JPS6324254A - Liquid developing composition for color photograph and method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled composition having less tendency for remarkably reducing a change on standing, and preventing an increase of a fog at the time of continuously processing by incorporating an aromatic primary amine coupler developing agent and a specific compd. to the titled composition. CONSTITUTION:The titled composition contains the aromatic primary amine coupler developing agent and the compd. shown by formula I wherein R<1> is hydroxyalkyl group (2-6C group) such as 2-hydroxyethyl group and 4- hydroxybutyl group, etc., R<2>-R<4> are each alkyl group (1-6C group) such as methyl, ethyl and propyl group, etc., Q is a substd. or an unsubstd. carbon ring (5-10C group) such as cyclohexane ring and benzene ring etc., (n) is an integer of 0-4. The concrete example of the compd. shown by formula I is exemplified by the compd. shown by formula I-1. The titled developing composition has an excellent stability and coloring property, and gives the color developer which is remarkably reduced the increase of the fog at the time of continuously processing, etc.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a color photographic developer composition and a method for processing silver halide color photographic light-sensitive materials using the same, and particularly relates to the stability of color developers. and improved color development,
And during continuous processing. The present invention relates to a color photographic developer composition in which an increase in fog is significantly reduced, and a processing method using the same.

(Prior Art) Color photographic developers using aromatic primary amine color developing agents (hereinafter simply referred to as color developers) have long been used in color image forming methods, and are currently used in color photographic image formation. It plays a central role in the method. However, the color developer mentioned above is highly susceptible to oxidation due to the presence of air and metals, and when a color image is formed using a developer that has changed over time, fog may increase by 1 level, and sensitivity and gradation may increase. changes or
It is well known that the photographic properties may differ from what is desired.

Various methods have been studied to improve the retention properties of color developing solutions, and the most common method is to use hydroxylamine and sulfite ions in combination. However, when hydroxylamine is decomposed, it generates ammonia, which causes fog, and sulfite ions act as competing compounds for developing agents, impeding color development. It's hard to call it a drug.

Other companies have been investigating preservatives and chelating agents in order to improve the stability of color developers. For example, as a preservative, JP-A-52-49828,
No. 9-160142, No. 56-47038, and aromatic polyhydroxy compounds described in U.S. Patent No. 3,746.544, etc.; Hydroxycarbonyl compound described in No. 176, JP-A-52-143020 and JP-A No. 53-8
Examples thereof include α-aminocarbonyl compounds described in JP-A No. 9425, alkanolamines described in JP-A-54-3532, and metal salts described in JP-A-57-44148 and JP-A-57-53749. In addition, as a chelating agent, Japanese Patent Publication No. 48-30496 and No. 44-3023
Aminopolycarboxylic acids described in No. 2, JP-A-56-97
No. 347, Special Publication No. 56-39359 and West German Patent No. 2
, 227,639, JP-A-5
No. 2-102726, No. 53-42730, No. 54-
No. 121127, No. 55-126241 and No. 55-
Examples include phosphonocarboxylic acids described in JP-A No. 65956, and other compounds described in JP-A-58-195845, JP-A No. 58-203440, and Jibun Iv153-40900.

(Problem to be solved by the invention) However, even if these conventional techniques are used, satisfactory results have not been obtained, with both advantages and disadvantages, such as insufficient stability and adverse effects on photographic properties. do not have.

Especially when it comes to color developers from which benzyl alcohol, which has many problems in terms of pollution prevention and liquid preparation, has been removed.

Although deterioration in coloring performance is inevitable, in such systems, preservatives that act as competing compounds significantly inhibit coloring performance, so the conventional techniques described above are often unsatisfactory.

Furthermore, color photographic materials containing silver chlorobromide emulsions with a high chlorine content are prone to fogging during color development, as disclosed in Japanese Patent Application Laid-Open Nos. 58-95345 and 59-232344.
As stated in the issue. When using such emulsions, it is essential to use a preservative that has less emulsion solubility and better preservability, but in this sense as well, there is a need for the development of new developing solutions. There is.

Therefore, the object of the present invention is to provide a developer composition for a silver halide color photographic light-sensitive material, which has excellent stability and color development properties, and significantly reduces the increase in fog during continuous processing.

A further object of the present invention is to provide a color developer composition that does not substantially contain benzyl alcohol but has excellent stability without decreasing color density.

Furthermore, the present invention improves the stability of the color developer,
An object of the present invention is to provide a method for processing a silver halide color photographic material, which significantly reduces changes over time during continuous processing and prevents an increase in fog.

(Means for Solving the Problems) The above object of Shukan 11 is to provide a silver halide color photograph characterized by containing an aromatic primary amine color developing agent and a compound represented by the following general formula (I). A silver halide characterized in that a developer composition for a light-sensitive material and a silver halide color photographic light-sensitive material are processed with a developer substantially free of benzyl alcohol and containing the above developer composition. This was achieved by a method of processing color photographic materials.

- General formula (I) (wherein, R1 is a hydroxyalkyl group (a group having 2 to 6 carbon atoms; for example, a 2-hydroxyethyl group, a 2-hydroxy-
1-methylethyl group, 4-hydroxybutyl group, etc.),
Alkoxyalkyl group (carbon a3-7 group, e.g. 2-
Methoxyethyl group.

2-methoxy-1-methylethyl group, 3-ethoxypropyl group, etc.), hydroxyalkoxyalkyl 7! (groups with 4 to 8 carbon atoms, such as hydroxyethoxyethyl group), alkoxyalkoxyalkyl groups (with 5 to 9 carbon atoms)
The basis of. For example, methoxyethoxyethyl group, etc.), and R2, R: ], R4 are alkyl 2! (having 1 to 6 carbon atoms), (e.g. methyl group, ethyl group, propyl group, etc.)
, aryl group (group having 6 to 10 carbon atoms, such as phenyl group), cycloalkyl group (group having 5 to 10 carbon atoms).

For example, it represents a cyclohexyl group) or a group similar to R1. Q is a saturated or unsaturated carbon ring (carbon e!!5~
10 bases. For example, cyclohexane ring, benzene ring, etc.)
Alternatively, it represents a hetero atom (a group having 1 to 8 carbon atoms, such as a pyridine ring), and n is an integer from O to 4.

Preferred substituents for R2, R3 and R4 in general formula (I) are the same groups as R1.

Preferred rings as Q in the general formula (I>) include saturated and unsaturated carbocycles, and most preferably saturated carbocycles.

In general formula (I), n is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 1.

The total number of carbon atoms from R to R4 in general formula (I) is 3
It is preferably 0 or less, and more preferably 20 or less.

Specific examples of the compound of general formula (I) according to the present invention are listed below, but are not limited to 151.

N−+C2H40CH3) 2 −+ I −(19) Ni (20) CH30 CH3 I −(21) I −(22) CH3 ~ Compounds of general formula (I) are generally synthesized by the following synthesis examples, or
Alternatively, it can be synthesized by S as described in Japanese Patent Publication No. 57-8096.

'Synthesis of 1M Exemplary Compound I-(1)) 14 g of 1.2-diaminocyclohexane (cis, trans mixture), 500 g of 2-furomonitanol, and 560 g of potassium carbonate were mixed with 3! ; The temperature was raised while stirring and kept at 20°C for 3 hours. After cooling, the system was poured onto wood and extracted with ethyl S-acid. After drying with magnesium sulfate for 1 hour, the solvent was distilled off. The obtained oil was distilled and a pale yellow liquid N,N was obtained as a water distillate.

210 g of N'-detrakis(2-hyroxyl)-2-diaminocyclohexane was obtained.

71 as C14H3oN204! State value C: 58.21 H: 10.18
N: 9.43") [i (i C: 57.
90H: 10.41N:
9.54]2 (Synthesis of Exemplified Compound I-(2)) 1,2-diaminocyclohexane in Synthesis Example 1 was
- N and N of the pale yellow liquid were added in exactly the same manner except that n was replaced with 108 g of phenylenediamine.

200 g of N',N'-tetrakis(2-hydroxyethyl)orthophenylenediamine was obtained.

Real 21 legs as C14H24N204 I〆X C: 59.52 H:
8.85 N: 9.5: f total 32 [I〆i C: 59. I4H:8. S.I.
The amount of the compound represented by the general formula (I) added is O, OJ, g to 50 g per 12 color developing solution.
, preferably 0.1 g to 20 g.

The color developer of the present invention will be explained below.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples include p-phenylenediamine derivatives, and two representative examples are shown below, but the invention is not limited thereto.

D-I N,N-diethyl-ρ-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-[N-ethyl -N-(β-hydroxyethyl)aminocoaniline D-52-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-6N-ethyl-N-(β-methanesulfonamide ethyl)-3-methyl-4-aminoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl -N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline These P-phenylenediamine derivatives may also be in the form of salts such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, and the like. The amount of the aromatic-grade amine developing agent used is in a concentration of about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g per developer solution.

The color developer of the present invention preferably contains a hydroxylamine represented by the following general formula (II).

General formula (n) R''-N-R6 H In the formula, R5 and R6 represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, and !!:.

It is preferable that R5 and R6 are an alkyl group or an alkenyl group, and it is more preferable that at least one of them has a substituent. Furthermore, R5 and R6 may be linked together to form a petero ring together with the nitrogen atom.

Alkyl groups and alkenyl groups may be linear, monobranched, or cyclic, and substituents include halogen atoms (F, C,
Br, etc.), aryl group (phenyl group, p-chlorophenyl group, etc.), alkoxy group (methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (phenoxy group, etc.), sulfonyl, 2! (Methanesulfonyl group, p-.

toluenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.)
, sulfamoyl group (diethylsulfamoyl group, unsubstituted sulfamoyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.), amitono. ((fuhytoamito group, benzamide group, etc.), ureido group (methylureido group, phenylureido group, etc.)
, alkoxycarbonylamino group (such as methoxycarbonylamino group), allyloxycarbonylamino group, ((
phenoxycarbonylamino group, etc.), alkoxycarbonyl group (mel-oxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.)
, cyano group, hydroxy group.

Carboxy group, sulfo group, nitro group, amino group (unsubstituted amino group, diethylamino group, etc.), alkylthio group (
(such as methylthio group), arylthio group (such as phenylthio group), and heterocyclic group (such as morpholyl group and pyridyl group). Here, R5 and R6 may be rotated or different from each other, and the substituents of R5 and R6 may be the same or different.

In addition, the nitrogen-containing heterocycle formed by linking R5 and R6 with +2, F, and number of R5 and R6 is preferably 1 to 1O, particularly preferably 1 to 5, and examples include a piperidyl group, a pyrrolisilyl group, an N-alkyl group, and a nitrogen-containing heterocycle formed by connecting R5 and R6. Examples include piperazyl group, morpholyl group, intolinyl group, and benztriazole group.

Preferred substituents for R5 and R6 are hydroxy group, alkoxyno, (, alkyl or arylsulfonylno,
They are an amide group, a carboxy group, a cyano group, a sulfo group, a nitro group, and an amino group.

Specific examples of the compound represented by the general formula (II) used in the present invention are shown below, but the scope of the present invention is not limited to these compounds.

U -(1) CH C2H3-N-C2H40CHa rl-(2) 11-(:l) CH CH3-N-C2H4QC2H5 n-(5) , LT-(6) Ir-(7) CH (:H3QC2H,QC2 )14-N-C2H4QC2
) 140C) 13n-(a) CH CH CH C2H50C2H4N-C2H5 CH C2H3QC,, H, NCH2-CH=CH,.

n -(1o) n -(11) II -(+2) CH CH-N-C2H,CONH2 n -(+3) II-(+4) 11-(+5) II-(+6) CH CH-N-C2H1S02C2H5 II -(17) CH C2H55o,,C2H,-N-C2)14S0202
H5■-(18) II-(19) n-(20) Low(22) 11-(2:l) n-(24) ■-(25) II-(26) CH HOOC-CH2-N-CH , -COOH+1-(27
) CH HOCH2CH2NCH2CH20H II-(28) IT-(29) [1(10) 113-M, M2H2LtH, 28t12LJI2
M13II-(Col) n-(32) ■-(33) CH CH3CH2NCH2CH3 n-(34) H2oH The compound represented by general formula (II) can be synthesized by the known method shown below. .

U.S. Patent No. 3,661,996, U.S. Patent No. 3,362.96
No. 1, No. 3,293,034-, Special Publication No. 1979-279
No. 4, U.S. Patent No. i3,491,151, t53,6
No. 55,764, No. 3,467.711, No. 3,
455, 9.16, 3.287, 125, f5
No. 3,287,124 These compounds may form salts with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, and acetic acid.

The amount of the compound represented by general formula (n) added to the color developer is 1! ; 0.1 g to 20 g, preferably 0.5 g to 10 g per liter.

The color developer of the present invention preferably does not substantially contain benzyl alcohol from the viewpoints of pollution prevention, liquid formulation properties, and fog prevention. Substantially free of color developer 1
2 ml or less of benzyl alcohol per mixture, preferably no preservatives, and sulfites and carbonyl sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, potassium metasulfite, potassium metasulfite, etc. Additives may be added as necessary, and the amount of these added is Og ~ 20 g/cross, preferably Og ~ 5 g/min, and if the stability of the color developer is maintained, smaller amounts are preferable. .

Other preservatives include hydroxyacetones described in U.S. Patent No. 3,615,503 and British Patent No. 1,306,176;
α-aminocarbonyl compound described in No. 425, JP-A No. 1973
Various metals described in JP-A-7-44148 and JP-A-57-53749, various saccharides as described in JP-A-52-102727, hydroxamic acids as described in JP-A-52-27638, α and α as described in JP-A-59-160141. '-Dicarbonyl compounds, salicylic acids described in No. 59-180588, alkanolamines described in No. 54-3532, No. 56
The poly(alkylene imine) described in No. 94349, the gluconic acid derivative described in No. 56-75647, etc. may be contained as necessary, and two or more of these preservatives may be used in combination as necessary. You may.

Also preferred is the addition of aromatic poly and troxy compounds.

The color developer of the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and may contain other known developer components.

In order to maintain the above pH, it is preferable to use various buffering agents.

Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N,N dimethylglycine salt, leucine salt, norleucine salt, guanine 4.3.4 -dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,
3-propanediol salt, valine salt, proline salt, trishydrodiaminomethane salt, lysine 111, etc. can be used, especially carbonate, phosphate, tetraborate, hydroxybenzoate, etc. It has the advantages of being excellent in buffering properties in the high pH range of pH 9.0 and above, having no adverse effects on photographic plasters (fogging, etc.) even when added to color developers, and being inexpensive. It is particularly preferred to use a buffer of

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (boric acid), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) ), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is preferably 0.1 mol/l-0 or more, particularly 0.1 mol/l-0,
Particularly preferred is 4 mol/liter.

In addition, various chelating agents can be used in the two-color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer.

The chelating agent is preferably an organic acid compound, such as the aminopolycarboxylic acids described in Japanese Patent Publication No. 48-30496 and Japanese Patent Publication No. 44-30232, Japanese Patent Publication No. 56-97347, Japanese Patent Publication No. 56-39359, and West German Patent No. 2,227. ，
Organic phosphonic acids described in No. 639, JP-A-52-102
No. 726, No. 53-42730, No. 54-12112
No. 7.

Phosphonocarboxylic acids described in No. 55-126241 and No. 55-65956, etc., and other JP-A-58-19
No. 5845, No. 58-203440 and Special Publication No. 53-
Compounds described in No. 40900 and the like can be mentioned.

Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid diethylenetriaminepentaacetic acidethylenediaminetetraacetic acidtosoethylenetetraminehexaacetic acidN,N,N-trimethylenephosphonic acidethylenediamine-N,N,N=,N'-tetramethylenephosphonic acid 1,3-diamino-2-propano- 4-acetic acid trans-cyclohexanediamine tetraacetic acid nitrilotripropionic acid 1,2-diaminopropane tetraacetic acid hydroxyethyliminonionicidane M glycol ethercyamine tetraacetic acid hydroxyethylenecyamine triacetic acid ethylenediamine orthohydroxyphenylacetic acid 2-phosphonobutane-1 , 2,4-1-licarboxylic acid ■-Hydroxyethylidene-1,1-cyphosboxylic acid N, N'-bis(2-hydroxypencyl)ethylenediamine-N, N'-cyaacetic acid These chelating agents may be used as necessary. Two or more types may be used in combination.

The amount of these chelating agents added may be a reasonable amount to sequester the metal ions in the color developer, for example, about 0.1 to 1 log per sentence.

Any development accelerator can be added to the color developer if necessary. As a development accelerator,
No. 16088, No. 37-5987, No. 3B-7826
No. 44-12380, No. 45-9019, and U.S. Pat. No. 3,813.247, etc.;
15554, JP-A-50-137726, JP-A-44-30
No. 074, JP-A-56-156826 and JP-A No. 52-4
Quaternary ammonium salts shown in US Pat. No. 3429, p-aminophenols described in US Pat. No. 2,610,122 and US Pat. No. 4,119,462,
No. 903, No. 3,128,182, No. 4,230,7
No. 96, No. 3,253,919, Special Publication No. 41-114
No. 31, U.S. Patent No. 2,482,546, U.S. Patent No. 2,596
, 926 and 3,582,346, etc., Japanese Patent Publication No. 37-16088, 42-25
No. 201, U.S. Patent No. 3,128,183, Special Publication No. 1977
-11431, No. 42-23883 and U.S. Patent 3
, 532.501, etc., 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. may be added as necessary.

In the present invention, any antifoggant can be added if necessary. Antifoggants include sodium chloride,
Alkali metal halides such as potassium bromide, potassium iodide and organic antifoggants may be used. Examples of organic antifoggants include benzotriazole, 6-nitroindazole, 5-nitroindazole, 5-nitroindazole, and 5-nitroindazole.
-Nitrogen-containing heterocyclic compounds such as methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylpenzimidazole, 2-thiazolylmethyl-benzimidazole, indazoles, hydroxyazaindolizine adenine; This can be cited as a representative example.

The color developer of the present invention preferably contains a fluorescent brightener. As an optical brightener, 4゜4'-diamino-
2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 5 g/cross, preferably 0.1 g to 4 g/cross.

Furthermore, various surfactants such as alkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. The amount of replenishment is preferably small, but is 20 to 600 prints, preferably 50 to 300 prints per rn' of photosensitive material. More preferably 100m
It is 1 to 2001 m.

Next, the bleach solution, bleach-fix solution, and fix solution used in the processing method of the present invention will be explained.

As the bleaching agent used in the bleaching solution or bleach-fixing solution used in the present invention, any bleaching agent can be used, but in particular organic complex salts of iron (m) (e.g., aminopolycarbonates such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid) can be used. Preferred are acids, complexes such as aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acids; organic acids such as citric acid, tartaric acid, and malic acid; persulfates; and hydrogen peroxide. Among these, organic complex salts of iron (m) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron ([) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β -oxyethyl)-N, N=.

N'-triacetic acid, 1,3-diaminopropanetetraacetic acid, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanecyaminetetraacetic acid, 1,3-diamino-2-propane Tools tetraacetic acid, methyliminodiacetic acid, iminodiacetic acid,
Hydroxyliminoniacetic acid, dihydroxyethylglycine ethyl ether diamisotetraacetic acid, glycol ethercyaminetetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminenibrobioneacetic acid, phenylenediaminetetraacetic acid, 2-phosphonobutane-1゜2. 4-triacetic acid, 1
．． 3-'diaminopropanol-N,N,N",N'-
Tetramethylenephosphonic acid, ethylenediamine-N, N
, N',N'-tetramethylenephosphonic acid, 1,3-propylenediamine-N,N,N',N'-tetramethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, etc. I'll come.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, ethylenecyaminetetraacetic acid, diethylenetosaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, iron (m) complex salts of methyliminodiacetic acid and bleaching blades are preferred because of their high cost.

These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate A ferric ion complex salt may be formed in a solution using iron or the like and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. When used in the form of a complex salt, one type of complex salt or two or more types of complex salts may be used. On the other hand, when forming a complex salt in a solution using a ferric salt and a chelating agent, one or more types of ferric salts may be used.

Furthermore, one or more types of chelating agents may be used. In addition, in any case, the chelating agent is ffrJ
It may be used in excess to form a diiron ion complex salt.

Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 moi/moi/moi, preferably 0.05 to 0.50 moi/moi/moi/moi/moi/moi/moi/moi/moi/moi/moi/moi to 0.50 moi/moi/moi/moi.

Further, a bleach accelerator can be used in the bleaching solution or the bleach-fixing solution, if necessary. Specific examples of useful bleach accelerators include U.S. Pat. No. 3,893,858, German Pat.
No. 53-32736, 53-57831, 53-37418, 53-65732, 5
No. 3-72623, No. 53-95630, No. 53-9
No. 5631, No. 53-104232, No. 53-124
No. 424, No. 53-141623, No. 53-2842
No. 6, Research Disclosure No. 1712
Compounds having a mercapto group or a disulfide group described in No. 9 (July 1978), etc.: JP-A-140-1989
Thiazolidine derivatives as described in Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832, Japanese Patent Publication No. 53-32735, U.S. Pat. No. 3,706,561 - West German Patent 1st °127.71
No. 5, Iodides described in Japanese Patent Publication No. 58-16235; Polyethylene oxides described in West German Patent No. 966.410 and West German Patent No. 2,748,430; Japanese Patent Publication No. 45-883
Polyamine compound described in No. 6; other JP-A-49-49
No. 2434, No. 49-59644, No. 53-9492
Compounds and iodine described in No. 7, No. 54-35727, No. 55-26506 and No. 58-163940,
Examples include bromine ions.

Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and in particular, US Pat. No. 3,893,858 and West German Patent No. 1,290,81
No. 2 and JP-A-53-95630 are preferred.

Additionally, the bleach or bleach-fix solutions of the invention may contain bromides (e.g. potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. iodide). It may contain a rehalogenating agent (ammonium). Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, as required
Adding one or more inorganic acids having a pH value such as sodium phosphate, citric acid, sodium citrate, and tartaric acid, organic acids, and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine. It comes.

The fixing agent used in the bleach-fixing solution or fixing solution in the present invention is a known fixing agent, namely sodium thiosulfate,
Thiosulfates such as ammonium thiosulfate: Thiocyanates such as sodium thiocyanate and ammonium thiocyanate: Water-soluble such as thioether compounds and thioureas such as ethylenebisthioglycolic acid and 3,6-cythia-1,8-octanediol There are several silver halide dissolving agents, and these can be used alone or in combination of two or more. In addition, a special bleach-fixing solution made of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354 may also be used. Preference is given to using salts, especially ammonium thiosulfate salts.

The amount of fixing agent per sentence is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

The pH range of the bleach-fix solution or fixer solution in the present invention is as follows:
3 to 10 are preferred, and 5 to 9 are particularly preferred.
If the pH is lower than this, the desilvering property is improved or the deterioration of the solution and the leucoization of the cyan dye are promoted. On the other hand, if the pH is higher than this, desilvering is delayed and staining is likely to occur.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

The bleach-fix solution may also contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

In the present invention, the bleach-fix solution and the fixing solution contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and ME salts (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives. ), metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately 0.0 in terms of sulfite ion.
It is preferable to contain 2 to 0.50 mol/statement, more preferably 0.04 to 0.40 mol/state.

As a preservative, sulfite is generally added, but ascorbic acid, carbonyl bisulfite adducts, carbonyl compounds, etc. may also be added.6 Furthermore, buffers, optical brighteners, A chelating agent, a fungicide, etc. may be added as necessary.

Next, the water washing process of the present invention will be explained.In the present invention, instead of the usual "water washing process", a simple processing method is used, such as performing only a so-called "stabilization process" without providing a substantial water washing process. You can also do that. In this way, in the present invention, “
"Water washing treatment" is used in a broad sense as described above.

The amount of washing water in the present invention is difficult to specify because it varies depending on the number of baths in multi-stage same-wave washing and the amount of prebath components of the photosensitive material brought in, or in the present invention, it is difficult to specify the amount of water used in the final washing bath. It is sufficient if it is less than or equal to 1×1O−4. For example, in the case of 3-tank countercurrent water washing, approximately 1
It is preferable to use north of 000d, more preferably 5o
oo11 or higher. In addition, in the case of water saving treatment, 100 to 1,0001,712 ml of water may be used per 1 ml of the photosensitive material.

Washing temperature is 15°C to 45°C, more preferably 20°C to
The temperature is 35°C.

In the water washing process, various known compounds may be added for the purpose of stabilizing precipitation disease IL and water precipitation. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid, fungicides and anti-inflammatory agents that prevent the growth of various bacteria, algae, and molds (for example, ``Journal of Antibacterial and Antibiotics'') J, Antibact, Antifun
g, Agents) Vol, 1 1, No.
, 5.9207-223 (1983) and compounds described in Hiroshi Horiguchi's "Antibacterial and Antibiotic Chemistry", metal salts such as magnesium salts and aluminum salts, alkali metal and ammonium salts, or dry loads. If necessary, a surfactant or the like may be added to prevent unevenness. Or West's ``Fuo 1 - Graphic Science and Engineering Link Magazine (
Photo.

A compound described in Sci. Eng.), Vol. 6, pp. 344-359 (1965) may be added.

Furthermore, the present invention is particularly effective in cases where a chelating agent, a bactericide, or an anti-pepper agent is added to the washing water, and the amount of washing water is significantly reduced by multistage countercurrent washing using two or more tanks. It is also particularly effective when carrying out a multi-stage countercurrent stabilization process (so-called stabilization process) as disclosed in Japanese Patent Application Laid-Open No. 57-8543 in place of the usual water washing process. In these cases, the whitening and fixing components in the final bath may be at most 5XIO', preferably at most 1XIO'.

Various compounds are added to the water stabilizing bath for the purpose of stabilizing the image. For example, adjusting the membrane P)t (e.g. pH 3
~8) various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) Typical examples include aldehydes such as formalin (used in combination) and formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (thiazole type, isothiazole type, halogenated phenol, sulfanilamide, benzotriazole) ), surfactants, optical brighteners, Fif! Each Katsura additive such as a film agent may be used, or two or more kinds of compounds for different purposes may be used in combination.

In addition, ammonium chloride,
Ammonium nitrate, ammonium sulfate.

It is preferable to add various ammonium salts such as ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve image storage stability.

In the case where the amount of washing water is significantly reduced as described above, it is preferable to flow some or all of the overflow liquid of washing water into the bleach-fixing bath or the fixing bath, which is a pre-bath, for the purpose of reducing the amount of drained liquid.

In this treatment step, during continuous treatment, a constant finish can be obtained by using a replenisher for each treatment solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount in order to reduce the cost.

Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen stirring, air stirring, etc., as necessary.

If the method of the present invention uses a color developer,
It can be applied to any processing process. For example, it can be applied to processing color vapor, color reversal vapor, color positive film, color negative film, color reversal film, etc.

/' , / /' The silver halide emulsion of the light-sensitive material to which the processing method of the present invention is applied may have any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide, silver chloride, etc. However, when performing rapid processing or low replenishment processing, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and more preferably a silver chloride content of 80 to 100 mol%. or particularly preferred.

It also requires high sensitivity during manufacturing and storage.

And/or when it is necessary to particularly suppress fog during processing, silver chlorobromide emulsions or silver bromide emulsions containing 50 mol% or more of silver bromide are preferred, more preferably 70 mol%.
The above is preferable. If the silver bromide content exceeds 90 mol%, rapid processing becomes difficult or means for accelerating development, such as using a development accelerator such as a silver halide solvent, fogging agent, or developer as described below during processing. In some cases, it may be preferable to use the method, since development can be accelerated to some extent without being limited by the content of silver bromide. In either case, it is not preferable to contain a large amount of silver iodide, and 3 mol%
The following is sufficient.

In the present invention, the silver halide grains of the silver halide emulsion may have different phases in the interior and surface, or may have a multiphase structure such as a bonded structure, or the entire grain may consist of a uniform phase. good.

Moreover, they may be mixed.

The average grain size of the silver halide grains (in the case of spherical or nearly spherical grains, the grain diameter is the grain size, and in the case of cubic grains, the grain size is the ridge length, and the grain size is expressed as the average based on the projected area. In the case of tabular grains, it is also expressed as the spherical ) is expressed in terms of
It is preferable that the hemorrhoid size is 2 or less and 0.1 hemorrhoid or more, and particularly preferably 1.5 or less and 0.15 p or more. The grain size distribution may be narrow or wide, but it is particularly preferably within 20% of the standard deviation value in the grain size distribution curve of the silver halide emulsion divided by the average grain size (variation rate). 15
It is preferable to use so-called monodisperse silver halide emulsions of up to % in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having substantially the same color sensitivity (monodispersity is defined as the above-mentioned type). (preferably those having a variable rate) may be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or used in a layered manner.

The silver halide grains used in the present invention have a regular shape such as a cube, octahedron, rhombidodecahedron, and dodecahedron.
ar) or coexistence of these concretions, or irregular (irre
The grains may have a crystal shape (gular), or may have a composite shape of these crystal shapes.They may also be tabular grains, especially when the length/thickness ratio value is 5 or more, especially 8 or more. It is also possible to use tabular grains, or emulsions that account for 50% or more of the total projected area of the grains. Emulsions consisting of a mixture of these various crystal forms may also be used. Either a surface latent image type formed on the particles or an internal latent image type formed inside the particles may be used.

The photographic emulsion used in the present invention is described in "Chemistry and Physics of Photography J" by Glafkides [P., Glafkides, Chi.
mieat Physique Photogra
phique (Paul 1Aontel Society, 1967) 1, "Photographic Emulsion Chemistry" by Duffin [G
, F. Duffin, Photographic
Emulsion Chemistry (Focal
Press, 1966) 1, Zelikman et al., "Manufacture and Coating of Photographic Emulsions J [V, L, Zelikwan
etal, “Making and CQt
Photographic Emul
sion (Focal Press, 1964) 1
It can be prepared using the method described in et al.

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. Good too.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As a form of simultaneous mixing method, p, A in the liquid phase in which silver halide is produced.
It is also possible to use the □ method of keeping the g constant, that is, the so-called Chondral double-shot method. According to this method, silver halide emulsions with crystalline form, regular grain size, and near uniformity can be obtained.

Furthermore, emulsions prepared by the so-called conversion method, which involves converting silver halide already formed into silver halide with lower solubility before the end of the silver halide grain formation process, and silver halide Emulsions which have undergone similar halogen conversion after the completion of the grain formation process can also be used.

In the process of silver halide grain formation or physical ripening,
Cadmium salts, zinc salts, lead salts, copper salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts,
Iron salts or iron complexes may also be present.

After grain formation, silver halide emulsions are usually subjected to physical ripening, desalting and chemical ripening before being used for coating.

Known silver halide solvents (e.g. ammonia, rotankali or U.S. Pat. No. 3,271,157, JP-A-5
1-12360, JP-A No. 53-82408, JP-A No. 53-144319, JP-A-54-100717 or JP-A-54-155828, etc.) by precipitation, It can be used for physical ripening and chemical ripening. In order to remove soluble silver salts from the emulsion after physical ripening, noodle wood washing, flocculation sedimentation method, ultrafiltration method, etc. are used.

The silver halide emulsion used in the present invention contains active gelatin and compounds containing Itt yellow that can react with silver (for example, thiosulfates, thioureas, mercapto compounds, rotanidines).
Sulfur sensitization method using reducing substances (e.g. stannous salts,
Reduction sensitization method using amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds): total complex salts (for example, total complex salts, as well as pt, Ir, Pd, Rh.

A noble metal sensitization method using complex salts of metals of group 1 of the periodic table with Fe may be used alone or in combination.

The blue-sensitive, green-sensitive and red-sensitive emulsions of the present invention are spectrally sensitized with methine dyes and other dyes so as to have their respective color sensitization properties. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, viroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei: and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, and thiobarbyl nucleus.

These @4 dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Representative examples are U.S. Patent No. 2,688,545, U.S. Patent No. 2,977.229,
Same No. 3,397,060, Same No. 3,522,052, Same No. 3.527.64-. No. 1, No. 3,617, 2
No. 93, No. 3,628,964, No. 3,666.
No. 480, No. 3,672,898, No. 3.679
．． No. 428, No. 3,703,377, No. 3.76
No. 9,301, No. 3,814,609, No. 3,8
37,862, British Patent No. 4.026.707, British Patent No. 1,344,281, British Patent No. 1,507,803, Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 53-12375, Japanese Unexamined Patent Publication No. 53-1237- No. 110618 and No. 52-109925.

Along with sensitizing dyes, there are dyes that themselves do not have a spectral sensitizing effect or substances that do not substantially absorb visible light.
A substance exhibiting supersensitization may also be included in the emulsion.

These sensitizing dyes may be added at any stage during particle formation, before or after chemical sensitization, during chemical sensitization, or during coating. Addition at the time of particle formation not only strengthens adsorption but also improves crystal shape. It is also effective in controlling the particles and the structure within the particles. Furthermore, addition during chemical sensitization does not strengthen adsorption, and is effective in controlling chemical sensitization sites and preventing crystal deformation. These addition methods are particularly effective in the case of emulsions containing a high content of silver chloride, and it is also particularly useful to apply them to grains with a high content of silver bromide or silver iodide on the grain surface. be.

It is preferable that the color coupler incorporated in the light-sensitive material has a ballast group or is polymerized so that it has diffusion resistance. The amount of coated silver can be reduced by using a two-equivalent color coupler substituted with a leaving group rather than a two-equivalent color coupler in which the coupling active position is substituted with a hydrogen atom. Couplers having a suitable diffusivity for coloring dyes, colorless couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

Typical yellow couplers that can be used in the present invention include oil-protected acylacetamide couplers. A specific example is U.S. Patent No. 2,40
No. 7,210, No. 2゜875.057 and No. 3
, No. 265, 506, etc. The use of two-equivalent yellow couplers is preferred for the present invention; U.S. Pat.
No. 3,933,501 and No. 4゜022.62
0, etc., or Japanese Patent Publication No. 58-10739, U.S. Patent No. 4,
No. 401,752, No. 4,326,024, RD1
8053 (April 1979), British Patent No. 1,425,
No. 020, West German Application Publication No. 2,219,917.

Typical examples include the nitrogen atom separation type yellow couplers described in Japanese Patent Nos. 2,261,361, 2,329,587, and 2,433,812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness;
-Penzoylacetanisode couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected intazolone or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the coloring dye, and representative examples thereof include U.S. Pat. No. 2,311,082; Same 2nd and 3rd
No. 43,703, No. 2,600,788, No. 2,
No. 908,573, No. 3.062.653, No. 3
, No. 152,896 and No. 3,936,015. As a leaving group for a two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or U.S. Pat.
．． The arylthio group described in No. 897 is preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369,879, preferably pyrazolo[5,1-cco[1,2,4co)-lyazoles as described in U.S. Pat. 24220(
Pyrazolotetrazoles and Research Disclosure 24230 (June 1984) and Research Disclosure 24230 (June 1984)
Examples include the pyrazolopyrazoles described in June 2003). The imidazo [1
, 2-b cobyrazoles are preferred and are described in European Patent No. 119
pyrazolo[1,5-b[1,2
゜4] Triazole is particularly preferred.

Cyan couplers that can be used in the present invention include:

Oil-protected naphthol-based and phenolic couplers are available, such as those described in U.S. Pat. No. 2,474.293, preferably U.S. Pat.
, 052,212, 4.146,396, 4,228,233, and 4,296,200, as a representative example. Can be mentioned. Further, specific examples of phenolic couplers include U.S. Patent Nos. 2,369,929, 2,801,171, 2,772.162,
It is described in the same No. 2,895,826. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention and are typically described in U.S. Pat.
, 772,002, a phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenolic nucleus, U.S. Pat. No. 2,772,162, U.S. Pat. , No. 126.396, No. 4,334,011, No. 4.327,173,
West German Patent Publication No. 3.329.729 and Patent Application 1983
2,5-diacylamino-substituted phenolic couplers described in US Pat. No. 42,671 and US Pat.
6゜622, same No. 4,333,999, same No. 4゜4
51.559 and m4,427,767, etc., having a phenylureido group at the 2-position, and
It is a phenolic coupler having an acylamino group at the 5-position.

It is possible to improve the graininess by using a coloring dye and a coupler having an appropriate diffusivity. Such dye-diffusive couplers are described as examples of magenta couplers in U.S. Pat. No. 234.533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451,82.
No. 0 and No. 4,080.211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102.173 and US Pat. No. 4,367.2.
It is described in No. 82.

The various couplers used in the present invention can be used in combination of two or more types in the same photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or the same compound can be used in combination with different couplers. It is also possible to introduce more than one layer.

The coupler used in the present invention can be introduced into the light-sensitive material by the oil droplet dispersion method in ice. 8 points or 1 for oil droplet dispersion method in ice
After dissolving in either a high-point organic solute at 75°C or higher and a low-point so-called auxiliary solvent alone or in a mixture of both, it is dissolved in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. finely dispersed. Examples of high clearing point organic solvents are described in U.S. Pat. No. 2,322,027 and others. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, etc. before use for coating.

Specific examples of high-elevation point organic solvents include phthalate esters (cyphthyl phthalate, dicyclohexyl phthalate,
(di-2-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-
ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridotesyl phosphate, driftoxyethyl phosphate, tosochlorobrobyl phosphate, cy-2-ethylhexylphenyl phosphate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyltodecane amide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (stearyl alcohol, 2,4-di-tert-amylphenol, etc.),
Aliphatic carboxylic acid esters (dioctyl azelate,
glycerol tributyrate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives (
N,N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. As the auxiliary solvent, an organic solvent having a ladder temperature 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,
Examples include ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

Standard usage amounts of color couplers range from o.oot to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.00 mole for yellow couplers.
5 mole, 0.003 to 0.3 for magenta coupler
moles, and 0.002 to 0.3 for cyan couplers
It is a mole.

The photosensitive materials to which the method of the present invention can be applied include hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfonamidophenol derivatives as color antifogging agents or color mixing prevention agents. It may also contain.

A known antifading agent may be used in the photosensitive material to which the method of the present invention is applied. Organic antifading agents include hydroquinones, 6-hydroxycoumaras, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, and methylenedioxybenzene. Typical examples include aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. In addition, gold Fl represented by (bissalicylaldoximate) nickel complex and (bis-N,N-dialkyldithiocarbamate) nickel complex,
Complexes etc. can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
As described in U.S. Pat. No. 4,268,593,
Compounds having a hindered amine and a hindered phenol structure in the same molecule give good results. In addition, in order to prevent the deterioration of magenta dye images, especially the deterioration caused by light, it is recommended to use spiroindanes described in JP-A-56-159644 and hydroquinone diether or monoether substituted as described in JP-A-55-89835. Chromans give favorable results.

In order to improve the storage stability of cyan images, especially the light fastness, it is preferable to use a benzotriazole ultraviolet absorber in combination. This UV absorber may be co-emulsified with the cyan coupler.

The amount of ultraviolet absorber applied should be sufficient to impart photostability to the cyan dye image; however, if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic material. Therefore, it is usually preferably 1X10-' mol/g to 2X10-3 mol/rd, especially 5x10-4 mol/rr? It is set in the range of ~1.5 x 10-3 mol/rf.

In the conventional light-sensitive material layer structure of color paper, an ultraviolet absorber is contained in one layer on both sides adjacent to the red-sensitive emulsion layer containing a cyan coupler, preferably in both layers. When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer may contain a matting agent of any particle size.

In the photosensitive material to which the present invention is applied, an ultraviolet absorber can be added to the wood-philic colloid layer.

The photosensitive material to which the present invention is applied includes, as a filter dye,
Alternatively, oxonol-based, anthraquinone-based, or azo-based dyes are preferred, which may contain water-soluble dyes in the wood-philic colloid layer for various purposes such as preventing irradiation or halation. Oxonol dyes that absorb green and red light are particularly preferred.

The photographic emulsion layer or other wood-philic colloid layer of the light-sensitive material to which the present invention is applied may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. A water-soluble brightener may be used, or a water-insoluble brightener may be used in the form of a dispersion.

The present invention, as described above, is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. Further, each of the above-mentioned emulsion layers may be composed of two or more emulsion layers having different sensitivities, or a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity.

In addition to the silver halide emulsion layer, the light-sensitive material to which the present invention is applied is preferably provided with auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, and a back layer.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material to which the present invention is applied, it is advantageous to use gelatin, or other hydrophilic colloids may also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfur esters, sugar derivatives such as sodium alginate, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, A wide variety of synthetic wood-philic polymeric materials can be used, such as single or copolymers of polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. The use of acrylic acid-modified polyvinyl alcohol as a protective layer is particularly useful, and becomes even more useful when rapidly processed with high silver chloride emulsions.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, Phot,
Japan.

Enzyme-treated gelatin as described in No. 16.30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

In addition to the above-mentioned additives, the photosensitive material to which the present invention is applied includes:
Furthermore, various stabilizers, antifouling agents, developing agents or their precursors, development accelerators or their precursors as mentioned above, lubricants, mordants, matting agents, antistatic agents, plasticizers, and other materials useful for photographic materials. Various additives may be added; representative examples of these additives are found in Research Disclosure 17643 (December 1978) and Research Disclosure 17643 (December 1978).
8716 (November 1979).

These additives are of great importance in rapid printing, rapid processing, and also in relation to compound (I) of the present invention. In addition, especially when the halogen composition of the emulsion used contains a high content of silver chloride, the combined use of mercaptoazole, mercaptothiadiazole, and mercaptobenzazole compounds is useful for the present invention in terms of color development and fogging. It is.

“Reflective support” that can be used in photosensitive materials to which the present invention is applied
This enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer.

Such reflective supports include those coated with hydrophobic 481 fat containing dispersed light-reflecting substances such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, or those containing dispersed light-reflective substances. Includes those using hydrophobic resin as a support 0 For example, baryta paper, polyethylene coated paper, polypropylene synthetic paper 1 Transparent support with a radiation layer or a reflective material, such as glass plate, polyethylene Examples include polyester films such as terephthalate, cellulose triacetate, and cellulose nitrate, polyamide films, polycarbonate films, and polystyrene films, and these supports can be appropriately selected depending on the purpose of use.

-~-1 (Effects of the Invention) The developer composition of the silver halide color photographic light-sensitive material of the present invention has excellent stability and color development properties, and provides a color developer with significantly reduced increase in fog during continuous processing. .

Furthermore, the above-mentioned effects are further enhanced when the developer composition of the present invention is used in a system substantially free of benzyl alcohol.

By using the developer composition of the present invention, stability can be increased without using S substances such as sulfite ions that act as competing compounds for developing agents. 1. Deterioration of color development can be prevented. can.

(Example) The present invention will be explained in more detail based on examples.

Example 1 A multilayer color photographic paper was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Yellow coupler (a) 19.1g and color image stabilizer (b)
) 4.4 g to 27.2 g of ethyl acetate and solvent (c) 7.
9fi was added and dissolved, and this solution was emulsified and dispersed in 185 ml of a 10% aqueous gelatin solution containing 8 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, a blue-sensitive sensitizing dye shown below was added to a compacted silver bromide emulsion (containing 1.0 mo1% silver bromide, 70 g/kg of Ag) per 10 β of silver chlorobromide. O
90 g of a blue-sensitive emulsion was prepared by adding xl□" mol. The emulsified dispersion and emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table B to prepare a first layer coating solution.

The 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-5-triazine sodium salt was used.

The following spectral sensitizers were used as the spectral sensitizers for each emulsion. Preparation of the coating solution for the first layer. Blue-sensitive emulsion layer. Green-sensitive emulsion layer (4°OX 10-'m per 1 mol of silver halide).
ol addition) (halogen northern limit 1 information reservation 7.0XIO dinner m
ol addition) Red-sensitive emulsion layer The following dyes were used as anti-irradiation dyes for each emulsion layer.

The structural formulas of the compounds used in this example, such as the coupler in the green-sensitive emulsion layer and the red-sensitive emulsion layer, are as follows.

+a+ Yellow coupler H3 IcI solvent (dl color mixture inhibitor 11J (e) solvent ffl color image stabilizer fnl solvent 02 (l mixture (gravity ratio)) (++l 1:5:3 mixture of ultraviolet absorber (molar ratio) (kl 1:1 mixture (molar ratio) of cyan coupler C1 (k2) (1) 1:3=3 mixture (molar ratio) of color image stabilizer (m) Magenta coupler - Color photographic paper obtained as above After the wedge-shaped exposure, the following processing steps were performed.

Processing process Temperature Time Color development 35°C 45 seconds bleach-fixing 35°C 45 seconds rinse 1 35°C 20 seconds rinse 2 35°C 20 seconds rinse 3 35°C 20 seconds drying 80°C 60 seconds The six solutions used are as follows. .

Color developer N, N-diethylhydroxylamine 4g Potassium carbonate 30g EDTA・2Na
・2H:Lo 2g sodium chloride
1.0g 4-amino-3-methyl-N
- Ethyl-N-(β-(methanesulfonamido)ethyl]-P-phenylenediamine sulfate 5.0g Fluorescent brightener (4,4'-diamino-stilbene type) 3.0g Compound of general formula (1) Add the first surface water
1000dPHto,i.

lWater constant1 EDTAFe (m)NH-2H2060gE D T
A ・2 N a ・2 H 204 g Ammonium thiosulfate (70%) 120 d Sodium sulfite
16g glacial acetic acid
Add 7g water
1000dpH5.5 Rinse solution l-Hydroxyethylidene-1,1'-diphosphonic acid (60%) 1.6% Bismuth chloride 0.35g Polyvinylpyrrolidone 0.25g Aqueous ammonia (26%)
2.5d nitrilotriacetic acid/3Na
1. OgEDTA・48
0.5g sodium sulfite
1.0g 5-chloro-2-methyl-4-isothiazolin-3-one 50mg formalin (37%) Add 0,1 ml of water
A portion of the color developer obtained in the above manner (1000 dpH 7.0) was left open at 40 DEG C. for 20 days, and then treated again in the above treatment steps.

The treatment using the color developer left for 20 days was referred to as the aged solution test, and the treatment using the color developer prior to awning was designated as the fresh solution test.

The photographic properties of the obtained fresh solution and the photographic properties of the aged solution test are shown in Table 1.

Photographic properties were expressed in three points: Dmin at yellow density, sensitivity, and gradation.

The sensitivity point is expressed by the density value of a constant exposure amount (100 CMS), and for one gradation, the point representing density 0.5 is crossed. gE
It is expressed as the density change up to the density point on the high exposure side of 0.3.

According to the present invention, even if the developer is stored in an open system for a long period of time, there is almost no change in photographic properties, and stable performance can be obtained.

On the other hand, when sodium fflite or triethanolamine is used, it changes over time, and the photographic image becomes foggy or one gradation changes.Example 2 As described in Table C, corona discharge processing was performed. 1st layer (lowest layer) to 7th layer (
(top layer) was applied to prepare a sample.

The coating liquid for the first layer was prepared as follows. That is, a mixture of 200 g of the yellow coupler shown in the table, 93.3 g of the antifading agent, and 5 g of the high clearing point solvents (p) log and (q), to which 600 rubs of ethyl acetate was added as an auxiliary solvent, was heated to 60°C and dissolved, and then the alkanol was dissolved. 5% aqueous solution of B (alkylnaphthalene sulfonate, manufactured by DuPont) 330
The mixture was mixed with 3,300rn2 of a 5% aqueous gelatin solution containing d, and emulsified using a colloid mill to prepare a coupler dispersion. Ethyl acetate was distilled off under reduced pressure from this dispersion, and a sensitizing dye for a blue-sensitive emulsion layer and 1-methyl-2-mercapto-5-acetylamino-1°3.4-)-riazole were added to emulsion 1. 400 g (containing 96.7 g as Ag and 170 g of gelatin) and further added 2,600 g of a 10% aqueous gelatin solution to prepare a coating solution. 2nd layer ~
The coating liquid for the seventh layer was prepared in the same manner as for the first layer.

Green-sensitive emulsion layer, anhydro-9-ethyl-5,5'-diphenyl-3,3''-cisulfoethyloxacarbocyanine hydroxyl red-sensitive emulsion layer; 3,3-diethyl-5-methoxy-9
, 9'-(2,2-dimethyl-1,3-propano)thiadicarbocyanine iodide.The following substances were also used as stabilizers for each emulsion layer. l-methyl-2-mercapto-5-acetylamino-1,3,
4-Triazole and the following were used as anti-irradiation dyes.

4-(3-carboxy-5-hydroxy-4-(3-(
3-Carboxy-5-oxo-1=(4-sulfonatophenyl)-2-pyrazolin-4-ylidene)-1-propenyl)-1-virazolyl)benzenesulfonate-di-potassium salt N,N'-( 4,8-dihydroxy-9,10-dioxo-3,7-cissulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt and 1,2-bis(vinylsulfonyl) as a hardening agent. ) using ethane.

The couplers used are as follows.

Yellow coupler magenta coupler C cyan coupler (C-1; C-2 = 50: 5 (1)
Mixing (Mole Ratio)] The multilayer color photographic paper obtained as follows was subjected to wedge-shaped exposure and then processed in the following processing steps.

Processing process Time Temperature color development
3 minutes 30 seconds 33℃ bleach fixing
1 minute 30 seconds 33°C rinsing (3 tank cascade) minutes 30'C drying
Drying 1 minute 80
The processing solution used in "C" is as follows.

Color developer water 8
00 Benzyl alcohol Table 2 Diethylene glycol Table 2 Diethylenetriaminepentabutyric acid i, OgN, N”-bis(2
-hydroxybenzyl)ethylenecyamine- N,N'-cyaacetic acid 0.1g nitrilo-
N,N,N-)-rimethylenephosphonic acid (40%) 1.0g Potassium bromide i, Og General formula (I)
Table 2 Hydroxylamines Table 2 Potassium carbonate
30g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl=4-aminoaniline sulfate 1f! 5.5g optical brightener (
4,4'-diaminostilbene type) Add 1.0g water and use 1ooo KOH
pH 1o, 10 bleach-fix ammonium thiosulfate (70%) 150fi sodium sulfite 15g ethylenecyamine iron(III) ammonium 60g ethylenediaminetetraacetic acid 10g optical brightener (4,4
'-Diaminostilbene series) 1.0g 2-mercapto-5-amino-3,4-thiadiazole 1.0g Add water, pH 7.0 with 1000d ammonium water Rinse solution 5-chloro-2-methyl-4-isothiazoline- 3-one 40 mg 2-methyl-4-inchazolin-3-one 10 mg 2-methyl-4-inchazolin-3-one l 0 mg bismuth chloride (40%) 0.5 g nitrilo-N,
N,N-trimethylenephosphonic acid (40%) 1.0g 1-hydroxyethylidene-1,1-diphosphonic acid (60%) 2.5g optical brightener (4,4'-diaminostilbene type) 1.0g ammonium Water (26%) Add 2.0m water
1000711 [at jKOH
pH 7.5 In the same manner as in Example 1, determine the magenta D■in, sensitivity, and gradation in the fresh solution and the preserved solution, and calculate the change value of each photographic performance based on the photographic properties in the fresh solution. It is shown in Table 2.

From the results in the table above, it can be seen that the developer composition of the present invention exhibits excellent effects in systems containing benzyl alcohol, and in particular, the photographic performance is significantly stabilized when used in systems that do not contain benzyl alcohol. Experiment No.
, 12.13.14°15.18.19.20,21.
22).

On the other hand, when using hydroxylamines alone,
The storage solution changes over time, and the photographic properties change greatly.

Example 3 The silver halide emulsion composition of the third layer of the sample photographic paper was changed to silver bromide 8.
Photographic paper was prepared in the same manner as in Example 2, except that the concentration was 0 mol%, and it was stored and tested for changes in photographic properties in the same manner as in Experiment No. 9 to 22. As in Example 2, hydroxylamines alone The photographic properties of the developer compositions significantly changed due to changes in the storage solution over time, whereas the developer compositions of the present invention exhibited remarkable stability, especially in systems that did not contain benzyl alcohol.

Claims (2)

[Claims] (1) A developer composition for a silver halide color photographic light-sensitive material, comprising an aromatic primary amine color developing agent and a compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 represents a hydroxyalkyl group, an alkoxyalkyl group, a hydroxyalkoxyalkyl group, or an alkoxyalkoxyalkyl group, ,R
^4 represents an alkyl group, an aryl group or a cycloalkyl group, or has the same meaning as R^1. Q represents a carbocycle or a heterocycle, and n is an integer from 0 to 4. ) (2) A silver halide color photographic light-sensitive material is processed with a developer that does not substantially contain benzyl alcohol and contains an aromatic primary amine color developing agent and a compound represented by the following general formula (I). A method for processing a silver halide color photographic light-sensitive material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 represents a hydroxyalkyl group, an alkoxyalkyl group, a hydroxyalkoxyalkyl group, or an alkoxyalkoxyalkyl group, ,R
^4 represents an alkyl group, an aryl group or a cycloalkyl group, or has the same meaning as R^1. Q represents a carbocycle or a heterocycle, and n is an integer from 0 to 4. )