JPH0426841A - Forming method for color picture of silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To prevent an increase in yellow stains under high temp. and humidity conditions by providing a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer and a non- photosensitive layer contg. at least one specified compd. on a support and treating the layers with a liq. stabilizer contg. an N-methylol compd. CONSTITUTION:A red-sensitive silver halide emulsion layer, a gree-sensitve silver halide emulsion layer, a blue-sensitive silver halide emulsion layer and a non- photosensitive layer contg. at least one compd. shown by formula I or II are respectively provided on a support, and the layers are treated with a liq. stabilizer contg. an N-methylol compd. In the formula I, R<12>-R<18> can be the same or different from one another and are hydrogen atom or a group capable of being replaced by a benzene ring, and Z is hydrogen atom or a protective group not capable of protecting under alkaline conditions. In the formula II, R<21> is an aromatic group, R<22> and R<23> are hydrogen atom, an aliphatic group and an aromatic group, R<24> is hydrogen atom, an alkyl group, etc., and G<21> is a carbonyl group, a sulfonyl group, etc. Consequently, an increase in yellow stains under high temp. and humidity conditions is controlled.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for forming a color image using a silver halide color photographic light-sensitive material, and more specifically, the present invention relates to a method for forming a color image using a silver halide color photographic light-sensitive material, and more specifically, a method for forming a color photographic image with less color contamination and yellow stain, and improved image storage stability. The present invention relates to a processing method for forming excellent color images.

(Prior art) In silver halide color photographic materials, during color development, the developing agent diffuses to other layers, causing undesirable color turbidity between different color-sensitive layers, which often has a negative effect on color reproducibility. Are known. As a means to prevent these, for example, U.S. Pat.
A method using a hydroquinone-based compound in JP-A-1-147455 has been proposed, or a method using a hydrazine-based compound in JP-A No. 1-147455. Although these compounds do have some effect in preventing color turbidity and improve color reproducibility, normal processing results in an increase in yellow stain when stored under high temperature and high humidity conditions, and they are particularly effective in preventing color turbidity. It has been found that there is a problem in that the compounds that are more effective tend to be more effective.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a method for forming a color image that reduces the increase in yellow stain under high temperature and high humidity conditions.

A second object of the present invention is to provide a method of forming color images with improved fading of cyan images.

(Means for Solving the Problems) The objects of the present invention have been achieved by the following color image forming method.

In a processing method for forming a color image with an imagewise exposed silver halide color photographic light-sensitive material, the light-sensitive material comprises a red-sensitive silver halide emulsion each containing one or more cyan couplers on a support. a green-sensitive silver halide emulsion layer containing a magenta coupler, a blue-sensitive silver halide emulsion layer containing a yellow coupler, and a compound represented by the following general formula (1) or general formula (II). 1. A color image forming processing method, comprising: a non-photosensitive layer containing at least one of the above, and processing with a stabilizing liquid containing an N-methylol compound.

General formula (1) General formula (II) R”-N-N6G2” Qi R21 R21R1! (In the general formula (1), R'' to R16 may be the same or different and are a hydrogen atom or a group capable of substituting a benzene ring. However, at least one of RI I and Rl t is a hydroxy group, a sulfone It is an amide group or a carbonamide group, and the total number of carbon atoms in R" to Rl 6 is 8 or more. Z is a hydrogen atom or a protecting group that can be deprotected under alkaline conditions. R" to R", 02 may jointly form a ring.

In general formula (II), R2l represents an aromatic group, R"R"
represents a hydrogen atom, an aliphatic group, or an aromatic group, and R'' represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amine group, an alkoxycarbonyl group, or an aryloxy group. Represents a carbonyl group, a carbamoyl group, or an acyl group. G I l is a carbonyl group, a sulfonyl group, -P-, a sulfinyl group,
or iminome R25 represents a tyrene group, R'' has the same meaning as R'', and n is 0 or 1. ) Next, the compound represented by general formula (I) will be explained in more detail.

In formula (I), R12 to R'' may be the same or different and are a hydrogen atom or a group capable of substituting on a benzene ring. Preferred examples of such substituents include a halogen atom, a hydroxy group, a sulfonate group, carboxyl group,
Cyano group, alkyl group, alkenyl group, alkynyl group,
Aralkyl group, aryl group, heterocyclic group, ether group,
Examples include thioether group, carbonamide group, sulfonamide group, ureido group, oxycarbonylamino group, acyloxy group, sulfamoylamino group, sulfonyloxy group, carbamoyl group, sulfamoyl group, acyl group, sulfonyl group, or oxycarbonyl group. It will be done. These groups may be further substituted with the groups mentioned herein.

However, at least one of Rl 2 and R1'' is a hydroxy group, a sulfonamide group, or a carbonamide group, and the total number of carbon atoms of R12 to R'' is 8 or more.

R12 to Rl 8 in formula (I) will be explained in more detail.

Rl! As the halogen atom of "R", for example, F,
CCBr, I can be mentioned. The alkyl group is an optionally substituted linear, branched or cyclic group having 1 to 3 carbon atoms, such as methyl, isopropyl, t-
Butyl, cyclohexyl, 2-ethylhexyl, octyl, 5ec-octyl, t-octyl, t-pentyl,
t-hexyl, pentadecyl, t-pentadecyl, 5e
Examples include c-octadecyl and 4-hexyloxycarbonyl-1°■-dimethylbutyl.

The alkenyl group is an optionally substituted linear, branched or cyclic group having 2 to 3 carbon atoms, such as vinyl, allyl, prenyl, l-octenyl, and ω-octadecenyl.

The alkynyl group is an optionally substituted linear or branched alkynyl group having 2 to 30 carbon atoms, such as ethynyl, 3-butynyl, and ω-hexadenyl.

The aralkyl group is an optionally substituted group having 7 to 30 carbon atoms, such as benzyl, l.

Examples include 1-dimethyl-1-phenylmethyl, 2-phenylethyl, 2-hydroxy-4-laurylamidophenylmethyl, and 3,5-di-t-butyl-2-hydroxyphenylmethyl.

The aryl group is an optionally substituted monocyclic or condensed ring having 6 to 30 carbon atoms, such as phenyl, naphthyl, 4-nonylphenyl, 3-hexadecaneamidophenyl, and 2-tetradenroxyphenyl. It will be done.

The heterocyclic group is a 3- to 12-membered ring containing at least one of oxygen, nitrogen, sulfur, phosphorus, selenium, or tellurium and which may have a substituent, such as 2-furyl, furfuryl, 2- Pyridyl, 4-pyridyl, 2-imidazolyl, morpholino, 1.2.4-triazole-3
Examples include 2-selenazolyl to -yl, -tetrazolyl, and pyrolisi.

Ether groups include optionally substituted alkokino groups (e.g. methquine, methoxyethoxy, hexadecylthio, isopropoxy, cyclohexyneloquino, pensiloquino), alkenyloxy groups (e.g. allyloxy, 2pentenyloquine), alkynyl groups having 1 to 3o carbon atoms, which may be substituted. radicals (e.g. propalkyloquino, 2-octinyloquine),
Acyloxy groups (e.g. fenoquine, 2,4-di-t-pentylphenoxy 1,3-pentadecylphenoxy, 2
- doboxyphenoxy).

Examples of the thioether group include optionally substituted alkylthio groups having 1 to 3 carbon atoms (e.g., methylthio, butylthio, dobnorthio, hexadecylthio, octadecylthio, 2-hekynrudecylthio, cyclohexylthio, benzylthio), alkenylthio groups (e.g. allylthio, 2-octenylthio), alkynylthio groups (e.g. propargylthio, 2-hexynylthio), arylthio groups (e.g. phenylthio, 2-octyroxy-5-t)
-octylphenylthio, 5-t-octyl-2-pivalylamidophenylthio).

The carbonamide group includes an optionally substituted alkanecarboxylic acid amide group having 1 to 30 carbon atoms (e.g., acetamide, 2-(2,4-di-t-pentylphenoxy)butanamide, dodecanamide, cyclohexanamide).
, alkene carboxylic acid amide group (e.g. acrylamide, methacrylamide), alkene carboxylic acid amide group (
(e.g. propiolamide), arenecarboxylic acid amide groups (e.g. benzamide, 3,5-bis(2-hexyldecanamide)benzamide), heterocyclic carboxylic acid amide groups (e.g. nicotinamide, thiazole-4-carboxylic acid amide) It is.

Examples of the sulfonamide group include an optionally substituted alkanesulfonamide group having 1 to 30 carbon atoms (for example, methanesulfonamide, octanesulfonamide, 2-hexyldecanesulfonamide, 4-(2,4-di-t -pentylphenoxy)butanesulfonamide, cyclohexanesulfonamide), alkenesulfonamide groups (e.g. 2-propenesulfonamide, ω-octensulfonamide), alkynesulfonamide groups (e.g. 2-propenesulfonamide, ω-octensulfonamide),
propynesulfonamide), arenesulfonamide groups (e.g. pencenesulfonamide, 2-octyloxy-5
-t-octylbenzenesulfonamide, 4-octadecyloxybenzenesulfonamide).

Examples of the ureido group include an optionally substituted alkylureido group having 2 to 30 carbon atoms (for example, N'N'-diethylureido, N/-benzyl-N'-methylureido,
Pyrrolidinocarbonylamino, Morpholinocarbonylamino, N'-cyclohexylureido, N'-(3-
(2,4-di-t-pentylphenoxy)propyl]ureido, N'-octadecylureido, N'-(3-decyloxypropyl)ureido), alkenylureido groups (e.g. N'-allylureido), alkynylureido groups (e.g. N'-propalkylureido group) arylureido group (e.g. N'-phenylureido, N'-(
2-tetradenloquinphenyl)ureido, N'-(
2-chloro-5-dobusyloxycarbonylphenyl)ureido, N'-(4cyanophenyl)ureido), peterocyclic ureido groups (e.g. N'-(2-imidazolyl)ureido, N'-(3-pyridyl)ureido, N'-(2-imidazolyl)ureido, '
-(2thiazolyl)ureido).

The oxycarbonylamino group has 2 to 3 carbon atoms.
Alkoxycarbonylamino groups (e.g. ethoxycarbonylamino, isobutyroxycarbonylamino, cyclohexylocarbonylamino, benzyloxycarbonylamino), alkenyloxycarbonylamino groups (e.g. allyloxycarbonylamino), which may have 0 substituents ), an alkenyloxycarbonylamino group (eg, propalkyloxycarbonylamino group), and an aryloxycarbonylamino group (eg, phenoxycarbonylamino).

As the acyloxy group, an alkylcarbonyloxy group which may have a substituent having 1 to 30 carbon atoms (for example, acetoxy, 2-(2,4-di-t-pentylphenyloxy)hexanoyloxy, dodecanoyloxy, dichloro acetoxy, 4-oxopentanoyloxy), alkenylcarbonyl oxyne groups (e.g. acryloyl oxine,
oleoyloxy), alkylcarbonyloxy groups (e.g. propioloyl oxine), arylcarbonyloxy groups (e.g. benzoyloxy, 3°5-bis(2-hexyldecanamido)benzoyloxy), heterocyclic carbonyloxy groups (e.g. nicotyloxy), Noyl okidi, furoyl okidi, thenoyl oxy).

The sulfamoylamino group may have a substituent having 1 to 30 carbon atoms, such as an alkylsulfamoylamino group (for example, N'-benzyl-N'methylsulfamoylamino, morpholinosulfonylamino, N'-octa densulfamoylamino), alkenylsulfamoylamino groups (e.g. N'-allylsulfamoylamino)
, alkynylsulfamoylamino group (e.g. N'propargylsulfamoylamino), arylsulfamoylamino group (e.g. N'-phenylsulfamoylamino group, N'-(3-octanesulfonamidophenyl)sulfamoyl amino), and a heterocyclic sulfamoylamino group (for example, N'-(4-pyridyl)sulfamoylamino).

Examples of the sulfonyloxy group include alkylsulfonyloxy groups (for example, methylsulfonyloxy, octylsulfonyloxy, 3-(2,4-sheet t-pentylphenoxy)propylsulfonyloxy) which may have a substituent having 1 to 30 carbon atoms. ), alkenylsulfonyloxy groups (e.g. 2-butenylsulfonyloxy), alkynylsulfonyloxy groups (e.g. propargylsulfonyloxy), arylsulfonyloxy groups (e.g. phenylsulfonyloxy, 5-t-octyl 2-pivaloylaminophenylsulfonyloxy) ).

The carbamoyl group includes an optionally substituted N-alkylcarbamoyl group having 1 to 30 carbon atoms (for example, N-
Ethylcarbamoyl, N-dodecylcarbamoyl, N-
isopropylcarbamoyl, N-cyclohexylcarbamoyl, N-[3(2,4-di-t-pentylphenoxy)propyl]carbamoyl, N-(3-dobutyloxypropyl)carbamoyl), N-alkenylcarbamoyl group (e.g. N -allylcarbamoyl), N-alkynylcarbamoyl group (e.g. N-butyrylcarbamoyl)
, N-carbamoyl group (e.g. N-phenylcarbamoyl, N-(4octyloxyphenyl)carbamoyl, N-[2-chloro-5-(1-dodecyloxycarbonylethyloxycarbonyl)phenylcarbamoyl)
, N-heterocyclic carbamoyl group (eg, N-(4-pyridyl)carbamoyl, N-(2-oxacylyl)carbamoyl).

Examples of the sulfamoyl group include alkylsulfamoyl groups (for example, ethylsulfamoyl, hexadecylsulfamoyl,
octadecylmethylsulfamoyl, 4-(2,4-the-t-pentylphenoxy)butylsulfamoyl),
Alkenylsulfamoyl groups (e.g. allylsulfamoyl), alkynylsulfamoyl groups (e.g. propargylsulfamoyl), arylsulfamoyl groups (e.g. phenylsulfamoyl, 2-tetradecyloxyphenylsulfamoyl), petro Ring sulfamoyl group (
For example, 2-imidazolylsulfamoyl).

Examples of the acyl group include an alkylcarbonyl group which may have a substituent having 1 to 30 carbon atoms (e.g., acetyl, octadecanoyl, 3-carboxypropanoyl, 4-dodecyloxycarbonylbutanoyl, phenylacetyl, cyclocarbonyl group). xylcarbonyl), alkenylcarbonyl groups (e.g. cinnamoyl, oleoyl), alkynylcarbonyl groups (e.g. phenylpropioloyl), arylcarbonyl groups (e.g. benzoyl, 3-hexadecanamidohendiyl), peterocyclic carbonyl groups (e.g. isonicotinoyl). .

Examples of the sulfonyl group include alkylsulfonyl groups (for example, methylsulfonyl, octylsulfonyl, octadecylsulfonyl, 4-(2,4-shethexylphenoquine)butylsulfonyl, which may have a substituent having 1 to 3 carbon atoms); cyclohexylcarbonyl), alkenylsulfonyl groups (e.g. allylsulfonyl), alkynylsulfonyl groups (e.g. phenylethynylsulfonyl),
Arylsulfonyl groups (e.g. phenylsulfonyl, 4
-dobushiroquine phenylsulfonyl).

Examples of the oxycarbonyl group include alkoxycarbonyl groups that may have a substituent having 2 to 30 carbon atoms (e.g., ethoxycarbonyl, dobcylokidicarbonyl, isopropoxycarbonyl, cyclohexyloxycarbonyl,
pendyloxycarbonyl, alkenyloxycarbonyl group (eg allyloxycarbonyl), alkenyloxycarbonyl group (eg propargyloxycarbonyl), aryloxycarbonyl group (eg phenoxycarbonyl group, 3-pentadecylphenoxycarbonyl).

Next, Z in formula (I) will be explained.

Z is a hydrogen atom or a protecting group that can be deprotected under alkaline conditions.

Examples of protecting groups for Z include acyl groups (e.g. acetyl,
Chloroacetyl, dichloroacetyl, benzoyl, 4-
cyanobenzoyl, 4-oxopentanoyl), oxycarbonyl groups (e.g. ethoxycarbonyl, phenoxycarbonyl, 4-methoxybenzyloxycarbonyl), carbamoyl groups (e.g. N-methylcarbamoyl,
N(4-nitrophenyl)carbamoyl, N-(2pyridyl)carbamoyl, N-(1-imidazolyl)carbamoyl), and JP-A-59-197.037, JP-A-59-197.037;
Examples include the protecting groups described in No. 9-201,057, No. 59-108,776, and U.S. Pat. No. 4,473.537.

When OZ, R12 to Rl 6 jointly form a ring, preferably 02 and R'', R11 and Rl 3, Rl
3 and Rl 1, R+ 4 and RI S, R15 and Rl
6 or R and OZ combine to form saturated or unsaturated 4
It forms a carbon ring or a petro ring consisting of 8 to 8 members. In this case, examples include the following: Here, the * mark represents the bonding position to the benzene ring in [Formula 13].

H* The compound represented by formula (I) may form a bis body, a tris body, an oligomer, a polymer, or the like. The total number of carbon atoms of RI I to Rl 6 in formula (1) is 8 or more, preferably 10 or more.

Among formula (I), preferably formulas (Ia) to (I
d).

General Formula (Ia)

General formula (Ib) In formula (Ib), X is a hydroxy group or a sulfonamide group, and Rl 2 to RI S have the same meanings as in formula (1).

In the general formula (Ic) and formula (rc), X is a hydroxy group or a sulfonamide group, Y is a carbamoyl group, an oxycarbonyl group, an acyl group, or a sulfonyl group, and R'', R
l 1 has the same meaning as that in general formula (I).

General formula (Id) In formula (Id), R" to R" is R12 of formula (I)
R" to R" are a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and m is an integer of 0 to 50.

In formula (Ia), R12, R13, RI I, R1
6 is preferably a hydrogen atom, a halogen atom, a sulfo group, an alkyl group, an ether group, a thioether group, a carbonamide group, a sulfonamide group, a ureido group, a sulfonyl group, a carbamoyl group, or an acyl group, and more preferably a hydrogen atom, A halogen atom, a sulfo group, an alkyl group, a carbonamide group, a sulfonamide group, or a sulfonyl group. Most preferably, one of R12 and R'' is an alkyl group, a carbonamide group, or a sulfonamide group, and the other is hydrogen. This applies to atoms, halogen atoms, sulfo groups, sulfonyl groups, and alkyl groups.

X is preferably a hydroquine group.

In formula (Ib), Rl2 to R'' is preferably a hydrogen atom, an alkyl group, an ether group, a thioether group, a carbonamide group, a sulfonamide group, a ureido group, a sulfonyl group, a carbamoyl group, an oxycarbonyl group, or an acyl group. More preferably a hydrogen atom, an alkyl group, an ether group, a thioether group, a carbonamide group, or a sulfonamide group, most preferably a hydrogen atom,
They are an alkyl group and an ether group. Rl,R'' is preferably a hydrogen atom, an alkyl group, a halogen atom, or an ether group, more preferably a hydrogen atom or an alkyl group, and most preferably a hydrogen atom.

X is preferably a hydroxy group.

In formula (Ic), X is preferably a hydroxy group, and Y is preferably a carbamoyl group or an oxycarbonyl group.

In formula (Id), Ri to Rif are preferably a hydrogen atom, a haloken atom, an alkyl group, an ether group, a thioether group, a carbonamide group, a sulfonamide group, a sulfonyl group, an acyl group, or a carbamoyl group,
More preferably, a hydrogen atom, a halogen atom, an alkyl group, a carbonamide group, a sulfonamide group, an ether group,
It is a thioether group, most preferably a hydrogen atom, a halogen atom, an alkyl group, or a carbonamide group. m=
When 0, R52 and Ri + are preferably an alkyl group, a carbonamide group, or a sulfonamide group. When m is other than 0, R5''' and Ril are preferably hydrogen atoms.

m is preferably 0 or an integer of 20 to 50.

General formula (II) will be explained in more detail below.

The aliphatic group represented by R'' and R21 preferably has 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms.
is a straight chain, branched or cyclic alkyl group. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfinyl group, a sulfonamide group, or a carbonamide group.

Examples include t-butyl, n-octyl, t-octyl, cyclohexyl, pyrrolidyl, imidazolyl, tetrahydrofuryl, and morpholinyl.

The aromatic group represented by R", R22, and R2s in the general formula (II) l, : is preferably a monocyclic or bicyclic aryl group. Here, the monocyclic or bicyclic aryl group is fused to form a heteroaryl group. It may also form a group.

Particularly preferred are aryl groups. The aryl group of R'' may have a substituent. Typical substituents include an alkyl group, an aralkyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, a ureido group, and a urethane group. group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroquine group, halogen atom, cyano group, sulfo group, and carboxyl group.

The aryl group represented by R'' preferably has 6 to 30 carbon atoms, and specific examples include phenyl and naphthyl.

Here, R24 may have a substituent, specifically R"
Examples of substituents include the same as those listed above.

Further, among those represented by the general formula (II), preferred are those represented by the general formula (II a).

General formula (IIa) R”-N-N-G”-R72 R7! R74 (wherein R", R?2 and G71 each have the general formula (
R73 and R74 are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group,
Represents either an arylsulfonyl group or an acyl group. However, the hydrazone structure (,:N-N=c
) may be formed. Further, the above-mentioned groups may be substituted with a substituent if possible. ) To explain in more detail, R71 may be substituted with a substituent, specifically R2 and R'' of the general formula (I[)
The same substituents as those mentioned above can be mentioned, and particularly preferred are a ureido group, an alkoxy group, an alkyl group, an acylamino group, a substituted amino group, a sulfonylamine group, a urethane group, an aryloxy group, a hydroquine group, and a carboxyl group.

Further, these substituents may be linked to each other to form a ring when possible.

R? Preferred as + are phenyl and naphthyl.

Among the groups represented by Rj 1, preferred are a hydrogen atom, an alkyl group (e.g. methyl), an aryl group (e.g. 2-hydroxymethylphenyl, 2-hydroxyphenyl, or an aralkyl group (e.g. hydroxybenzyl)). .

As the substituent for R72, in addition to the substituents listed for R" and R'" above, examples include an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, a sulfonyl group, a cyano group, Halogen atoms, nitro groups, etc. can also be applied.

These substituents may be further substituted with these substituents. Further, if possible, these groups may be linked to each other to form a ring.

Preferably, at least one of R71 and R'' has a ballast group incorporated therein, which is commonly used in immobile photographic additives such as couplers.
It is a relatively inert group with respect to photography and has the above carbon number, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoquino group, an alkylcarbonyloxy group, an alkoxycarbonyl group. , ether group, amide group, ureido group, urethane group, sulfonamide group, thioether group, alkyloxycarbonyl group, alkylcarbonyloxy group, sulfonyl group, acyl group, hydroxy group, etc., and combinations of these groups. You can choose from. R?
The total number of carbon atoms in + and R72 is preferably 13 or more, more preferably 20 to 60 carbon atoms.

A preferred example is a case where the substituent for R'' and R+2 has at least one polar group.

As a polar group, C. Hansch et al. Journal
of Organic Chemistry, Vol. 11, p. 1207-1216 (1973) It is a group smaller than 1,0. Some specific examples of polar groups have already been mentioned as substituents for R71 and R'', but collectively they include, for example, sulfonamide groups (methanesulfonamide, benzenesulfonamide), hydroxy groups, hydroxyphenyl group, hydroxymethyl group, amino group,
carboxyl group, carbamoyl group, N-hydroxycarbamoyl group, ureido group, thioureido group, sulfamoyl group, ammonium group, sulfo group, sulfinic acid group,
Sulfonyl group (methylsulfonyl group, phenylsulfonyl, 4-hydroxyphenylsulfonyl), sulfinyl group (methylsulfinyl, phenylsulfinyl),
Phosphate group (dimethylphosphono), heterocyclic group (
5 tetrazolyl) and ether groups (methoxyethoxy,
4-(4-hydroxyphenylsulfonyl)phenoxy) and the like.

When at least one of R'' and R72 has a ballast group, the above polar group is preferably substituted.

More preferably, a ballast group is incorporated.

R" and R" are hydrogen atoms, alkylsulfonyl groups having 20 or less carbon atoms, and arylsulfonyl groups (preferably phenylsulfonyl groups or phenyl substituted so that the sum of Hammett's substituent constants is -0.5 or more) sulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted such that the sum of Hammett's substituent constants is -0.5 or more, or a linear, branched, or cyclic Unsubstituted and substituted aliphatic acyl groups (
Examples of the substituent include a haloken atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group. )) R"% R" is most preferably a hydrogen atom.

G+lR? ! Specifically, those represented by formyl group, acyl group (acetyl, propionyl, trifluoroacetyl, chloroacetyl, benzoyl, 4-chlorobenzoyl, pyruvoyl, 2-hydroxybenzoyl, 2-hydroxymethylbenzoyl, 5- Dodecanamido-2-hydroxybenzoyl, 2- (4-(4-
hydroxyphenylsulfonyl) phenoxy] dodecanoyl, methoxalyl group, methyloxamoyl), alkylsulfonyl group (methanesulfonyl, 2-chloroethanesulfonyl), arylsulfonyl group (pensenesulfonyl), alkylsulfinyl group (methanesulfinyl), arylsulfinyl group ( pensencesulfinyl), carbamoyl group (methylcarbamoyl, phenylcarbamoyl), sulfamoyl group (dimethylsulfamoyl), alkoxycarbonyl group (methquinecarbonyl, methoxyethoxycarbonyl, methoxyethoxycarbonyl), aryloquine carbonyl group (phenoxycarbonyl) ), a sulfamoyl group (methylsulfinamoyl), an alkoxysulfonyl group (methoxysulfonyl, ethoxysulfonyl), a thioacyl group (methylthiocarbonyl), a thiocarbamoyl group (methylthiocarbamoyl), or a heterocyclic group (pyridyl). Particularly preferred are formyl group and acyl group.

In the general formula (I[I), G71, R7! , R7 (and a hydrazone structure including hydrazine nitrogen) In the above, R75 represents an alkyl group, an aryl group, or a heterocyclic group. R76 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Specific examples of the compound represented by general formula (I) or (II) are described below. However, the present invention is not limited to the following compounds.

CH CH CH CH cv-6 cv-7 CH C,Ha(t) CH.

cv CH cv-10 CH Ca　R13(II) Co　H+3(II) cv H cv-12 cv-14 cv-15 cv SO2C,,H3゜ cv cv COC+s H31 (1) Cs Hy (II) H H cv-20 cv cv 5H (II) C15H31(II) C+ Hy(i) H H cv cv-25 CH.

6CH2- (II)C (Average value of II 30) 6CH CH2±-i CH-CH2 well CHCL7; CV-26 cv-28 cv (J　　　　　L;++ki2e cv-30 cv cv cv t-1 cv-33 cv cv 5cv-36 Scv Scv-38 Scv-39 Scv-40 Scv-41 Scv Scv-43 Scv-44 l1H2S Sc~' Scv Scv Scv 5 hours [ NHCOC,,H.

The compound represented by formula [I] according to the present invention can be synthesized by the methods described in the patents shown below and the patents cited therein, and by methods analogous thereto.

Among the compounds represented by formula [Ia), monoalkyl-substituted hydroquinones are used in U.S. Pat.
, 960.570, 3.700.453, and JP-A-49-106,329 and JP-A-50-156,438, di-substituted alkylhydroquinones are disclosed in U.S. Pat.
No. 28,659, No. 2,732,300, No. 3,24
No. 3゜294, No. 3,700,453, JP-A-1973-
No. 156,438, No. 53-9,528, No. 53-5
No. 5,121, No. 51-29,637, No. 6.0-5
No. 5.339, hydroquinone sulfonates are disclosed in U.S. Pat.
No. 40, No. 61-48゜855, No. 61-48, 85
No. 6, amidohydroquinones are disclosed in U.S. Patent No. 4.
198. No. 239, No. 4,732,845, JP-A-62-150.346, and JP-A-63-309,949 describe hydroquinones having an electron-withdrawing group.
No. 5-43.521, No. 56-109,344, No. 5
No. 7-22,237 and No. 58-21゜249.

A compound of formula CIb1 is disclosed in U.S. Pat. No. 4.447.
．． No. 523, No. 4,525,451, No. 4.530,
No. 899, No. 4,584,264, No. 4,717,6
No. 51, JP-A No. 59-220゜733, JP-A No. 61-16
No. 9,845, Special Publication No. 62-1386B, West German Patent No. 2. 732. No. 971, a compound represented by the formula [IC] is disclosed in U.S. Pat. No. 4,474,874, No. 4. 4
76, No. 219, JP-A-59-133,544,
The compound represented by formula [Id] is disclosed in U.S. Patent No. 2,710
．． No. 801, No. 2,816,028, No. 4.717
, No. 651, JP-A-57-17,949, JP-A No. 61-1
No. 69,844, Japanese Patent Application No. 62294.676, No. 62
-294,681, 62-258,696, 6
No. 3-25483, No. 63-234,895, No. 63
-217.290 and 63-240,699.

In addition, as an alkali precursor of hydroquinone,
U.S. Patent No. 4,443,537, Japanese Unexamined Patent Publication No. 59-108
, 776.

Examples of the compound of general formula (II) and its synthesis method are disclosed in, for example, JP-A-57-86,829, U.S. Patent No. 4.560,
No. 638, No. 4,478,928, and No. 2,
No. 563,785, No. 2,588.982, Japanese Unexamined Patent Publication No. 5
6-67.843, U.S. Pat. No. 4,030,925;
4,080゜207, 4,031,127, 3゜718.470, 4,269,929
No. 4,276.364, No. 4. 278.
No. 748, No. 4,385,108, No. 4,459
．． No. 347, No. 4,478,928, No. 4゜560.
No. 632, British Patent No. 2. 011. 391B, JP-A-54-74,729, JP-A No. 55163.533,
No. 55-74,536, No. 60-179,734,
No. 61-236548, No. 61-270,744,
No. 62-270゜948, No. 63-234,244, No. 63234.245, No. 63-234.246, No. 63-223,744, No. 63-121,838
No. 338,785A2.

The compound represented by the general formula (1) of the present invention, the compound represented by the general formula (II)
) (hereinafter referred to as the compound of the present invention)
may be used in combination of two or more. Also,
The compounds of the present invention may be added separately to two or more non-photosensitive layers and used in combination, or may be used in combination in the same non-photosensitive layer.

The compound of the present invention can be used as a protective layer in a light-sensitive material, a non-light-sensitive fine grain emulsion layer, and a non-light-sensitive intermediate layer 1 having substantially no sensitivity.
It can be used by being included in at least one layer such as a filter layer, an undercoat layer, an anti-halation layer, etc.
It is preferably used in an intermediate layer between two light-sensitive emulsion layers (which may have the same or different color sensitivities), and most preferably in the intermediate layer. Further, the compound of the present invention can also be used by being included in a photosensitive emulsion layer together with the intermediate layer.

In order to add the compound of the present invention to these layers, it can be added to the coating solution as it is without dissolving it in an organic solvent or the like, or it can be added to the coating solution as it is without dissolving it in an organic solvent or the like, or it can be added using alcohol (for example, methyl alcohol, etc.) that does not affect the silver halide color photographic light-sensitive material. It can be added after being dissolved in a low boiling point organic solvent. Further, it can be dispersed and impregnated into a polymer such as latex, or it can be dissolved in a high boiling point organic solvent and emulsified and dispersed in an aqueous solution. Furthermore, it can also be added to the coating liquid as a microcrystalline dispersion.

The coating amount of gelatin in the non-photosensitive layer to which the compound of the present invention is added is preferably 0.2 to 2.0 g/n (0.3 to 1 g/n).
．． It is preferable that it is 2g/a, and it is 0°4 to 1. Og/
More preferably, it is rd.

The total amount of the compound of the present invention added to the sensitizer is l×10=
~I X l O-2mof/m, preferably 1 x 10
-6 to 3 X 10-'moA/bo, more preferably 1
×10′ to 1 × 10−3 mof/rri.

In the present invention, an N-methylol compound is contained in the stabilizing solution used in the stabilizing step during the development process.

The N-methylol compound of the present invention refers to a compound having a structure in which at least one methylol group is directly bonded to a nitrogen atom in the molecule.

The N-methylol compound used in the stabilizer of the present invention is
Compounds represented by the following general formulas (IVa), (IVb) or (■C) are preferred.

General formula (IVa) R' General formula (IVb) General formula (IVc) R' During the ceremony, represents a hydrogen atom or a methylol group vinegar.

Specific examples of preferred N-methylol compounds are shown below, but the present invention is not limited thereto.

(rVa-1) (IVa-2) (rVb ■) (rVb-2) (IVb (IVb-4) (IVc-1) The compound represented by the general formula (IVa), (IVb) or (IVc) is Many are commercially available (and can be easily obtained).

The amount of N-methylol compound added to the stabilizer of the present invention is:
Preferably, the amount of N-methylol compounds is 1X10-'' mol-1 mol per 11 of the stabilizer, especially 1X10-'mol-1X10-' These N-methylol compounds are described in US Pat.
No. 574, it is disclosed as a compound to replace formalin as a stabilizer for improving the stability of macenta images, but the general formula (I) or the general formula (
This was a surprising improvement in that the effect of the present invention was different from the fact that in light-sensitive materials that do not contain the compound represented by II), the occurrence of yellow stain is even worse.

In the present invention, known stabilizers can be used in combination within the range that does not impair the effects of the present invention. However, it is preferable that formalin is not substantially contained.

Here, "substantially free" means 1/11 stabilizer.

It means that it is 5X10-2 mol or less. Preferably 1
．． 0x10-'' mole or less, more preferably 0.5
It is preferably not more than X10-' mole, and is particularly preferably not contained at all.

The stabilizer of the present invention contains a chelate compound and 1 or p
It is preferable to contain an H buffering agent.

As the chelate compound, compounds such as aminocarboxylic acid, aminophosphonic acid, polyphosphonic acid, and phosphonocarboxylic acid can be added, but it is particularly preferable to include the following compounds or their alkali metal salts and ammonium salts.

・Ethylenediaminetetraacetic acid ・Diethylenetriaminepentaacetic acid ・Triethylenetetraminehexaacetic acid ・l 2-Propylenediaminetetraacetic acid ・2-propanoldiamineacetic acid ・1. 3-Propanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, cyclohexanediaminetetraacetic acid, ethylenediaminetetramethylenephosphonic acid, hydroquinethyliminodiacetic acid, iminodiacetic acid, methyliminodiacetic acid, hydroxyethylethylenediaminetriacetic acid It is preferable to add compounds such as ethylenediaminediacetic acid, ethylenediaminenipropionic acid, dihydroxyethylglycinenitrilotripropionic acid, and l-hydroxyethylidene-1,l diphosphonic acid. These compounds are present in amounts ranging from 1X10-" mol to 1XIO-' mol per 11 stabilizers.
It is preferable to add mole, especially l×10~4 mole
Preferably, 5XlO-' moles are added.

The stabilizer of the present invention may optionally contain an ammonium compound, a metal compound such as Bi or Af, a fluorescent brightener, a chelating agent (for example, EDTA, l-hydroxyethylidene-1
．． (1-diphosphonic acid), bactericides, fungicides, hardening agents, surfactants, etc. can be used. As a fungicide, 5-chloro-2-methyl-isothiazolin-3-one and 1.

Thiazolone compounds such as 2-benzisothiazolin-3-one are effective.

Further, as the surfactant, a silicone compound represented by the following general formula is preferable because it has an effect of preventing water droplet unevenness and defoaming.

a, b, dXe are integers of 5 to 30, C is an integer of 2 to 5, or R is an alkyl group having 3 to 6 carbon atoms.

Further, it is preferable to add an alkanolamine to the stabilizing liquid in order to prevent sulfurization of thiosulfate ions brought in by the photosensitive material. The use of alkanolamines is described in US Pat. No. 4,786,583.

The pH of the stabilizer of the present invention is 3-8, preferably 5-7.

The temperature of the stabilizing liquid is preferably 56°C to 45°C, more preferably 1080°C to 40°C.

Further, the stabilization step is preferably performed using a multistage countercurrent method, and the number of stages is preferably 2 to 4 stages. Two or more types of stabilizing solutions may be used in multiple stages. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

The shorter the treatment time of the stabilization step, the more effective the present invention will be.
In terms of rapid processing, the total processing time of the stabilization process is 10 to 50
Seconds are preferable, and the effect is particularly significant in 10 to 30 seconds.

Furthermore, the smaller the amount of replenishment in the stabilization step, the greater the effect of the present invention, and it is preferably 50 m47 to 400 m per 1 exposure of the photosensitive material.
Especially 50-200mj! is particularly preferred.

In addition to tap water, the water used in these stabilization steps includes ion exchange resin, etc., to reduce Ca and Mg concentrations to 5.
It is preferable to use water that has been deionized to a concentration of less than /l, or that has been sterilized using halogen, an ultraviolet germicidal lamp, or the like.

In each of the above processing steps for photosensitive materials, when continuous processing is performed using an automatic processor, concentration of the processing solution due to evaporation may occur, especially when the processing amount is small or the opening area of the processing solution is large. becomes. In order to correct such concentration of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the stabilization step flows into a pre-bath having a fixing ability.

Next, other processing steps of the present invention will be explained.

First, the steps after color development will be explained.

4) Color development - Adjustment - Bleach - Fixed - Wash - Stable - Wash 5) Color development - Wash - Adjust - Bleach - Constant - Wash - Stable - Wash 6) Color development - Adjust - Bleach - Wash - Constant - Stable - Stable - Wash 7) Color development - washing with water, bleaching, washing with water, constant washing, stabilizing with water, washing with water 8) Color development - bleaching, constant washing with water, washing with water, stable, washing with water 9)
Color development - Bleach - Bleach fixing - Washing - Stable - Washing with water 10) Color development - Bleach - Bleach fixing - Constant fixing - Washing - Stable - Washing with water 11) Color development - Bleach - Washing - Constant fixing - Washing - Stable -
Washing with water 12) Color development - Adjustment - Bleach-fixing - Washing with water - Stable washing with water 13) Color development - Washing with water - Washing - Bleach-fixing - Washing with water - Stable washing with water 14) Color development - Bleach-fixing - Washing with water - Stable - Washing with water 15)
) In the processing steps 4) to 15), the washing step immediately before the stabilization step may be removed, or the washing step after the stabilization step may be omitted. In the present invention, it is preferable to perform the treatment in place of the rinsing step.

The present invention can also be applied to the processing of color reversal photographic materials. In this case, prior to color development, the following processes are usually carried out: 1) black and white development - water washing and reversal, one color development; 2) black and white development - water washing, light reversal and one color development; 3) black and white development - water washing and one color development.

A known developing agent can be used in the black and white developer used in the present invention. As the developing agent, dihydroxybenzene M (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone),
Aminophenols (e.g. N-methyl-p-aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid and the 1,2,3,4-tetrahydroquinoline ring described in U.S. Pat. No. 4,067,872. Heterocyclic compounds in which a and an intrene ring are bonded can be used alone or in combination.

The black and white developer used in the present invention may also include preservatives (e.g. sulfites, bisulfites, etc.), buffers (e.g. carbonates, boric acid, borates, alkanolamines), alkaline agents (e.g. oxides, carbonates), dissolving tablets (e.g. polyethylene glycols, esters thereof)
, pH! It is possible to contain III stabilizers (for example, organic acids such as acetic acid), sensitizers (for example, quaternary ammonium salts), development accelerators, surfactants, antifoaming agents, hardeners, viscosity imparting agents, etc. can.

The black and white developer used in the present invention must contain a compound that acts as a silver halide solvent, and the sulfite added as a preservative as described above usually plays this role. The sulfite and other silver halide solvents that may be used include, specifically, KSCN, Na SCN, K15Oi
, NazSO* , KzSzOs, NatSzOs ,
KtSzOz, NazS, O=, etc. can be mentioned. Also, the description was made regarding the color developing solution. Organic thioether compounds can also be used as silver halide solvents.

If the amount of these silver halide solvents used is too small, the progress of development will be slowed down, and if it is too large, the silver halide emulsion will fog, so there is a preferable amount to use, but it is difficult to determine the amount. can be easily determined by a person skilled in the art.

For example, 5CN- is 0.005 to 0.0 per 11 developer solution.
2 mol, especially 0.01 to 0.015 mol, so," is preferably 0.05 to 1 mol, especially 0.1
It is preferable that it is 0.5 mol.

When the organic thioether compound is added to the black and white developer of the present invention, the amount added is preferably 5 X 10-' mol to 5 X 10-' mol, more preferably I X 10-' mol per 12 of the developer. ˜2×10 moles.

Various chelate compounds are used in the black and white developer of the present invention for the purpose of softening water hardness. As these chelate compounds, it is preferable to use aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids described in the color developing solution.

Further, in addition to the above-mentioned sulfite salt, various compounds described in the color developing solution may be added to the black and white developer of the present invention as preservatives.

Various antifoggants may be added to the black and white development process of the present invention for the purpose of preventing development fog.

Antifoggants include potassium bromide, sodium bromide,
Preferred organic antifoggants include alkali metal halides such as potassium iodide and organic antifoggants.
For example, benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorohenzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, hydroxy nitrogen-containing heterocyclic compounds such as azaindolizine and mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole 2-mercaptobenzimidazole and 2-mercaptobenzothiazole;
Additionally, mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. These antifoggants include those that are eluted from color photosensitive materials during processing and accumulate in these developers.

The OpH value of the developer thus adjusted is selected to be sufficient to provide the desired density and contrast, but is in the range of about 8.5 to about 11.5.

In order to carry out sensitization processing using such a black and white developer, it is usually sufficient to extend the time up to three times as long as the standard processing; if the processing temperature is raised at this time, the extension time for aggravation processing can be shortened. be able to.

After black development, a water washing process is usually performed, but fogging may be performed immediately without passing through the water washing process.
The rinsing treatment described in No. 616 can be performed to simplify the treatment and reduce waste liquid.

The reversal bath used after black and white development can contain a known fogging agent. Namely, stannous ion-organophosphoric acid complex salt (U.S. Pat. No. 3,617゜282), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No.
-32616) stannous ion-aminopolycarboxylic acid complex salt (U.S. Patent No. 1,209,050)
stannous ion complex salts such as, borohydride compounds (US Patent No. 2,984,567), heterocyclic amine poran compounds (UK Patent No. 1,011,000)
The pH of this fogging bath (reversal bath) ranges widely from the acidic side to the alkaline side, with a pH of 2 to 12, preferably 2.5 to 10.
In place of the 0 reversal bath, which is particularly preferably in the range of 3 to 9, a light reversal process by re-exposure may be performed, and the reversal step may be omitted by adding the above-mentioned fogging agent to the color developing solution. can.

The aromatic primary amine color developing agent used in the color developer of the present invention is preferably a p-phenylenediamine derivative, and representative examples are shown below, but the invention is 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-64-amino-3-methyl-N-ethyl N-[ β−
(methanesulfonamido)ethyl]-aniline 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 Among the above p-phenylenediamine derivatives, exemplified compounds D-2, D-4, D-5 and D-6 are particularly preferred.

Furthermore, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. Preferably about 0.1 g to about 20 g,
More preferably a concentration of about 0.5g to about 15g.

Benzyl alcohol may or may not be added to the color developing solution of the present invention. When adding benzyl alcohol, the amount added is 1 part of the color developer! per 1×1
0-3 mol - 0,3X10-'' mol, preferably lXl
Preferably it is 0-2 mol-2X 10-' mol.

The color developing solution of the present invention can contain sulfite as a preservative.

The sulfite contained in the color developer of the present invention refers to sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, potassium metabisulfite, etc. The preferable amount of sulfite added is sulfite After changing to sodium, use the color developer 1! Hit lXl
0-' mol to 5 x 10 i mol, more preferably l
Xl0-'mol-5X10-'' mol, more preferably lXl0-' mol to 2X10-'' mol.

In addition to sulfites, the color developing solution of the present invention may contain hydrazine compounds described in Japanese Patent Application No. 1-207514, various hydroxylamines described in Japanese Patent Application No. 1-207514, etc., as preservatives for the color developing agent. Hydroxamic acids described in No. 63-43138, hydrazines and hydrazides described in No. 63-146041, phenols described in No. 63-44657 and No. 63-58443, 63-
It is preferable to add α-hydroxyketones and α-aminoketones described in No. 44656 and/or various vMs described in No. 63-36244.

In addition, in combination with the above compounds, JP-A Nos. 63-4235, 63-24254, 63-21647, 6
No. 3-146040, No. 63-27841 and No. 6
Monoamines described in No. 3-256'54, etc., No. 63-
No. 30845, No. 6314640, No. 63-4313
Diamines described in No. 9 etc., polyamines described in No. 63-21647, No. 63-26655 and No. 63-345, nitroxy radicals described in No. 63-53551, No. 63-43140 and 63-53549
It is preferable to use the alcohols described in No. 63-56654, the oximes described in No. 63-239447, and the tertiary amines described in No. 63-239447.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in US Pat. No. 349, US Pat.
The aromatic polyhydroxy compound described in No. 746.544 may be included if necessary, and addition of an aromatic polyhydroxy compound is particularly preferred.

The amount of these preservatives added is 1! Hit 5x
The range is from 10 i mol to 4 X 10-' mol, preferably from 5 X 10-' mol to 2 X 10-' mol, more preferably from 4 X 10-' mol to I X 10-' mol.

The color developing solution used in the present invention preferably has a pH of 9 to
14, more preferably 9 to 13, and the color developer may contain other known compounds as components of the color developer.

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

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, 0-
Sodium hydroxybenzoate (sodium salicylate), potassium 〇-hydroxybenzoate, 5-sulfo-2
h) jc + $ Sodium sulfosalicylate (sodium 5-sulfosalicylate), 5-sulfo-2-hydroxyammonium, l
! , potassium fragrant (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/
j! It is preferable that it is more than 0. 1 mol/j
! -0.4 mol/l is particularly preferred.

In addition, various caloric acid agents can be used in the color developing solution as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developing solution.

As the chelating agent, organic acid compounds are preferred, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids.

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

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N, NN', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 12-diaminopropanetetraacetic acid , hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid,
2-phosphonobutane-1,2,4-)licarboxylic acid, 1
-hydroxyethylidene-1,1-diphosphone a, N,
N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid.

These chelating agents may be used in combination with 2N or more, if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 1j
It is about 0.1g to 10g per 2.

If necessary, any development accelerator can be added to the color developing solution, but US Pat. No. 3,574.628, US Pat.
No. 3,038,805, No. 3,813,24
No. 7, No. 4,276.374, No. 4,297,4
No. 39, No. 3.704.130, Special Publication No. 3B-78
No. 26, No. 44-16590, No. 46-4552,
No. 37-16088, Japanese Unexamined Patent Publication No. 49-90536, No. 57-104.926, Japanese Patent Application No. 1998-1999. Organic thioether compounds described in No. 207514 etc., JP-A-52
P-phenylenediamine compounds shown in No.-49829 and No. 50-15554, JP-A-50-137
No. 726, Japanese Patent Publication No. 1973-30074, Japanese Patent Publication No. 1987-1
Quaternary ammonium salts represented by No. 56826 and No. 52-43429, etc., U.S. Patent No. 2,494.90
No. 3, No. 3,128,182, No. 4,230,796
No. 3,253,919, Special Publication No. 41-11431
No. 2,482,546, U.S. Pat. No. 2,596,
Amine compounds described in Japanese Patent Publications No. 37-16088 and Japanese Patent Publication No. 42-252, etc.
No. 01, U.S. Patent No. 3゜128.183, Special Publication No. 1973
Polyalkylene oxides shown in US Pat. No. 11,431, No. 42-23883, and US Pat. No. 3,532,501, as well as 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary.

The amount of these development accelerators added to the color developing solution of the present invention is preferably 5 x 10-mol to 5 x 10-' mol, more preferably 1 x 10-' mol, per 11 of the color-developing solution. ~4 moles to lXl0-' moles.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylhencitriazole, 5-nitropenztriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Thiazolylmethyl-
Representative examples include nitrogen-containing heterocyclic compounds such as benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The amount of the alkali metal halide added is preferably 1X10-' mol-1X10-mol per 11 of the color developing solution. The amount of organic antifoggant added is 1 x 101 mol to 1
Xl0-" mol is preferred, especially 5X10-6 mol-5
X10-' moles are preferred.

The color developing solution used in the present invention may contain a fluorescent whitening agent, such as a 4゜4'-diamino-2,2'-disulfostilbene compound. is preferred. The amount added is 0 to 5 g per 12 color developer, preferably 0.
．． It is 1g to 4g.

In addition, various surfactants such as alkyl sulfonic acid, ary-phosphonic acid, aliphatic carboxylic acid, aromatic carboxylic acid, etc. may be added as necessary.The amount of surfactant added is as follows: 0.001g to 5g, preferably 0.0
It is 1g to 2g.

In addition, the color developing solution of the present invention contains so-called competing compounds that produce colorless compounds by reacting with oxidized products of color developing agents, such as citrazic acid, J acid, and H acid, for the purpose of Section 1IIUR. It can be included. The amount of these competing compounds added is 1X10-'mol-1X10-' mol, preferably 5X10'' to 5x
1O-' mole.

The processing temperature with the color developing solution of the present invention is 20 to 50°C, preferably 30 to 40°C. The treatment time is 20 seconds to 8 minutes, preferably 30 seconds to 6 minutes. Although it is preferable that the replenishment amount is small, it is 100 to 3000 m, preferably 100 to 2500 m, and more preferably 1
00-2000d.

Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment. .

Further, in order to prevent thickening due to evaporation, a portion of washing water, rinsing liquid, or stabilizing liquid may be added to the color developing solution.

The silver halide color photographic window optical material of the present invention is subjected to a bleaching treatment or a bleach-fixing treatment after color development.

These treatments may be performed immediately without going through the color developing agent processing step, or in order to prevent unnecessary post-development and air fog, and to reduce the carry-over of the color developer into the desilvering process. In addition, sensitizing dyes contained in photographic light materials,
In order to wash out and render harmless the color developing agent impregnated in the photosensitive material parts such as dyes and the photographic window light material, after color development processing, processing steps such as stopping, adjustment, and washing with water are carried out, followed by bleaching or bleach-fixing. May be processed.

The above preparation solution contains aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-prongediaminetetraacetic acid, cyclohexanediaminetetraacetic acid, sulfites such as sodium sulfite, ammonium sulfite, and thiosulfite. Various bleaching accelerators such as glycerin, aminoethanethiol, sulfoethanethiol and the like explained in the bleaching solution section can be included. In addition, for the purpose of preventing scum, sorbitan esters of fatty acids substituted with ethylene oxide as described in U.S. Pat. No. 4,839.262, U.S. Pat.
It is preferable to contain the polyoxyethylene compounds described in 980).

As the bleaching agent used in the bleach solution and/or bleach-fix solution, ferric complex salts of aminopolycarboxylic acids, peroxides (e.g., sodium persulfate), etc. can be used, but ferric complex salts of aminopolycarboxylic acids are preferred. . Such aminopolycarboxylic acids include ethylenediaminetetraacetic acid, 1,
3-'; Aminopropanetetraacetic acid acetic acid recall ether diaminetetraacetic acid, cyclohexanediaminetetraacetic acid, 1,
4-diaminobutanetetraacetic acid, 1,2-propylenediaminetetraacetic acid, thioglycol ether diaminetetraacetic acid, 1
．． Examples include 3-butylenediaminetetraacid and methyliminodiacetic acid. Among these, ferric salt of 13-diaminopropanetetraacetic acid is particularly preferred.

The amount of the above bleaching agent added is 0.05 mol to 1 mol, preferably 0.1 mol per 11 of the bleaching solution or bleach-fixing solution.
It is 0.5 mol. Moreover, two or more kinds of compounds among the above-mentioned ferric aminopolycarboxylic acid complex salts can be used in combination as a bleaching agent. In this case, the mixing ratio of both is l
:10 to 10:1 is preferable, and the total concentration of both iron complex salts is 0.05 mol to 1 mol, preferably 0.1 to 0.5 mol, per 1142 treatments.

In addition, aminopolycarboxylic acid salts can be added to the bleach solution and/or bleach constant solution of the present invention in addition to the above-mentioned iron aminopolycarboxylate (f [83).

The amount added is preferably 0.0001 mol to 0.1 mol/l, more preferably 0.003 to 0.05 mol/l.

Aminopolycarboxylic acids and their ferric complex salts are usually preferably used in the form of alkali metal salts or ammonium salts, and ammonium salts are particularly preferred because they have excellent solubility and bleaching properties.

Further, the bleaching solution and/or bleach-fixing solution containing the above-mentioned ferric ion complex salt may contain a metal ion complex salt other than iron, such as cobalt or copper.

Various bleach accelerators can be added to the bleach solution and/or bleach-fix solution of the present invention.

Such bleach accelerators are described, for example, in U.S. Patent No. 3,893,858, German Patent No. 1,290
, No. 812, British Patent No. 1138.842, JP-A-53-95630, and Research Disclosure No. 17129 (July 1978 issue). preferable.

The amount of bleaching accelerator added is 0.0 per 12 bleaching solutions.
The amount is 1 g to 20 g, preferably 0.1 g to 10 g.

In addition to bleaching agents and the above-mentioned compounds, the bleaching solution and/or bleach-fixing solution constituting the present invention may contain bromides such as potassium bromide, sodium bromide, ammonium bromide or chlorides such as potassium chloride, sodium chloride, Re-/'trogen compounds such as ammonium chloride may be included. The concentration of rehalogenating agent is bleach solution 1! 0.1 to 5 mol, preferably 0.5 to 3 mol. In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate,
One or more types of inorganic acids and organic acids having pH buffering ability such as potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc., and salts thereof, which are commonly used in bleaching solutions. Additives can be added.

Thiosulfate can be used as a fixing agent in the bleach-fixing solution and/or fixing solution of the present invention. The amount of thiosulfate added is 0.1 mol/2 to 3 mol/2, and 0.3 mol/jl! ~2 mol/j2 is preferred.

Examples of the thiosulfate compound include ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, calcium thiosulfate, and magnesium thiosulfate, but ammonium thiosulfate is preferred because it has good solubility and has the highest fixing speed.

In addition to the above-mentioned thiosulfate compounds, thiocyanic acid compounds (especially ammonium salts), thiourea, thioether, urea, etc. may be used as fixing agents or fixing accelerators for the bleach-fix solution and/or constant I solution of the present invention. can. The concentration of these auxiliary fixing agents or fixing accelerators together with the thiosulfate compound is 1.11 to 3.0 mol/l,
Preferably it is 1.4 to 2.8 mol/l.

The bleach-fix solution and/or fix solution of the present invention contains sulfites as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite, and hydroxylamine.
It can contain hydrazine and the like. Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained, but in particular, as preservatives, Japanese Patent Application No. 60-2838
It is preferable to use the sulfinic acid compound described in the specification of Japanese Patent Application No. 31 and/or the bisulfite adduct described in the specification of Japanese Patent Application No. 1-298935.

Furthermore, for the purpose of stabilizing the liquid, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids.

Particularly effective is 1-hydroxyethylidene-1,1-diphosphonic acid. The amount of these additions is 0.01 to 0.
．． It is 3 mol/l, preferably 0.05 to 0.2 mol/l, and is particularly effective in fixers.

The pH of the bleaching solution and/or bleach-fixing solution of the present invention is generally 9 to 1, preferably 7.5 to 1.5, and most preferably 7.0 to 2.0.

For bleaching solutions, 5.0 to 2.0 is particularly preferred.

In a preferred pH range, there is little bleaching edge blur and excellent desilvering performance.

The pH of the fixer of the present invention is generally 9.0 to 5.0, particularly preferably 7.5 to 5.5.

The amount of replenishment of the bleaching solution and/or bleach-fixing solution of the present invention is 50d to 3000d, preferably 100af, per one photosensitive material.
~1000d.

The amount of replenishment of the fixer is preferably from 300 m to 3000 I11 per batch of photosensitive material, more preferably from 300 m to 3000 m11.
IIi! From 1000jli! It is.

However, the above-mentioned replenishment amount can be reduced to a smaller amount if, for example, a regeneration treatment is performed, such as oxidation regeneration of the processing solution and silver recovery treatment.

In addition, as a replenishment method for the desilvering process mentioned above, it is normal to replenish each processing bath with the corresponding replenisher solution and dispose of the overflow solution as waste. It is also possible to use a replenishment system or a countercurrent replenishment system in which the overflow liquid of the subsequent bath is introduced into the prebath.

For example, the wash water or overflow liquid of the stabilizing bath can be conducted to a fixing bath or a bleach-fixing bath.

The shorter the total time of the desilvering step of the present invention, the more remarkable the effects of the present invention can be obtained. The preferred time is 1 minute to 10 minutes, more preferably 1 minute to 6 minutes. Also, the processing temperature is 25°C.
~50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate improves, and
The occurrence of staining after treatment is effectively prevented.

In the desilvering step of the present invention, it is preferable that the stirring be as strong as possible in order to more effectively exhibit the effects of the present invention.

A specific method for strengthening stirring is disclosed in Japanese Patent Application Laid-Open No. 62-18346.
No. 0, No. 62-183461, U.S. Patent No. 4,758
, 858, a method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material, a method of increasing the stirring effect using a rotating means of JP-A-62-183461, and a method of increasing the stirring effect by using a rotating means provided in the liquid. Examples include a method of improving the stirring effect by moving the light absorbing material while bringing the wiper blade into contact with the emulsion surface to create a turbulent flow on the emulsion surface, and a method of increasing the circulation 'tRW of the entire processing liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate.

Further, the agitation improvement means is more effective when a bleach accelerator is used, and can significantly increase the acceleration results and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used in the present invention is JP-A-60-191
No. 257, No. 60-191258, No. 60-1912
No. 59, Re5earch DisclosureIt
eII No. 29118 (July 1988), the above-mentioned JP-A-60-1 preferably has a photosensitive material conveying means described in U.S. Pat. No. 4,758,858.
As described in No. 91257, such a conveying means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing deterioration in the performance of the processing liquid. The means described in the above RD are also preferable. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

These agitation strengthening means are effective in addition to the desilvering process, and are preferably applied to the water washing process and the developing process to shorten the processing time and reduce the amount of replenishment.

The processing method of the present invention comprises processing steps such as color development, bleaching, bleach-fixing, and fixing as described above.

Here, after the bleach-fixing or fixing process, processing steps such as washing with water and stabilization according to the present invention are generally carried out. It is also possible to use a convenient treatment method for carrying out the stabilization treatment of the present invention.

The rinsing water used in the rinsing step may contain known additives as required. For example, hard water softeners such as stepless phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid;
Disinfectants and anti-fungal agents (for example, isothiazolones, organochlorine disinfectants, benzotriazole, etc.) that prevent the growth of various bacteria and algae, surfactants that prevent drying load and unevenness, and the like can be used. Or, L, [:
, West@Water Quality Cr1te
ria”+Phot, Sci, and Eng.

Vol, 9,816, pages 343-359 (19
65) etc. can also be used. In addition, in order to prevent sulfurization of thiosulfate ions introduced by photosensitive materials, sulfites, sulfinic acid compounds described in Japanese Patent Application No. 1983-283831, bisulfite adducts described in Japanese Patent Application No. 1-298935, and U.S. Patent Application No. 1-298935 are used. It is preferred to add compounds such as alkanolamines described in No. 4,786,583.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer, which is a blue-iron-sensitive layer, a green-sensitive layer, and a red-sensitive layer, on the support. There are no particular restrictions on the number or order of the non-photosensitive layers; a typical example is to include multiple silver halide emulsions with substantially the same sensitivity but different sensitivities on the support. A silver halide photographic light-sensitive material having at least one light-sensitive layer consisting of a layer, the light-sensitive layer being a unit light-sensitive layer having sensitivity to any of blue light, green light, and red light; In a multilayer silver halide color photographic optical material, unit photosensitive layers are generally arranged in the following order from the support side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1,121,470 or British Patent No. 923.045. A two-layer structure can be preferably used0
Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 112751, No. 62-200350, No. 62-2
As described in Nos. 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive layer (GL ) / High-sensitivity red-sensitive layer (RH) / Low-sensitivity red-sensitive layer (RL)
or BH/BL/GL/G) I/RH/l? L
or BH/BL/Gl(/GL/RL/R1(
They can be installed in the following order:

Furthermore, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/G)! /
They can also be arranged in the order of RH/GL/RL. Further, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/Gl(/R)l is arranged in the order from the farthest side from the support. You can also do that.

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, the medium-sensitivity emulsion layer/high-speed pore side layer/low-speed pore side layer may be arranged in this order from the side remote from the support.

Other high-sensitivity emulsion layer/low-speed pore side layer/medium! ! 5It emulsion layer, or low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc. in this order! may have been done.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

To improve color reproduction, U.S. Patent No. 4.66327
No. 1, No. 4,705.744, No. 4,707.4
No. 36, JP-A-62-160448, JP-A No. 63-898
The multilayer effect donor layer (CL) described in the specification of No.
) is preferably arranged adjacent to or close to the main photosensitive layer.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material of the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing 0.1 to 30 mol% silver iodide. be.

Particularly preferred are silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

The silver halide grains in the photographic whey include those with regular crystal shapes such as cubes, octahedrons, and dodecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. It may also be a material with crystal defects such as, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic aperture side that can be used in the present invention is, for example, Research Disclosure (RD) N [L17643
(December 1978), pp. 22-23 1 "1. Emulsion preparation an
d types)'', same 18716 (1979
January), 648 pages, same N [L307105 (19B
(November 1999), pp. 863-865, and Grafkide, “Physics and Chemistry of Photography,” published by Beaumontel (P.
, Glafkidea, Chemie et Ph1
sique Photograph-ique, Pa
ul Montel+ 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duf
finPhotographic Emulsion
Chemistry (Focal Press19
66) “Production and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L, Zelikma)
net al.

Gate making and coating Photog
rapic Emulsion Focal Pres
s, 1964).

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering)
, Vol. 14, pp. 248-257 (1970);
U.S. Patent Nos. 4.434,226 and 4.414.31
No. 0, No. 4,433.048, No. 4,439.520
and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. They may also be bonded with compounds other than silver halide, such as silver rhodan or lead oxide, and mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are Research Disclosure Sou 17
643, Dotetsu 18716, and Dotetsu K 307105, and the relevant parts are summarized in the table below.

In the present invention, it is preferable to use non-light-sensitive fine-grain silver halide. Non-light-sensitive fine-grain silver halide is not exposed to light during imagewise exposure to obtain a dye image, but is not exposed to light during the development process. They are fine silver halide grains that are not substantially developed and are preferably not fogged.

The fine-grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and/or silver iodide as necessary, preferably silver iodide in a content of 0.5 to 100 mol%. It contains 10 mol%.

The fine grain silver halide preferably has an average grain size (average diameter equivalent to a circle of the projected area) of 0.01 to 0.5 μ-, and 0.01 to 0.5 μm.
02 to 0.2 μ- is more preferable.

Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, nor is spectral sensitization necessary. However, prior to adding this to the coating solution, it is preferable to add in advance a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound, or a zinc compound.

Known photographic additives that can be used in the present invention are also described in the three Research Disclosures mentioned above, and the relevant descriptions are shown in the table below.

In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Patent No. 4,411.987 and US Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde, as described in No. 435,503.

Various color couplers can be used in the present invention, and specific examples thereof include the aforementioned Research Disclosure 〼17643, ■-C-G, and Research Disclosure 〼307105,
■It is described in the patent described in -〇-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4.3
No. 26,024, No. 4.401,752, No. 4,
248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425.020, British Patent No. 1,476.760, U.S. Patent No. 3,973.968, British Patent No. 4.314,
No. 023, No. 4,511.649, European Patent No. 24
9.473A, etc. are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, European Patent No. 4,351,897, European Patent No. 73,636, US Patent No. 3,061,432, US Patent No. 3725.067, Research Disclosure No. 24220 (June 1984) , JP-A-60-33
No. 552, Research Disclosure Stone 24230
(June 1984), JP 60-43659, JP 61-72238, JP 60-35730, JP 55-
No. 118034, No. 60-185951, U.S. Patent No. 4.500.630, U.S. Patent No. 4,540,654, U.S. Pat.
Particularly preferred are those described in No. 5 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4.052.212.
No. 4,146.396, No. 4,228.23
No. 3, No. 4.296.200, No. 2,369.9
No. 29, No. 2,801.171, No. 2,772.
No. 162, No. 2,895.826, No. 3,772
, No. 002, No. 3,758,308, No. 4,33
4.011, 4.327.173, West German Patent Publication No. 3゜329.729, European Patent No. 121, 36
No. 58, No. 249453A, U.S. Patent No. 3.446
, No. 622, No. 4.333.999, No. 4,77
No. 5.616, No. 4,451,559, No. 4,4
No. 27,767, No. 4,690,889, No. 4
, 254.

No. 212, No. 4,296.199, JP-A-61-4
Those described in No. 2658 and the like are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820; U.S. Pat. No. 4,080,211; U.S. Pat.
No. 4,576°910, British Patent No. 2.102.
No. 137, European Patent No. 341°188A, etc.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, No. 570, European Patent No. 96,570, West German Patent (
The one described in Japanese Publication No. 3,234,533 is preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research Disclosure Sou 17643.
-G section, ■-G section of No. 307105, U.S. Patent No. 4.
163.670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929, U.S. Pat. No. 4,774,181, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released during coupling, and U.S. Pat. No. 4,777,
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in No. 120.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. A DIR coupler emitting the development inhibiting side is the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
Preferably, those described in U.S. Pat. No. 63-37346, U.S. Pat.

British Patent No. 2.097.140,
Those described in JP-A No. 2.13L188, JP-A-59-157638, and JP-A-59-170840 are preferred.

Other compounds that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , the multi-equivalent couplers described in JP-A-60-185950, etc.
DIR redox compound releasing coupler, DIR coupler releasing coupler, D as described in JP-A-62-24252 etc.
IR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173゜30
2A, couplers that release dyes that recolor after separation as described in No. 313,308A, bleaching accelerator-releasing couplers as described in R, D, Ren 11449, No. 24241, JP-A-61-201247, etc. U.S. Patent No. 4,555.477
Ligand-releasing coupler described in JP-A-63-75
Couplers that release leuco dyes as described in US Pat. No. 747, couplers that release fluorescent dyes as described in US Pat. No. 4,774,181, and the like.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2.322.027 and the like.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above high boiling point organic solvents include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-amylphenyl) phthalate, bis(2-ethylhexyl phthalate), bis(2,4-di-amylphenyl) phthalate, , 4-di-t-amyl phenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2
-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides If (N,N-
diethyldodecaneamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols If (isostearyl alcohol,
2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like.

As the auxiliary solvent, organic solvents having a boiling point of about 30"C or more, preferably 50 to about 160C, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
Examples include 2-ethoxyethyl acetate and dimethylformamide.

Specific examples of latex dispersion processes, effects, and latex for impregnation are disclosed in U.S. Pat. No. 4,199,363, OLS No. etc. are listed.

These couplers can also be impregnated into rhodapuru latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents described above.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. 088100723 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization.

The color photosensitive material of the present invention contains phenethyl alcohol and JP-A-63-257747, JP-A-62-272248
1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-
Dimethylphenol, 2-phenoxyethanol, 2-
It is preferable to add various preservatives or antifungal agents such as (4-thiazolyl)benzimidazole.

The present invention can be applied to various color photosensitive materials, but representative examples include color negative films for general use or motion pictures.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
It is described on page 28 of D, Ike 17643, page 647 right column to page 648 left column of Dotetsu 18716, and page 879 of Ncc 307105.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 18 μm or less, and 16 μm or less. - The following is particularly preferable, and the membrane swelling rate T is 7! is preferably 30 seconds or less, more preferably 20 seconds or less, and the WA thickness is measured at 25°C relative temperature 55% m humidity (
2 days), and the membrane swelling rate T17. can be measured according to techniques known in the art, e.g., Green
) et al. Photography Inc. Science &amp;
Engineering (Photogr, Sci, Eng,
), 19@, No. 2, pages 124-129, it can be measured by using a swellometer (swelling membrane), and TI/! The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when treated with a color developing solution at 30° C. for 3 minutes and 15 seconds, and is defined as the time until the saturated film thickness reaches 172.

The membrane swelling rate T17□ can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The light-sensitive material of the present invention may incorporate a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of color developing agents.
For example, indoaniline compounds described in U.S. Patent No. 3,342,597, U.S. Patent No. 3.342.599, Research Disclosure Nα14,850 and U.S. Pat.
Rumpf base type compound described in 5.159, 13.92 of the same
Aldol compound described in No. 4, U.S. Patent No. 3.719,
Metal salt complex described in No. 492, JP-A-53-135628
Examples include the urethane compounds described in No.

The light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones, if necessary, for the purpose of promoting color development.
No. 39, No. 57-144547, and No. 58-11
It is described in No. 5438, etc.

(Examples) Hereinafter, the present invention will be specifically explained by examples, but the present invention is not limited thereto.

Example 1 (Sample 101) A multilayer color light-sensitive material consisting of each layer having the composition shown below was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm, and designated as Sample 101. The numbers represent the amount added per bottle. Note that the effects of the added compound are not limited to the described uses.

1st layer: Antihalation layer Black colloidal silver 0.25g Gelatin 1.9g Ultraviolet absorber U-1
0.04g Ultraviolet absorber U-20.1g Ultraviolet absorber U-30.1g Ultraviolet absorber U-40.1g Ultraviolet absorber U-60.1g High boiling point organic solvent 0i1-10.1g Second layer/intermediate layer Seratin 0.40g Compound C
pd-D 10 ■High boiling point organic solvent 0i1-30.1g Dye D-40,4■ Third layer: Fine grain silver iodobromide emulsion covered with the surface and inside of the intermediate layer (average grain size 0.06 μm, coefficient of variation) 18%, All content 1 mol%
) Gelatin 4th layer: Low sensitivity red-sensitive emulsion layer Emulsion A Emulsion B Gelatin coupler C-1 Coupler C-2 Coupler C-9 Compound Cpd-D High boiling point organic solvent Oi1-2 Silver amount 0.05 g 0.4 g Silver Amount 0.2g Silver amount 0.3g 0,8 g O,15g 0.05g 0.05g 1O■ 0,1 g 5th layer, medium red-sensitive emulsion layer Emulsion B Emulsion C Gelatin coupler C-1 Coupler C- 2 Coupler C-3 High-boiling organic solvent 0i1-2 6th layer: High sensitivity red-sensitive emulsion layer Emulsion D Ceratin coupler C-1 Coupler C-3 Additive P-1 7th layer Intermediate layer gelatin color mixing inhibitor Cpd- A 8th layer: Low-sensitivity green-sensitive emulsion layer Emulsion E Emulsion F Silver amount Silver amount Silver amount Silver amount Silver amount g g g g 5g g g Emulsion G Silver amount Ceratin coupler C-7 Coupler C-8 Compound Cpd-B Compound Cpd-D Compound Cpd-E Compound Cpd-F Compound Cpd-G Compound Cpd-H High boiling point organic solvent 0i1-1 High boiling point organic solvent 0i1-2 9th layer: Medium-sensitivity green-sensitive emulsion layer Emulsion G Emulsion H Gelatin coupler C-7 Coupler C-8 Compound Cpd-B Compound Cpd-E Silver amount Silver amount g g 5g 0g 3g O■ 2g 2g 2g 2g g g g g g g g 3g 2g Compound Cpd-F Compound Cpd-G Compound Cpd- H High-boiling organic solvent Oi1-2 10th layer: High sensitivity green-sensitive emulsion layer Emulsion I Silver content Gelatin Coupler C-4 Coupler C-8 Compound Cpd-B Compound Cpd-E Compound Cpd-F Compound Cpd-G Compound Cpd- H High boiling point organic solvent 0i1-1 High boiling point organic solvent 0i1-2 11th layer: Intermediate layer gelatin dye D-1 Dye D-2 2g 5g 5g 1g g g g g g 8g 2g 2g 2g 2g 2g 2g 5g Dye D-3 12th layer: yellow filter layer yellow colloidal silver silver amount gelatin color mixing inhibitor Cpd-A high boiling point organic solvent 0il-1 13th layer: intermediate layer gelatin 14th layer: low sensitivity blue sensitive emulsion layer emulsion J silver amount emulsion K silver Emulsion L Silver amount Gelatin coupler C-5 15th layer: Medium sensitivity blue sensitive emulsion layer Emulsion L Silver amount Emulsion M Silver amount Gelatin coupler C-5 Coupler C-6 7g g g 1g 1g 16th layer: High sensitivity blue sensitivity Emulsion layer Emulsion N Silver amount Gelatin coupler C-6 17th layer: 1st protective layer gelatin UV absorber U-1 UV absorber U-2 UV absorber U-3 UV absorber U-4 UV absorber U-5 Ultraviolet absorber U-6 High boiling point organic solvent 0i1-1 Formalin scavenger pci-c pd-1 Dye D-3 18th layer: 2nd protective layer Colloidal silver Silver amount fine grain silver iodobromide emulsion (average grain size 0゜0゜1゜0゜g 4g 1g 3g 3g 5g 5g 2g 0, 2 g 0.4 g 0.05g 0゜1 ■ 06μm1 AgI content 1 mol%) Silver amount 0.1g Seratin
0.4g 19th layer, 3rd protective layer Ceratin 0.4g polymethyl methacrylate (average particle size 1.5μ) 0.1g 4/6 copolymer of methyl methacrylate and acrylic acid (average particle size 1.5μ) 0.1g silicone oil
0.03g Surfactant W-13.0■ Surfactant W-20.03g In addition to the above composition, additive F-
1-F-8 was added. Furthermore, in addition to the above composition, gelatin hardening agent H-1 and coating and emulsifying surfactants W-3 and W-4 were added to each layer.

Furthermore, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol,
Phenethyl alcohol was added.

The silver iodobromide emulsion used in sample 101 is as follows.

Monodisperse engineering particles Monodisperse tetradecahedral particles Polydisperse twin particles Monodisperse cubic particles Monodisperse cubic particles Monodisperse cubic internal latent image particles Monodisperse cubic internal latent image particles I'm going to choose a giant 14-hour race - Hot Seven Aspects 1st Ti.

Monodispersed tetradecahedral particles Monodispersed tetradecahedral particles Monodispersed cubic particles Monodispersed cubic particles 1.0 0.30 0.30 0.60 0.17 0.20 0.25 0.30 0.80 0.30 0.37 0.46 0.55 1.00 3.3 5, 0 2.0 4゜0 4.0 3.5 3.5 1, 5 4.0 4. 0 3.5 4.0 1, 3 Spectral sensitization of emulsion AN (Samples 102 to 110) Compound Cpd-A (ScV-3
) was replaced with the compound shown in Table 1 by the equivalent mole to prepare sample 1.
02-110 were created. The compounds shown in Table 1 were used after being emulsified and dispersed in an aqueous gelatin solution using a known dispersion technique.

These samples were cut into strips, subjected to imagewise exposure, and then subjected to the following development processing steps A and B at 38°C.
The concentration of the obtained treated strips was measured. Next, the sample was stored at 80° C. and 70% relative humidity for 7 days to examine the occurrence of yellow stain. The stain was evaluated by measuring the density under blue light and calculating ΔDB, which is the increase in density in the white exposed area compared to before storage, and is shown in Table 1.

△DB = DB (Concentration in blue light after storage) - DB
(Concentration under blue light before storage) [Processing process] (Processing A) Processing process Time Temperature Tank capacity Replenishment amount Black and white development 6 minutes 38°C 1212, 2 A/m' 1st water wash 21138114117.5g Reversal 2
/l 38/l 4 Horn 1.1 Color development 611381112/2.2/l
White 3/I 3811 6 〃 0
．． 15 //Fixed 4/l 3811
8 〃 2.2 -/Second water washing (1) 211
38/14〃 Second water wash (2) 2 no/38 nol 4/l 7.5
No/Stable 2/l 3811 4 ll
1. l 〃3rd Wash 1l138114ノ'1
．． 1” Transfer the overflow liquid from the second washing (2) to the second washing (
1) Led to bath.

Nitrilo-N,N,N-trimethylenephosphonic acid 5 sodium trilam salt diethylenetriaminepentaacetic acid 5 Sodium salt 2.0g 3.0g 2.0g 3.0g Potassium sulfite 30.0g 30
．． 0g hydroquinone/potassium monosulfonate 20.0g 20.
0g potassium carbonate 33.0g
33.0g 1-phenyl-4-methyl-4 monohydroxymethyl-3-pyrazolidone 2.0g 2.0g
Potassium bromide 2.5g 1.4
g Potassium thiocyanate 1.2g 1.
2g potassium iodide 2.0■ 2.0
Add ■1. OA 1. O
A'pH (25°C) 9.60 9
．． A pH of 70 was adjusted with hydrochloric acid or potassium hydroxide.

Nitrilo-N, N, N4 Lime Styrenephosphonic acid, 5-sodium um salt Tin chloride dihydrate p-aminophenol 3.0g 1.0g 0.1g Same as mother liquor Sodium hydroxide glacial acetic acid add water pH (25°C) pH is determined by hydrochloric acid or hydroxide 8.0g 15, O- 1.Ol 6.00 Adjusted with thorium.

Nitrilo-N,N,N-trimethylenephosphonic acid 5-sodium salt Diethylenetriaminepentaacetic acid 5 Sodium salt Sodium sulfite Tripotassium phosphate 12 hydrate Potassium bromide Potassium iodide Sodium hydroxide N-ethyl citrazate (β -Methanesulfonamidoethyl)-3 2.0g 2.0g 7.0g 36.0g 1.0g 90.0■ 3.0g 1.5g 2.0g 2.0g 7.0g 36.0g 3.0g 1, 5g Methyl-4-aminoaniline sulfate 10.5g 10.
5g 3.6-cythiaoctane-l.

8-diol 3.5g 3.5g
Add water 1. Or! 1.01p
H (25°C) 11.90 12.
0') pH was adjusted with hydrochloric acid or potassium hydroxide.

two-blooded deer Mother liquor 1.3-diaminopropane tetra acetic acid 13-diaminopropane tetra Ferric ammonium acetate Monohydrate salt ammonium bromide ammonium nitrate hydroxyacetic acid acetic acid add water 2.8g 138, 0g 5o, 0g 20.0g 50.0g 50.0g 1.01 replenisher 4.0g 207, 0g 120, 0g 30.0g 75.0g 75.0g 1.0J pH (25°C) 3.40 2.80 The pH was adjusted with acetic acid or aqueous ammonia.

Huangho Liquor Mother Liquor Replenisher Ethylenediaminetetraacetic acid / Mother Liquor Disodium Dihydrate 1.7g Benzaldehyde
〇-Titrium sulfonate 20.0g Sodium bisulfite 15.0g Ammonium thiosulfate
340.0i (700g/I2) Add imidazole 28.0g water
1.01pH (25℃)
A pH of 4.00 was adjusted with acetic acid or aqueous ammonia.

Fixative solution Filled with ethylenediaminetetraacetic acid, same as mother liquor, disodium salt, dihydrate salt 1.0g sodium carbonate
6.0g formalin (37%),
Add 5.0ml and get 1.0!
pH (25°C) 10.00 pH was adjusted with acetic acid or sodium hydroxide.

In the mother liquor, the same ethylenediaminetetraacetic acid, disodium salt, dihydrate 0.2g hydroxyethylidene-1゜■-diphosphonic acid 0.05g ammonium acetate 2.0g sodium dodecylbenzenesulfonate 0.3 pH (25℃) 4.50pH was adjusted with acetic acid or aqueous ammonia.

(Process B) is the same as (Process A) except that the stabilizing liquid in (Process A) was changed to the following.

Ethylenediaminetetraacetic acid, same as mother liquor, disodium salt, dihydrate 1.0g sodium carbonate 6.0g dimethylol urea
Add 8.0g and 1.0 Z
pH (25°C) 10.00 pH was adjusted with acetic acid or sodium hydroxide.

The invention is shown within the double frame.

From Table 1, it is clear that when processing B containing an N-methylol compound is applied to a photosensitive material using the compound of the present invention in the seventh layer, yellow stain is less likely to occur and an excellent image forming method is provided. .

Example 2 New samples 111 to 112 were prepared by replacing the compound Cpd-A (Scv-3) in the 7th layer of sample 101 prepared earlier in the same manner as in Example 1 with the compound shown in Table 2 in equimolar amounts.
It was created.

These samples were cut into strips, subjected to imagewise exposure, and then subjected to the following development processing steps A to E at 38°C.
The concentration of the obtained treated strips was measured. Treatments A and B are the same as described in Example 1. Next, the sample was stored at 80° C. and 70% relative humidity for 7 days to examine the occurrence of yellow stain. Evaluation of stain was performed by calculating ΔD8 according to Example 1, and is shown in Table 2.

(Processing C) Processing process Time Temperature Tank capacity Black and white development 6
Minutes 38°CIM First water wash 2” 3B” 4” Reversal 2 ll 38/4
ll color development 61138/12/l adjustment 2 〃 38!7 4
/ Bleach-fixing 61138 ml 12〃Second washing (1) 27138//411 Second washing (2+2”3 total liters 4/l 7.5 liters
l Stable 2/l 38/l 4 ll
1. l ll Third water wash 1//38/)
41/7.571 Replenishment amount 2.2 f/m2 7.51/ 1.1 2.2〃 1.1 l' 1.3〃 Overflow liquid of second water wash (2) to second water wash (1) bath lead.

The composition of the color developer to the black and white developer is the same as in Process A.

! ! Coffin replenishment ethylenediaminetetraacetic acid, same disodium salt and dihydrate as mother liquor 8.0g sodium sulfite
12.0g2-mercapto-1,3,4-triazole 0.5gTWEEN
20” 2. Add Od
1.01pH (25°C)
6.20 pH was adjusted with hydrochloric acid or sodium hydroxide.

TWEEN 20”: ICI America
n Inc.

Same surfactant bleach-fix solution replenisher mother liquor as ethylenediaminetetraacetic acid, disodium salt, dihydrate salt 2. Add 70.0g ammonium thiosulfate (700g/1) 200.0g ammonium sulfite 20.0g
1,01pH (25°C)
The pH of 6.60 was adjusted with acetic acid or aqueous ammonia.

Ethylenediaminetetraacetic acid, disodium salt, dihydrate salt 1.0g imidazole
1.0g dimethylol urea
Add 8.0g water 1.01p
H (25°C) 7.50 pH was adjusted with acetic acid or aqueous ammonia.

(Processing D) Processing process: black and white development 6 minutes - washing 2 // reversal 2 // color development 5 // bleach-fixing 811 Stable (1) 2" Stable (2) 211 Temperature Tank capacity 38°C 121 38〃 ' 4 〃 38// 4 〃 381/ 12 〃 38// 1611 38// 4 〃 38 horn 4 〃 Replenishment amount 2.21/m" 7.5 1.1 2.2 1.3 〃 The stable (3) overflow liquid was led to stable (2), and the stable (2) overflow liquid was led to stable (1).

The composition of each treatment liquid was as follows.

The compositions of the black and white developer to the color developer are the same as in Process A.

The composition of the bleach-fix solution is the same as in Process C.

Main indigo mother liquor Replenisher Same as mother liquor Diethylenetriaminepentaacetic acid, disodium salt, dihydrate salt 0.5g imidazole
1.0g dimethylol urea
8. Ogp-h Sodium luenesulfinate 1.0g Add sodium dodecylbenzenesulfonate 0.3g
1.01pH (25°C)
A pH of 7.50 was adjusted with acetic acid or aqueous ammonia.

(Processing E) Processing process Time Temperature 9') Capacitive black and white development
6 minutes 38°C121 1st water wash 2 Noah 38 no! 4/1 reversal
2//38/4/1 color development
6 no 138 // 1').

Stop 2/l 3811 4 ll bleach fixing 41 = 38 no = 8” stable (1)
2/= 38// 4 // Stable (2
)2 no 138//411 stable j3) 2// 381/4 //
Stabilize the overflow liquid of 1.1 Stability (3) (2)
The overflow liquid of stable (2) was led to stable (1).

The composition of each treatment liquid was as follows.

The composition of the black and white developer to the color developer is the same as Process A. Replenishment amount: 2.2 r/m2 7,5 7/1.1 l1 2.2/no 1.111 131 Mother liquor Replenisher Acetic acid 30. 0 g Same as mother liquor Sodium oxide 1.65 pH (25°C) 3.20 pH was adjusted with acetic acid or sodium hydroxide.

2.8 g of the same tetraacetic acid in 3-diaminopropane mother liquor 1.3-diaminopropane tetraacetic acid ferric ammonium monohydrate ammonium thiosulfate (700 g/l) Sodium bisulfite benzaldehyde -〇- 144 , 0g 200, Om/ 21.0g Sodium sulfonate 42.0g Imidazole
28.0pH (25℃)
A pH of 6.80 was adjusted with acetic acid or aqueous ammonia.

Diethylenetriaminepentaacetic acid, disodium salt, dihydrate Hydroxyethylidene - 1°0.5g Same as mother liquor ■-Diphosphonic acid 0.05g Imidazole
1.0g dimethylol urea
8. Add 1.0 g of sodium Ogp-1-luenesulfinate and 0.3 g of sodium dodecylbenzenesulfonate.
1.0lpH (25°C)
A pH of 7.50 was adjusted with acetic acid or aqueous ammonia.

From Table 2, it can be seen that treatments B to E produced less yellow stain, and in particular treatment B was significantly improved over treatment A using conventional Polmarine. Therefore, it is clear that the processing method of the present invention can provide an image forming method with less occurrence of yellow stain under high temperature and high humidity conditions and excellent image storage stability.

/ / / / / Example 1. Compound used in 2 ShiN H3 6℃H2 CH te π-1----i CH2C 辷.

(t)CIH1□ II il dibutyl phthalate tricresyl phosphate pd (Same as compound example 5cv-3) H Cpd-B CH.

Hr H Cpd ■ CH.

(t)Ct Hz (t) C, H9 S ■ (CH2), So.

(CH2) l Sol Na C,H.

C, H5 ■ So, K So, K SO,K 03K HO7,/ N' voice, C, H, C, H.

W-1 C,F,,5O2NHCH2CH,CH20CH2CH
2N(CH,)IC,F,? SO2NCH2C00K C,H.

CH2C00CH, CHCC2Ha)C,H.

Nap, 5-CHCOOCH,CH(C,H,)C,H
eCH CH CH Example 3 (Samples 201 to 205) Photosensitive material 9 of Example of JP-A-2-93641 was used as Sample 2.
It was set to 01.

Compound Cpd-1 (Scv-8) in the fifth layer of sample 201
Sample 20 was obtained by replacing the equivalent mole of with the compound shown in Table 3.
2 to 205 were created.

After imagewise exposure was applied to these samples in the same manner as in Example 1, the following development processing step F was carried out.

G was carried out at 38°C and the resulting treated strips were densitometrically measured. Next, the sample was stored at 80° C. and 70% relative humidity for 7 days to examine the occurrence of yellow stain. The stain was evaluated by measuring the density under blue light and calculating ΔDa, which is the increase in density in the unexposed area compared to before storage, and is shown in Table 3.

△DB = DB (Concentration in blue light after storage) - DB
(Concentration under blue light before storage) [Processing process] (Processing F) Process Processing time Processing temperature Replenishment amount Color development 3 minutes 15 seconds 38°C 45-Bleach 1
Minutes 00 seconds 38°C2〇-Bleach fixing 3 minutes 15 seconds
38℃ 307nl Tank capacity 0 A l Water washing (2) 1 minute 00 seconds 35℃ 30 - Stable
40 seconds 38°C 20-drying 1 minute 15 seconds
55°C The replenishment amount is per 35 mm width and 1 m length Next, the composition of the processing solution is described.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.11
-Hydroxyethylidene-3,03゜21, 1-Diphosphonic acid Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5■ Hydroxylamine sulfate 2.4 2.84-[N-ethyl-N-
β-4,5 Hydroxyethylamino] Add 2-methylaniline sulfate solution 1. Ofp H10,0
5 (Bleach solution) Common to mother solution and replenisher (Unit g) Ferric ethylenediaminetetraacetate 12 ammonium dihydrate Ethylenediaminetetraacetic acid disodium chloride Ammonium bromide Ammonium nitrate Bleach accelerator 10,0 100.0 10゜o, o o s mol 5.5 ■, 01 10, 10 0゜Ammonia water (27%) Add water to pH Bleach-fix solution 15゜1゜6゜m1 0I! Mother liquor Replenisher 1.3-diaminopropanetetraacetic acid 2.8g 1.3-diaminopropanetetraacetic acid ferric ammonium monohydrate 144.0g ammonium thiosulfate 200.0d (700g/l> Sodium bisulfite 21.0g benzaldehyde -〇- Sodium sulfonate 42.0g imidazole
28.0pH (25℃)
A pH of 6.80 was adjusted with acetic acid or aqueous ammonia.

(Water solution) Mother solution and replenisher A mixture of common tap water filled with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas). Water was passed through a bed type column to treat the calcium and magnesium ion mother liquor to the same concentration of 3/1 or less, followed by sodium isocyanurate dichloride 20/l and tetamine sulfate 0.1/l.
5g/A' was added. The pH of this solution is 6. 5-7.
It was in the range of 5.

Replenisher Diethylenetriaminepentaacetic acid, disodium salt, dihydrate 0.5g Hydroxyethylidene-1゜1-diphosphonic acid o, 05g Imidazole 1.0g Formalin (37%)
2. (Add 1.0 g of ip-sodium toluenesulfinate and 0.3 g of sodium dodecylbenzenesulfonate to 1.0 f pH (25°C) 7.50 pH was adjusted with acetic acid or aqueous ammonia.

Treatment G is the same as the formali mother liquor in the stabilizing solution in treatment F. hmm 8 dimethylol urea per 11 The process is the same as process F except for the above.

Change to 0g *) Mixing ratio is equimolar.

As is clear from Table 3, the image forming method of the present invention resulted in excellent image storage stability with little increase in yellow stain under high temperature and high humidity conditions.

(Effects of the Invention) By carrying out the present invention, it is possible to obtain an image in which yellow stain does not increase even if the image is stored under high temperature and high humidity conditions after processing.

Claims (1)

[Claims] A processing method for forming a color image using a silver halide color photographic light-sensitive material imagewise exposed, the light-sensitive material comprising:
A red-sensitive silver halide emulsion layer each containing one or more cyan couplers, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a blue-sensitive silver halide emulsion layer containing a yellow coupler on a support; General formula (
1) or a non-photosensitive layer containing at least one of the compounds represented by formula (II), and comprising processing with a stabilizing liquid containing an N-methylol compound. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the general formula (I), R^1^2 or R^1^6 are They may be the same or different and are substitutable groups to a hydrogen atom or a benzene ring.However, R^1^2 and R^1
At least one of ^4 is a hydroxy group, a sulfonamide group, or a carbonamide group, and the total number of carbon atoms in R^1^2 to R^1^6 is 8 or more. Z is a hydrogen atom or a protecting group that can be deprotected under alkaline conditions. R^1^2 to R^1^6 and OZ may jointly form a ring. In general formula (II), R^2^1 represents an aromatic group, and R^2
^2 and R^2^3 represent a hydrogen atom, an aliphatic group, or an aromatic group, and R^2^4 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an aryloxy group. , represents an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, or an acyl group. G^2^1 is carbonyl group, sulfonyl group, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ represents a sulfinyl group or iminomethylene group, and R^2^5 is R^2^4
and n is 0 or 1. )