JPS6344655A - Color photographic developer composition and method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve stability and a color developing property of the titled composition, and to reduce an increase of fog in a continuous processing, etc. by incorporating the color developing agent of an aromatic primary amine and a specific compd. to the titled composition. CONSTITUTION:The titled composition contains the color developing agent of the aromatic primary amine and the compd. shown by formula I, wherein R<1> is a n-valent org. group, R<1>-R<4> are each a monovalent org. group, at least two groups among R<2>-R<4> groups together with each other may form a heterocyclic ring contg. a quarternary ammonium atom, (n) is an integer of >=1, X<-> is a counter anion. Thus, the titled composition which has the improved stability and color developing property, and is capable of remarkably reducing the increase of fog in the continuous processing, etc., is obtd.

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 a silver halide color photographic light-sensitive material using the composition, and in particular, to a method for processing a color photographic color photographic material. and improved color development,
The present invention also relates to a color photographic developer composition in which an increase in fog during continuous processing 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 oxidized by the presence of air and metals, and when a color image is formed using a developer that has changed over time, fog may increase or the sensitivity may decrease in one gradation. It is well known that changes may occur and the photographic characteristics may differ from what is desired.

Accordingly, various methods have been studied to improve the preservation properties of various color developing solutions, and among them, a method using a combination of hydroxylamine and sulfite ion, and an acid method are common. However, when hydroxylamine is decomposed, ammonia is generated, which causes fog, and sulfite ions act as competing compounds for developing agents and impede color development. It is hard to say that it is a permanent drug.

In addition, in order to improve the stability of color developers, various preservatives and chelating agents have been investigated.
No. 9-160142, No. 1, 56-47038, and aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746.544, etc., as described in U.S. Pat. Hydroxycarbonyl compound of JP-A-52-143020 and IT45
α-aminocarbonyl compound described in No. 3-89425,
Flukanolamines described in JP-A No. 54-3532,
Gold PAIt described in JP-A-57-44148 and JP-A-57-53749! , etc. can be given. In addition, as a chelating agent, Japanese Patent Publication No. 48-30496 and No. 4
7-minopolycarboxylic acids described in JP-A-56-97347, JP-B-56-39359 and West German Patent No. 2.227,639, JP-A-52-102726, No. 53 -42730
No. 54-121127, No. 55-126241, No. 55-65956, etc., and other JP-A IIig Nos. 58-195845 and 5
Examples thereof include compounds described in Japanese Patent Publication No. 8-203440 and Japanese Patent Publication No. 53-40900.

(Problems to be Solved by the Invention) However, even if these conventional techniques are used, the preservation performance is insufficient, the photographic properties are adversely affected, and the results are not satisfactory11). Not yet.

Especially in color developing solutions from which benzyl alcohol has been removed, which poses many problems in terms of pollution prevention and solution preparation.

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 a silver chlorobromide emulsion with a high chlorine content of 1 are likely to cause fogging during color development, as reported in Japanese Patent Application Laid-open Nos. 58-95345 and 59-23233.
As described in No. 2. When such an emulsion is used, a preservative that has low emulsion solubility and excellent preservative performance is essential, and in this sense as well, there is a demand for the development of a new developer.

Therefore, the complete Ug+ had excellent stability and color development, and significantly reduced the increase in fog during continuous processing. An object of the present invention is to provide a developer composition for silver halide color photographic materials.

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, Suekan 1!1 improves the stability of the color developer, significantly reducing changes over time during continuous processing, etc.
An object of the present invention is to provide a method for processing a silver halide color photographic material that prevents an increase in fog.

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

General formula (I) (wherein R represents an n-valent organic group, R2, R3 and R represent a monovalent organic group, at least two of R2, R3 and R4 are bonded to form a quaternary may form a heterocyclic ring containing a class ammonium atom, n is an integer of 1 or more -H, and X○ represents a counter anion.) In general formula (I), R1 is monovalent or more, preferably 1
Examples of monovalent groups for R1, which are valent to trivalent organic groups, include 21-substituted or non-substituted alkyl groups (carbon atoms 1 to 2).
0 alkyl groups 0 For example, methyl group, ethyl group, 2-hydroxyalkyl, 2-ethoxyethyl group, carboxymethyl group, 3-hydroxypropyl group, 3-sulfopropyl group.

benzyl group, cyclohexyl group, cyclohexylmethyl group, isobutyl group, etc.), aryl group (carbon number 6-20
7-aryl group 0 e.g. phenyl group, 4-methoxyphenyl 3.2.4-dichlorophenyl group, etc.), heterocyclic group (
Substituents that these groups may have include halogen atoms, hydroxyl groups, sulfono,
(, a carboxyl group, an alkyl group which may be further substituted, an aryl group, a heterocyclic group, an alkoxyl group, an aryloxy group, a sulfonyl group, an acyl group, an amine group, etc.).

Examples of divalent groups for R1 include substituted or unsubstituted alkylene groups (alkylene groups having 1 to 20 carbon atoms, such as ethylene groups, tetramethylene groups, propylene groups, etc.), arylene groups (alkylene groups having 6 to 20 carbon atoms, etc.); 7 Leerenno,!i,p
-phenylene group, m-phenylene group, 0-phenylene group, etc.); Substituents for these include halogen atoms, hydroxyl groups, sulfo groups, carboxyl groups,
An alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a sulfonyl group, an acyl group, an amide group, etc. which may be loosely substituted are preferable.

R, R and R4 are monovalent organic groups, and preferred among them are the specific examples of monovalent groups listed for R1. R
, R and R4, a particularly preferred monovalent group is a substituted or converted alkyl group, and at least one of R, R and R4 is a hydroxyalkyl group, alkoxyalkyl group, H or carboxyalkyl group. The case is most preferred.

At least two of R, R, and R4 may be bonded to form a heterocycle containing a quaternary ammonium atom (eg, pyrrolidinium ring, pyridinium ring, etc.).

n is an integer of 1 or more, and 1. The present invention also includes cases where the compound of general formula (1) is an oligomer, but n is preferably 1.
It is an integer of ˜3, more preferably 1 or 2.

xO represents any counter anion; examples of xO include halogen ions (4N, 1fCfL-, Br-.

F-, I-, etc.), various dilute acids (sulfuric acid, nitric acid, phosphoric acid, p-
Examples include acid radicals of organic or inorganic acids such as toluenesulfonic acid and acetic acid.

The compound represented by the general formula (I) may be contained as a side group in the polymer added to the color developer.

In undeveloped IJI, the content of the compound (or side group) represented by -, shell formula (r) during development is 0.01 to 50 g per color developer, preferably 0.1 to 20 g. .

Specific examples of the compound represented by the general formula (I) used in the developer composition of the present invention are listed below, but the present invention is not limited thereto. In the specific examples below, the counter anion is optional. Therefore, it is omitted.

■ C2H5-' + C2H40H)3 I-(3) I-(4) I-(5) I-(6)! -(7) I-(8)! -(10) 1-CIL) ω r-(12) Hatake I-(13) ♀ C,,H,OH I-(14) I-(15) I-(16) I-,(17) ■ N -(-C4H3)4 I-(1B) ■ To÷C2H,0CH3)4 I-(19) Fuku I-(20) ■ (c 2 Hs line → (C) I2COOH) 2I-(21
) I-(22) I-(23) I-(24) I-(25) The following describes the color developing solution.

The color developer used for undeveloped II contains a known aromatic primary amine color developing agent. Preferred examples are P-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-L N,N-diethyl-P-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-7 Minnow 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-(2-7minor-5-diethylaminophenylethyl)methanesulfonamide D-88,N-dimethyl-p-phenylenediamine D-94-amino-3-methyl -N-ethyl-N-methoxyethylaniline D-104-7 minnow 3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-butoxyethylaniline These p-phenylenediamine derivatives are also I! Acid,! The aromatic-grade amine developing agent, which may be a salt such as an octate, a sulfite, or a P-toluenesulfonate, is used in a developer solution of about 1 g to about 20 g, more preferably Concentrations range from about 0.5 g to about Log.

It is preferable that the color developer of [End Page 1] contains a hydroxylamine represented by the following general formula (11).

General formula (II) R5-N-R6 (I)H In the formula, R5 and R6 are a hydrogen atom, a non-21-substituted or substituted alkyl group, or a %21-substituted or substituted alkenyl group,
Represents an unsubstituted or substituted aryl group.

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 group. Also, R5 and R6 may be connected to form a petero ring together with a nitrogen atom. .

The alkyl group and alkenyl group may be straight chain, branched chain, or cyclic.
Br, Br, etc.), aryl groups (phenyl, p-chlorophenyl, etc.), alkoxy groups (methoxy, ethoxy, methoxyethoxyno, etc.), aryloxy groups (phenoxy, etc.), sulfonyl groups (methanesulfonyl, etc.) group, p-toluenesulfonyl group, etc.), sulfonamyl group (methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (diethylsulfamoyl group, % substituted sulfamoyl group, etc.), carbamoyl group (unsubstituted carbamoyl group) , diethylcarbamoyl group, etc.), amide 2!i (futamide group, benzamide group, etc.), ureido,!! (methylureido group, phenylureido group, etc.), alkoxycarbonylamino,
Si (methoxycarbonylamino 7 groups, etc.), allyloxycarbonylamino group (phenoxycarbonylamino group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), cyano group, hydroxy group, carboxy group, sulfo group, nitro group, amino (unsubstituted amine 7 group,
(diethylthio group, etc.), alkylthio group (methylthio group, etc.), arylthio group (phenylthio group, etc.),
and hetero g5 groups (morpholyl group, pyridyl group, etc.). Here, R5 and R6 may be the same or different from each other, and the 2I test groups of u 5 and R8 may also be the same or different.

Further, the number of carbon atoms in R5 and R8 is preferably 1 to 10, particularly 1.
~5 is preferred. The nitrogen-containing heterocycle formed by connecting R5 and R6 includes a bi-1 nodyl group, a pyrrolysilyl group,
Examples include N-furkylpiperazyl group, morpholyl group, indolinyl group, and benztriazole group.

Preferred substituents for R5 and R8 are a hydroxy group, an alkoxy group, an alkyl or arylsulfonyl group, an amide group, a carboxy group, a cyano group, a sulfo group, a nitro group and an amine group.

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

II -(1) H CH-N-C2H,QC) (3 ■-(2) n-(ko) H CH-N-C2H4QC2H5 n -(4) If-(S) n-(s) II -( 7) OH C)130C21140C2)+4-N-C2H4QC
2H40CH3n-(a) II-(9) ■-(lO) n-(11) ■-(12) ? 1 CH3-N-C2H4CONH2 II-(13) U -(14) 11-(Is) U -(ta) OH CH-N-C2H4SO2C2H5 +1-(17) OH C2H5502C2H4-toC2H,So,,C2H3
II-(18) II-(19) ■Direct 20) n-(22) ■-(2) ■-(24) ■-(25) ■-(26) HOOC-CH-N-CI(2- Coo)(u-(2
7) OH HOCH2CH2NCH2CH20H II-(28) n-(29) U-(:JG) 1l-CF+) U-(32) n-(co3) II-(34) H20H Compound represented by general formula (II) can be synthesized by the known methods shown below.

U.S. Patent No. 3,661,996, U.S. Patent No. 3.362.96
No. 1, No. 3,293.09, Special Publication No. 42-2794
No. 3,491,151, U.S. Patent No. 3,655
, No. 764, same! No. 13,467.711, times i3,4
55,916, 3.287,125, 3.2
No. 87,124 These compounds are hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.

It may form a salt with each of the 8 acids such as oxalic acid and acetic acid.

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

The color developer of the present invention preferably does not substantially contain benzyl alcohol from the viewpoint of pollution prevention, liquid preparation properties, and fog prevention.
It is meant to contain less than 2 ml of benzyl alcohol per sentence, preferably no benzyl alcohol, and as a preservative, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite. Additives may be added as necessary, and the amount of these added is preferably og ~ 20g/ml, preferably og ~ 5g/ml, and the smaller the amount, the better if the stability of the color developer is maintained. .

Other preservatives include hydroxyacetones described in U.S. Patent No. 3,615,503 and British Patent No. 1,306,176;
α-Ami described in No. 425,! Carbonyl compounds, various metals described in JP-A-57-44148 and JP-A-57-53749, various saccharides as described in JP-A-52-102727, hydroxamic acids as described in JP-A-52-27638,
α,α′-dicarbonyl compounds described in No. 59-160141, salicylic acids described in No. 59-180588,
Alkanolamines of No. 54-3532, No. 5
Boli(alkyleneimine)s described in No. 6-94349,
The gluconium derivative described in No. 56-75647 may be contained as necessary, and two or more of these preservatives may be used in combination as necessary.

Further, it is preferable to add an aromatic borohydroxy compound.

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 fil, N, N
Dimethylglycine salt, leucine salt.

norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyric Mm, 2-7
Mi/-2-mef-1.3-7"Ohanshiol salt, valine salt, proline salt, trishydrodiaminomethane salt,
Lysine salt and the like can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are
It has the advantage of having excellent buffering ability in the high pH range of 9.0 or higher, having no adverse effects on photographic surfaces (fogging, etc.) even when added to color developers, and being inexpensive. Particular preference is given to using a buffer.

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 sulfur added to the color developing solution as a buffering agent is preferably 0.1 mol/l or more, particularly 0.91 mol/l to 0.1 mol/l.
Particularly preferred is 4 mol/view.

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

As the chelating agent, m-acid compounds are preferred, such as the aminopolycarboxylic acids described in Japanese Patent Publication Nos. 48-30496 and 44-30232, JP-A-56-97347, 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, No. 55-126241 and No. 55-65956
Phosphonocarboxylic acids described in No. 1, etc., and other JP-A-58
Examples thereof include compounds described in Japanese Patent Publication No. 195845, No. 58-203440, and Japanese Patent Publication No. 53-40900. Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid diethylenetriamine pentaacetic acid ethylenediamine tetraacetic acid triethylenetetramine hexafluoric acid N,N,N-trimethylenephosphonic acid ethylenediamine = N,N,N',N'-tetramethylenephosphonic acid 1,3-diamino-2-propano -4-acetic acidtranscyclohexanediaminetetraacetic acidnitrilotripropionic acid1,2-diaminopropanetetraacetic acidhydroxyethyl Aminoniacetic acid glycol etherdiaminetetraacetic acidhydroxyethylenediaminetriacetic acidethylenediamineorthohydroxyphenylacetic acid2-phosphonophthane-1,2,4 -)-Ricarboxylic acid 1-hydroxyethylidene-1,1-cyphosphonic acid N, N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid Two or more of these chelating agents may be used as necessary. - May be used in combination.

The amount of these chelating agents added may be sufficient to sequester metal ions in the color developer. For example, 19
．． The hit is about o, ig to log.

Any development accelerator can be added to the color developer if necessary. As a development accelerator,
No. 16088, No. 37-5987, No. 38-7826
, IF7144-12380, IF45-9019, and U.S. Pat. No. 3,813.247, etc.; Compounds, JP-A-50-137726, JP-A-1973
-30074, JP-A No. 56-156826 and No. 5
Quaternary ammonium salts represented by No. 2-43429 etc., U.S. Pat. No. 2,610,122 and U.S. Pat.
p-aminophenols described in No. 62, U.S. Pat. No. 2,4
No. 94,903, No. 3,128,182, No. 4,23
No. 0,796, No. 3,253,919, Special Publication No. 1979-
No. 11431, U.S. Pat. No. 2,482,546, U.S. Patent No. 2,
Amine compounds described in Japanese Patent Publications No. 596,926 and No. 3.582,346, Japanese Patent Publication No. 37-16088, No. 42
-25201, U.S. Patent No. 3,128,183, Japanese Patent Publication No. 11431-1983, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3,532.501, etc., and other l-phenyl-3-pyrazolidones. , hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. may be added as necessary.

In the present invention, any antifoggant can be added as required. Antifoggants include sodium chloride,
Alkali metal halides such as potassium bromide and potassium iodide and organic antifoggant II-shavings can be used. Examples of organic antifoggants include 1, such as benzotriazole, 6-
Nitroindazole, 5-nitroindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazoles, hydroxyazaindolizine A typical example is a nitrogen-containing heterocyclic compound such as adenine.

It is preferable that the color developer of the finished product contains a fluorescent whitening agent. As the fluorescent brightening agent, a 4゜4'-diamino-2,2'-disulfostilbene compound is preferable, and the amount added is as follows: O to 5 g/b, preferably O, Ig to 4 g/b.

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 time between treatment surfaces is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. Although it is preferable that the replenishment amount be small, it is preferably 50 to 300 ml per 41 photosensitive material wheels. More preferably food~
It is 200 lessons.

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. acids, aminopolyphosphonic acids, phosphonocarboxylic acids, organic phosphonic acids, etc.) or organic acids such as citric acid, tartaric acid, malic acid; persulfates:
Hydrogen peroxide and the like are preferred; among these, organic complex salts of iron (m) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution; aminopolycarboxylic acids useful for forming organic complex salts of iron (m); Aminopolyphosphonic acids, organic phosphonic acids, or salts thereof are listed as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxydiethyl)-N, N'.

N'-triacetic acid, 1,3-diaminopropanetetraacetic acid, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, 1,3-diamino-2-propatol tetraacetic acid Acetic acid, methyliminodiacetic acid, iminodiacetic acid,
Hydroxyliminoniacetic acid, dihydroxyethylglycine ethyl ether diamisotetraacetic acid, glycol ethercyaminetetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediamineniprobionic 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, l,3-propylenediamine-N,N,N'',N''-tetramethylenephosphonic acid, l-hydroxyethylidene-1,l-diphosphonic acid, etc. may be mentioned. .

These compounds may be sodium, potassium, lithium or ammonium salts; among these compounds are ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid.

Iron (m) complex salt of methyliminodiacetic acid is preferable because it has high bleaching properties.

These ferric ion complex salts may be used in the form of complex salts, such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc. A ferric ion complex salt may be formed in a solution using iron, etc. and a chelating agent such as aminopolycarbonate, aminopolyphosphonic acid, phosphonocarboxylic acid, etc. When used in the form of a complex salt, 1 Different kinds of complex salts may be used, or two kinds of complex salts may be used.
On the other hand, the complex f! may be used in solution using a ferric salt and a chelating agent. ! If it forms, ferric salt 1
One type or two or more types may be used.

Furthermore, one type or two or more types of chelating agents may be used, and in any case, the chelating agent may be
Aminopolycarboxylic acid iron complexes are preferred among iron complexes, which may be used in excess to form an iron ion complex salt, and the amount added is 0.01 to 1,0soJL/1. Preferably it is 0.05 to 0.50 liter/view.

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. Patent No. 3,706,561; West German patent 1st °127.71
No. 5, Iodides described in JP-A-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 ion.

Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred in US Pat.
Compounds described in JP-A-53-95630, No. 2, No. 4, are preferred.

Other 1 The bleach or bleach-fix solution of the present invention may contain bromides (e.g. potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium dichloride, ammonium chloride) or iodides (e.g. A rehalogenating agent (ammonium iodide) may be included. Boric acid, borax, sodium metaborate, acetic acid, as necessary
Sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, sodium phosphate, citric acid, sodium citrate,
18! Contains pH buffers such as tartaric acid! Inorganic acids, organic acids, alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine may be added.

The fixing agent used in the bleach-fixing solution or fixing solution in the present invention is a known fixing agent, namely sodium thiosulfate,
Thiosulfate Ma such as ammonium thiosulfate! ; Thiocyanate salts such as sodium thiocyanate and ammonium thiocyanate: ethylene bisthioglycolic acid, 3,6-
There are water-soluble silver halide dissolving agents such as thioether compounds such as 1,8-octanediol and thioureas, and these can be used alone or as a mixture of two or more. 55-155354 and a large amount of a halide such as potassium iodide may also be used. Preference is given to using ammonium sulfate salts.

The amount of fixing agent per No. 21 is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution or fixing solution in Undeveloped No. 11 is preferably 3 to 10, and more preferably 5 to 9. If the pH is lower than this, the desilvering property improves, but the solution deteriorates and the cyan dye is removed. Leukization is promoted. On the other hand, if the pH is higher than this, staining is more likely to occur during desilvering.

To adjust the pH, use Ii! as necessary. Acids, sulfuric acid, nitric acid, acetic acid, heavy acid salts, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added.

Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

In the present invention, the bleach-fixing solution and the fixing solution contain sulfite (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) as a preservative. (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfite Ii! (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds have approximately 0.0% in terms of sulfite ion.
The content is preferably from 0.2 to 0.50 mol/ml, more preferably from 0.04 to 0.40 mol/ml.

As a preservative, sulfite may be added in general, or ascorbic acid, carbonyl bicarbonate, acid adducts, carbonyl compounds, etc. may be added.

Furthermore, buffering agents, optical brighteners, chelating agents, antifungal agents, etc. may be added as necessary.

Next, the water washing process for undeveloped IJI 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. It can also happen. As described above, the term "water washing treatment" as referred to in the present invention is used in a broad sense as described in 1-.

It is difficult to specify the amount of washing water for unreleased 11 because the number of multistage countercurrent washing baths and the pre-bath components of the photosensitive material differ depending on the equipment used to bring the photosensitive material. For example, in the case of 3-tank countercurrent water washing, it is preferable to use about 1000 d or more per 1 m' of photosensitive material, more preferably 5
000d or more. In addition, in the case of water-saving treatment, it is preferable to use 100 to 1000 centimeters per rn' of photosensitive material Neo.

Washing humidity is 15℃~45℃, more preferably 20℃
~35°C.

In the washing process, various known compounds may be added for the purpose of preventing precipitation and stabilizing the washing water. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, etc. Disinfectants and antifungal agents that prevent the growth of bacteria, algae, and mold (e.g., Journal of Antibacterial and Antifungal Agents) (J, ^nLibact, Antifung, ^
gents) Vol, l l.

No. 5, p. 207-223 (1983), compounds described in "Chemistry of antibacterial control" by Hiroshi Horiguchi, and gold Ii represented by magnesium salts and aluminum salts.
! Salts, alkali metal and ammonium salts, surfactants for preventing drying load and unevenness, etc. can be added as necessary. Or by West [Photographic Science and Engineering Magazine (Photo.

A compound described in Sci.

Furthermore, the present invention is particularly effective in cases where a chelating agent, a bactericide, or an anti-piping 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. Also, instead of the normal washing process.

It is also particularly effective when carrying out a multi-stage countercurrent stabilization treatment process (so-called stabilization treatment) as disclosed in Japanese Patent Application Laid-Open No. 57-8543. In these cases, the bleaching and fixing components of the final bath may be no more than 5XIO-2, preferably no more than 1xlo'.

Various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, adjusting the membrane pH (for example, pH 3 to
8) Various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia wood, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) Typical examples include aldehydes such as (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 1-inch azole type, halogenated phenol, sulfanilamide °, benzotria) Various additives such as surfactants, optical brighteners, and hardeners may be used, and two or more compounds for the same or different purposes may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium fEa, ammonium phosphate, ammonium sulfite, ammonium thiosulfate, etc. as a membrane pH2g1 adjuster for the processor to improve image storage stability.

When the amount of washing water is significantly reduced as described above, some or all of the overflow liquid of the washing water may be allowed to flow into the pre-bath, such as a bleach fixation bath or fixation bath, or for the purpose of reducing the amount of waste water. preferable.

In this processing step, a constant finish can be obtained by preventing fluctuations in the liquid composition by using a replenisher for each processing liquid during continuous processing. The replenishment V can be reduced to half or less than the standard replenishment for cost reduction.

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, such as color vapor, color reversal vapor, color positive film, color negative film, color reversal film, etc.

Silver halide emulsions of light-sensitive materials to which the processing method of the present invention is applied include silver iodobromide, silver bromide, silver chlorobromide, It! Any halogen Mllb such as silver chloride can be used, or when performing rapid processing or low replenishment processing, silver chloride should be added at 60 mol%.
A silver chlorobromide emulsion or a silver chloride emulsion containing the above is preferred, and a silver chloride content of 80 to 100 mol % is particularly preferred.

It also requires high sensitivity during manufacturing and storage.

And/or in cases where fog during processing can be kept particularly low, silver chlorobromide emulsions or silver bromide emulsions containing 50 mol% or more of silver bromide are preferable, more preferably 70 mol% or more. ``If the silver bromide content exceeds 90 mol%, rapid processing becomes difficult.Means for accelerating development For example, treatment with development accelerators such as silver halide solvents, fogging agents, and developers as described below. If you use the G-stage of the rod that acts at the same time,
Development can be carried out to a certain extent without being limited by the content of silver bromide.
There are times when it is desirable to be faster. In either case, it is undesirable to contain a large amount of silver iodide;
It is sufficient if it is less than mol%.

In the end, silver halide grains in a 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.

Also, they may be mixed.

The average grain size of the silver halide grains (in the case of spherical or near-spherical grains, the grain diameter is used, and in the case of cubic grains, the grain size is expressed as the ridge-long grain size, and is expressed as the average based on the projected area. ) is expressed in terms of
2 or less and preferably 0.1p or more, particularly preferably 1.5μ or less and 0.15JL or more 0 Grain size distribution may be narrow or wide, grain size distribution curve of silver halide emulsion The value obtained by dividing the standard deviation value by the average particle size (variation rate) is within 20%, particularly preferably 1
It is preferable to use a so-called monodisperse silver halide emulsion of 5% or less in the present invention, and also in order to satisfy the target gradation of the light-sensitive material.

Two or more types of monodisperse silver halide emulsions (preferably monodispersity having the above-mentioned fluctuation rate) having different grain sizes in an emulsion layer having substantially the same color sensitivity are mixed in the same layer, or Can be applied in multiple layers. 2 more! It is also possible to use polydisperse silver halide emulsions of class I or higher or a combination of monodisperse emulsions and polydisperse emulsions by mixing or layering them.

The silver halide grains used in the present invention have a regular shape such as a cube, octahedron, rhombidodecahedron, and dodecahedron.
It may have an ar) crystalline structure or a coexistence of these crystals, or it may have an irregular shape such as a spherical shape.
They may have a crystalline form (gular) or a composite form of these crystalline forms, or they may be plate-like particles, especially those with a length/thickness ratio of 5 or more, especially 8
Or more tabular grains?

An emulsion that occupies 50% or more of the total projected area of the grains may be used, or an emulsion consisting of a mixture of these various crystal forms may be used. Either an IPi image type or an internal latent image type formed inside one particle may be used.

The photographic emulsion used in the present invention is described in "Chemistry and Physics of Photography J" by Glafkide [P, Glafkide S, Chi.
sieeL Physique PhMograp
hique (Paul Montel, 1967), Duffin, “Photographic Emulsion Chemistry” [G
, F. Duffin, Photographic
Emulsion Chemistry (Focal
Press, February 1966, Zelikman et al., “Manufacture and Coating of Photographic Emulsions J [V, L, Zeliksan
etal, “Making and Coa+ting”
Photographic Emulsion (Fo
Cal Press, 1964) 1. 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 is a one-sided mixing method or a simultaneous mixing method.

Any combination thereof may be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). Simultaneous mixing method 1
PAg in the liquid phase formed by silver halide as two forms
The method of keeping constant is the so-called chondral
A double jet method can also be used. According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained.

Furthermore, emulsions produced 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 that have undergone similar halogen conversion after the grain formation process can also be used.

In the process of halogenated fii particle formation or physical ripening, cadmium salt, zinc salt, lead salt, copper salt, thallium salt,
An iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be coexisting.

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, rhodankali or U.S. Pat. No. 3,271,157, JP-A-5
1-12360, JP-A No. 53-82408, JP-A-53-144319, JP-A-54-100717 or JP-A-54-155828, etc.). , Physical Maturation, Chemistry V
It can also be used as a percentage. In order to remove soluble l:#l salts from the emulsion after physical ripening, washing with water,
Follow flocculation sedimentation method or ultrafiltration method.

The silver halide emulsion used in the final step 11 was prepared using a sulfur IA sensitization method 2 reduction using active gelatin and sulfur-containing compounds that can react with silver (for example, thiosulfates, thioureas, mercapto compounds, rhodanines). chemical substances (e.g. stannous salts,
amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds) (for example, total complex salts, as well as pt, Ir, Pd, Rh.

A different metal sensitization method using complex salts of metals of group 1 of the periodic table with Fe, etc. can 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 others so that they have color sensitivity. 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.

For these pigments! ! ! Any of the nuclei commonly used for cyanine dyes can be used as the basic ring nucleus. Namely, pyridine nucleus, oxazoline tower, 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 an aromatic hydrocarbon ring fused to these nuclei Nuclei, ie, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be modeled 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, thiobarbic acid nucleus, etc. can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Typical examples are U.S. Patent No. 2,888,545, U.S. Patent No. 2,977.229, U.S. Pat.
No. 2, No. 3,527.6 Cattle No. 1, No. 3,617.
No. 293, No. 3,628,964, No. 3,666
．． No. 480, No. 3,672,898, No. 3,67
No. 9.428, No. 3,703.377, No. 3.7
No. 69,301, No. 3,814,609, No. 3,
837,862, British Patent No. 4.026.707, British Patent No. 1,344,281, British Patent No. 1,507,803,
It is described in Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 53-12375, Japanese Patent Application Publication No. 110618/1982, and Japanese Patent Publication No. 52-109925.

Along with sensitizing dyes, dyes that do not themselves have spectral sensitizing effects or substances that do not substantially absorb visible light, 1
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 is effective not only to strengthen adsorption but also to control chemical sensitization sites and prevent 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 to have diffusion resistance, and has a leaving group in the coupling active position or a hydrogen atom rather than a 4'-5-5 color coupler. A two-button color coupler that has been replaced with a coating, a zero-coloring dye that can be reduced by coating, a coupler that has moderate diffusivity, a non-coloring coupler, or a coupler that releases a development inhibitor along with the coupling reaction. DIR couplers or couplers that release development accelerators can also be used.

Typical examples of yellow couplers that can be used in Shukan 111 include oil-protected acylacetamide couplers. A specific example is U.S. Pat.
No. 407,210, No. 2875.057, and No. 3,265,506. The use of dual yellow couplers is preferred for the present invention, and U.S. Pat.
No. 3,933,501 and No. 4゜022.
Oxygen atom separation type yellow couplers described in Japanese Patent Publication No. 58-10739, U.S. Pat. No. 4,401,752, U.S. Pat. No. 4,326,024, R
D18053 (April 1979), British patent ff1l
, No. 425,020, West German Application No. 2,219,91
No. 7, No. 2,261,361, No. 2,329,5
Typical examples include the nitrogen atom separation type yellow couplers described in No. 87 and No. 2,433,812. α-pivaloylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon 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 21-substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the coloring dye, and a representative example thereof is U.S. Pat. No. 2,311,082. , same second,
No. 343,703, No. 2,600,788, No. 2
, No. 908,573, No. 3,062.653, No. 3,152,896, and No. 3,936,015. As a leaving group for a 29-mer 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. 1.897 is preferred,
Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. M73,636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369,879, preferably pyrazolo[5,1-c][1,2,4] triazoles as described in U.S. Pat. No. 3,725,087, Research Disclosure 24220
(June 1984) and Research Disclosure 24230 (198
Imidazo[1,2-b]pyrazoles described in European Patent No. FF1119.741 in terms of low yellow side absorption and light fastness of color-forming dyes. preferred, European Patent No. 1
Pyrazolo[1,5-b] [1 as described in No. 19,860
, 2°4] triazoles are 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 typical examples. Can be mentioned. Further, specific examples of phenolic couplers are disclosed in U.S. Pat. No. 2,369,929, l.
T111n2,801,171, T111n2,772.1
No. 62, No. 2,895,826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in undeveloped IJ1, typical examples of which are:
A phenolic cyan coupler having an alkyl group greater than or equal to ethyl group at the meta-position of the phenol nucleus described in U.S. Patent No. FF13,772,002, U.S. Patent No. 2,772
, No. 162, No. 3,758,308, No. 4,12
No. 6.396, No. 4,334,011, No. 4.3
No. 27,173, West German Patent Publication No. 3.329.729 and Japanese Patent Application No. 58-42671, etc.
5-Diacylamino substituted phenolic couplers and U.S. Pat. Nos. 3,446°622 and 4,333,99
No. 9, No. 4゜451.559 and No. 4,427
, No. 767, etc., which have a phenylureido group at the 2-position and an acylamino group at the 5-position.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusive couplers are disclosed in U.S. Pat. No. 234.533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and specialty couplers described above may form dimers or more polymers; typical examples of polymerized dye-forming couplers are described in 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 an oil-in-water dispersion method. In the oil droplet dispersion method, the boiling point or 1
After dissolving in either a high boiling point organic solvent of 75°C or higher and a low boiling point so-called auxiliary solvent, either alone or in a mixture of both, finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. do. Examples of high-boiling organic solvents include those described in U.S. Pat. It may be used for coating after being removed or reduced by method 6 or the like.

Specific examples of high-boiling organic solvents include phthalate esters (dibutyl 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, tridodecyl phosphate, tributoxyethyl phosphate, tosochloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), ben9oic acid ester (2-ethyl-hexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyltodecane amide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (instearyl), alcohol, 2,4-di-tart-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. 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, cyclohexanone, -Ethoxyethyl acetate, dimethylformamide and the like.

Specific examples of latex dispersion process steps, effects, and latex for impregnation are described in U.S. Pat.
jS2,541,230, etc.

Typical amounts of color couplers used range from o.ooi to 1 mole per mole of photosensitive silver halide, preferably from 0.0 to 0.0 mole for yellow couplers.
5 mole, 0.003 to 0.3 for magenta coupler
moles, and for cyan couplers 0.002 to 0.3
It is a mole.

The photosensitive materials to which the undeveloped lJ1 method can be applied include hydroquinone derivatives,
Aminophenol derivatives, amines.

It may contain gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamidophenol derivatives, and the like.

Known antifading agents can be used in the light-sensitive materials 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. Further, metal complexes such as (bissalicylaldoximate) nickel complex and (bis-N,N-dialkyldithiocarbamate) nickel complex 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 the internal structure of a hindered amine and a hindered phenol 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 the cyan image, especially the light fastness, it is preferable to use a benzotriazole ultraviolet absorber in combination. This ultraviolet 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, but if too many values are used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. Since there are
-'mol/rrf is set in the range of 1.5x10-3 mol/rrf.

In the conventional light-sensitive material layer structure of color vapor, an ultraviolet absorber is contained in one layer on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers. When the UV 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 the UV absorber is added to the protective layer, it may also be co-emulsified as the outermost layer. A separate M retaining layer may be applied, and 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, water-soluble dyes may be contained in the wood-philic colloid layer for irradiation or anti-halation + F and other various purposes. Oxonol-based, anthraquinone-based, or azo-based dyes are preferred; green light, red Oxonol dyes that absorb light are particularly preferred.

The photographic emulsion layer or other wood-philic colloid layer of the light-sensitive material to which Suekan 151 is applied may contain a water-soluble brightener such as a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. Alternatively, 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 emulsion layers may be made up of two or more emulsion layers having different sensitivities, or a non-light-sensitive 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.

Is it advantageous to use gelatin as a 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?

Other wood-loving colloids may also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein:
mAA such as cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, sodium alginate, starch derivatives, etc.
Conductor: Various synthetic hydrophilic polymers such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Substances can be used. The use of acrylic acid modified polyvinyl alcohol in the 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., p. 18.30 (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 1 to which the present invention is applied also contains various stabilizers, anti-staining agents, developing agents or their precursors, development accelerators or their precursors as described above,
Lubricants, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. Representative examples of these additives are listed in Research Disclosure 17643 (December 1978). and 18716 (November 1979).

These additives are quick print, i, f! ! Compound (I) is very important in rapid processing and has 11 undeveloped compounds.
important in relation to In addition, especially when the halogen composition of the emulsion used contains a high content of silver chloride, mercaptoazole, mercaptothiadiazole, or mercaptobenzazole compounds may be used in combination to improve color development.
The present invention has an advantage in preventing fogging.

“Reflective support” that can be used in photosensitive materials to which the present invention is applied
This type of reflective support enhances the reflectance and sharpens the dye image formed in the silver halide emulsion layer.Such reflective supports include titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, Examples include baryta paper, polyethylene-coated paper, and polypropylene-based synthetic paper. Paper 1 Transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide films, polycarbonate films, polystyrene films, etc.
These supports can be appropriately selected depending on the purpose of use.

(Effects of the Invention) The developer composition for a silver halide color photographic light-sensitive material of the present invention has poor stability and color development, and provides a color developer in which increase in coupler during continuous processing is significantly reduced.

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 and deterioration of color development can be prevented without using substances such as sulfite ions that act as competing compounds for the developing agent.

(Example) The present invention will be explained in more detail based on Examples II+.

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.

First layer coating solution preparation Yellow coupler (a) 19.1g and color image stabilizer (b)
) to 4.4 g, 27.2 volumes of ethyl acetate and solvent (c)7.
9 mi was added and dissolved, and this solution was emulsified and dispersed in 185 d of a 10% gelatin aqueous solution containing 8 parts of 10% sodium dodecylbenzenesulfonate. - The blue-sensitive sensitizing dye shown below was added to a carbromide emulsion (a11.o++oλ% bromide, Ag70 [containing 7 kg)] using chlorobromide [1 tablet 0β dust 5.0x]
90 g of a blue-sensitive emulsion was prepared by adding lO-" mol. The emulsified dispersion and emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table 1 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 m1 layer coating solution. As the gelatin hardening agent for each layer, 1-year-old xy3,5-cyclosh lyazine sodium salt was used.

The following spectral sensitizers were used as the spectral sensitizers for each emulsion, and the blue-sensitive emulsion layer and green-sensitive emulsion layer (4.OX 10-
' mol addition) (per mol of halogenated fl?
OX 10-') mol added) Red-sensitive emulsion layer The following dye was used as the irradiation prevention binder 4 of 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.

(81 yellow coupler H3 fc) Solvent + dl color mixture inhibitor II (4 solvent ffl Color image stabilizer (g) 211 mixture of solvent (weight ratio) tbl I:5:3 mixture of ultraviolet absorber (molar ratio) fkl Cyan 1=1 mixture (molar ratio) of coupler (k2) (1) 1:3:3 mixture (molar ratio) on the color image stable side <m) Magenta coupler The color photographic paper obtained as above was shaped into a wedge. After 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 E D T A
・2 Na ・2 Hz 0 2 g Sodium chloride 1.0 g 4-Amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido)ethyl)-p-phenylenediamine sulfate 5.0 g Fluorescence enhancement Whitening agent (4,4”-diamino-stilbene type) 3.0g Compound of general formula (I) Add the first table wood
1000 Print pH 10,10 1 page
60g EDTA ・2Na ・2H 204g Thio f! Ammonium acid (70%) 1201d
Add 16g of sodium sulfite and 7g of glacial acetic acid.
1ooodpH5,5 Rinse solution l-Hydroxyethylidene-1,1'-diphosphonic acid (60%) 1.6 Bismuth chloride 0.35g Bobvinylpyrrolitone 0.25g Aqueous ammonia (26%)
2.5 lessons Nitrilotriacetic acid/3Na
1. OgEDTA・48
0.5g Sodium Shield Sulfate
To 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 5011, add 0.1 ml of formalin (37%) and
1000 PH7.0 A part of the color developer obtained above was lfL
After being left in an open system at 40° C. for 20 days under the bead force, it was treated again in the above treatment step.

Processing using the color developer left for 20 days was used as a time-lapse method test, and processing using the color developer before aging was used as a fresh solution test.

Table 1 shows the photographic properties of the fresh solution obtained and the photographic properties of the aged test.

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

The sensitivity point is expressed as the density value of constant exposure i (100 cMs), and one gradation represents a density of 0.5, so logE
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 properties can be obtained. On the other hand, when sodium sub-VLM or triethanolamine is used, it changes over time, and the photographic image becomes foggy or the gradation changes. Example 2 As described in Table C, both sides of the corona discharge processed 1st layer (M lower 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, 200 g of the yellow coupler shown in the table, 93.3 g of anti-fading agent, 10 g of high-elevation point solvents (p) and 5 g of (q), and 600 mfl of ethyl acetate as an auxiliary solvent! After heating and dissolving the mixture to 60°C, it was mixed with 3,300'd of a 5% gelatin aqueous solution containing 5% aqueous solution 3301 of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont), and emulsified using a colloid mill. A coupler dispersion was prepared. Ethyl acetate was distilled off under reduced pressure from this dispersion, and a sensitizing dye for a blue-sensitive emulsion layer and l-methyl-2-mercapto-5-acetylamino-1°3.4-) riazole were added to emulsion 1. 400g (96.7g as Ag,
(containing 170 g of gelatin), and further added 2,600 g of 10% gelatin aqueous solution to prepare a coating solution. Second
The coating liquids for the layers to the seventh layer were prepared in the same manner as for the first layer.

n2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole o2-(2-hydroxy-3,5-di-tart-butylphenyl)benzotriazole p di(2-ethylhexyl) phthalate 9 dibutyl phthalate r2,5-di-tert-amylphenyl-3,5-
di-tert-butylhydroxybenzoate s 2,5-di-tert-octylhydroquinone tl, 4-di-tert-amyl-2,5-dioctyloxybenzene u2,2=-methylenebis(4-methyl-6-tert
-butylphenol) The following were used as sensitizing dyes for each emulsion layer.

Blue-sensitive emulsion layer: Anhydro-5-methoxy-5'-methyl-3,3'-cisulfoprovir selenacyanine hydroxide Green-sensitive emulsion layer: Anhydro-9-ethyl-5,5'-diphenyl-3,3 ”-Disulfoethyloxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3'-diethyl-5-methoxy-9
, 9'-(2,2-dimethyl-1,3-propano)thiadicarbocyanine yositoide and l-methyl-2=mercapto-5-acetylamino-1,3,4- as a stabilizer for each emulsion layer. Triazole was used.

The following dyes 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-pyrazolyl)benzenesulfonate di-potassium salt N,N'-. (4,8-dihydroxy-9,10-dioxo-3,7-cissulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt Also as a hardening agent 1,2-bis( (vinylsulfonyl)ethane was used.

The couplers used are as follows.

Mixture of yellow coupler magenta coupler 2 cyan coupler CC-1; C-2 = 50: so (molar ratio)] The multilayer color photographic paper obtained as follows was exposed to wedge-shaped light and then processed in the following processing steps. did.

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

L no Niri Eikanki
800 Benzyl alcohol Table 2 Diethylene glycol Table 2 Diethylenetriaminepentaacetic acid 1.0gN,N'-bis(
2-Hydroxybenzyl)ethylenediamine-N,N''-diacetic acid 0.1g Nitrilo-N,N,N-)-rimethylenephosphonic acid (40%) 1.0g Potassium bromide l.Og General formula (I)
Table 2 Hydroxylamines Table 2 Potassium carbonate
30g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.5g optical brightener (4,4'-diaminostilbene type) 1.0g Add water 1ooodKOH At
pH 1O, 101 constant A smoked ammonium thiosulfate (70%) 150d
sodium acid 15g ethylenediamine iron (m) ammonium 60g ethylenediaminetetraacetic acid 10g optical brightener (4,4
1.0g 2-mercapto-5-amino-3,4-thiadiazole 1.0g water Add 1000d ammonium water to pH 7.0 Rinse solution 5-chloro-2-methyl-4-isothiazoline 3-one 40 mg 2-methyl-4-isothiazolin-3-one 10 mg 2-octyl-4-isothiazolin-3-one l Om g bismuth chloride (40% > o, 5 g nitrilo-
N,N,N-)-limethylenephosphonic acid (40%) 1.0g 1-hydroxyethylidene-1,1-diphosphonic acid (60%) 2.5g optical brightener (4,4”-diaminostilbene type) i, add 0g ammonium water (26%) and 2.0ml water
At 1000 Suri KOH
p) 17.5 In the same manner as in Example 1, determine the Dmin, sensitivity, and gradation of magenta in the fresh solution and the preserved solution, and calculate the change value of each photographic property based on the photographic properties in the fresh solution. It is shown in Table 2.

From the above results, the developer composition of the present invention shows excellent effects even in systems containing benzyl alcohol;
In particular, it can be seen that photographic performance is significantly stabilized when used in a system that does not contain benzyl alcohol (Experiment N
o, 12.13.14.15.18.19, 20.21
．． On the other hand, when hydroxylamines are used alone, the storage solution changes over time, resulting in large changes in photographic properties.

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 did not In contrast to the photographic properties which changed significantly due to aging of the storage solution, the developer composition of the present invention showed remarkable stability, especially in a system not containing benzyl alcohol.

Procedure 7 Yamasho (self-proposal) io month 31, 1985 [1] Director General of the Patent Office Kuro 1) Mr. IJI Yu ■, Indication of the case 1988 Patent Application No. 188619 2, Name of the invention Color photographic developer composition and Processing method for silver halide color photographic light-sensitive materials 3, relationship with the case of the person making the amendment Patent applicant address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52)
0) Fuji Photo Film Co., Ltd. Representative: Minoru Ohnishi 4, Agent address: 3-chome, Shinbashi, Minato-ku, Tokyo 105 [17-3 Midoriya 2nd Building, 7th floor 6, Supplementary 1F Number of All will increase 07.
Subject of amendment: Column 8 of “Detailed description of the invention” in II.
Contents of the amendment (1) "Fuhitoamito group" in lines 6 to 7 on page 20 of the specification will be corrected to "acetamido group."

(2) Correct "Processing machine" in the 5th line of page 49 of Time-S to "After processing".

(3) Correct "(Anti-fading layer)" in the second layer of the layer name in Table C on page 95 of circulation to "(Anti-color mixing layer)".

(4) Rounds on the same page! Corrects the "anti-fading agent (S)" in the second layer of the product to "anti-color mixing agent (S)".

(that's all)

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 an n-valent organic group, R^2, R^3
and R^4 represents a monovalent organic group. At least two groups among R^2, R^3 and R^4 may be combined to form a heterocycle containing a quaternary ammonium atom, n is an integer of 1 or more, and X^■ indicates a counter-anion. ) (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 an n-valent organic group, R^2, R^3
and R^4 represents a monovalent organic group. At least two groups among R^2, R^3 and R^4 may be combined to form a heterocycle containing a quaternary ammonium atom, n is an integer of 1 or more, and X^■ indicates a counter-anion. )