JPS6344657A - Color photographic developing composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having improved stability and color developing property of a color developing solution, and capable of reducing an increase of fog in a continuous processing by incorporating a 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 X is hydrogen atom or a group capable of hydrolyzing, Y and Z are independently hydrogen atom, a substd. or an unsubstd. alkyl group or a substd. or an unsubstd. aryl group, R1-R4 are each hydrogen atom, a substd. or an unsubstd. alkyl group or a substd. or an unsubstd. aryl group, R1 and R2, R2 and R3 and R4 together with each other may independently form a ring structure. Thus, the titled composition having the improved stability and color developing property of the color developing solution and capable of preventing the increase of for and change of gradient can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a developing processing composition for color photography, which particularly improves the stability and coloring properties of color developing solutions, and reduces fogging during continuous processing. The present invention relates to a development processing composition in which an increase in .

(Prior Art) In recent years, in the field of color photographic light-sensitive materials, there has been a desire to shorten processing time due to shorter finishing delivery times and lighter laboratory work. Increasing the processing temperature and increasing the amount of replenishment are common methods to shorten the time of various processing steps, but many other methods have been proposed, such as increasing stirring or adding various accelerators. It's here.

Additionally, color developers have the problem of being easily oxidized by air and metals, and when color images are formed using oxidized developers, fog increases and sensitivity and gradation change. It is well known that, because of this, desired photographic characteristics cannot be obtained. In particular, when the processing temperature is raised or the stirring is strengthened for the purpose of shortening the processing time, the color developer becomes more easily oxidized and the photographic properties tend to deteriorate further.

Accordingly, various methods have been studied to improve the stability of color developing solutions, and among them, the most common method is the use of hydroxylamine. However, when hydroxylamine is reductively decomposed, ammonia is generated.
Conventional silver iodobromide emulsions and silver chlorobromide emulsions also cause fogging, and are therefore not suitable as preservatives.

In addition, for the purpose of speeding up color development processing and/or reducing the amount of replenishment, a method for processing a color photographic material containing a silver chloride emulsion is disclosed in JP-A-58-95345 and JP-A-58-95345.
No. 9-232342, No. 60-19140 and No. 61
-70552. However, when processing a photosensitive material using such an emulsion with a high chlorine content, hydroxylamine cannot be used because it causes silver development and significantly reduces dye density (
(See Japanese Patent Application Laid-Open No. 1983-19140). Further, even if the techniques described in these patents are used, sufficient stability of the color developer cannot be obtained.

Furthermore, since hydroxylamine itself is highly toxic,
A color developer preservative that would replace hydroxylamine was desired.

In addition, various preservatives and chelating agents have been studied in order to improve the stability of color developers. For example, as a preservative, JP-A-52-49828,
No. 9-160142, No. 56-47038, and U.S. Pat. 746. Aromatic polyhydroxy compounds described in U.S. Pat.
α-aminocarbonyl compound described in No. 425, JP-A No. 1973
Alkanolamines described in No. 4-3532, JP-A-5
Examples include the metal salts described in No. 7-44148 and No. 57-53749. In addition, as the chelating agent, aminopolycarboxylic acids described in Japanese Patent Publication Nos. 48-30496 and 44-30232, JP-A-56-9734
No. 7, Special Publication No. 56-39359 and West German Patent No. 2.22
Organic phosphonic acids described in No. 7.639, JP-A-52-1
No. 02726, No. 53-42730, No. 54-121
No. 127, No. 5.5-126241 and No. 55-65
Examples include phosphonocarboxylic acids described in JP-A No. 58-195845, JP-A No. 58-203440, and JP-B No. 53-40900. However, none of these methods provide sufficient stability of the color developer.

Furthermore, color photographic materials containing silver chlorobromide emulsions with a high chlorine content tend to cause fogging during color development, as disclosed in JP-A-58-95345 and JP-A-59-232342.
listed in the number. However, even with the techniques disclosed in these specifications, sufficient fog prevention cannot be achieved.

Conventionally, as a method for preventing the occurrence of fogging, for example, 1.
-Phenyl-5-mercaptotetrazoles (Helgie Patent No. 671,402, U.S. Patent Box 3.295,97)
No. 6, No. 3. 376, 310, 3,615
．． 616, 3.071.465, 3.42
No. 0,664, No. 2,403,927, Japanese Unexamined Patent Publication No. 1973
-37436, British Patent No. 58-95728, etc.), pembbutriapools (British Patent No. 919,061, British Patent No. 76),
8.438, U.S. Pat. No. 3,157,509, U.S. Pat.
No. 578, same No. 3. 148゜066, same No. 3,51
1,663, British Patent No. 271,475, British Patent No. 1,
No. 344,548, No. 3,148,066, No. 3
．． 511. No. 663, German Patent No. 708,424
No. 635.769, No. 2,205,539, etc.), imidazoles (U.S. Pat. No. 3,106,467)
No. 3,420,670, No. 1.763°99
There are known methods of adding heterocyclic compounds such as No. 0, No. 2,271.229, etc.) into photosensitive materials or into processing solutions, but none of them have been able to achieve a sufficient antifogging effect. .

(Problems to be Solved by the Invention) Therefore, even if these known techniques are used alone or in combination, the retention performance is insufficient, so the fog density of color images obtained using the developer after aging is insufficient. increases or
In addition, most of the known preservatives act competitively with the developing agent and have an adverse effect on photographic properties such as sensitivity and gradation, so that satisfactory results have not been obtained.

Furthermore, benzyl alcohol, which is very effective as a color development accelerator for color developing agents, is widely used in developing solutions for color photographic materials and is an effective means to solve the problem of color development inhibition caused by preservatives. Since HENSYL alcohol has problems such as pollution hazards and difficulty in liquid preparation, it has been desired to develop a technique that can still provide sufficient color development even after removing HENSYL alcohol.

In particular, color photographic materials containing silver chlorobromide emulsions with a high chlorine content tend to inhibit color development and are prone to fogging during color development, so even when such emulsions are used, excellent storage performance is and anti-fogging performance,
Furthermore, there was a desire to develop a preservative that would also make it possible to remove Hensyl alcohol.

Accordingly, an object of the present invention is, first, to provide a color photographic development processing composition which has excellent color developer stability and which significantly reduces the increase in fog during continuous processing.

A second object of the present invention is to provide a color photographic processing composition that exhibits excellent color development even though it is a color developer that does not substantially contain benzyl alcohol.

(Means for solving the problem) The above object could be achieved by the color photographic development processing composition described below.

(1) A color photographic development composition comprising an aromatic primary amine color developing agent and a compound represented by the following general formula (1).

General formula (1) Represents a substituted aryl group. R1, R2, R3 and R4 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom, a nitro group, a cyano group, a sulfo group, a carboxy group, a substituted or unsubstituted aryl group, It represents a substituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, an alkoxy group, an aryloxy group, a sulfonyl group, a sulfonamido group, an amide group, a ureido group, an alkylthio group, or an arylthio group. R, and Rz, Rt and R3, and R3 and R4 may each work together to form a ring structure.

(2) The color photographic developing composition according to configuration (1) of the invention, wherein the color photographic developing composition does not substantially contain benzyl alcohol.

Next, the compound of general formula (1) will be explained in detail.

In general formula (I), X represents a hydrogen atom or a hydrolyzable group. A hydrolyzable group is a group that can become a hydrogen atom through a hydrolysis reaction, and specific examples include X-CR5 (where R3 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or represents a substituted or unsubstituted amine group).

That is, this is a method of protecting with an ester bond or a urethane bond. As another example, JP-A-57-15
protection with an imidomethyl blocking group as described in 8638. That is, it represents -C- or -8-, and Z represents a plurality of atoms necessary to complete a heterocycle having at least one 5- or 6-membered ring. ). The number of carbon atoms in X is preferably 1 to 1O.

Y and Z each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Y and Z may be the same or different.

When Y and Z are further substituted, the substituents include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a sulfonyl group, a sulfonamide group, a sulfamoyl group, a carbamoyl group, an amide group,
Ureido group, alkoxycarbonylamino group, allyloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, hydroxy group, carboxy group, sulfo group, nitro group, amino group, alkylthio group, arylthio group, heterocyclic group (morpholyl group,
pyridyl group, etc.).

Y and Z are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom is particularly preferred.

R+ SRz, R3 and R4 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom CC1, F, Br
), nitro group, cyano group, sulfo group, carboxy group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, alkoxy group, aryloxy group, sulfonyl group, sulfonamide group, amide group,
Represents a ureido group, an alkylthio group, or an arylthio group. R5 and R, R, and R3, and R3 and R4 may each work together to form a ring structure. The ring structure is 5~
It is a 6R ring, composed of carbon atoms, hydrogen atoms, oxygen atoms, nitrogen atoms, and sulfur atoms, and may be saturated or unsaturated.

When R1 to R4 are further substituted, examples of these substituents include the same substituents as those listed for Y and Z.

Preferred R1, R2, R1, and R4 are a sulfo group, a carboxy group, a sulfamoyl group, and a sulfonamide group, and have 1 to 5 carbon atoms.

Specific examples of the compound represented by the general formula (1) used in the present invention are shown below, but the scope of the present invention is not limited to these compounds.

SO, H I l OH OH2 03H l-(7) OH OH CH3 OH3 O3H 03H OH OH H S 03H 303H Nawate 03H H I -(20) j2 S (J z M H3 I -(28) OHl -(2
9) SOzN(CH3)z I-(34) I-(35) H I-(38) H I-(39) H OH 03H CH.

The compound represented by general formula (I) is Be11. ．． 1 Sat.

It can be synthesized by the known method described in 814.

The amount of the compound represented by the general formula (1) to be added to the color developer is preferably 0.50% per 1N of electrolyte.
The amount is 1 g to 20 g, more preferably 0.5 g to 10 g.

The color developer according to the present invention will be explained below.

The color developer according to 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-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl -N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-[β-hydroxyethyl)aminocoaniline D-6N-ethyl-N-(β-methanesulfonamide ethyl)-3-methyl-4-aminoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N5N-dimethyl-p-phenylenediamine D-94-amino-3-methyl-N -ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-butoxyethylaniline These p-phenylenediamine Bg conductors may also be salts such as sulfate, hydrochloride, sulfite, and p-1-luenesulfonate. The amount of the aromatic-grade amine developing agent used is preferably about 0.1 g to about 2 g per 11 of the developer solution.
0 g, more preferably from about 0.5 g to about 10 g.

The color developer according to the present invention preferably does not contain hydroxylamine. Even when it is contained, it is preferable that the amount added is as small as possible.

Further, it is preferable that benzyl alcohol is substantially not contained in terms of preventing fogging. "Substantially not containing benzyl alcohol" means that the amount of benzyl alcohol per 11 color developing solutions is 21 Tll or less. Preferably, it does not contain any benzyl alcohol.

Further, as a preservative, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts can be added as necessary. The amount of these additives added to the color developer is 1.0 g/I or less, preferably 0.5 g/I or less. When the preservative according to the present invention is used in a color developer that does not contain Hensyl alcohol, it is preferable that the amount of sulfite ion added be small in terms of preservability and/or photographic properties.

Other preservatives include hydroxyacetones described in U.S. Patent No. 3,615,503 and British Patent No. 1,306,176, and JP-A-52-143020 and JP-A-53-8.
α-aminocarbonyl compounds described in JP-A-57-44148 and JP-A-57-53749, various saccharides described in JP-A-52-102727, hydroxams described in JP-A-52-27638, etc. Acids, α, α'-dicarbonyl compounds described in No. 59-160141, salicylic acids described in No. 59-180588, alkanolamines described in No. 54-3532, No. 56
Poly (alkylene imine)s described in -94349,
Examples include gluconic acid derivatives described in No. 56-75647. Two or more of these preservatives may be used together if necessary.

Particularly preferred is the addition of alkanolamines (triethanolasin, jetanolasin, etc.) and/or aromatic polyhydroxy compounds.

The color developer according to the present invention preferably has a pH of 9 to 1.
2, more preferably 9 to 11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, 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-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. Can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent solubility and buffering ability in the high pH range of pH 9.0 or higher, and even when added to color developers, they have no effect on photographic performance. It is particularly preferable to use these buffers because they have the advantages of having no adverse effects (fogging, etc.) 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 0-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 0. 1 mole/
It is preferably 1 or more, particularly 0. 1 mole/I!
~0.4 mol/I! It is particularly preferable that

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

The chelating agent is preferably an organic acid compound, such as the aminopolycarboxylic acids described in Japanese Patent Publication No. 48-30496 and Japanese Patent Publication No. 44-30232; 227
, organic phosphonic acids described in No. 639, JP-A-52-10
No. 2726, No. 53-42730, No. 54-1211
No. 27, No. 55-126241 and No. 55-6595
Phosphonocarboxylic acids described in No. 6, etc., and other JP-A No. 1973
Examples thereof include compounds described in Japanese Patent Publication No. 8-195845, 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 ・Diethylenetriaminepentaacetic acid ・ethylenediaminetetraacetic acid ・triethylenetetraminehexaacetic acid ・N,N,N-trimethylenephosphonic acid ・ethylenediamine-N, N, i'J ', N'-tetramethylenephosphonic acid ・1 .3-diamino-2-propatol 45gM, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylenediamine triacetic acid, Ethylenediamine orthohydroxyphenylacetic acid/2-phosphonobutane-1,2,4-)licarboxylic acid/1-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 if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example, 1β
It is about 0.1g to 10g 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. Patent No. 3. 813. 1,000-onythyl compounds expressed in No. 247, etc., JP-A-52-49829 and JP-A No. 52-49829,
p-phenylenediamine compounds represented by No. 0-15554, JP-A-50-137726, and JP-B No. 44-
30074, JP-A-56-156826 and JP-A-56-156826
Quaternary ammonium salts represented by U.S. Patent Nos. 2,610,122 and 4,119,
p-aminophenols described in No. 462, US Patent No. 2
, No. 494,903, No. 3゜128.182, No. 4,
No. 230,796, No. 3.253,919, Special Publication No. 4
No. 1-11431, U.S. Patent No. 2,482,546,
Amine compounds described in 2,596.926 and 3,582,346, etc., Japanese Patent Publication No. 37-16088,
No. 42-25201, U.S. Patent No. 3,128.183
No. 41-11431, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3. 532. Polyalkylene oxide represented by No. 501, etc., and other 1-phenyl-3
- Pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

Any antifoggant can be added to the color developer according to the present invention, if necessary. As an antifoggant,
Alkali metal halides such as sodium chloride, potassium bromide, potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidrohenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-
Typical examples include nitrogen-containing heterocyclic compounds such as nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, hydroxyazaindolizine, 5-nitroindazole, and mercaptotriazoles. I can give it to you.

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

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 according to the present invention is 20 to 50°C.
Preferably it is 30 to 40°C. Processing time is 20 seconds ~ 5
Preferably 30 seconds to 2 minutes.

It is preferable to replenish a small amount, but Angry Light is 20 per d of charge.
~600mI2 preferably 50-300m7! It is.

More preferably, it is 100ml to 200rrl.

Next, the bleaching solution, bleach-fixing solution, and fixing solution used in 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 (II Complex salts of polycarboxylic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, and organic phosphonic acids) or persulfates of organic acids such as citric acid, tartaric acid, and malic acid; hydrogen peroxide, etc. are preferred.

Among these, organic complex salts of 钖(I[l) are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution. aminopolycarboxylic acids useful for forming organic complex salts of iron (flu),
Aminopolyphosphonic acids, organic phosphonic acids, or their salts are listed as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)N, N
', N'-triacetic acid, ■, 3-diaminopropanetetraacetic acid, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, 1,3-diamino-2-propyl acetate Tool Tetraacetic Acid, Methyliminodiacetic Acid, Iminoniacetic Acid, Hydroxyliminodiacetic Acid, Dihydroxyethyl Glycine Ethyl Ether Diamine Tetra Acetic Acid, Glycol Ether Diamine Tetra Acetic Acid, Ethylene Diamine Tetra Propionic Acid, Ethylene Diamine Nipropion Acetic Acid, Phenyl Diamine Tetra Acetic Acid, 2-Phosphonobutane-1 , 2,4-triacetic acid, 1,3-diaminopropanol-N, N, N'.

N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N
'-tetramethylenephosphonic acid, 1,3-propylene diamine-N, N, N'.

N'-tetramethylenephosphonic acid, ■-Hydroxyethylidene-1.1. -diphosphonic acid, etc. can be mentioned.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, iron (DI) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because they have a high bleaching edge.

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

In any case, the chelating agent may be used in excess of the amount needed to form the ferric ion complex.

Among iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is preferably 0.01 to 1.0 mol/l, more preferably 0.05 to 0.50 mol/7! It is.

Further, a bleach accelerator may be used in the bleaching solution or bleach-fixing solution, if necessary. Specific examples of useful bleach accelerators include U.S. Pat. No. 3,893.858, West German Pat. No. 57831, same 5
No. 3-37418, No. 53-65732, No. 53-7
No. 2623, No. 53-95630, No. 53-9563
No. 1, No. 53-104232, No. 53-124424
No. 53-141623, No. 53-28426,
Research Disclosure Arashi No. 17129 (1978
Compounds having a mercapto group or disulfide group as described in JP-A No. 140-129-1987; Thiazolidine derivatives as described in JP-A No. 140-129-1987; Japanese Patent Publication No. 45-85
No. 06, JP-A-52-20832, JP-A No. 53-3273
No. 5, thiourea derivatives described in U.S. Pat. No. 3,706,561 1 West German Pat.
8-16235; West German Patent No. 966.
No. 410, 2. 'za, polyethylene oxides described in No. 430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others described in Japanese Patent Publication No. 49-42434, No. 4
No. 9-59644, No. 53-94927, No. 54-3
No. 5727, No. 55-26506 and No. 5B-16
Examples thereof include the compound described in No. 3940 and iodine and bromide ions. Among these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and in particular, compounds described in U.S. Pat. Compounds are preferred.

In addition, the bleach or bleach-fix solution used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodides. (
For example, a rehalogenating agent such as ammonium iodide) may be included. If necessary, one or more inorganic substances having pHfft buffering ability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. organic acids and their alkali metal or ammonium salts or ammonium nitrate,
Corrosion inhibitors such as guanidine and the like can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, that is, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; a thiocyanate such as sodium thiocyanate or ammonium thousocyanate; Ethylene bisthioglycolic acid, 3,6-cythia 1
, 8-octanediol and other water-soluble silver halide melting agents such as thioureas, and these can be used alone or in combination of two or more. It is also possible to use a special bleach-fixing solution consisting of a combination of a fixing agent described in JP-A No. 55-455354 and a large amount of a halogenated potassium iodide compound. In the present invention, the use of thiosulfates, particularly ammonium periosulfate salts, is preferred.

The amount of fixing agent per 1β is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol.

The pH fi JT range of the bleach-fix solution or fix solution in the present invention is preferably 3 to 10, and particularly preferably 5 to 9.

If the pH is lower than this, the desilvering performance is improved, but the deterioration of the solution and the leucoization of the cyan dye are accelerated. On the other hand, if the pH is higher than this, desilvering is delayed and staining is likely to occur.

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

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

The bleach-fix solution and fixer in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (e.g.,
containing sulfite ion-releasing compounds such as ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately 0 in terms of sulfite ion.
．． It is preferable to contain 02 to 0.50 mol/β,
More preferably, it is 0.04 to 0.40 mol/i.

As a preservative, sulfite is commonly added, but ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

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

Next, the water washing step in the present invention will be explained.

In the present invention, instead of the usual "water washing treatment", a simple treatment method may be used in which only a so-called "stabilization treatment" is performed 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. In addition, the "washing process" here includes water washing alternative processes such as rinsing process.

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 brought into the photosensitive material. It is sufficient if the liquid component is 1×10 −4 or less.

For example, in the case of 3-tank countercurrent water washing, the photosensitive material 1. (It is preferable to use about 1000 mβ or more per unit, more preferably 500 QmJ or more. Also, in the case of water-saving treatment, it is preferable to use 100 to 1000 mβ per 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 sedimentation 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; bactericides and antihyperglycants that prevent the growth of various bacteria, algae, and molds (for example, ``Journal of Antibacterial J, Antibact, Antifung
, Agents), Vol. 11° 5. p2
07-223 (1983) and the compounds described in Hiroshi Horiguchi's "Chemistry of Antibacterial and Antifungal", metal salts such as magnesium salts and aluminum salts, alkali metal and ammonium salts, or dry load and unevenness. A surfactant or the like may be added as necessary to prevent this.

Or West's ``Photographic Science and Engineering Link It'' (Photo.

It is also possible to add compounds described in Sci.

Furthermore, chelating agents, bactericides, and anti-piping agents are added to the washing water.
The present invention is particularly effective when the amount of washing water is significantly reduced by multistage countercurrent washing using two or more tanks. It is also particularly effective when carrying out a multi-stage countercurrent stabilization process (so-called stabilization process) as described in JP-A-57-8543 instead of the usual water washing process. In these cases, the bleaching and fixing components in the final bath should be less than 5 x 10-", preferably 1
It is sufficient if it is not more than ×10−2.

Various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, adjust the membrane pH (e.g. pH 3~
8) various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) (used in combination) and aldehydes such as formalin are representative examples. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (thiazole series, isothiazole series, halogenated phenols, sulfanilamide, henctriazole, etc.) ), surfactants, fluorescent whitening agents, hardeners, and other various additives may be used, and two or more compounds for the same or different purposes 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.

Significantly reduce the amount of water used for washing as described above! In this case, it is preferable for the purpose of reducing the amount of waste liquid to flow some or all of the overflow liquid of the washing water into a bleach-fixing bath or a fixing bath which is a pre-bath.

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 skewer 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.

The processing composition of the present invention can be applied to any processing step that uses a color developer.

For example, it can be applied to processing color paper, color reversal paper, color positive film, color negative film, color reversal film, etc.

The silver halide emulsion of the light-sensitive material used in the present invention can have any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide, silver chloride, etc., but when performing rapid processing or low replenishment processing For this purpose, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol % or more of silver chloride is preferable, and a silver chloride content of 80 to 100 mol % is particularly preferable. In addition, when high sensitivity is required and capri during production, storage, and/or processing must be kept particularly low, silver chlorobromide emulsions containing 50 mol% or more of silver bromide or Silveride emulsions are preferred, and more preferably 70 mol% or more. If silver bromide exceeds 90 mol %, rapid processing becomes difficult, but there are ways to accelerate development, such as using a development accelerator such as a silver halide solution, a fogging agent, or a developer as described below during processing. By using , it is possible to speed up the development to some extent without being limited by the content of silver bromide.
It may be preferable. 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. These silver halide emulsions are preferably used mainly for color papers and the like. Color light materials for photography (negative film, reversal film, etc.) include silver iodobromide,
Silver chloroiodobromide is preferred, where the silver iodide content is between 3 and 15
Mol% is preferred.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed.

Average grain size of silver halide grains used in the present invention (
In the case of spherical or near-spherical particles, the particle size is the particle diameter, and in the case of cubic particles, the particle size is the ridge length, and it is the average based on the projected area.

In the case of tabular grains, it is also expressed in terms of spheres. ) is 0 below 2μm
．． 1 μm or more is preferable, and 1.5 μm is particularly preferable.
m or less and 0.15 μm or more.

The particle size distribution can be narrow or wide, but
A so-called monodisperse silver halide emulsion in which the value (variation rate) obtained by dividing the standard deviation value of the grain size distribution curve of the silver halide emulsion by the average grain size is within 20%, particularly preferably within 15%, is used in the present invention. It is preferable to do so. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having substantially the same color sensitivity. (preferably one with a variable rate) can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
r) crystals or coexistence of these crystals, or irregular (irregular) crystals such as spherical
It may have a crystal form such as u jar), or it may have a composite form of these crystal forms. Tabular grains may also be used, especially those having a length/thickness ratio of 5 or more, particularly 8.
An emulsion in which the above tabular grains account for 50% or more of the total projected area of the grains may be used. An emulsion consisting of a mixture of these various crystal forms may also be used. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is described by Glafkides [Chemistry and Physics of Photography J (P., Glafkides, Chi.
mie etPhysique Photography
ique, published by Paul Monte1.

1967], "Photographic Emulsion Chemistry" by Duffin [G.

Written by F. Duffin, Photographic Em
Ulsion Chemistry.

Focal Press, 1966], Zelikman et al.
Making and C by kman etal
oating Potographic Emulsio
It can be prepared using the method described in J.D., Focal Press, 1964].

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root 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). As one type of simultaneous mixing method, a method in which Ag in the liquid phase in which silver halide is produced is kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a 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 silver halide grain formation process is completed, into silver halide with a smaller solubility product, and Emulsions which have undergone similar halogen conversion after the completion of the silver grain formation process can also be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a 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 present.

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

Known silver halide solvents (e.g. ammonia, 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 root salts from the emulsion after physical ripening, Nudel water washing, flocculation sedimentation, ultraleakage, etc. are used.

The silver halide emulsion used in the present invention can be prepared using a sulfur-enhanced method using active gelatin or a sulfur-containing compound that can react with silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances; (For example, stannous salt,
amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); metal compounds (e.g., zinc salts, as well as Pt, Ir, Pd, Rh, F
A noble metal sensitization method using complex salts of metals from Group I of the periodic table such as e) can be used alone or in combination.

The premalignant, green zl and red light emulsions used in the present invention have been spectrally enhanced with methine dyes and others so as to have color sensitivity. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes.

Namely, viroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei;
and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., an indolenine nucleus, a henzindolenine nucleus, an indole nucleus, a henzoxazole nucleus, a naphthoxazole nucleus, a henzothiaso/half-pig, a naphthothiazole nucleus, A benzoselenazole nucleus, a penzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxapridine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl nucleus, and the like 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 US Patent 2
, No. 688,545, No. 2゜977.229, No. 3,
No. 397,060, No. 3.522,052, No. 3,5
No. 27,641, No. 3,617,293, No. 3,62
No. 8,964, No. 3,666.480, No. 3. 67
2. No. 898, No. 3,679.428, No. 3,70
3゜377, 3,769,301, 3,814
．． No. 609, No. 3,837.862, No. 4°026.
707, British Patent No. 1,344,281, British Patent No. 1,50
No. 7,803, Special Publication No. 43-4936, No. 53-12
No. 375, JP-A-52-110618, JP-A No. 52-10
No. 9925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

These sensitizing dyes may be added at any stage during particle formation, before or after chemical sensitization, during chemical sensitization, or during coating. Addition during particle formation is effective not only to strengthen adsorption but also to control crystal shape and particle structure. In addition, addition during chemical sensitization is effective not only to strengthen adsorption (control of chemical sensitization sites? It is effective in preventing Itl and crystal deformation. In the case of emulsions containing a high content of silver chloride, these The addition method is particularly effective, and it is also particularly useful to apply it to grains with increased silver bromide or silver iodide content on the grain surface.

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group can reduce the amount of silver coated than a four-equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction 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
．． 265.506, etc. The use of two-equivalent yellow couplers is preferred for the present invention; U.S. Pat.
No. 3,933,501 and No. 4,022゜62
The oxygen atom separation type yellow coupler described in No. 0, etc., Japanese Patent Publication No. 10739/1982, and 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, No. 2. 261. No. 361, No. 2,329,587
Typical examples thereof include the nitrogen atom separation type yellow couplers described in No. 1, No. 2, 433.812, and the like. α-piparoylacetanilide couplers have excellent color fastness, especially light fastness;
- 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 substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and representative examples thereof include U.S. Pat. Same No. 2゜3
No. 43,703, No. 2,600,788, No. 2,
No. 908,573, same No. 3. 062. No. 653, No. 3,152,896 and No. 3936.015
It is written in the number etc. As a leaving group for two-equivalent 5-pyrazolone couplers, U.S. Pat.
or U.S. Pat. No. 4,3
51,897 is preferred. Further, the 5-pyrazolone coupler having a belast group described in European Patent No. 73,636 provides a 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. 3,725.067, Research Disclosure 24220
(June 1984) and Research Disclosure 24230 (19
Examples include the virazolopyrazoles described in June 1984). Imidazo(
1,2-b) Virazoles are preferred, as described in European Patent No. 11
Pyrazolo (1°5-b) CI described in No. 9,860,
2.4)) Riazoles 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 and preferably U.S. Pat.
, No. 212, No. 4゜146.396, No. 4.22
Typical examples include the oxygen atom elimination type two-equivalent naphthol couplers described in No. 8.233 and No. 4,296,200. Further, specific examples of phenolic couplers are disclosed in U.S. Patent Nos. 2□369.929 and 2.
No. 801,171, same No. 2. 772. No. 162, No. 2,895,826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention and are typically described in U.S. Pat.
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. 772,002, US Pat. No. 2,772,162, US Pat.
．． No. 758.308, No. 4.126,396, No. 4.334,011, No. 4,327゜173, West German Patent Publication No. 3,329,729, and Patent Application No. 1983-
2,5-diacylamino substituted phenolic couplers such as those described in US Pat. No. 42,671 and U.S. Pat.
, No. 622, No. 4,333,999, No. 4. 4
51. 559 and 4.427,767, etc., having a phenylureido group at the 2-position and 5
These include phenolic couplers having an acylamino group at the - position.

In particular, by using at least one cyan coupler represented by the following general formulas (C-1) and (C-11) in the photochromic material used in the present invention, good photographic properties with less fog can be obtained. I was able to do that. Such an effect is noteworthy.

Cyan couplers represented by general formulas (C-1) and (C-11) will be explained in detail below.

General formula (C-1) ○H (In the formula, R11 represents an alkyl group, cycloalkyl group, aryl group, or heterocyclic group. R and □ represent an alkyl group or an aryl group. RI3 is a hydrogen atom, a halogen atom , represents an alkyl group or an alkoxy group, and R+1 may be combined with R, □ to form a ring. Zl+ represents a hydrogen atom, a halogen atom, or an oxidized product of an aromatic primary amine color developing agent. General formula (C-II) OH (In the formula, RI4 represents an alkyl group, a dichlorofurkyl group, an aryol group, or a heterocyclic group. RI5 represents a group having 2 or more carbon atoms. Represents an alkyl group. R16 represents a hydrogen atom, a halogen atom, or an alkyl group. Z1□ represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. ) In cyan couplers of general formulas (C-I) and (C-[1), R11% R12 and Rz have 1 to 32 carbon atoms
Examples of the alkyl group include methyl group, butyl group, tridecyl group, cyclohexyl group, allyl group, etc., examples of the aryl group include phenyl group, naphthyl group, etc., and examples of the heterocyclic group include Examples include 2-pyridyl group, 2-imidazolyl group, 2-furyl group, and 6-quinolyl group. These groups may further include alkyl groups, aryl groups, heterocyclic groups, alkoxy groups (e.g.
methoxy group, 2-methoxyethoxy group, etc.), aryloxy group (e.g., 2,4-diLert-amylphenoxy group, 2-chlorophenoxy group, 4-cyanophenoxy group, etc.), alkenyloxy group (e.g., 2- propenyloxy group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g., butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, 1-luenesulfonyloxy group, etc.) ), amide groups (e.g., acetylamino group, methanesulfonamide group, dipropylsulfamoylamino group, etc.), carbamoyl groups (e.g., dimethylcarbamoyl group, ethylcarbamoyl group, etc.), sulfamoyl groups (e.g., butylsulfamoyl group, etc.) ), imide groups (e.g., succinimide group, hydantoinyl group, etc.), ureido groups (e.g., phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl groups (e.g., methanesulfonyl group, phenylsulfonyl group, etc.), Even if it is substituted with a group selected from the fatty acid group or an aromatic thio group (e.g., ethylthio group, phenylthio group, etc.), hydroxy group, cyano group, carboxy group, nitro group, sulfo group, halogen atom, etc. good.

In general formula (C-I), when RI3 is a substitutable group, it may be substituted with the optional substituent described for R11.

In the general formula (C-11), examples of the optionally substituted alkyl group having a small number of carbon atoms (both 2 or more) in RI5 include ethyl group, propyl group, butyl group, pentadecyl i
, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, phenylthiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, methoxymethyl group, and the like.

General formula (C-1) and general formula (C-formerly Zll
and Z1□ are each a hydrogen atom or a coupling-off group (including a coupling-off atom).

Examples include halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, etc.),
Alkoxy groups (e.g., ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group, etc.)
, aryloxy groups (e.g., 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group, etc.), acyloxy groups (e.g., acetoxy group,
(tetrazokayloxy group, benzoyloxy group, etc.)
, sulfonyloxy group (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (
For example, dichloroacetylamino group, heptafluorobutylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (for example, ethoxycarbonyloxy group, hensyloxycarbonyloxy group, etc.), aryloxycarbonyloxy groups (e.g., fenoquine carbonyloxy group, etc.), aliphatic or aromatic azo groups (e.g., ethylthio group, phenylthio group, tetrazolylthio group, etc.),
Examples include imide groups (eg, succinimide groups, hydantoinyl groups, etc.), aromatic azo groups (eg, phenylazo groups, etc.). These leaving groups may include photographically useful groups.

Preferred examples of the cyan coupler represented by the above-mentioned type (C-I) or (C-old) are as follows.

In general formula (C-1), R1+ is preferably an aryl group or a heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryoloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, or a sulfamoyl group. , a sulfonyl group, a sulfamide group, an oxycarbonyl group, or an aryl group substituted with a cyano group is more preferable.

-C When R13 and RI□ do not form a ring in formula (C-1), R1□ is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group. , R13 is preferably a hydrogen atom.

In general formula (C-II), R14 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted -ruoxy-substituted alkyl group.

In general formula (C-11), preferred RIS has 2 carbon atoms.
It is a methyl group having a ~15 alkyl group and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In the - format (C-n), RIS is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

In general formula (C-II), R16 is preferably a hydrogen atom or a halogen atom, with chlorine and fluorine atoms being particularly preferred.

In general formulas (C-I) and (C-11), Zl+ and Z1□ are preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryoloxy group, an acyloxy group, or a sulfonamide group, respectively.

In the -i formula (C-II), 21□ is more preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

In general formula (C-1), Z is more preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

Specific examples of the cyan couplers represented by the above-mentioned formulas (C-I) and (C-11) are listed below, but the present invention is not limited thereto.

(C-1)
0H (C-2)
OHshi1 (C-3)
0H(CzHtnzNsOzNH (C-4) 0
HC1 (C-5)
OH (C-6)
OHN (C-16) 0
H(C-17) 0H(
C-18) H CHy (C-19) 0H(C
-20) 0HQ)CsH
++ (C-22) l1 (C-23) 2 (C-24) HCAL (C-25) 0H(t
)CsH++ (C-26) H (t)CsHry (C-27) (L)CsH+t (C-28) (t)CsH++ (C-29) H (t)CsH,.

(t)CsHn (C-32) H CH3 (t)CsH+t (c-35) H (t)CsH++ (υCs H+ l (C-381 (C-41) (C-44) (C-45) 0g ( C-46) (C-47) (C-48) C* Hq (iso) These type (C-I) and (C-n) couplers are disclosed in JP-A-59-t66956 and JP-B-11572.
It can be synthesized based on the number.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such dye-diffusive couplers are described in U.S. Pat. Examples of magenta couplers are found in European Patent No. 366.237 and British Patent No. 2.125.57Cl, as well as in European Patent No. 96.570 and German Published Application No. 3. 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. No. 173 and U.S. Pat. No. 4,367
．． It is described in No. 282.

The various couplers used in the present invention can be used in combination with Type 211 or higher in the same photosensitive layer, or in two different layers using the same compound. It is also possible to introduce more than one.

Four couplers used in the present invention can be formed in a light-sensitive material by the oil-in-ice droplet dispersion method. In the oil-in-water dispersion method, the boiling point is 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 are described in U.S. Pat. No. 2,322,027 and others.

Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of high boiling point 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-ethylhexyl Henshade,
dodecylhenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amyl) phenol, 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. In addition, as an auxiliary solvent, those with a boiling point of about 30°C or higher,
Preferably, an organic solvent having a temperature of 50° C. or more and about 160° C. or less can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-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 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 material used in the present invention contains hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamidophenol derivatives, etc. as color fogging inhibitors or color mixing inhibitors. May contain.

Known anti-fading agents can be used in the photosensitive material used in the present invention. Organic antifading agents include hydroquinones, 6-hydroxychromans, 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 KM R forms 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 due to light, spiroindanes described in JP-A-56-159644 and substituted hydroquinone diethers or monoethers as described in JP-A-55-89835 are recommended. Chromans give favorable results.

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

The amount of ultraviolet absorber applied should be sufficient to impart photostability to the cyan dye image, but if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. Therefore, it is usually preferably set in the range of lX10-' mol/yl2 X 10-' mol/d, particularly 5X10-' mol/m to 1.5 X 10-'mol/l'+ (.

In the normal color vapor light-sensitive material layer structure, a single layer of water on both sides adjacent to a red-sensitive emulsion layer containing a cyan coupler,
Preferably, both layers contain an ultraviolet absorber.

When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer can contain a matting agent of any particle size.

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

The photosensitive material used in the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation or halation. Oxonol-based, anthraquinone-based, or azo-based dyes are preferred. Oxonol dyes that absorb green and red light are particularly preferred.

Stilbene-based, triazine-based,
It may also contain a brightening agent such as an oxazole type or a coumarin type. Water-soluble brighteners may be used, or water-insoluble brighteners may be used in the form of dispersions.

The invention is applicable to multilayer, multicolor photographic materials having two different spectral sensitivities on the support.

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

In addition to the silver halide emulsion layer, the light-sensitive material used in the present invention 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 used in the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin hardening agents, graft polymers of gelatin and other polymers, albumin, casei 7, etc. (7) proteins; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, sodium alginate, starch derivatives, etc. sugar derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc.; Molecular substances can be used. The use of acrylic acid modified polyvinyl alcohol in the protective layer is particularly useful, and even more so when rapidly processed with silver chloride emulsions.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, Phot, Japa.
Enzyme-treated gelatin such as that described in No. 16, p. 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 used in the present invention further contains various stabilizers, anti-staining agents, developing agents or their precursors, development accelerators or their precursors as described above,
Lubricants, mordants, capping agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. Representative examples of these additives are described in Research Disclosure No. 17643 (December 1978) and Research Disclosure No. 18716 (November 1979).

These additives are very important in rapid printing, rapid processing, and also in relation to the compound of formula (1) of the present invention. In addition, especially when the halogen composition of the emulsion used contains a high content of silver chloride, the combined use of mercaptoazole, mercaptothiadiazole, and mercaptobenzazole compounds is useful in the present invention in terms of color development and fogging. be.

The "reflective support" that can be used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Examples include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as temporary glass, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
There are polystyrene films and the like, and these supports can be appropriately selected depending on the purpose of use.

(Example) The effects of the present invention will be explained below using Examples.

Example 1 Table A was placed on a paper support laminated on both sides with polyethylene.
A multilayer color photographic paper with the layer structure shown below was created. The coating solution was prepared as follows.

First layer coating solution preparation Yellow coupler (a) 19.1g and color image stabilizer (b)
) 4.4g, ethyl acetate 27.2ml and solvent (c) 7
．． 9mjl! was added and dissolved, and this solution was emulsified and dispersed in 185 mJ of a 10% aqueous gelatin solution containing 8 ml of 10% sodium dodecylbenzenesulfonate. - In a silver carbromide emulsion (containing 11 mol % of i bromide and 70 g/kg of Ag), the following venement sensitizing dye was added at 5.0X per mol of silver chlorobromide.
90 g of a blue-sensitive emulsion was prepared by adding 10-' mole of the compound. The emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table A 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 1N coating solution.

The gelatin hardening agent for each layer is 1-oxy-3,5-
Dichloro-5-) riazine sodium salt was used.

The following spectral enhancers were used for each emulsion.

The following dyes were used as anti-irradiation dyes in 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.

(al yellow coupler l7 CI+.

(C)? Container (d) Color mixture prevention agent 0 [1 CH tel Magenta coupler <r) Color image stabilizer (g)? Container (hl Ultraviolet absorber CHzclI zcOOcstl l 7 1:5:3
Mixture (molar ratio) (11 Color mixing inhibitor CH (j) Solvent (iso C9+1190 +T-P = 0('k
) 1:1 mixture of cyan coupler (mole ratio) (1:3:3 mixture of 11 color image stabilizers (mole ratio) (ml ?) It was processed in the following processing steps with different values.

Processing jLL course once, one time color development
35℃ 45 seconds bleach fixing 35℃
45 seconds rinse 1 35℃ 20
Second rinse 2 35℃ 20 second rinse 3
Dry at 35℃ for 20 seconds at 80℃
The 60-second rinse was a 3-tank countercurrent flush from rinse 3 to rinse 1. The processing solutions used are as follows.

Temporary additives for the image of Sadan's second son Benzyl alcohol (see Table 1) M1 (see Table 1) ft1i (diethylene glycol See Table 1) Sodium sulfite
0.2g potassium carbonate
30gE DTA・2Na
l g sodium chloride 1
．． 5g D-6 sulfate 5.0g Brightener (4,4'-diaminostilbene type) 3.0g Add water
1000m lp H10,05 EDTAFe (III) NH4・2HzO60gEDT
A ・2Na ・2Hz0 4g ammonium thiosulfate (70%) 120n+j! Sodium sulfite 16g ice #acid
Add 7g water 1
000ml lp H5,5 Yue Gosha Formalin (37%>0. In+
11-Hydroxyethylidene-1,1-diphosphonic acid (60%) 1.6 nA' Bismuth chloride 0.35 g Aqueous ammonia (26%) 2.5 ml Nitrilotriacetic acid/3Na 1. OgEDTA
・4HO, 5g Sodium sulfite 1.0g 5-chloro-2-methyl-4-50mg Isothiazoline-3-
Two types of 10100O color developing solutions were used for each composition: immediately after preparation (fresh solution) and after preparation and left at 40° C. for 14 days (aged solution).

The photographic properties of the obtained fresh solution and aged solution were determined, and the difference between the photographic properties obtained with the fresh solution and the photographic properties obtained with the aged solution, that is, the change in photographic properties, is shown in Table 1. .

The photographic characteristics are Dmin at 4 degrees magenta and 2 gradations.
The points were measured. Here, Dmin is the minimum density, and the gradation is a density change from a point representing density 0.5 to a density point on the high exposure side of 0.3 in logE.

As is clear from Table 1, there was no preservative (1) (
No. 3), if it is hydroxylamine (No.
, 1.2), fogging occurs or the gradation changes over time.

However, in the present invention, the occurrence of fog and changes in photographic properties over time were small (No. 4 to 13), and particularly, better results were shown in the absence of benzyl alcohol (No. 6.7.9). .11.12.13).

Example 2 In Example 1, the bromide ion content of the Green Angry layer emulsion was changed to 8.
When the change in photographic properties of the solution over time was evaluated in the same manner as in Example 1, the composition of the present invention showed a small increase in fog (good results were obtained).

Example 3 Compound 1- used in Example 1 N095 and 7
Compounds 1-(8), 1-(11), I instead of (7)
−(16), r −(22), I −(24), r
When carried out in the same manner as NO65 and 7 except for using -(33), 1-(37) or I-(41), the same results as in Example 1 were obtained.

Example 4 The first layer (bottom layer) to the seventh layer (
(top layer) was applied to prepare a sample.

The coating liquid for the first layer was prepared as follows. A mixture of 200 g of yellow coupler, 93°3 g of antifading agent, 5 g of high boiling point solvents (p) Log and (q), and 600 ml of ethyl acetate as an auxiliary solvent was dissolved by heating at 60°C, and then Alkanol B (alkylnaphthalene sulfonate, The mixture was mixed with 3300 mJ of a 5% aqueous gelatin solution containing 330 ml of a 5% aqueous solution (manufactured by DuPont) and emulsified using a colloid mill to prepare a coupler dispersion. Ethyl acetate was distilled off under reduced pressure from this dispersion, and 1,400 g of emulsion (1,400 g) was prepared by adding sensitizing dye for the front window emulsion layer and 1-methyl-2-mercapto-5-acetylamino-1,3,4-)riazole.
(containing 96.7 g of Ag and 170 g of gelatin), and further added 2600 g of a 10% aqueous gelatin solution to prepare a coating solution.

The coating liquids for the second to seventh layers were prepared in the same manner as for the first layer.

(blank below) Table B The following substances were used as aggravating dyes in each emulsion layer.

Front window emulsion layer; anhydro-5-methoxy-5'-methyl-3,3'-disulfopropylselenacyanine hydroxide green arbitrary emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3' -Disulfoethyloxacarbocyanine hydroxide red arbitrary emulsion layer; 3,3'-diethyl-5-methoxy-9
, 9'-(2,2-dimethyl-1,3-propano)thiadicarpocyanine iodide.The following substances were also used as stabilizers for each emulsion layer.

1-Methyl-2-mercapto-5-7 cetyl 7 minnow 1
．． 3.4-) The following were used as lyazole and 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 I,2-bis(vinylsulfonyl)ethane were used as a hardening agent.

The couplers used are as follows.

yellow coupler l magenta coupler Cl The cyan coupler was changed as shown in Table 2.

The compounds used in this example are as follows.

UV absorber (n): 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole UV absorber (0): 2-(2-hydroxy-3,5-di-tert-butylphenyl) Benzotriazole? Container (p) Ni(2-ethylhexyl)phthalate? Container (q) Nidibutyl phthalate anti-fading agent (r): 2.5-di-tert-amylphenyl-3,5-di-tert-butyl hydroxydihenzoate color mixing inhibitor (S): 2.5-di-tert-amylphenyl-3,5-di-tert-butyl hydroxydihenzoate color mixing inhibitor (S): ter t-octylhydroquinone anti-fading agent (t): 1.4-di-ter t-amyl-2,5-dioctyloxybenzene anti-fading agent (U): 2.2°-methylenebis-(4-methyl-6- ter
t-Butylphenol The multilayer color photographic paper obtained as described above was subjected to wedge-shaped exposure and then troweled in the following processing steps.

1 minute 30 seconds Color development at 33°C Bleach fixing at 33℃ 1 minute 30 seconds
33°C Rinse (3 tanks 2 minutes 30°C cascade) Drying 1 minute 80°C The processing solution used is as follows.

Left i two development Kaisui 800n
+j'triethanolamine 10
m15.6-cyhydroxy-1.2.4-benzenetrisulfonate sodium 300mgN,
N'-bis(2-hydroxybenzyl)ethylenediamine-N.

N'-Diacetic acid 0.1g Nitrilo-N,N,N)rimethylenephosphonic acid (40%) 1.0g Potassium bromide 0.6g Additives
Table 2 Sodium sulfite Table 2 Potassium carbonate
30gN=ethyl-N(β-methanesulfonamidoethyl)-3-methyl=4-aminoaniline sulfate 5.5g fluorescent brightener (4,4'-diaminostilbene type) 1.0g Add water to 1000ml KOH pH 10,10 drifting 1 part ammonium periosulfate (70%) 150mA
Sodium sulfite 15g Ethylenediamine iron (I[[) ammonium 60g Ethylenediaminetetraacetic acid 10g Fluorescent brightener (4
,4'-diaminostilbene series) 1.0g2-
Add 1.0 g of mercapto-5-amino-3,4-thiadiazole and add 1000 mJ of ammonia water to pH 7.0 solution 5-chloro-2-methyl-4-inthiazolin-3-one 40□82- Methyl-4-isothiazolin-3-one 10 mg 2-octyl-4-isothiazolin-3-one 10 mg Bismuth chloride (40%) 0.5 g Nitrilo-N, N, N-)rimethylenephosphonic acid (40%
) 1.0g 1-hydroxyethylidene-1,1-diphosphonic acid (60%) 2.5g fluorescent brightener (4,4'-diaminostilhene type) 1.0g aqueous ammonia (26%) 2. 0m+2
Add water 1000ralK
At OH pH 7.5 color developer is tested for each composition immediately after preparation (fresh: night) and after 11 months at 38°C after preparation (aged solution).
Two types were used.

The Dmin and gradation of cyan were determined for the fresh solution and the aged solution, and the differences between the results obtained for the aged solution and the fresh solution are shown in Table 2.

*: Cyan coupler A DI j2 Cyan coupler B H 1] 31 l As is clear from Table 2, when hytroquineluamine is used (NO, 14 to 16), the occurrence of fog and gradation over time decrease In contrast, in the present invention (Nos. 17 to 31), the change in photographic properties was significantly small.

In particular, when a preferred cyan coupler is used, the change in photographic properties is even smaller (No, 19.20.23.24.2
7.28.29.30.31).

Furthermore, the results were even better when the concentration of sodium sulfite, which is commonly used, was lower.

(No, 23.24.27.28.29.30.31)
.

Example 5 Using the color photographic paper obtained in Example 1, a running test was conducted until three times the tank capacity (60a) of color developer was replenished in the following processing steps. However, the composition of the color developer was changed as shown in Table 3.

Color development 35°C 45 seconds 160m (1/rrl Bleach fixing 35°C 45 seconds 100Ill/
rd rinse ■ 30℃ 20 seconds - rinse ■
30℃ 20 seconds - rinse ■ 30℃
20 seconds 200ml/rrr drying 60~
Rinsing at 70°C for 30 seconds was carried out in a 3-tank countercurrent flow direction from Rinse (■) to Rinse (■).

The composition of each treatment liquid used is as follows.

Left Puni developer 1 liquid Capture liquid triethanolamine 8.0 g 10.
0 g Additive See Table 3 Fluorescent brightener (4,4'-diaminostilbene type) 3.0 g 4
．． 0g ethylenediaminetetraacetic acid 1.0g
1.5g potassium carbonate 30
．． 0 g 30.0 g Sodium chloride
1.4g 0.1g4-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido)ethyl)-aniline sulfate 5.0g 7.0
g9y liquid Benzyl alcohol See Table 3 Diethylene glycol See Table 3 5-Methyl-7-hydroxy-3,4-triazaindolizine 30mg -
Add water to 1000ml 1
000ml! pH 10, 1010, 50 ゞ, white (tankun and shi are the west) EDT
AFe(In)NH4・2H2060gEDTA・2
Na ・2Hz0 4 g Ammonium 1000 sulfate (70%) 120 mff Sodium sulfite 16 g Glacial acetic acid
Add 7g water
1000rrlp) (5,5 rinses (5 minutes for methane) EDTA ・2
Add Na ・2 HzO0.4g water
1000mj! pH 7.0 Processing was performed according to the above processing method, and the B (blue), G (green), and R (red) concentrations of the unexposed areas at the start and end of running were measured using a Fuji self-recording densitometer. Furthermore, the sample at the end of the run is 60°
After leaving it under C170%RH for 2 months, the unexposed areas B, G, R? The Q degree was measured.

The results obtained are shown in Table 3.

As is clear from Table 3, according to the present invention, the increase in stain caused by running is significantly reduced, and at the same time, the increase in stain caused by forced aging of color photographic paper after processing is also significantly reduced (NO034 ~40).

In particular, it shows better performance in the absence of benzyl alcohol (NO, 34, 36, 38, 39,
40).

(Effect of the invention) The present invention significantly improves the stability and color development of color developers, and as a result, increases in fog and gradation changes are significantly suppressed even in processing methods using color developers after aging. A color image with excellent photographic properties was obtained.

Such effects of the present invention were particularly remarkable in color developing solutions that do not substantially contain benzyl alcohol, which has a high pollution load.

Furthermore, the effects of the present invention were more pronounced when the sulfite ion concentration in the treatment liquid was lower. Furthermore, the effects of the present invention were remarkable when processing light-sensitive materials containing specific cyan couplers.

Furthermore, even in continuous processing, the increase in fog was significantly reduced, and the obtained color images had excellent stability over time.

Procedural amendment Z month 30, 1986

Claims (2)

[Claims] (1) A color photographic processing composition comprising an aromatic primary amine color developing agent and a compound represented by the following general formula (I). General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the general formula (I), X represents a hydrogen atom or a group that can be hydrolyzed. Y and Z each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, R_1, R_2,
R_3 and R_4 are each independently a hydrogen atom,
Substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, halogen atom, nitro group, cyano group, sulfo group, carboxy group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, alkoxy group, It represents an aryloxy group, a sulfonyl group, a sulfonamido group, an amide group, a ureido group, an alkylthio group, or an arylthio group. R_1 and R_2, R_2 and R_3, and R_3 and R_4 may each work together to form a ring structure. (2) The color photographic processing composition according to claim (1), wherein the color photographic processing composition does not substantially contain benzyl alcohol.