (hereinafter referred to as RD) N
o. 17643 (December 1978), pp. 22-23, “I. Emulsion preparation
tion and types)”, and the same No.
18716 (November 1979), p. 648, etc. Monodisperse emulsions such as those described in US Pat. No. 3,574,628, US Pat. No. 3,655,394 and British Patent No. 1,413,748 are also preferred. Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
rapic science and engine
ering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,434,226, No. 4,414,
No. 310, No. 4,433,048, No. 4,439,5
20 and British Patent No. 2,112,157. The crystal structure may be uniform, the inside and outside may have different halogen compositions, it may have a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide. Also, mixtures of particles of various crystal forms may be used. The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical sensitization and spectral sensitization. During the physical ripening process, various polyvalent metal ion impurities (salts or complex salts of cadmium, zinc, lead, copper, thallium, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc.) can be introduced. . Compounds used for chemical sensitization are described in JP-A-62-21
Examples include those described in the lower right column on page 18 to the upper right column on page 22 of the specification of Japanese Patent No. 5272. Moreover, the additives used in such a process are RD No. 17643 and the same No.
18716, and the relevant parts are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the above two RDs, and the relevant descriptions are shown in the table below. Additive type RD17
643 RD18716 1 Chemical sensitizer page 23
Page 648 right column 2 Sensitivity enhancer

Same as above 3 Spectral sensitizer, pages 23-24
Page 648 right column ~ Super sensitizer

Page 649 right column 4
Brightener page 24
5 Antifoggant 24-25
Page 649, right column - and stabilizers

6 Light absorber, 25-26
Page 649 Right column ~ Filter dye,
Page 650 left column Ultraviolet absorber 7 Stain inhibitor Page 25 right column Page 650 left to right column 8 Dye image stabilizer Page 25 9
Hardener page 26
Page 651 left column 10 Binder page 26
Same as above 11 Plasticizer, lubricant page 27
Page 650 right column 12 Coating aid,
Pages 26-27 650
Page right column Surfactant 13 Static inhibitor Page 27 Same as above 00
30] In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, compounds that can react with and fix formaldehyde as described in U.S. Pat. Nos. 4,411,987 and 4,435,503 are added to photosensitive materials. It is preferable to add it to Various color couplers can be used in the present invention, and specific examples thereof include the above-mentioned RD No. 1
No. 7643, VII-CG. Examples of yellow couplers include U.S. Pat. No. 3,933,501, U.S. Pat. No. 4,022,620, U.S. Pat.
, 248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, British Patent No. 1,476,760, U.S. Patent No. 3,973,968, British Patent No. 4,314,0
No. 23, No. 4,511,649, European Patent No. 249,
Preferred are those described in No. 473A and the like. As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and are disclosed in US Pat. Nos. 4,310,619 and 4,351,897;
European Patent No. 73,636, US Patent No. 3,061,4
No. 32, No. 3,725,064, RD No. 242
20 (June 1984), JP-A No. 60-33552,
RDNo. 24230 (June 1984), JP-A-6
No. 0-43659, No. 61-72238, No. 60-3
No. 5730, No. 55-118034, No. 60-185
No. 951, U.S. Pat. No. 4,500,630, U.S. Pat.
No. 40,654, No. 4,556,630, WO (PC
Particularly preferred are those described in No. T) 88/04795 and the like. Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,21.
No. 2, No. 4,146,396, No. 4,228,233
No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162,
No. 2,895,826, No. 3,772,002, No. 3,758,308, No. 4,334,011, No. 4
, 327,173, West German Patent Publication No. 3,329,72
9, European Patent No. 121,365A, European Patent No. 249,45
3A, U.S. Patent No. 3,446,622, U.S. Patent No. 4,33
No. 3,999, No. 4,753,871, No. 4,451
, No. 559, No. 4,427,767, No. 4,690,
No. 889, No. 4,254,212, No. 4,296,1
99, JP-A No. 61-42658, etc. are preferred. Colored couplers for correcting unnecessary absorption of coloring dyes include RD No. VII of 17643
- Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4,138,258, British Patent No. 1,146,368
Preferably, those described in No. Also, U.S. Patent No. 4,77
A coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released during coupling as described in No. 4,181;
It is preferred to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in US Pat. No. 4,777,120. Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4,366,237 and British Patent No. 2,125,570.
No., European Patent No. 96,570, West German Patent (Publication) No. 3
, 234,533 is preferred. Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820;
, No. 211, No. 4,367,282, No. 4,409,
No. 320, No. 4,576,910, British Patent No. 2,10
It is described in No. 2,173, etc. Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the above-mentioned patents described in RD17643, VII to F, and in JP-A-57-151944 and JP-A-57-151944.
No. 154234, No. 60-184248, No. 63-3
7346, U.S. Pat. No. 4,248,962, U.S. Patent No. 4,7
82,012 is preferred. Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,1.
No. 31,188, JP-A-59-157638, JP-A No. 59
-170840 is preferred. Other couplers that can be used in the photosensitive material of the present invention include US Pat. No. 4,130,42
Competitive couplers such as those described in U.S. Pat. No. 4,283, et al.
No. 472, No. 4,338,393, No. 4,310,6
Multi-equivalent coupler described in No. 18 etc., JP-A-60-185
DIR described in No. 950, JP-A No. 62-24252, etc.
Redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 1
RD No. 73,302A, a coupler releasing a dye that recolors after separation, as described in RD No. 73,302A; 11449, 24241,
Bleach accelerator-releasing couplers described in JP-A No. 61-201247, ligand-releasing couplers described in U.S. Pat. No. 4,553,477, and leuco dye-releasing couplers described in JP-A-63-75747. , U.S. Patent Nos. 4 and 7
Examples include couplers that emit fluorescent dyes as described in No. 74,181. The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are U.S. Pat.
Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, dicyclohexyl phthalate, etc.). 2-ethylhexyl phthalate, decyl phthalate, bis(2,4-
Di-t-amylphenyl) phthalate, bis(2,4-
di-t-amyl phenyl) isophthalate), bis(1
, 1-diethylpropyl) phthalate, etc.), esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, butoxyethyl phosphate,
trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N,N-diethyldodecanamide, N , N-diethyl laurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (
isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (
bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-2-butoxy-5-te)
rt-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone,
Examples include cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like. Specific examples of the latex dispersion process, effects, and latex for impregnation are described in US Pat. No. 4,199,36.
No. 3, West German Patent Application (OLS) No. 2,541,274 and OLS No. 2,541,230. These couplers can also be impregnated into loadable latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents described above.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 88/00723 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization. The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, direct positive color photosensitive materials, color positive film, and color reversal paper. Suitable supports that can be used in the present invention include, for example, the above-mentioned RD. No. 28 of 17643
page, and the same no. 64 from the right column of page 647 of 18716
It is written in the left column of page 8. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is 25 μm or less, preferably 20 μm or less, and the film swelling rate is T1/2.
is preferably 30 seconds or less (preferably 15 seconds or less). The film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate T1/2 can be measured according to a method known in the art. For example, A. Green et al., Photographic Science and Engineering (Photogr. Sci. Eng.), Vol. 19, 2.
T1/2 is the maximum swollen film thickness reached when treated with a color developer at 30°C for 3 minutes and 15 seconds. 90% of the saturation film thickness is defined as the time required to reach 1/2 of this film thickness. The membrane swelling rate T1/2 is determined by adding a hardening agent to gelatin as a binder;
Alternatively, it can be adjusted by changing the aging conditions after application. Further, the swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness - film thickness)/film thickness. The above-mentioned color photographic light-sensitive material has the above-mentioned RD.
No. 17643, pages 28-29, and the same No. 1
Development processing can be carried out by the usual methods described in 615 left column to right column of 8716. The color developing solution used for developing the photosensitive material is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and a representative example thereof is 3-methyl-4
-amino-N,N diethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-
Examples include amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. These compounds are used depending on the purpose2
It is also possible to use more than one species in combination. The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It generally contains an agent or an antifoggant. In addition, as necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids,
Triethylenediamine (1,4-diazabicyclo[2,
2,2] Various preservatives such as octane), organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, and competitive couplers. , fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids. Various chelating agents such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,
N-trimethylenephosphonic acid, ethylenediamine-N,
Fluorescent brighteners such as N,N,N-tetramethylenephosphonic acid, ethylenediamine-di(o-hydroxyphenylacetic acid) and their salts), and 4,4'-diamino-2,2'-disulfostilbene compounds Various surfactants such as surfactants, alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added. [0041] However, it is preferable that benzyl alcohol is substantially not contained in view of pollution, liquid preparation properties, and prevention of color staining. Here, "substantially" means 2 ml or less (more preferably not at all) per liter of color developer. Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-3
Known black and white developing agents such as 3-pyrazolidones such as -pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination. [0042] The pH of these color developing solutions and black and white developing solutions
is generally from 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but is generally less than 3 liters per square meter of light-sensitive material, and can be reduced to less than 500 ml by reducing the bromide ion concentration in the replenisher. You can also. In particular, when using so-called high silver chloride light-sensitive materials, by lowering the bromide ion content and relatively increasing the chloride ion content in the color developing solution, it is possible to achieve excellent photographic properties and processability, and to suppress fluctuations in photographic properties. This is particularly preferable because it allows The replenishment amount in such cases can be reduced to about 20 ml per square meter of light-sensitive material, which substantially eliminates overflow in the color developing bath. When reducing the amount of replenishment, reduce the contact area with the air in the processing tank to prevent evaporation of the liquid.
Preferably, air oxidation is prevented. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer. [0043] The processing temperature of the color developing solution of the present invention is from 20 to
The temperature is 50°C, preferably 30-45°C. The processing time is
The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent. After color development, the photographic emulsion layer is usually bleached. The bleaching process is carried out simultaneously with the fixing process (bleach-fixing process), but in order to further speed up the process, a bleach-fixing process may be performed after the bleaching process. Alternatively, a method of bleaching → bleach-fixing → fixing may be used. Furthermore, treatment in two continuous bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. As the bleaching agent used, those mentioned above are used. A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification. U.S. Patent No. 3,893,858, West German Patent No. 1
, No. 290,812, JP-A-53-95630, RD
No. Compounds having a mercapto group or a disulfide bond described in No. 17129 (July 1978) and the like;
Thiazolidine derivatives described in JP-A-50-140129; thiourea derivatives as described in US Pat. No. 3,706,561; iodide salts as described in JP-A-58-16,235; West German Patent No. 2, Polyoxyethylene compounds described in Japanese Patent Publication No. 748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as disclosed in US Pat.
Preferred are the compounds described in No. 93,858, West German Patent No. 1,290,812, and JP-A-53-95630. Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography. Known additives such as rehalogenating agents such as ammonium bromide and ammonium chloride, pH buffering agents such as ammonium nitrate, and metal corrosion inhibitors such as ammonium sulfate may be added to the bleach-fixing solution of the present invention. can. As a preservative for the bleach-fix solution, sulfites, bisulfites, carbonyl bisulfite adducts, and sulfinic acid compounds may be added. In order to improve stability, aminopolycarboxylic acids and organic phosphonic acid chelating agents (preferably 1-hydroxyethylidene-1,1-diphosphonic acid and N,N,N',N'-ethylenediaminetetraphosphonic acid) are also used. ) is preferably contained. The bleach-fix solution also contains various optical brighteners, antifoaming agents, surfactants,
Polyvinylpyrrolidone, methanol, etc. can be contained. From the viewpoint of shortening the desilvering treatment time, it is preferable that the stirring of each treatment solution in the desilvering step be as strong as possible. As a stirring means, JP-A-62-18346 is used.
Examples include methods such as those described in No. 0 and No. 62-183461, and in the case of a means of colliding jets, the time until collision is within 15 seconds after the photosensitive material is introduced into the processing solution. is preferred. In the present invention, the crossover time from the color developer to the bleach-fix solution (the time in the air from when the photosensitive material leaves the color developer to when it enters the bleach-fix solution) improves bleach fog and dirt adhesion on the surface of the photosensitive material. The time is preferably within 10 seconds. Here, the amount of replenishment of the bleach-fixing solution is as follows:
12 g/m2), it is preferably 800 ml/m2 or less, and in the case of color photographic paper, it is preferably 60 ml/m2 or less. The silver halide color photographic light-sensitive material used in the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment. The amount of washing water in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the washing water temperature, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the S
Ociety of Motion Picture
and Television Engineers
Volume 64, P. 248-253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, such problems were solved by the method disclosed in Japanese Patent Application Laid-open No. 62-28.
The method of reducing Ca ions and Mg ions described in No. 8838 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi , "Sterilization, sterilization, and anti-mildew technology of microorganisms" edited by Sanitation Technology Society, and "Encyclopedia of anti-bacterial and anti-mold agents" edited by Japan Antibacterial and Mildew Society can also be used. The pH of the washing water used in the processing of the photosensitive material of the present invention is from 4 to 9, preferably from 5 to 8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally, it is carried out at 15 to 45°C for 20 seconds to 10 minutes.
Preferably, the temperature range is 30 seconds to 5 minutes at 25 to 40°C. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Laid-Open Nos. 57-8543 and 58
All known methods described in Japanese Patent No. 14834 and No. 60-220345 can be used. Further, following the water washing treatment, there are cases where a further stabilization treatment is performed, and an example of this is a bath used as a final bath for color photosensitive materials for photography.
Examples include stabilizing baths containing dye stabilizers typified by formalin, hexamethylenetetramine, hexahydrotriazine, and N-methylol compounds. This stabilizing bath may also contain ammonium compounds, Bi, Al, etc., if necessary.
metal compounds such as fluorescent whitening agents, various chelating agents, membrane p.
It is also possible to add an H regulator, a hardening agent, a bactericide, a fungicide, an alkanolamine, and a surfactant (preferably a silicone type). In addition to tap water, the water used in the washing process or stabilization process is carbonated by ion exchange resin, etc.
It is preferable to use water that has been deionized to a concentration of a ions and Mg ions of 5 mg/liter or less, or water that has been sterilized with a halogen or ultraviolet germicidal lamp. The amount of water washing and/or stabilizing solution to be refilled is 1 to 50 of the amount brought in from the bath per unit area of the photosensitive material.
twice, preferably 2 to 30 times, more preferably 2 to 15 times. The overflow liquid accompanying this replenishment can also be reused in other processes such as the desilvering process. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, U.S. Pat. No. 3,342,599, RD
No. Schiff base type compounds described in Nos. 14,850 and 15,159, aldol compounds described in No. 13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, and described in JP-A-53-135628. The following urethane compounds can be mentioned. The silver halide color photosensitive material of the present invention is
If necessary, various types of 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64339 and JP-A-57-14.
No. 4547, No. 58-115438, etc. Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out. One example of a silver halide color light-sensitive material is one using direct positive type silver halide. Processing using this photosensitive material will be explained below. After or during fogging treatment with light or a nucleating agent after imagewise exposure of a silver halide color photographic light-sensitive material, p containing an aromatic primary amine color developing agent is used.
It is also preferable to directly form a positive color image by performing color development, bleaching and fixing with a surface developer of H11.5 or less. It is more preferable that the pH of this developer is in the range of 11.0 to 10.0. The fogging treatment in the present invention is a method of applying a second exposure to the entire surface of the photosensitive layer, which is called a "photofogging method", and a method of developing in the presence of a nucleating agent, which is called a "chemical fogging method". Either can be used. Development may be carried out in the presence of a nucleating agent and fogging light. Furthermore, the photosensitive material containing the nucleating agent may be exposed to fog light. Regarding the light fogging method, see page 47, lines 4 to 49 of the above-mentioned Japanese Patent Application No. 61-253716.
Nucleating agents that can be used in the present invention are described on page 49, line 6 to page 67, line 2 of the same specification, particularly for general formulas [N-I] and [N- It is preferable to use a compound represented by 2]. Specific examples of these include [N-I-1] to [N-
I-10] and [N-I
I-1] to [N-II-12] are preferably used. Regarding the nucleation accelerator that can be used in the present invention,
It is described on page 68, line 11 to page 71, line 3 of the same specification, and as a specific example, it is particularly preferable to use (A-1) to (A-13) described on pages 69 to 70 of the same specification. . The color developer used in the development of the light-sensitive material of the present invention is described in the same specification from page 71, line 4 to page 72, line 9, and in particular aromatic primary amine color developer. As a specific example, p-phenylenediamine type compounds are preferable, and representative examples thereof include 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, 3-methyl-4-amino -N-ethyl-N-(β-
Examples include hydroxyethyl)aniline, 3-methyl-4-amino-N-ethyl-N-methoxyethylaniline, and salts thereof such as sulfates and hydrochlorides. [0053] As in the present invention, when a specific bleaching agent and a thioether having a carboxylic acid are used in combination, a stable bleach-fixing solution with less bleach fog can be provided. Furthermore, a bleach-fixing method with excellent desilvering properties can be provided. [Examples] Examples of the present invention will be specifically shown below, but the present invention is not limited thereto. Example 1 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows. First layer coating solution preparation Yellow coupler (ExY) 19.1g, color image stabilizer (Cpd-1) 4.4g and color image stabilizer (Cpd-7)
) to 0.7 g, 27.2 cc of ethyl acetate and solvent (So
lv-1) 8.2g was added and dissolved, and this solution was mixed with 10% sodium dodecylbenzenesulfonate containing 8cc.
% gelatin aqueous solution (185 cc). On the other hand, silver chlorobromide emulsion (cubic, 3:7 mixture of average grain sizes of 0.88 μm and 0.70 μm (silver molar ratio)
. The coefficient of variation of the grain size distribution is 0.08 and 0.10, and each emulsion contains 0.2 mol% of silver bromide locally on the grain surface), and the blue-sensitive sensitizing dye shown below is added to a large size per mol of silver. For emulsions, add 2.0 x 10-4 mol each, and for small size emulsions add 2.5 x 10-4 mol each.
mol was added and then sulfur sensitized. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below. Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. The following spectral sensitizing dyes were used in each layer. ##STR6## (per mole of silver halide, 2.0 x 10-4 mol each for large size emulsions, and 2.5 x 10-4 mol each for small size emulsions) 4 moles) 0058
] [0059] (per mole of silver halide, 4.0 x 10 -4 mol for large size emulsions, 5.6 x 10 -4 mol for small size emulsions) and [ [0060] [0061] (per mole of silver halide, 7.0 x 10-5 mol for large size emulsions, and 1.0 x 10-5 mol for small size emulsions) ##STR9## (per mole of silver halide, 0.9 x 10-4 mol for large size emulsions, and 1.1 x 10-4 mol for small size emulsions) ) For the red-sensitive emulsion layer, the following compound 2.6× per mole of silver halide
10-3 mol was added. ##STR10## Further, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, 1-(5-methylureidophenyl)-
5-mercaptotetrazole to 1 silver halide each
8.5x10-5 mol, 7.7x10-4 mol, and 2.5x10-4 mol were added per mole. In addition, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer at 1 x 10-4 mol and 2 mol per mol of silver halide, respectively. ×10-
4 mol was added. The following dyes were added to the emulsion layer to prevent irradiation. ##STR12## (Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m2). The silver halide emulsion represents the coated amount in terms of silver. Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiO2) and a bluish dye (ulmarine blue)] First layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion

0.30 Gelatin

1.86 Yellow coupler (ExY)
0.82
Color image stabilizer (Cpd-1)
0.
19 Solvent (Solv-1)

0.35 Color image stabilizer (Cpd-7)

0.06 Second layer (color mixing prevention layer) Gelatin

0.99 Color mixing prevention agent (Cpd-5
)
0.08 Solvent
-1)
0.16
〃(Solv-4)

0.08 [0069] Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.55μ
1:3 mixture (Ag molar ratio) of 0.39μm and 0.39μm. The coefficient of variation of particle size distribution is 0.
10 and 0.08, each emulsion contained 0.8 mol% of AgBr locally on the grain surface)

0.1
2 Gelatin

1.24 Magenta coupler (E
xM)
0.20 Color image stabilizer (C
pd-2)
0.03 Color image stabilizer (Cpd-3)
0.15
Color image stabilizer (Cpd-4)
0
．． 02 Color image stabilizer (Cpd-9)

0.02 Solvent (Solv-2)

0.40 Fourth layer (ultraviolet absorption layer) Gelatin

1.58 Ultraviolet absorber (UV-1
)
0.47 Color mixing prevention agent (C
pd-5)
0.05 Solvent (
Solv-5)
0.2
4. Fifth layer (red-sensitive layer) Silver chlorobromide emulsion [cubic, average grain size 0.58μ
1:4 mixture (Ag molar ratio) of 0.45 μm and 0.45 μm. The coefficient of variation of particle size distribution is 0.
09 and 0.11, each emulsion contained 0.6 mol% of AgBr locally on a part of the grain surface)

0.23
gelatin

1.34 Cyan coupler (ExC)

0.32 Color image stabilizer (Cpd
-6)
0.17 Color image stabilizer (Cpd-7)
0.40 Color image stabilizer (Cpd-8)
0.0
4 Solvent (Solv-6)

0.15 6th layer (ultraviolet absorption layer) Gelatin

0.53 Ultraviolet absorber (UV-1
)
0.16 Color mixing prevention agent (C
pd-5)
0.02 Solvent (
Solv-5)
0.0
8 Seventh layer (protective layer) Gelatin

1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17
liquid paraffin

0.03 [0078] After imagewise exposure of the above photosensitive material, continuous processing (a running test ) was carried out. Treatment process temperature time
Refill amount Tank capacity


(liter) Color development 35℃
45 seconds 109ml
17 Bleach fixing 35℃ 45 seconds
61ml 17
Rinse ■ 35℃ 30 seconds
-10 Rinse ■ 35℃ 30 seconds
-10 Rinse■
35℃ 30 seconds 300
ml dry 80℃ 60
seconds *The amount of replenishment is per 1 m2 of photosensitive material *The bleach-fixing solution includes bleach-fixing replenisher and rinse solution (12
1 ml) is replenished. *(Rinsing is 3-tank countercurrent method from ■ to ■) 0081
] The composition of each treatment solution is as follows. color developer
tank liquid
replenisher water

800ml 800m
l Ethylenediamine-N,N,N,N-tetra
methylene phosphonic acid
3.0g
3.0g triethanolamine
5.
0g 5.0g Potassium chloride

3.1g -
potassium bromide
0.015
g - potassium carbonate

25g 25
g hydrazinodiacetic acid
5.0g
7.0g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4
-Aminoaniline sulfate

5.0g 9.5g Fluorescent brightener (WHITEX-4 manufactured by Sumitomo Chemical)
1.0g 2.5g
add water
1000ml
1000ml pH (add potassium hydroxide) 1
0.05 10.60 0082 Bleach-fix solution
tank liquid
replenisher water

600ml 150
ml ammonium thiosulfate (70wt%)
100ml
245ml or the compound of the present invention

0.4 mol 1.0 mol Ammonium sulfite
45g 10
5g ethylenediaminetetraacetic acid iron (III) ammonium

55g 135g Ethylenediaminetetraacetic acid
3.0g 8.0
g ammonium bromide
30g
75g nitric acid (67%)

27g 68g
add water
1000ml
1000ml pH

5.80
5.60 Rinse solution (tank solution and refill solution are the same) Ion-exchanged water (calcium, magnesium each 3 ppm or less) After processing, measure the amount of residual silver in the unexposed area of the sample using a fluorescent X-ray analyzer. did. In addition, the presence or absence of precipitates in the bleach-fix bath and rinse bath after the completion of the running process was visually inspected. Furthermore, the magenta reflection density (Dmi) of the unexposed area is
n) was measured using an X-rite densitometer. Furthermore, the same mole of 1,3-propylenediaminetetraacetate iron(III) ammonium was substituted for the ethylenediaminetetraacetate ammonium in the bleach-fix solution, and the same running process was performed to check the amount of residual silver, presence of precipitation, and unexposed areas. The magenta reflection density was determined. For comparison, U.S. Patent No. 2,748,
Potassium ferricyanide (redox potential 460 mV), quinone (redox potential 346 mV) described in No. 000
mV (pH 6)) of iron(III) ethylenediaminetetraacetate
) was used in an equimolar amount with ammonium. The results are shown in Table 1. [Table 1] Table 1 shows that when the compound of the present invention is used as a fixing agent in place of thiosulfate, precipitation does not occur even during running processing, the liquid stability is excellent, and the fixing agent is not exposed to light. It can be seen that good results with low density (Dmin, bleaching fog) were obtained. Furthermore, this result is particularly remarkable when a bleaching agent with a high redox potential is used as the bleaching agent. On the other hand, the redox potential is too high (300mV
When using a bleaching agent (exceeding 20%), the amount of residual silver and the density of unexposed areas are insufficient compared to the combination of the present invention. Example 2 Compound I-1 of Example 1 was converted into compounds I-3, I-4, I-
5, I-12, I-13, I-14, I-19, I-2
The same test as in Example 1 was conducted except for using 1 and 1-22. As a result, as in Example 1, good results were obtained in that no precipitate was formed during the running treatment, and the amount of residual silver and bleaching fog were small. Example 3 After imagewise exposure of a photographic color photosensitive material prepared as sample 201 of Example 2 of JP-A-2-90151, it was subjected to the following processing steps until twice the capacity of the bleach-fixing tank was replenished. Continuous processing (running test) was performed.
Processing process Process
Processing time Processing temperature Refill amount*
tank capacity

(liter) Color development
3 minutes 15 seconds 38.0℃ 23
ml 15 bleach fixing
2 minutes 30 seconds 38.0℃ 20
ml 5 water wash (1)
30 seconds 38.0℃
-3 Washing with water (2)
20 seconds 38.0℃
34 ml 3 cheap
Constant 20 seconds 38.0℃
20 ml 3 Dry 1 minute 55
℃ *Replenishment amount is per meter of 35mm width Washing water is countercurrent method from (2) to (1) Furthermore, the amount of developer carried into the bleaching process, the amount of bleaching solution carried into the fixing process, and the amount of bleaching solution carried into the fixing process are The amount of liquid carried into the washing process is 35 m.
2.5ml and 2.0ml per 1m length of photosensitive material of m width, respectively
．． They were 0ml and 2.0ml. Further, the crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step. The composition of the treatment liquid is shown below. (Developer)
Mother liquor (g)
Replenisher (g) diethylenetriaminepentaacetic acid
2.0
2.2 1-hydroxyethylidene-1,
1-diphos 3.3
3.3 Sodium phonate sulfite
3.9
5.2 Potassium carbonate
37.5
39.0 Potassium Bromide

1.4 0.4 Potassium iodide
1.3mg
- Hydroxylamine sulfate
2.4
3.3 2-Methyl-4-[N-ethyl-N-(
β-hydroxyethyl)amino]aniline sulfate
salt
4.5
6.1 Add water

1000ml 1000ml pH

10.05
10.15 (Bleach-fix solution) Mother liquor (g) Replenisher (g)
Ammonium thiosulfate (700g/liter) 2
80ml 560ml or compound of the present invention
1.32 mol 2.64 mol Ammonium sulfite
40.0 80
．． 0 1,3-propylenediaminetetraacetic acid ferric a
ammonium monohydrate
144.0 28
8.0 Ammonium Bromide
40.0
80.0 Ammonium nitrate
20
．． 0 40.0 Add water

1000ml 1000m
l pH (25℃)
5.8
5.6 (Adjusted with acetic acid and aqueous ammonia) (washing water) Common tap water for mother liquor and replenisher is mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic Anion exchange resin (Amberlite IRA-4
00) to reduce the concentration of calcium and magnesium ions to 3 mg/liter or less, followed by 20 m of sodium isocyanurate dichloride.
g/liter and 150 mg/liter of sodium sulfate were added. The pH of this solution was in the range of 6.5-7.5. (Stable solution) Common to mother solution and replenisher solution
(Unit: g)
Formalin (37%)
2.0m
lPolyoxyethylene-p-monononylphenyl ether 0.3 (average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt
Add 0.05 water

1000mlpH

5
．． Bleach-fixing bath and water washing after completion of 0-8.0 running process (1) The presence or absence of precipitates in the bath was visually inspected. Furthermore, the transmission density (Dmin) of magenta in the unexposed area was measured using an X-rite densitometer. Furthermore, a similar test was conducted by replacing the bleaching agent with ferric ammonium 1,3-propylenediaminetetraacetic acid monohydrate and equimolar amount of potassium ferricyanide. The results are shown in Table 2. [Table 2] Table 2 shows that when the compound of the present invention is used as a fixing agent in place of thiosulfate, no precipitate is formed in the coexistence with a bleaching agent having a high redox potential or during running treatment. The liquid stability is excellent, and the density of the unexposed area (
It can be seen that good results with low Dmin (bleaching fog) were obtained. Furthermore, when potassium ferricyanide, which has an excessively high redox potential, is used as a bleaching agent, the density (Dmin, bleaching fog) of the unexposed area is large and is insufficient compared to the combination of the present invention. Example 4 Compound I-1 of Example 3 was converted into compounds I-3, I-4, I-
The same test as in Example 3 was conducted except that No. 11, I-14, I-16, I-18, and I-19 were used. As a result, as in Example 3, it was found that good results were obtained when the fixing agent of the present invention was used.

Claims (3)

[Claims] Claim 1: Contains as a fixing agent at least one thioether compound substantially free of thiosulfate ions and having at least one carboxylic acid group or a salt thereof;
A photographic bleach-fixing composition comprising at least one bleaching agent having an oxidation-reduction potential of 300 mV or less. 2. A processing method in which a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support is subjected to color development and processing with a bleach-fix solution after exposure, wherein the bleach-fix solution is Contains at least one thioether compound containing at least one carboxylic acid group or a salt thereof as a fixing agent, substantially free of thiosulfate ions, and at least one bleaching agent having a redox potential of 300 mV or less. A method for processing a silver halide color photographic material, characterized in that: 3. The method for processing a silver halide color photographic material according to claim 2, wherein the thioether compound is represented by the following general formula (I). General formula (I) L1 -(A-L2)n -B-L3 (wherein, L1
and L3 may be the same or different and each represents an alkyl group, aryl group, aralkyl group, alkenyl group, or heterocyclic group, and L2 represents an alkylene group, arylene group, aralkylene group, heterocyclic linking group, or a combination thereof. Represents a linking group. A and B may be the same or different, respectively -S-, -O-, -NR-, -CO-,
-CS-, -SO2- or any combination thereof. n represents an integer of 1 to 10. However, L1
and L3, at least one of which is substituted with a -COOM group. M represents a hydrogen atom or a counter cation, and R represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an alkenyl group. However, A and B
At least one of represents -S-.