JPS6321647A - Color photographic developing solution composition and method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve stability and color developing performance and to reduce rise of fog at the time of continuous processing and the like by incorporating a specified compound in a color developing solution. CONSTITUTION:The color developing solution contains the compound represented by formula I in which each of R<1>-R<4> is H or optionally substituted alkyl; each of R<5>-R<7> is a divalent organic group; each of X and Y is -O-, -S-, or the like; and n is 1, 2, or 3. This developing solution contains an aromatic primary amine color developing agent, and the compound of formula I, and preferably, one of hydroxylamines represented by formula II (each of R<9> and R<10> is H or optionally substituted alkyl), but it contains substantially no benzyl alcohol, thus permitting the obtained color developing solution to be enhanced in stability and color developing performance and reduced in rise of fog at the time of continuous processing and the like.

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 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 phenomenon 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 deteriorate. It is well known that the image may change or the photographic characteristics may differ from what is desired.

Accordingly, various methods have been studied to improve the stability of color developing solutions, and among them, the most common method is the combination of hydroxylamine and sulfite ions. However, when hydroxylamine is decomposed, ammonia is generated, which causes fog, and sulfite ions act as competing compounds for developing agents, impeding color development. It's hard to call it a drug.

In addition, various preservatives and chelating agents have been investigated in order to improve the stability of color developers.
Aromatic polyhydroxy compounds described in No. 9-160142, No. 56-47038, and U.S. Patent No. 3,746.544, etc., U.S. Patent No. 3,615,503 and British Patent No. 1,306,176 Hydroxycarbonyl compounds described in JP-A-52-143020 and JP-A-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-
121127 No. 1 55-126241 and 55-
Examples include phosphonocarboxylic acids described in JP-A-58-195845, JP-A-5B-203440, and JP-B-Sho 53-40900.

(Problems to be Solved by the Invention) However, even if these conventional techniques are used, satisfactory results have not been obtained, as they have both advantages and disadvantages, such as insufficient storage performance and adverse effects on photographic properties. do not have.

In particular, in color developers from which benzyl alcohol, which is often problematic in terms of pollution prevention and solution preparation, is removed, it is inevitable that color development will be slow or deteriorate, or that preservatives that act as competing compounds in such systems The conventional techniques described above are often unsatisfactory because they significantly impede color development.

Furthermore, color photographic materials containing silver chlorobromide emulsions with a high chlorine content tend to cause fogging during color development, as disclosed in Japanese Patent Application Laid-open Nos. 58-95345 and 59-232344.
As stated in the issue. When such emulsions are used, it is essential to have a preservative that reduces the solubility of the emulsion and has better retention properties.In this sense, there is also a demand for the development of a new developing solution.

Therefore, an 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, and which 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 deteriorating the degree of color development.

Furthermore, the present invention improves the stability of the color developer,
It is an object of the present invention to provide a method for processing a silver halide color photographic material that significantly reduces changes over time during continuous processing and 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 photosensitive material containing an aromatic primary amine color developing agent and a compound represented by the following general formula (I). A silver halide color characterized in that a developer composition for a material 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 by a method of processing photographic materials.

General formula (I) (wherein R, R, R and R4 represent a hydrogen atom, an unsubstituted or substituted alkyl group, and the alkyl group has 1-1 carbon atoms.
10 may be linear, branched, or cyclic;
Examples of substituents for alkyl groups include halogen atoms (fluorine atoms, base atoms).

bromine atom), alkoxy groups (methoxy group, methoxyethoxy group, etc.), sulfonyl group (methanesulfonyl group, methoxyethylsulfonyl group, etc.).

Sulfonamide group (methanesulfonamide group, ethanesulfonamide group, etc.), sulfamoyl group (dimethylsulfamoyl group, unsubstituted sulfamoyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.).

Amide group (acetamido group, etc.), ureido group (methylureido group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, etc.), cyano group, hydroxy group, carboxy group, sulfo group, and -Y-R7-OH
Particularly preferred substituents are the hydroxy group and the -Y-R70H group.

R, R and R7 represent divalent organic groups, and examples of the organic groups include alkylene groups (methylene group, dimethylene group, trimethylene group, methyldimethylene group, etc.), alkenylene groups (vinylene group, butenylene group, etc.). X and Y are -o-, -s-, 1°N- -co-1-so2-1-so- Or these, 8
In 12-1, R has the same meaning as R, R and R4, and n represents 1 to 3, where any one of R, R, R and R4 is a hydroxy group or Y -R7-
Represents an alkyl group substituted with OH, R1, R2, R
3 and R4 may be the same or different. Also, n
or 2 or 3, X may be the same or different.

Specific examples of the compound represented by the general formula (I) of the terminal IJ are shown below, but the compound is not limited thereto.

-'- 21) The compound represented by the general formula 〇) can generally be synthesized by reacting an amino compound with an alkylating agent such as an alkyl halide or an alkyl tosylate in the presence of a base, or by introducing a hydroxyethyl group. In this case, it can also be synthesized by reacting an amino compound with ethylene oxide.

The synthesis of specific compounds will be explained below.

Synthesis of Exemplified Compound I-(1) 104 g (1.0 mol) of bisaminoethyl ether and 475 g (4.4 mol) of bromoethanol were mixed with 1.0 g of dimethylformamide. Dissolved in On, potassium carbonate 1.38
kg (10 mol) was added, the mixture was reacted for 5 hours with stirring at 80°C, and then cooled to room temperature. The reaction solution was then filtered under reduced pressure, and the filtrate was concentrated under reduced pressure. The remaining oil was subjected to molecular distillation in 1. #ItA 100g of Exemplified Compound 1-(1) was obtained.

The content of the compound represented by general formula (I) is 1! The amount is 0.01 to 50 g per L, preferably 0.01 to 50 g per L.
It is 1 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 are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-I N,N-diethyl-p-phenylenecyamine 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-methanesulfone (amidoethyl)-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 Also, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, p-toluenesulfonate, etc. The amount of the aromatic-grade amine developing agent used is The degree of C per developer solution is about 0.1 g to about 20 g, more preferably about 0.5 g to about log.

It is preferable that the color developer having a final finish contains a hydroxylamine represented by the following general formula (II).

General Formula (■) In the formula, R9 and R10 represent a hydrogen atom unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, or a substituted or t-substituted aryl group.

It is preferable that R9 and R10 are an alkyl group or an alkenyl group, and it is more preferable that at least one of them has a substituent. Further, R9 and RlO may be connected to form a petero ring together with the nitrogen atom.

Alkyl groups and alkenyl groups may be linear, branched, or cyclic, and substituents include halogen atoms (F, C,
Br, etc.), aryl groups (phenyl L p-chlorophenyl group, etc.), alkoxy groups (methoxy group, ethoxy group, methoxyethoxyno, (etc.), aryloxy group (
phenoxy group, etc.), sulfonyl group (methanesulfonyl group, p-toluenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (diethyl 1-sulfamoyl group, unsubstituted sulfamoyl group, etc.) , carbamoyl group (
carbamoyl group, diethylcarbamoyl group, etc.)
, amide group (futamide group, benzamide group, etc.),
Ureido groups (methylureido groups, phenylureido groups, etc.), alkoxycarbonylamino groups (methoxycarbonylamino groups, etc.), allyloxycarbonylamino groups (
phenoxycarbonylamino group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), cyano group, hydroxy group.

Carboxy group, sulfo group, nitro group, amino group (non-substituted amino group, diethylamino group, etc.), alkylthio group (
methylthio group, etc.), arylthio group (phenylthio group, etc.), and peterocyclic group (morpholyl group, pyridyl group, etc.). Here, R9 and R10 may be the same or different from each other, and the substituents of R9 and Rlo may also be the same or different.

Further, the number of carbon atoms in R9 and R10 is preferably 1-10,
Particularly preferably 1 to 5. Examples of the nitrogen-containing heterocycle formed by linking R9 and R10 include a piperidyl group, a pyrrolisilyl group, an N-alkylpiperacyl group, a morpholyl group, an indolinyl group, and a benztriazole group.

Preferred substituents for R9 and RlO 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 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.

1l-(1) H CH-N-C2H40CH3 H CH-N-C2H40C2H5 u-(4) u-(S) H 1I-(6) H C2H50C2H4-N-C2H4oC2H5U -(
7) H ■ 0H3QC2H4QC2H4-N-C2H, 0C2H4
0CH3n -(a) H C2H50C2H4N-C2H5 n -(9) H C2H50C2H4NCH2-CH=CH2n -(1
0) II-(11) II-(12) H CH-N-C2H,CONH2] -(1) n-(14) n-(ts) n-(16) H Ch-N-C2H4S02C2H5 II- (17) H C2H5S02C2H4-N-C2H4S02C2H5
n-(18) n-(19) ff -(2G) II-(22) ■-(23) n-(24) n-(zs) II-(26) H Hot HOOC-CH-N-CH2- COOHII-(27
) H HOCH2CH2NCH2CH20H n -(2B) II -(29) II -(30) I'+3-8, -11, female H21,;112I'I and 112bit21'1. Steam H3n -(31) n-(32) n-(co3) H CHCHNCH2CH3 II -(:14) H20H The compound represented by general formula (II) can be synthesized by the known method shown below. I can do it.

U.S. Patent No. 3,661,996, U.S. Patent No. 3,362.96
No. 1, No. 3,293.03+, Special Publication No. 42-2794
No. 3,491,151, U.S. Patent No. 3,655
, No. 764, No. 3,467.711, No. 3,45
5,916, 3.287,125, 3.28
No. 7,124 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 the general formula (n) to be added to the color developer is 1 g to 20 g, preferably 0.5 g to log o per color developer.

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.
This means that it contains less than 2 parts of benzyl alcohol per part, preferably none at all.

In addition, as a preservative, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and other sulfites or carbonyl sulfite adducts may be added as necessary. The amount is Og to 20 g/l, preferably Og to Sg
/l, and if the stability of the color developer is maintained,
Less is better.

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 No. 7-44148 and JP-A No. 57-53749, various citrates described in JP-A No. 52-102727, hydroxamic acids described in JP-A No. 52-27638, α described in JP-A No. 59-160141, α'-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. Good too.

Further, it is preferable to add an aromatic polyhydroxy 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 pH as described in 1., it is preferable to use various buffers.

Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N,N dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxy Phenylalanine salt, alanine salt, aminobutyric salt, 2-amino-2-methyl-1,
3-propanediol salts, valine salts, proline salts, trishydrodiaminomethane salts, lysine salts, etc. can be used, especially carbonate salts, phosphates, tetraborates, hydroxybenzoates, etc. Raw, high pH over 9.0
It is particularly preferable to use these buffering agents because they have the advantages of being excellent in buffering in the H region, having no adverse effects on photographic surfaces (fogging, etc.) even when added to color developers, and being inexpensive. .

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 (borax), 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/ml or more, particularly 0.1 mol/ml or more.
Particularly preferred is 4 mol/liter.

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.

The chelating agent is preferably an am compound.

For example, Special Publication No. 4B-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,
Organic phosphonic acids described in No. 227,639, JP-A-52
-102726, 53-42730, 54-
No. 121127, No. 55-126241 and No. 55-
Examples include phosphonocarboxylic acids described in JP-A-58-195845, JP-A-58-203440, and JP-B-Sho 53-40900. Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriamine, pentaacetic acid, ethylenediamine, tetraacetic acid, triethylenetetramine, hexaacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N",N"-tetramethylenephosphonic acid, 1,3-diamino-2-propano- -4-acetic acid transcyclohexanecyamine tetraacetic acid nitrilotripropionic acid 1,2-diaminopropane hydroxyethyl tetraacetate )-ricarboxylic acid l-hydroxyethylidene-1,1-diphosphonic acid N,N''-bis(2-hydroxybenzyl)ethylenediamine-N,N''-diacetic acid Two or more of these chelating agents may be used in combination as necessary. It's okay.

The amount of these chelating agents added may be sufficient to sequester the metal ions in the color developer. For example, 11
It is about 0.1 g to 10 g per serving.

Any development accelerator can be added to the color developer if necessary. As a development accelerator,
No. 16088, No. 37-5987, No. 38-7826
No. 44-12380, No. 45-9019, and U.S. Pat. No. 3,813.247, etc.;
p-phenylenediamine compounds shown in No. 15554, JP-A-50-137726, JP-B No. 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. Pat. No. 2,482,546.

Amine compounds described in Japanese Patent Publication No. 2,596,926 and No. 3,582,346, Japanese Patent Publication No. 37-16088,
42-25201, U.S. Patent No. 3,128,183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3,532.501, etc.; Pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added as necessary.

In the present invention, any antifoggant can be added as necessary. Antifoggants include sodium chloride,
Alkali metal halides such as potassium bromide, potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole,
5-Methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-
Representative examples include nitrogen-containing heterocyclic compounds such as benzimidazole, indazoles, and hydroxyazaindolizine adenine.

The color developer of the present invention preferably contains a fluorescent brightener.
2,2'-disulfostilbene compounds are preferred. The amount added is O~5g/liter, preferably O,1g~4g/
It is l.

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 photosensitive material trn'. More preferably 100d~2
It is 00 print.

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 unreleased Polycarboxylic acids.

Complex salts with aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; hydrogen peroxide, etc. are preferred; among these, iron (m) Lists aminopolycarboxylic acids, aminopolyphosphonic acids, organic phosphonic acids, or salts thereof useful for forming organic complex salts of iron (m), which are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution. Then, 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, cyclohexanediaminetetraacetic acid.

1.3-diamino-2-propatoltetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, hydroxyliminodiacetic acid, cyhydroxyethylglycine ethyl etherdiamisotetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminetetraacetic acid Propionacetic acid, phenylenediaminetetraacetic acid, 2-phosphonobutane-1゜2.4-triacetic acid, 1,3-diaminopropano-
Ru N, N, N'', N''-tetramethylenephosphonic acid, ethylenediamine-N,N,N'', N'-tetramethylenephosphonic acid, 1,3-propylenecyamine-N,N
, N',N''-tetramethylenephosphonic acid, and 1-hydroxyethylidene-1,1-diphosphonic acid.

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

Iron(III) complex salt of methyliminodiacetic acid is preferred because it has a high bleaching strength.

These ferric ion complex salts may be used in the form of complex salts, and ferric salts 1 such as ferric sulfate, ferric chloride, nitrate f
A ferric ion complex salt is formed in a solution using iron 52, ferric ammonium sulfate, ferric phosphate, etc., and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc. 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 using a ferric salt and a chelating agent in a solution, When forming a complex salt, one or more ferric salts may be used.

Furthermore, one or more types of chelating agents may be used. In any case, the chelating agent may be used in excess of the amount required to form the ferric ion complex. Among the iron fillers, aminopolycarboxylic acid iron chains are preferable, and the amount added is 0. O1~t, omo1/1, preferably 0
．． 05 to 0.50 mof-/sentence.

Further, a bleach accelerator may be used in the bleaching solution or the bleach-fixing solution, if necessary. Examples of useful bleach accelerators include U.S. Pat. No. 3,893,858; German Pat. No. 1,290,812;
No. 53-32736, 53-57831, 53-37418, 53-65732, 5
No. 3-72623, No. 53-65732, No. 53-9
No. 5631, No. 53-104232, No. 53-124
No. 424, No. 53-141623, No. 53-2842
No. 6, Research Disclosure Y-NO-17129
Compounds having a mercapto group or a disulfide group described in No. (July 1978), etc.; JP-A-50-1401
Thiazolidine derivatives such as those described in No. 29;
Thiourea derivatives described in No. 3-3741 and US Pat. No. 3,706,561; iodides described in West German Patent No. 1.127.715 and JP-A-58-16235; West German Patent No. 966.410 Polyethylene oxides described in Japanese Patent Publication No. 2,748,430; Polyamine compounds described in Japanese Patent Publication No. 45-8836; Other JP-A No. 49-424
Examples thereof include compounds described in No. 34, No. 49-59644, No. 53-94927, No. 54-35727, No. 55-26506, and No. 58-163940, as well as iodine and bromide ions.

Among these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of having a large promoting effect.

In particular, U.S. Patent No. 3,893,858, West German Patent No. 1,
Compounds described in No. 290,812 and JP-A-53-95630 are preferred.

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 chloride, ammonium chloride) or iodides (e.g. iodide). (ammonium) rehalogenating agents. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, as necessary.
one or more non-IlA, acids having pH buffering properties such as sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.
Organic acids and their alkali or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine can 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,
Thiosulfates such as sodium thiosulfate; thiocyanine m salts such as sodium thiocyanate and ammonium thiocyanate; thioether compounds such as ethylene bisthioglycolic acid and 3,6-cythia-1,8-octanediol, and water-soluble thioureas. These silver halide solubilizers can be used alone or as a mixture of two or more of them. A special bleach-fixing solution consisting of a combination of halides and the like can also be used. In the present invention, it is preferable to use thiosulfates, particularly ammonium thiosulfates.

The amount of fixing agent per 1M is preferably in the range of 0.3 to 2 moles, more preferably in the range of 0.5 to 1.0 moles.

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 performance will be improved, but the deterioration of the solution and the leucoization of the cyan dye will be 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 monobicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

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 are used as preservatives such as sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), methane, etc. Contains sulfite ion releasing compounds such as bisulfites (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately 0.02 to 0.5 in terms of sulfite ion.
It is preferable to contain 0 mol/metal, more preferably 0.04 to 0.40 mol/vertical.

As a preservative, sulfite is generally added, but ascorbic acid, carbonyl bisulfite adducts, carbonyl compounds, etc. may also be added.

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

Next, the water washing step of the present invention will be explained. For undeveloped II+, a more advanced treatment method may be used instead of the usual "water washing treatment", such as performing only a so-called "stabilization treatment" without providing a substantial water washing step. As described above, the term "water washing treatment" as used in the present invention is used in the broad meaning 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 multistage countercurrent washing and the amount of pre-bath components of the photosensitive material brought in. However, in the present invention, the bleaching and fixing solution components in the final washing bath For example, in the case of 3-tank countercurrent water washing, it is preferable to use about 10,001 i or more per rn' of photosensitive material, more preferably 5,000 d or more. In addition, in the case of water saving treatment, it is preferable to use 100 to 1000 d per lrn' of the photosensitive material.

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

In the washing process, for the purpose of preventing precipitation and stabilizing the washing water,
Various known compounds may be added. 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'') ``Antifungal Agents'' (J,
, ^gents) Vol, l l.

No. 5, p. 207-223 (1983) and compounds described in Hiroshi Horiguchi's "Chemistry of Antibacterial Defense Team", metal salts such as magnesium salts and aluminum salts, alkali metal and ammonium salts, or A surfactant or the like may be added as necessary to prevent drying load and unevenness. Ori (Mas West) ``Odographic 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 antipyretic agent is added to the washing water, and the size of the washed wood is significantly reduced by multistage countercurrent washing of two or more types. Also, instead of the normal washing process.

It is also particularly effective when carrying out a multistage countercurrent stabilization treatment process (so-called stabilization treatment) as described in JP-A-57-8543. In these cases, the bleaching and fixing components in the final bath may be less than 5xto-2, preferably less than 1xio'.

Various compounds are added to this stabilizing bath for the purpose of stabilizing images. ipH adjustment (e.g. pH
3-8) various buffering agents (e.g. borate, metaborate, borax, phosphate).

Typical examples include carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and aldehydes such as formalin. Other chelating agents (
Inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid,
(aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), disinfectants (thiazole type, inthiazole type, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, hardening agents, etc. Additives may be used, and two or more of the same or different desired compounds may be used in combination.

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

As mentioned above, the amount of water for washing can be significantly increased! If i decreases,
It is preferable to allow part or all of the overflow liquid of the washing water to flow into a bleach-fixing bath or a 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 liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

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,
Applicable to any processing, for example, color vapor, color reversal paper, 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 be of any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide, silver chloride, etc. When performing replenishment treatment, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol % or more of silver chloride is preferred, and a silver chloride content of 80 to 100 mol % is particularly preferred.

In addition, high sensitivity is required, and during manufacturing, storage, and/or
Alternatively, if it is necessary to particularly suppress fog during processing, a silver chlorobromide emulsion or silver bromide emulsion containing silver bromide of 50 mol % or more is preferable, and 70 mol % or more is more preferable. If the silver bromide content exceeds 90 mol %, rapid processing becomes difficult, but there are ways to accelerate development, such as using development accelerators such as silver halide solvents, fogging agents, and developers as described below during processing. If used, development can be made faster to some extent without being limited by the content of silver bromide, which may be preferable in some cases. In either case, it is not preferable to contain a large amount of silver iodide, and it is sufficient if the content is 3 mol % or less.

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

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 size 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 projected surface printing; also in the case of tabular grains. ) is expressed in ball terms.
It is preferable that 2AL or less is O, t= or more, and particularly preferable is 1.5 pots or less 0. ts, the 0 grain size distribution that is above may be narrow or wide, but the value (variation rate) obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size is 20 % or less, particularly preferably 15% or less, is preferably used in the present invention, and in order for the light-sensitive material to satisfy the target gradation, substantially the same color sensitivity. In an emulsion layer having , two or more types of monodisperse silver halide emulsions with different grain sizes (preferably monodispersity having the above-mentioned fluctuation rate) are mixed in the same layer or coated in separate layers in layers. I'll come. 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 layered for use.

The shape of the silver halide grains used in the present invention is regular (regu I
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.
It may have a crystalline form (gular), or it may have a composite form of these crystalline forms. Tabular grains may also be used, especially those having a length/thickness ratio of 5 or more, particularly 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 a latent image type 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 Glafckide [P., Glalides, Chim.
ieeL Physique Phatography
que (Paul Monte1 company f41.L967
``Photographic Emulsion Chemistry'' by Duffin [G, F, Du
ffin, Photographic Emulsio
n Chemistry (published by Focal Press,
1, Zelikman et al., “Photographic Emulsion Preparation and Coating J [V, L., Zelikman et al., 1966]
Making and COcLing Pho
tographic E+5ulsion (Foca
It can be prepared using the method described in, for example, 1964, published by I Press. 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 any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

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 regular crystal shape and nearly uniform grain size can be obtained.

Furthermore, emulsions prepared by the so-called conversion method, which involves a process of converting silver halide that has already been formed before the completion of the silver halide grain formation process to silver halide with a lower solubility, and silver halide Emulsions that have undergone similar halogen conversion after 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 complex salts may also be present.

Silver halide emulsions are usually physically ripened after grain formation.

It is desalted and chemically aged 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-53-82408, JP-A-53-144319, JP-A-54-100717, JP-A-54-155828, etc.) by precipitation, physical Can be used for ripening and chemical ripening. In order to remove soluble silver salts from the emulsion after physical ripening, the Knoopple water washing, 4 flocculation sedimentation method or ultrafiltration method may be used.

The silver halide emulsion used in the present invention contains active gelatin and sulfur-containing compounds that can react with silver (for example, thiosulfate,
1ti, eA sensitization method using thioureas, mercapto compounds, rhodanines); reduction sensitization method using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds) Dimetallic compounds (e.g., total complex salts, pt, Ir, Pd, R
h.

A sensitization method using a complex of a metal of group 1 of the periodic table with Fe or the like 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 other dyes so as to have their respective color sensitization properties. The dyes used include cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holopolar cyanine dye, hemicyanine color M,
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, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole 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, 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. A typical example is the U.S. patent m
No. 2,688,545, No. 2,977.229, No. 3,397,060, No. 3,522,052,
Same No. 3.527.64-・1, Same No. 3,617,29
No. 3, No. 3.628,964, No. 3,666.4
No. 80, No. 3,672,898, No. 3,679.
No. 428, No. 3,703,377, No. 3.769
, No. 301, No. 3,814,609, No. 3,83
No. 7,862, same No. 4. o26.707, 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 Patent Publication No. 53-12375
It is described in No. 2-110618 and 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 for controlling I+ of the intraparticle structure. Furthermore, the addition of chemical sensitizers (v, gin) is effective not only for strengthening adsorption, but also for 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 to have diffusion resistance, and the coupling active position is substituted with a leaving group rather than a four-equivalent color coupler with a hydrogen atom. A two-equivalent color coupler, a coupler in which the color-forming dye has appropriate diffusivity that can reduce the amount of silver coated, a non-color-forming coupler, a DIR coupler that releases a development inhibitor upon coupling reaction, or a DIR coupler that releases a development inhibitor or accelerates development. Couplers that release agents can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2,40
No. 7,210, No. 2゜875.057 and No. 3
, US Pat. No. 3,408,194, US Pat. No. 3,447,928;
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 No. 2,219,917, West German Application No. 2,261,361, West German Application No. 2,329,587 and West German Application No. 2,433,812, etc. Yellow coupler is a typical example. 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. 5-Pyrazolone couplers are preferably substituted at the 3-position 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, same No. 3. o62.653, same 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 European Patent No. 897 is preferred, and the 5-pyrazolone couplers having a ballast group as described in European Patent No. 73,636 provide high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
No. 369,879 pyrazolobenzimidazoles, preferably the pyrazolo[5,1-cl[1,2,4] triazoles described in U.S. Pat. No. 3.7'25,067, Research Disclosure 2422
0 (June 1984) and Research Disclosure 24230 (1
The imidazo[1,2-bl pyrazole described in European Patent No. 119.741] is mentioned in terms of low yellow side absorption and light fastness of color-forming dyes. preferred, European Patent No. 1
Pyrazolo [1,5-bl [1
, 2°4] triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, such as the naphthol-based couplers described in U.S. Pat. No. 2,474.293, preferably U.S. Pat.
, No. 212, No. 4.146,396, No. 4,22
Typical examples include the two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 8,233 and No. 4,296,200. Specific examples of phenolic couplers include U.S. Pat. No. 2,369,929, U.S. Pat.
No. 801,171, No. 2,772.162, No. 2
, No. 895, 826, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Pat. No. 3,77
Phenolic cyan coupler having an alkyl group greater than or equal to ethyl group at the meta-position of the phenol nucleus described in US Pat. No. 2,002, US Pat.
No. 58,308, No. 4.126.396, No. 4,
No. 334,011, No. 4.327,173, West German Patent Publication No. 3,329.729 and Japanese Patent Application No. 1986-42
2,5-diacylamino substituted phenolic couplers described in US Pat. No. 671, etc. and U.S. Pat.
No. 22, No. 4,333,999, No. 4゜451.
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in No. 559 and No. 4,427,767.

Granularity can be improved by using a coloring dye or a coupler with appropriate diffusivity. Examples of such dye-diffusing couplers are magenta couplers in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570; 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 in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or the same compound can be used in two different layers. It is also possible to introduce more than one.

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 point organic solvents include those described in U.S. Pat. It may be used for coating after being removed or reduced by a filtration method 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, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoic acid esters (2-ethyl- hexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecane amide, N-tetradecylpyrrolitone, etc.), alcohols or phenols (stearyl alcohol, 2,4-di- tert-amylphenol, etc.),
Aliphatic carboxylic acid esters (dioctyl azelate,
glycerol tributyrate, isostearyl 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 iao"c or lower, can be used. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, -Ethoxyethyl acetate, dimethylformamide and the like.

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

Typical usage amounts for color couplers range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.1 mole for yellow couplers.
5 mol, magenta coupler 0.003 to 0.3
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.

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 S derivatives, and methylenedioxybenzene. Typical examples include aminophenols, hindered amines, and ether or ester conductors 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 a hindered amine and a hindered phenol structure in the same molecule give good results. In addition, in order to prevent deterioration of magenta dye images, especially deterioration caused by light, it is necessary to Chromans give favorable results.

In order to improve the storage stability and light fastness of the cyan image, 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; however, if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. Note.

Usually preferably lXl0-4 mol/rrf ~2X
l O-3 mol/rn', especially 5X10-' mol/lr
It is set in the range of i' to 1.5×10 −3 mol/ba.

In the conventional color vapor photosensitive material layer structure, W! An ultraviolet absorber is contained in either one of the layers on both sides that are in contact with each other, 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 mixture prevention agent. When the ultraviolet absorber is added to the protective layer, it may also be co-emulsified as the outermost layer. A separate protective layer may be applied, and this protective layer can 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, a water-soluble dye may be contained in the hydrophilic colloid layer for irradiation or antihalation and other various purposes, preferably oxonol-based, anthraquinone-based, or azo-based dyes, green light, red light, etc. 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 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-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.

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, but other wood-philic colloids can 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 T and acid esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, boc acrylic 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 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. 16.30 (1966) may be used, and gelatin hydrolysates and 82 element decomposition 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 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 in connection with compound (I) of the present invention. In addition, especially when the halogen composition of the emulsion used contains a high content of silver chloride, it is useful for the present invention to use mercaptoazole, mercaptothiadiazole, or mercaptobenzazole compounds in combination with 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
5 enhances the reflectivity and sharpens the dye image formed in the silver halide emulsion layer.Such reflective supports include titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate on the support. Examples include baryta paper, polyethylene-coated paper, and polypropylene-based synthetic paper. Paper, transparent supports with a reflective layer or reflective materials, 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 of the silver halide color photographic light-sensitive material of the present invention has excellent stability and coloring 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 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.

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.

19.1 g of yellow coupler (a) and color image stabilizer (b)
) 4.4 g to 27.2 g of ethyl acetate and solvent (c) 7.
9m was added and dissolved, and this solution was emulsified and dispersed in a 10% aqueous gelatin solution 185ml containing 8ml of 10% sodium dodecylbenzenesulfonate. On the other hand, the blue-sensitive sensitizing dye shown below was added to a silver bromide emulsion (containing silver bromide 1.0mo9%, Ag 70g/kg) at 110 silver chloride bromide S, 0xl.
90gXgl of blue-sensitive emulsion added with O-"mol
Manufactured. A first layer coating solution was prepared by mixing and dissolving the emulsified dispersion and emulsion and adjusting the gelatin concentration so as to have the composition shown in Table 1B.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. l-oxy-3,5-dichloro-5-triazine sodium salt was used as the gelatin hardening agent for each layer.

The following spectral sensitizers were used for each emulsion: blue-sensitive emulsion layer, green-sensitive emulsion layer (4.OX 10-' m/mol silver halide)
ol addition) (7.0% per tiq l mol of halide)
OX I O-+mo! 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 (C) Solvent (d+ color mixing prevention agent 0■ (e) Solvent (fl Color image stabilizer (1’:l ?Container 2ζ1 mixture (weight ratio) (11) Ultraviolet absorber l:5:3 mixture (molar ratio) + to + cyan coupler C1 (Niri l:, 1 mixture (molar ratio) (1) Color image stabilizer 1:3:3 mixture (molar ratio) of (m) Magenta coupler Fortune telling H1 OCaHl.

C@H+t(tl The color photographic paper obtained as described above was subjected to wedge-shaped exposure and then processed through the following processing steps.

Processing steps Temperature Time Color development 35° C. 45 seconds Bleach-fixing 35° C. 45 seconds Rinse 1 35° C. 208 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 202g Sodium chloride 1.0g 4-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido)ethyl)-P-phenylenediamine sulfate 1125.0g Fluorescent brightener (4
, 4"-diamino-stilbene system) 3.0g Compound of general formula (1) Add the first table wood
1000 practice p) (10,10 Ebhangju 1 Kaoru EDTAFe (III) NH・2H2060gEDT
A・2Na・2H2o 4g ammonium thiosulfate (70%) 120d sodium sulfite
16g aqueous acetic acid
Add 7g water
1000 Suri pH 5,5 Rinse liquid l-Hydroxyethylidene-1,1'-diphosphonic acid (60%) 1.6d Bismuth chloride 0.35g Polyvinylpyrrolidone 0.25g Aqueous ammonia (26%)
2.5 nitrilotriacetic acid/3Na
1. OgEDTA・4H0.5g Sodium sulfite 1.0g5-chloro-2-methyl-4-isothiazoline-3-year-old 50＠g formalin (37%) Add O,1TIII water and mix for 1000 to pH 7.0 as above. A portion of the obtained color developer was left in an open system at 40° C. for 20 days under a single bee force, and then treated again in the above treatment steps.

The treatment using the color developer left for 20 days was referred to as an aged solution test, and the treatment using the color developer before being left was designated as a fresh solution test.

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

Photographic properties were expressed in three points: Dsin (yellow density), sensitivity, and gradation.

The sensitivity point is expressed by the density value of constant exposure i (100 cMs), and the gradation is expressed by the intersection ogE from the point representing density 0.5.
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 sulfite or triethanolamine is used, it changes over time, and the photographic image becomes foggy or the gradation changes. 1st layer (bottom layer) to 7th layer (
@upper layer) was applied to prepare a sample.

The coating liquid for the first layer was prepared as follows. That is, after heating and dissolving a mixture of 200 g of yellow coupler shown in the table, 93.3 g of antifading agent, 10 g of high point solvents (p) and 5 g of high temperature point solvents (p) and 5 g of (q) to which 600 d of ethyl acetate was added as an auxiliary solvent at 60''C, 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) 33
Mix with 3,300 d of 5% gelatin aqueous solution containing 0 ml.

A coupler dispersion was prepared by emulsification using a colloid mill. Ethyl acetate was distilled off under reduced pressure from this dispersion, and the sensitizing dye for the blue-sensitive emulsion layer and 1-methyl-2-mercapto-
A coating liquid was prepared by adding 1,400 g of an emulsion (containing 96.7 g of Ag and 170 g of gelatin) to which 5-acetylamino-1°3.4-triazole had been added, and further adding 2,600 g of a 1O% gelatin aqueous solution. 2nd layer to 7th layer
The coating liquid for the layer was prepared in the same manner as for the first layer.

Green-sensitive emulsion layer: anhydride-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 yossite The following was used as a stabilizer 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-pyrazolyl)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 Cyan coupler (C-1, C-2 = 50250 mixture (
Molar 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℃ rinse (3 tank cascade) 3 minutes 30℃ dry
Drying: 1 minute at 80°C The processing solution used is as follows.

Stand up:” [i Kousui 80
0ml Pencil alcohol Table 2 Diethylene glycol Table 2 Diethylenetriaminepentaacetic acid i, OgN, N”-bis(2
-Hydroxybenzyl)ethylenediamine- N,N'-diacetic acid 0.1g Nitrilo-N,N;N-)-rimethylenephosphonic acid (40%) 1.0g Potassium bromide 1.0g 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. Add Og water at 1ooOdKOH
pH 10,101 1j Ammonium thiosulfate (70%) 150d Sodium sulfite 15g Ethylenediamine iron (m) Ammonium 60g Ethylenediaminetetraacetic acid 10g Fluorescent brightener (4,
4゛-Diaminos.

Chilbene type) 1. og2-mercapto-5-amino-3,4-thiadiazole 1.0g Add water 1,000 ml with ammonium water pH 7.0 Rinse solution 5-chloro-2-methyl-4-isothiazolin-3-one 40mg2-methyl- 4-inchazolin-3-one 10 mg 2-cutyl-4-inchazolin-3-one l 0 mg bismuth chloride (40%) 0.5 g nitrilo-N,
N,N-1-rimethylenephosphonic acid (40%) l 0g 1-hydroxyethylidene-1,1-diphosphonic acid (60%) 2.5g Optical brightener (4,4”-diaminostilbene type) 1.0g Ammonium water (26%) 2.0 addition
At 1ooodKOH
pH 7,5 In the same manner as in Example 1, the magenta Dmin, sensitivity, and gradation in the fresh solution and the preserved solution were determined, and the change value of each photographic performance when the photographic performance in the fresh solution was taken as the standard was calculated as the second Shown in the table.

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 pencil alcohol, and in particular, that photographic properties are significantly stabilized when used in systems that do not contain benzyl alcohol. (Experiment No.
, 15.16.17.18.21.22.23.24.
25).

On the other hand, when using hydroxylamines alone,
The storage solution changes over time, and the photographic quality changes 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 in the same manner as in Experiment Nos. 12 to 25 and tested for changes in photographic properties.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.

7111 Official internal dispute proceedings 1j Official document (spontaneous) 1 ■ October 31, 1961 Commissioner of the Japan Patent Office Black 1) Akio Yu 1, Indication of the case 1986 Patent Application No. 165621 2, Name of the invention Color Photographic developer composition and processing method for silver halide color photographic light-sensitive materials 3, relationship with the amendment person case Patent applicant address 210ffi Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (5
20) Fuji Photo Film Co., Ltd. Representative: Minoru Ohnishi 4, Agent Address: 6th Floor, 7th Floor, Midoriya 2nd Building, 3-7-3 Shinbashi, Minato-ku, Tokyo 105 Subject of Amendment: “Scope of Claims” in the Specification and"
``Detailed Description of the Invention'' column: ``Critique of Fake Affair (1) The ``Claims'' column of the specification will be amended as shown in the attached sheet.

(2) Correct the "combination of linking groups" in the second line of page 10 of the same harm to "combination of linking groups and alkylene groups."

(3) In the 5th line of the same page of the same book, "represents 1 to 3" is replaced with "
1 to 3, preferably n is 1. ” will be corrected.

(4) Correct “hydrogen atom unsubstituted” in line 5 of page 18 of the same book to “hydrogen atom, ’p!A21 substitution”.

(5) "Fuhitami" in line 8 of page 19 of the same book will be corrected to "acetami".

(Above) (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 (1).

General formula (I) (In the formula, RI, R2, R3, R4 represent a hydrogen atom, an unsubstituted or t-substituted alkyl group. However, 12) At least one of R, R, R and R4 is a hydroxy group or - (means the same as R, R and R7R4, representing an alkyl group substituted with Y-R' -OH)
, -CO-1-so2-1-so-, or a linking group composed of a combination of these linking groups and an alkylene group, and n represents 1-3. ) (2) A silver halide color photographic light-sensitive material is developed using a developer which does not substantially contain benzyl alcohol and which contains an aromatic primary amine color developing agent and a compound represented by the following general formula (1). 1. A method for processing a silver halide color photographic material, the method comprising: processing a silver halide color photographic material;

General formula (1) (wherein R1, R2, R:l, R4 represent a hydrogen atom, an unsubstituted or substituted alkyl group, provided that R1,
At least one of R2, R3 and R4 represents a hydroxy group or an alkyl group substituted with -Y-R7-OH, R5, R6 and R7 represent a divalent organic group,
X and Y mean the same as 10-1R4), -
co-.

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, R^2, R^3, R^4 are hydrogen atoms,
Represents an unsubstituted or substituted alkyl group. However, R^
At least one of 1, R^2, R^3 and R^4 represents a hydroxy group or an alkyl group substituted with -Y-R^7-OH. R^5, R^6 and R^7 represent divalent organic groups, X and Y are -O-, -S-, ▲numerical formulas, chemical formulas, tables, etc.▼(R^8 is R^1 , R^
2, meaning the same as R^3 and R^4), -C
It represents a linking group composed of O-, -SO_2-, -SO-, or a combination of these linking groups, and n represents 1-3. ) (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, R^2, R^3, R^4 are hydrogen atoms,
Represents an unsubstituted or substituted alkyl group. However, R^
At least one of 1, R^2, R^3 and R^4 represents a hydroxy group or an alkyl group substituted with -Y-R^7-OH. R^5, R^6 and R^7 represent divalent organic groups, X and Y are -O-, -S-, ▲numerical formulas, chemical formulas, tables, etc.▼(R^8 is R^1 , R^
2, meaning the same as R^3 and R^4), -C
It represents a linking group composed of O-, -SO_2-, -SO-, or a combination of these linking groups, and n represents 1-3. )