JPS63259659A - Color image forming method - Google Patents

Abstract

PURPOSE:To obtain the excellent stability of a color developer by processing a silver halide color photographic sensitive material contg. a specified compd. with the color developer contg. a compd. selected from monoamines and diamines. CONSTITUTION:The silver halide color photographic sensitive material comprising a layer contg. at least one kind of the compd. shown by formulas I-III is image-wisely exposed, and then, the obtd. material is processed with the color developer contg. at least one kind of the compd. selected from the condensed ring amines and the monoamines, etc. and an aromatic primary amine color developing main agent. In formulas I-III, A is alkyl or a heterocyclic ring group, etc., R1 and R2 are each hydrogen atom or alkyl group, R3 and R4 are each hydrogen atom or aryl group, etc., R5 is alkyl or aryl group, etc., P is oxygen or sulfur atom, Ro is alkyl or a heterocyclic ring group, etc., X is hydrogen atom or an alkali metal atom, etc., R is alkyl or alkenyl group, etc. Thus, the excellent stability of the color developer itself is obtd.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is an image forming method for a silver halide color photographic light-sensitive material, which particularly has excellent stability of a color developer and does not easily cause staining after photographic processing. The present invention relates to an image forming method.

(Prior Art) Color developers containing aromatic primary amine color developing agents have long been used to form color images, and currently play a central role in image forming methods for color photographs. Fulfilling.

However, the color developer described above has the problem of being easily oxidized by air and metals, and when a color image is formed using an oxidized developer, fog may increase or the sensitivity may change by one gradation. It is well known that desired photographic characteristics may not be obtained due to

Accordingly, various means for improving the preservation properties of color developing solutions have been studied, and among them, the most common method is the combination of hydroxylamine and sulfite ions. However, when hydroxylamine decomposes, it generates ammonia, which causes fog, and also reduces color development by reacting with the oxidized product of the developer.On the other hand, sulfite ions act as a competitive compound for the developer, causing color development. Since they have drawbacks such as inhibiting the properties of the color developer, it is difficult to say that any of them is preferable as a compound (preservative) for improving the preservation property of a color developer.

In particular, sulfite ions have been used for a long time as compounds that improve the retention of various developing agents and prevent the decomposition of hydroxylamine, but they greatly inhibit color development, and in particular benzyl ions, which are harmful to pollution and liquid preparation. When used in a system that does not contain alcohol, the color density decreases significantly.

However, when sulfite ions are removed, the concentration fluctuations of hydroxylamines and color developing agents in the developing solution increase, which also has an adverse effect on photographic properties.

Therefore, there is a need for a preservative to replace sulfite ions,
Even when triethanolamines described in US Pat. No. 417,048 and polyethyleneimine described in US Pat. No. 4,252,892 were added, a sufficient effect on the retention of aromatic primary amines could not be obtained.

On the other hand, staining in the unexposed areas of a silver halide color photographic light-sensitive material not only determines the quality of white areas in an image, but also worsens color staining of a color image.

Especially in the case of reflective materials (e.g. color paper), which is undesirable because it impairs visual sharpness, the reflection density of the stain will theoretically be enhanced several times the transmission density, and even a weak stain will impair image quality. This is a very important element for damage.

Therefore, an object of the present invention is to provide an image forming method for a color photographic light-sensitive material that exhibits excellent color developer stability and significantly suppresses the increase in post-processing stain without adversely affecting photographic properties. It is in.

(Means for solving the problem) As a result of various studies to achieve the above object of the present invention,
A silver halide color photographic light-sensitive material containing at least one of the compounds represented by the following general formulas (A) to (C) is mixed with monoamines, diamines, polyamines, quaternary ammonium salts, nitrooxy radicals, and alcohols. , ethers, oximes, and amides by processing with a color developer containing at least one compound selected from among ethers, oximes, and amides.

The compounds represented by general formulas (A) to (C) will be explained in detail below.

General formula CA) In the formula, A is a substituted or unsubstituted alkyl group, aryl group, heterocyclic group, acyl group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, or t is amino Represents a group, R) 't? and R2 each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, and R3 and R4 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, or Arylthio group kW, R5 represents a substituted or unsubstituted alkyl group or aryl group, fc represents a heterocyclic group, and P represents a sulfur atom between an oxygen atom.

Next, 16 compounds represented by the general formula [AJ'''C] will be explained in detail. A is a substituted or unsubstituted alkyl group (
For example, methyl group, ethyl group, benzyl group, allyl group,
Cyclohexyl group, octyl group, hydroxymethyl group,
hexanoyloxymethyl group, coethylhexyl group,
dodecyl group, hekyptefyl group, octadecenyl group, etc., aryl group (e.g., phenyl group, u-t
er t -7-f ruphenyl group, 3--: ntadecylphenyl i, J-(J-ethylhexinamide) phenyl group, 3-naphthyl group, etc.), heterocyclic group (for example, furfuryl group).

pyridyl group, etc.), acyl group (e.g. acetyl group, heptanoyl group, coethyl hechitinyl group).

benzoyl group, dodecanoyl group, etc.), alkoxy group (
For example, methoxy group, hexyl group, λ-ethylhexyl group, dobufluoxy group, hexadecyloxy group, codedecyloxyethoxy group, co(octyloxy-j-1ert-octylbenzenesulfonamide)ethoxyft, etc.), aryloxy group (For example, phenyloxy group, -1-amylphenoxy group, J- is ntadecylpheno group, cholestane-j
-, heterocyclic oxy group (e.g., J-pyridyloxy group, cofurfuryloxy group, etc.), alkylthio group (e.g., ethylthio group, hexylthio group,
dodecylthio group, benzylthio group, cyclohexylthio group, octylthio group, etc.), 7-lylthio group (e.g., phenylthio, 4,4 cm octerooxydiphenylthio group-1crt-butylphenylthio group, 3-bankdecyl 7enylthio group) , etc.), amino groups (e.g., amino groups).

~-methylamino group, N, N-diethylamino group, N,
N-dihekynolamino group, anilino group, -monoroloanily7 group, Hiro-anisidinyl group, ≠-cyanoanilino group,
-(dodecyloxy)ethylami/group, goo (λ, gooji tert-amylphenoquine) butylamino group,
copyldylamino group, λ, A-pyrimidylamino group,
N-dodecylamino group, etc.) fully represented. General formula tl[I
The compound of l may form a total dimer via At. R1
゜The substituted or unsubstituted alkyl group, aryl group of R2, R3, R4, and R5, and the alkoxy group, aryloxy group, alkylthio group, arylthio group of R3, R4, and the hetea ring group of R5 are explained by the above person. It has the same meaning as . In the general formula (I[Il, R5 is particularly preferably an aryl group. P is an oxygen atom - 19 represents a sulfur atom, but an oxygen atom is particularly preferred. A is a substituted or fc is an unsubstituted alkoxy group) It is preferable that the substituent defined by fcA does not contain an acid group such as carboxylic acid or sulfonic acid.

Next, specific examples of typical compounds represented by the general formula [A] according to the present invention will be shown, but the present invention is not limited thereto.

(8-1) (A-2) ○ (A-31 (A-”) (A-5) ○ (A-6) (A-251 (A-26nt A-271+ A-28+ IA-301 (A (8-32) (8-29) (8-33) IA-3'l) (A-351 (A-361 +A-371 +A-381 +A-39) (8-IIo 1 (A-411 +A-1121 (8-43) (A-Yu) (8-115) (A-06) C12H25(nl (8-'+7) H3 (8-Jun 8) IA-'191 +A-501 +A-511 General Formula (B) RoSO 2

X is a hydrogen atom, an alkali metal atom, or an alkaline earth gold! j
It represents an i atom, a nitrogen-containing organic base, an ammonium group, or the following structural formula (D).

Structural formula (D) (Rt + represents a hydrogen atom, each substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, R
12 represents a hydrogen atom, a herogen atom, a substituted or unsubstituted alkyl group, an aryl group, an acyloxy group, or a sulfonyl group, and 5R1 represents a hydrogen atom or a group that can be hydrolyzed)) The compound of general formula (n) used in the present invention will be described below.

In the general formula ([ll, a plurality of -SO2X groups may be bonded, and in that case, the groups may be the same or different from each other. Ro covers a bulky skin group, but is not a polymer chain. The compound of the general formula (1'31) preferably has a molecular weight of less than /,000.

When Ro is an alkyl group, this alkyl group may be straight, branched, or cyclic. For example, groups such as di, butyl, hexyl, octyl, decyl, donol, hexadecyl, and octadecyl can be mentioned, but among the above groups, in the case of groups with 7 or less carbon atoms, the total number of carbon atoms is 1 to strengthen lipophilicity. That's all KII! A KJt substituent is attached. The "alkyl group" described herein also includes alkenyl groups.

Other alkyl groups may also have substituents.

Examples of the substituent include a phenyl group (this phenyl group may have a substituent), a nitro group, an ami7 group, a water group, a cyano group, a sulfoy-)5.7, It/ Koxy group (e.g. methoxy group, ethoxy group, etc.), aryloxy group (e.g. phenoxy group, etc.), acyloxy group (
(e.g., acetoxy group), acylamino group (e.g., acetylamino group, etc.), sulfonamide group (e.g., methanesulfonamide group, etc.), sulfamoyl group (e.g., methylsulfamoyl group, etc.), halogen atom (e.g., fluorine, chlorine, , iodine), carboxyl group, carbamoyl group (eg, methylcarbamoyl group, etc.), alkoxycarboxyl group (eg, methoxycarbonyl group, etc.), and sulfonyl group (eg, methylsulfonyl group, etc.). When there are d or more substituents, they are mutually [
It may be the same or different.

When an alkyl group is substituted with a phenyl group, this phenyl group may have a substituent.

This If group is an alkyl group (for example, a methyl group,
(ethyl group, pentyl group, etc.), aryl group, and other substituents for the alkyl group mentioned above.

When Ro is an aryl group, the following general formula (nlB
Compounds represented by are advantageously used.

General formula ([3)B % Formula % Examples of the aromatic ring formed by condensation with a benzene ring include a naphthalene ring, a quinoline ring, an indole ring, a benzothiophene ring, and the like.

The It substituents on the aromatic ring of the benzene ring include the above-mentioned halogen atom, nitro group, amino group, hydroxy group, alkyl group (cycloalkyl-containing trl,
Examples include aryl group, acyl group, acyloxy group, acylamino group, carbamoyl group, sulfamoyl group, alkoxy group, and aryloxy group. These substituents are 2
There may be more than one.

The alkali metal atom represented by X is Na,
Examples of alkaline earth metals such as Ll include Ca and Ba. Maku contains g1 element +! Examples of bases include common amines that form salts with sulfinic acids; This is not included because it tends to happen. In addition to NH, the ammonium represented by A group represented by the structural formula (1') is preferable.

When X is structural formula (D), the compound vJ represented by the general formula +n+ is considered to function as a sulfinic acid precursor. That is, it is thought that sulfinic acid is released at the current time.

There are groups such as C. One or more of these substituents may be present.

The alkali metal atoms represented by X include N&, K,
Examples of alkaline earth metals such as Ll include Ca and Ba. Examples of 2I-containing organic bases include ordinary amines that form salts with sulfinic acids; however, color developing agents may unnecessarily react with dye-containing couplers contained in lipophilic fine particles. This does not include this because it tends to deteriorate the image quality. In addition to NH4, the ammonium represented by A group represented by (1)) is preferable.

When X is structural formula (1)), the compound represented by general formula ([1)] is considered to function as a sulfinic acid precursor. That is, it is thought that sulfinic acid is released during development.

/' Structural formula (1)) % formula % In the formula, R11 is a hydrogen atom; an alkyl group (preferably a linear, branched or cyclic alkyl group having 20 carbon atoms),
Examples include groups such as methyl, ethyl, t-butyl, t-amyl, cyclohexyl, etc.) Niaryl group (preferably an aryl group having 6 to 30 carbon atoms, such as phenyl, naphthyl, etc.) :Ma'fc is a heterocyclic group (preferably a 7-membered ring, which may be condensed to form two or two rings, and the condensed ring is an aromatic ring such as a benzene ring or a naphthalene ring) Specific examples of the heterocyclic group include pyridyl, pyrimidyl, indolyl, isoquinolyl, and the like.

The above alkyl group, aryl group, and heterocyclic group may be substituted, and lf substituents include halogen atom, nitro group, amino group, hydroxy group, carboxyne group, alkyl group, cycloalkyl group, and aryl group. , allyl group, acyl group, acylamino group, carbamoyl group, sulfamoyl group, alkoxy group and the like.

There may be more than iλ of these lf substituents.

R12 is a hydrogen atom; a halogen atom (base, ionic acid);
Alkyl group (preferably a linear or branched alkyl group having 1 or 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, etc.) Niaryl group (preferably an aryl group having 6 to 30 carbon atoms, such as phenyl,
Naphthyl, etc.); Acyloxy (preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms) and an acyloxy group having an aryl group, such as an acetoxy group; or a sulfonyl group (
Preferably, it represents a sulfonyl group having a substituted or unsubstituted alkyl group or aryl group having 30 to 30 carbon atoms (eg, benzenesulfonyl, tosyl, etc.).

The above alkyl group and aryl group may be substituted, and specific examples of tit return groups include the following as examples of substituents for the alkyl group and aryl group of R1.

113 represents a hydrogen atom or a hydrolyzable group. ``The hydrolyzable group can be represented by, for example, -CRI4. Here, R4 is a hydrogen atom, the number of carbon atoms) - 1 of λO
4IIIf Quaternary or branched alkyl groups (for example, methyl, ethyl, butyl, pentadecyl, etc.), aryl groups having t to 30 carbon atoms (for example, phenyl, naphthyl, etc.), carbon atoms having 1 to 20 Acyl group (e.g. benzoyl, stearoyl, etc.)
, t7t represents an alkoxy group having 20 carbon atoms (for example, a methoxy group, an ethoxy group, etc.).

Furthermore, the alkyl group and aryl group of R14 may be substituted, and examples of the substituent include a halogen atom, a nitro group, an amine group, a hydroxy group, an alkyl group, a cycloalkyl group,
Examples include aryl group, allyl group, acyl group, acylamino group, carbamoyl group, sulfamoyl group, and alkoxy group. Two or more of these substituents may be present.

The compound of the present invention represented by the general formula (13) must be lipophilic and have a water solubility (tt) of less than or equal to r'C/h. Preferably θ,! It is less than 1, preferably less than θ and λ. That is, the research results
The compound of general formula (13) of the present invention can effectively prevent staining only by coexisting in the same lipophilic fine particles as the coupler. The reason for this is that, although it is not clear, one of the sources of staining is due to the developing agent remaining in the photosensitive material, more specifically, in the lipophilic fine particles in which the coupler exists in the photosensitive material. It is presumed that one source of this is the coupler itself. That is, the general formula (n
It is believed that the coexistence of the compound 1 effectively nullifies stain generation sources such as the remaining developing agent and prevents stain generation. Therefore, if the distribution of the compound of general formula (n) into the aqueous phase, that is, the aqueous gelatin solution phase becomes large, the anti-staining effect will be significantly reduced. If the water solubility is even higher, it will be eluted from the photosensitive material during the development process, and it will be obvious that it will not be able to contribute to preventing staining after processing. There is also a risk that the stability over time of the photographic properties of the photosensitive material before processing may deteriorate due to desensitization or adsorption to silver halide.

From the above points, it will be understood that the compound of the present invention (Bl) is more preferably lipophilic and has a lower solubility in water.

Therefore, when RO is an alkyl group, the total number of carbon atoms including substituents is 1 or more, preferably 7.2 or more.

Also, when Ro is an aryl group, the total number of carbon atoms including substituents! It is preferable that it is above.

Below, the compound represented by the general formula of the present invention ([31] [3-
2 t, -C, I-(.

+3 - 10 [1+, 12 +3 - 13 rJ -17 [3-20 B -23 QC16T3'33 [3-2 bus S (J 2ki pJflL:O to I 11-123 El -31 B-dan0C12Hzs H Dan++ Q -112 ++ B -JōB -450 B-Ro8°+3-5 no n -580 CgHts +3 - 66 n -670 〇C12H25 +1-70 0 11-71. () +3 - 72 n -73 I-LBn17 Representative examples of the compound represented by the general formula (C) are shown below, but the compounds used in the present invention are not limited thereby.

H C12H25 H C-381( OC81-11□ C-581-1 C143 C15"'31 QC8H17(J, 111 □ l-I H H H C1"3 C-17 C-18 H CI]3 C-20C1oH □1811 c -21C1□ I-1□ 5 S tlC
-22C14H29S1] 0-23016F13.511 C-24C18[-13□5l-I CHC0N)JCJi□ C1-I□C) (□ SHm
29 COOC2H5 C1□H25-CH-8H C~31 0 The compound represented by the general formula (C) is described in U.S. Patent No. 1t, 3
It can be synthesized according to the method described in J/, /j'ri No. 7.

In the present invention, lipophilic fine particles refer to fine particles that do not dissolve in an aqueous gelatin solution and exist as a separate phase in the aqueous gelatin solution, and the lipophilic fine particles include a lipophilic coupler or a compound represented by the general formula [C]. The term "containing" a lipophilic mercazoto compound is used to include not only the embodiment in which these compounds are dissolved in the lipophilic fine particles, but also the embodiment in which they are impregnated.

In addition, the substances constituting the "oleophilic particles" include not only oil-based solvents for additives such as couplers (including those that are solid at room temperature such as wax), but also latex polymers, couplers, and color mixing prevention agents. It also includes substances such as additives that also serve as oily solvents, such as UV absorbers and ultraviolet absorbers.

The color developer used in the present invention will be explained below.

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

(D-1) N,N-diethyl-p-phenylenediamine (D-2) 4-(N-ethyl-N-(β-hydroxyethyl)aminocoaniline (D-3) 2-methyl-4-[ N-ethyl-N-(β
-hydroxyethyl) aminocoaniline (D-4) 4-amino-3-methyl-N-ethyl-N
-(β-methanesulfonamidoethyl)aniline These P-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, sulfite, pt-luenesulfonate, etc. The amount of amine developing agent used is preferably about 0.1 g to about 20 g per developer solution IQ.
g, more preferably from about 0.5 g to about 10 g.

Next, fused cyclic amines and diamines used in the present invention,
Polyamines, quaternary ammonium salts.

Nitroxy radicals, alcohols, ethers, oximes, amides, and sulfonamides will be explained.

The condensed amines used in the present invention include:

Examples include compounds represented by the following general formula (I).

General Formula (I) In the formula, X represents a trivalent atomic group necessary to complete the condensed ring, and R1 and R represent an alkylene group, an arylene group, an alkenylene group, or an aralkylene group. Here R1,
R may be the same or different.

-I゛//P In the general formula (■), the number of carbon atoms in X is preferably 20 or less, more preferably 10 or less, and even more preferably 6 or less. X may contain atoms such as nitrogen, oxygen, and sulfur.

In the general formula rIl, R1 and R2 may each be substituted with another group. Further, the number of carbon atoms in R1 and R2 is preferably 10 or less, more preferably 1 or less, and even more preferably 3 or less. R1 and R2 are preferably an alkylene group or an arylene group, and more preferably an alkylene group.

The compound of the general formula (I+) may be a bis-form, a tris-form, etc. connected by X.

As a specific example of X in the general formula rI), '>c=N-5H be able to.

Specific examples of R1 and R2 in general formula II) include methylene group, ethylene group, propylene group, butylene group, hauntylene group, /, 2-cyclohexylene group, l-methylethylene group, /l 2-dimethylethylene group. Examples include l-carboxyethylene group, /, j-phenylene group, /, λ-vinylene group, i, 3--7 nylene group, etc.; A carboxyl group, a sulfo group, a hydroxyl group, an alkoxy group, an alkylthio group, an amino group, an amide group, an anlu group, a carbamoyl group, a sulfamoyl group, a heterocyclic group, etc. may be further substituted.

Among general formulas (I), particularly preferred ones are general formulas (■-
a) and (I-b).

ll R3 represents the same group as R1 and R2 or -CH2C-.

In the general formula (1-al, X is preferably -N. The number of carbon atoms in R1, R2, and R3 is preferably 6 or less, more preferably 3 or less, and most preferably λ. Preferably. R1, R2, and R are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

In the formula, R1 and R2 are defined as in general formula CI.

In the general formula (J-bl), the number of carbon atoms in R1 and R2 is preferably 6 or less. R and R are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

Among the compounds represented by the general formula (■-al, (I-b 1), the compound represented by the general formula (■-al) is particularly preferred.

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

■-(/l I -1zl■-(
3) I −(≠) I −Isl I −(Al1−(7
) I' 了）■－(りI
I-(10) Su ■-(//) ■-(/+21 H 1-(/3) ■-(/≠) Many of the compounds of general formula (I) according to the present invention are readily available commercially. Is possible.

The amount of the compound of the general formula (I) added is the color developer lt.
per, preferably 0177 to j09, more preferably 0
．． 22 to λO.

The monoamines used in the present invention have the following general formula (II):
It is a compound represented by

General formula (■) R-L N-R13 In the formula, B21 and Hag each independently represent a hydrogen atom,
It represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group, and R23 is an alkyl group.

represents an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group, where R21 and R2Z, R21 and R2)
Alternatively, R22 and Ro may be linked to form a nitrogen-containing heterocycle. However, when R21 is a hydroxyalkyl group having 2 to 6 carbon atoms, R22 and R2) simultaneously have 1 to 6 carbon atoms.
6 unsubstituted alkyl group, hydroxyalkyl group having 2 to 6 carbon atoms, or benzyl group.

R11, H2! , The alkyl group represented by R11 preferably has 1 to 12 carbon atoms, even if it is a 5-straight chain.

It may be branched or cyclic (specifically, methyl group, ethyl group, lopropyl group + 1so-propyl group, n-butyl group, t-butyl group, t-amyl group, n-hexyl group, cyclohexyl group, etc.) ); The alkenyl group preferably has 2 to 6 carbon atoms, and may be linear, branched, or cyclic (specifically allyl group, impropenyl group,
(cyclohexenyl group, etc.); Aryl groups preferably have 6 to 12 carbon atoms (specifically phenyl, tolyl, naphthyl, etc.); Aralkyl groups preferably have 7 to 12 carbon atoms ( Specifically, benzyl group,
phenethyl group, etc.); the heterocyclic group preferably contains a nitrogen atom, an oxygen atom and/or a sulfur atom as a heteroatom, and has 1 to 12 carbon atoms (specifically, an imidazolyl group, a pyrazolyl group, a triazolyl group, a pyridyl group) Such).

R21. , alkyl group (methyl group, ethyl group,
butyl group, t-butyl group, methoxyethyl group, carboxymethyl group, hydroxyethyl group, etc.), aryl group (phenyl group, tolyl group, naphthyl group, etc.), alkoxy group (methoxy group, ethoxy group, methoxyethoxy group, hydroxyethoxy base, etc.).

Aryloxy group (phenoxy group, ρ-nitrophenoxy group, etc.), sulfonyl group (methanesulfonyl group, benzenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (unsubstituted sulfamoyl group, etc.) group, dimethylsulfamoyl method, ethylsulfamoyl-substituted carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, etc.), amide group (acetamide group, benzamide group, etc.), ureido group (methylureido group, ethylureido group) group, phenylureido group, etc.), alkoxycarbonylamino group, methoxyethoxycarbonylamino group, etc.),
Acyl group (acetyl group, benzoyl group, etc.).

formyl group, cyano group, carboxy group, sulfo group, hydroxy group, nitro group, alkylthio group (methylthio group,
(hydroxyethylthio group, carboxymethylthio group, etc.), arylthio group (phenylthio group, etc.), and when there are two or more substituents, they may be the same or different.

B21 and Ro, R21 and R″3 or 822 and B23
The nitrogen-containing heterocyclic group formed by linking is a saturated or unsaturated 3- to 8-membered ring that may contain an oxygen atom, a sulfur atom in addition to carbon atoms and nitrogen atoms, and a benzene ring, a double M
It may be fused with a ring, specifically.

aziridine ring, azetidine ring, pyrrolidine ring, piperidine ring, piperazine ring, biroline ring, imidazolidine ring,
Pyrazolidine ring, indoline ring, morpholine ring, virol ring, imidazole ring, pyrazole ring, indole ring,
Examples include an indazole ring, a triazole ring, a tetrazole ring, a phenokilidine ring, a tetrahydrothiazine ring, and more preferably a saturated or unsaturated 5- to 6-membered ring. Further, these nitrogen-containing heterocycles may have a substituent, and specific examples of the substituent include the above-mentioned R21, R12゜R
The same substituents as for X3 can be mentioned.

, , B11. When any of R23 has a carboxy group, the compound of general formula (II) preferably has 3 or more carbon atoms, and furthermore, when any of Hml, Hml, 1 (z3) is a carboxyphenyl group, the substitution position of the amino group is carboxy The meta or para position of the group is preferred.

R21 and Hml are particularly preferably a hydrogen atom or an alkyl group, and R22 is particularly preferably an alkylnor.

Specific examples of the compound represented by the general formula (II) are listed below, but the present invention is not limited thereto.

If-20N-CH,CH,OH\-1/■-4CH,-N NCH,CH,OH\-1/11-6 (HOCH,CH,hNcH2CH,SO
, CH.

n 7 HN-(CHzCOOH)xll-9H,
NCH2CH, So, NH.

If-10C2H.

N-CH, CH, ○CH, CH20H C2H.

○CH3 Specific examples other than the above include compound examples A-1 to A-12 described on pages 9 to 10 of Japanese Patent Application No. 147823/1982.
Compound examples I-(1) to I-(22) described on pages 10 to 14 of Specification No. 61-166674; No. 61-1
Compound Example 1 described on pages 11 to 14 of Specification No. 65621
-(1) to I -(21); Compound examples 1-(1) to I described on pages 10 to 16 of Specification No. 61-164515
-(42); Specification No. 61-170789, page 9~
Compound examples 1-(1) to I-(11) described on page 11
; Compound Examples 1-(1) to [(24); Patent No. 61-168159, pages 11 to 16;
Compound Example 1-(1
)~I-(20) ; Specification of No. 61-186561!
Compound examples 1-(1) to X-(t
S); Specification No. 61-197420, page 10, line 4~
Compound examples 1-(1) to I-(35
); etc.

These compounds represented by the general formula (II) are
No. 1-147823, No. 61-166674, No. 61
-165621, 61-164515, 61-
No. 170789, No. 61-168159, No. 61-1
No. 69789, No. 61-186561, No. 61-19
It can be obtained by the method described in the specification of No. 7420 and the like.

The diamines used in the present invention have the following general formula (III):
It is a compound represented by

General formula (m) In the formula, R31, R''w R23, and R34 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group, and specifically, the general formula (It ) has the same meaning as R21 and R12.

However, when R31 is a hydroxyalkyl group having 2 to 6 carbon atoms, R32, R33, and R34 do not simultaneously include a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 2 to 6 carbon atoms.

Here, R31 and 1(32, R33 and R34 may be connected to form a nitrogen-containing heterocycle, and specific nitrogen-containing heterocycles include R11 and R22, R21 and R
It has the same meaning as a nitrogen-containing heterocycle formed by connecting Z3 or Ro and R23.

R31 represents a divalent organic group, specifically an alkylene group, an arylene group, an aralkylene group, an alkenylene group, or a heterocyclic group. Here, the alkylene group and alkenylene group may be linear, monobranched, or cyclic. Preferably, the carbon number is 1 to 6, and specific examples include methylene group, dimethylene group, trimethylene group, methyldimethylene group, dimethyltrimethylene group, hexamethylene group, ethylene group, butenylene group, etc. Can be mentioned. The arylene group preferably has 6 to 10 carbon atoms, and specific examples include the following. The aralkylene group preferably has 7 to 12 carbon atoms, and specific examples thereof include -CH2-0-, -CH, and -〇-CH□-2. As the 'a a ring group, one having 1 to 8 carbon atoms is preferable, and specific examples thereof include Hashiri7 and the like. These alkylene groups, alkenylene groups, arylene groups, aralkylene groups, and heterocyclic groups may have substituents, and specific substituents include the general formula (T
It has the same meaning as the substituent for R21, R22 and R12 in I), and when there are two or more substituents, they may be the same or different.

In general formula (III), PL, 83m, R33,
The total carbon number of R34 and R3g is at least 2.

R31,83m, R3:1 and R34 are particularly preferably a hydrogen atom or an alkyl group, and R3S is particularly preferably an alkylene group.

Specific examples of the compound represented by the general formula (III) are listed below, but the present invention is not limited thereto.

m-8HO□CCH,NHCH,CH,NHCH□C0
OH■-90”NCH,CH,NH.

Specific examples other than the above include compound examples r-(1) to ■
-(20); Specification No. 61-164515, page 10~
Compound examples 1-(1) to I-(42) described on page 16
Compound Examples 1-(1) to I-(24) described on pages 11 to 16 of Specification No. 61-168159; No. 61-169
Compound Example I-(1
) to I-(20); Compound Example 1-(1
)~2-(13), I-(15) and I-(19)~
I-(25); etc. can be mentioned.

The compound represented by the above general formula (III) is
-173595, 61-164515, 61-
No. 168159, No. 61-169789 and No. 61-
It can be obtained by the method described in No. 186560.

The polyamines used in the present invention have the following general formula (IV
) is a compound represented by

General formula (rV) In the formula, R41, R42, R43 and R44 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group, and specifically, the above general formula (II) 821.1 (synonymous with 22).

R41 and H4N, R4' and R44 may be linked to form a nitrogen-containing heterocycle, specifically, R21 and R1, R21 and R23, or R22 and Ro of the general formula (II) are linked to form a nitrogen-containing heterocycle. It has the same meaning as the nitrogen-containing heterocycle.

H2N, R41+, and R47 each independently represent a divalent organic group, specifically -〇〇-1-so, -, -5o- of the general formula (Ill) or a combination of these linking groups. represents a connecting group, R4″′ is R
41, R42, R43, and R44.

m represents an integer of 0 or 1 or more.The upper limit of 0m is not particularly limited, and as long as the compound is water-soluble, it may have a high molecular weight, but usually m is preferably in the range of 1 to 3.

However, when m = Q and R41 is a hydroquine alkyl group having 2 to 6 carbon atoms, R41, 84M, R4
3゜R44 is also a hydrogen atom, illll having 1-6 carbon atoms
l to the sialkyl group? Do not include 2 to 6 hydroxyalkyl groups.

Specific examples of the compound represented by the general formula (IV) are listed below, but the present invention is not limited thereto.

rV-2()foot,Ql,)i-NC&CH,OC
H,Ol,N-act(-,01()ffiIV-6H
,N(CH,CH,NHhH(n=500-20,00
0) Specific examples other than the above include Japanese Patent Application No. 16562/1986
Examples of compounds described on pages 11 to 14 of Specification No. 1! -(1)
~! -(21); Specification No. 61-169789, page 9~
Compound examples listed on page 12! -(1) to I-(20); and the like.

The compound represented by the above general formula (IV) is
It can be obtained by the method described in No. 165621 and No. 61-169789.

The quaternary ammonium salts used in the present invention are compounds represented by the following general formula (V).

General formula (V) (wherein R5L represents an n-valent organic group, R51, R0 and R54 each independently represent a monovalent organic group R2,
At least two groups among R9 and R54 may be bonded to form a heterocycle containing a quaternary ammonium atom, n is an integer of 1 or more, and Xθ represents a counter anion.) General formula ( In V), R5L is a monovalent or more, preferably monovalent to trivalent organic group. Examples of monovalent groups for R51 include substituted or unsubstituted alkyl groups (having 1 to 1 carbon atoms).
20 alkyl groups, such as methyl, ethyl, 2-
Hydroxyethyl group, 2-ethoxyethyl group, carboxymethyl group, 3-hydroxypropyl group, 3-sulfopropyl group, benzyl group, cyclohexyl group, cyclohexylmethyl group, isobutyl group, etc.), aryl group (having 6 to 20 carbon atoms) Aryl group, such as phenyl group, 4-methoxyphenyl group, 2,4-dichlorophenyl group)
, heterocyclic groups (heterocyclic groups having 1 to 20 carbon atoms, such as pyridin-4-yl group), etc. Examples of substituents that these groups may have include halogen atoms.

Preferred are a hydroxyl group, a sulfo group, a carboxyl group, an optionally substituted alkyl group, an aryl group, an m-ring group, an alkoxy group, an aryloxy group, a sulfonyl group, an acyl group, an amino group, and the like.

R5! Examples of divalent groups include substituted or unsubstituted,
Alkylene group (alkylene group having 1 to 20 carbon atoms, such as ethylene group, tetramethylene group, propylene group, etc.)
, arylene group (arylene group 1 having 6 to 20 carbon atoms, such as ρ-phenylene group, 0-phenylene group, 0-phenylene group, etc.), heterocyclic group (carbon 14 w′, l ・!
The heterocyclic group 1 of O (for example, 2,3-pyridinium, etc.) or a divalent group in which two or more of these are linked, and substituents for these include a halogen atom, a hydroxyl group, a sulfo group, a carboxyl group, and further substituents. Preferred are alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, sulfonyl groups, acyl groups, amino groups, etc., which may be fused.

R5'', RS3 and R%4 are monovalent organic groups, and preferred among them are the specific examples of the monovalent groups listed for -R%''. Particularly preferred monovalent groups among HSl, R53 and Rs4 The group is a substituted or unsubstituted alkyl group, and R'
Most preferably, at least one of ``Z, 8%3, and RS4 is a hydroxyalkyl group, an alkoxyalkyl group, or a carboxyalkyl group.

At least two groups among Rsz, Rs) and R[4 may be bonded to form a heterocycle containing a quaternary ammonium atom (eg, pyrrolidinium ring, pyridinium ring, etc.).

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

Xθ represents any counter-anion, examples of which include Tehahalokene ion (e.g. Eva CQe, Bre, Fe, Ie, etc.), various acids (sulfuric acid, nitric acid, phosphoric acid, P-toluenesulfonic acid, acetic acid, etc. Examples include the acid roots of inorganic acids).

Note that the compound represented by the above general formula (V) may be contained as a side chain group of a polymer added to the color developer.

Specific examples of the compound represented by the general formula (V) are listed below, but the present invention is not limited thereto.

■-1″″′-CH, N'-fC, H, OH), C
Q"V-2C,H,-N'(C,H40H),
1/2 So.

V-3N”(C,H40H)4No3θV-4(C,H
,)rN@-fC,H,OH), CQθv-6
0-N'(C,H,OCH,), cneV-8(H
OC1H4 juice N@-C2H4-N”-(C,H40H)
, 2NO, ``Specific examples other than the above include Patent Application 1986.
Compound examples 1-(1) to I-(25) described on pages 12 to 16 of Specification No. 188619 can be mentioned.

The compound represented by the above general formula (V) is
It can be obtained based on the method described in No. 813619.

The nitroxy radicals used in the present invention are compounds represented by the following general formula (VI).

General formula (Vl) R"N-○*R" RGL, in which R'1 and Ro each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

P2 may be the same or different from each other, and R″1 and R
'i may be connected to form a ring structure, provided that R'
1 and RGt are not hydrogen atoms at the same time, and these alkyl groups, aryl groups, or heterocyclic groups may have a substituent. Examples of such substituents include a hydroxy group, an oxo group, and a carbamoyl group. group, alkoxy group,
Examples include sulfamoyl group, carboxy group, and sulfo group. Examples of the heterocyclic group include a pyridyl group and a piperidyl group.

Preferably RGI, m is a substituted or unsubstituted aryl group or tertiary alkyl group (eg, t-butyl group, etc.).

Specific examples of the compound represented by the general formula (VI) are listed below, but the present invention is not limited thereto.

Specific examples other than the above include compound examples I-(1) to
-(36) etc. can be mentioned.

The compound represented by the above general formula (VI) is
It can be obtained based on the method described in No. 197760.

The alcohols used in the present invention are compounds represented by the following general formula (■).

General formula (■) In the formula, Rtt represents a hydroxy-substituted alkyl group (preferably 1 to 101 carbon atoms, e.g., hydroxymethyl group, hydroxyethyl group, etc.), and R72 represents an unsubstituted alkyl group (preferably 1 to 101 carbon atoms). for example.

methyl group, ethyl group, etc.) or a group similar to Rtt, R13 represents a hydrogen atom or a group similar to R7ff, X71 represents a hydroxy group, carboxyl group, sulfo group, nitro group, unsubstituted or hydroxy-substituted Alkyl group (preferably 1 to 10 carbon atoms, e.g. methyl group, hydroxymethyl group, ethyl group, etc.), unsubstituted or substituted amide group (preferably 2 to 10 carbon atoms, e.g. acetamido group, 2-hydroxybenzamide group) ), or unsubstituted or substituted sulfonamide group (preferably 1 to 10 carbon atoms, for example, methanesulfonamide group, 4
- methylbenzenesulfonamide group, etc.).

In the general formula (■), x71 is preferably a hydroxy group, a carboxyl group, or a hydroxyalkyl group.

Specific examples of compounds represented by the general formula (■) are listed below, but the present invention is not limited thereto.

CHko■■-480-CH云CH,OH)! VIE-5 (HOCH, Soup C-C0OH■-6C-+C
H, OH).

■-7 (HOCH, Soup C-CH.

-8 (HOCH, +TC-NHCOCH.

Vll-10HO-CH-CH,C:H,OHCH,C
H Specific examples other than the above include compound examples 1-(1) to ■- described on pages 8 to 10 of Japanese Patent Application No. 186561/1986.
(15); Compound Examples 1-(1) to r-(9) described on pages 8 to 9 of Specification No. 61-197419; and the like can be mentioned.

The compound represented by the above general formula (■) is
It can be obtained based on the method described in No. 86561 and No. 61-197419.

The ethers used in the present invention are compounds represented by the following general formula (■).

General formula (■) In the formula, R11, Raz, and m are each independently a hydrogen atom or an alkyl group (preferably a carbon number of 1 to 10°, for example,
methyl group, ethyl group, etc.), and n represents a positive integer up to 500.

As the alkyl group represented by Rol, Raz, R@).

The number of carbon atoms is preferably 5 or less, more preferably 2 or less, and Rsl, R'2.R@3 is very preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom. .

n is preferably a positive integer of 3 or more and 100 or less, more preferably 3 or more and 30 or less.

Specific examples of the compound represented by the general formula (■) are listed below, but the present invention is not limited thereto.

■-I HO-(CH, CH, ○ soup OH■-2CH,
0(CH,CH,O soup OH■-3CH,○-(CH,C
H, O soup ○CH.

しh□ ■-5HOCH,CH,OCH3 ■-6C,H,○-(CH,CH,○juice0HVlll-
7HO (CH2CH, OhH average molecule fA$f300V
ll-8HO(CH,CH,O juice H average molecule-1jlJ
800W1-9 HO*CH,CH,O Soup H average molecular weight, 000W-10HO-fCH,CH,0)iH average molecular weight approximately 8,000 The compound represented by the general formula (■) is easily available as a commercial product. be able to.

The oximes used in the present invention are compounds represented by the following general formula (■).

-OH In the formula, R91 and R'2 are each independently a hydrogen atom,
R9L and R9 represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group;
2 may be the same or different, and these groups may be connected.

Substituents for alkyl groups and aryl groups include halogen atoms, alkyl groups, aryl groups, hydroxyl groups,
Alkoxyl group 1, aryloxy group, amino group, carboxyl group, sulfo group, phosphonic acid group, carbamoyl group, sulfamoyl group.

Examples include sulfonyl group, ureido group, acyl group, acylamino group, sulfonamide group, alkylthio group, arylthio group, nitro group, cyano group, etc., and these include two or more or two or more kinds of substituents on alkyl and aryl groups. It's okay, again.

Hydroxyl groups, carboxyl groups, and sulfo groups are
It may be a salt of an alkali metal (eg, sodium, potassium, etc.).

Preferred examples of R91 and R92 are alkyl groups substituted with halogen atoms, hydroxyl groups, alkoxyl groups, amino groups, carboxyl groups, sulfo groups, phosphonic acid groups, nitro groups, and unsubstituted alkyl groups.

Further, the total number of carbon atoms in general formula (IX) is preferably 30 or less, and more preferably 20 or less.

Specific examples of the compound represented by the general formula (IK) are listed below, but the present invention is not limited thereto.

IX-I N-OH 1X-5N-OH ■ Specific examples other than the above are Compound Example 1-(1) described in Japanese Patent Application No. 198987, page 4111-14.
~■(20) etc. can be mentioned.

The compound represented by the above general formula (IK) is
-198987 based on the method described.

The amide and sulfonamide compounds used in the present invention are compounds represented by the following general formula (X).

General formula (X) In the formula, X101 and xi02 are each independent knee C0-1
Or bar So□-ヲ table, R101,1+12.
R103, HLa4, R10S and R16G each independently represent a hydrogen atom or an unsubstituted or substituted alkyl group; 1Blot represents an unsubstituted or substituted alkylene group, an unsubstituted or substituted arylene group, or an unsubstituted or substituted aralkylene group e Q, m and n each independently represent 0 or 1.

R=01. RL″i, RLO3, R1114, R1
05 and R-06 table f.

The alkyl group used may be linear, monobranched, or cyclic, and preferably has 1 to 12 carbon atoms.

Substituents include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms), alkoxy groups (methoxy groups).

ethoxy group, etc.), aryloxy group (phenoxy group, etc.), sulfonyl group (methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, etc.).

Sulfonamide group (methylsulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (unsubstituted sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, etc.) group, methylcarbamoyl group, phenylcarbamoyl group, etc.), amide group (acetylamide group, phenylamide group, etc.), ureido group (methylureido group, phenylureido group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, ethoxycarbonyl group, etc.) (amino group, etc.), cyano group, 7
Syl group (acetyl group, benzoyl method, etc.), nitro group,
Examples include alkylthio groups (such as methylthio groups), arylthio groups (such as phenylthio groups), hydroxyl groups, sulfo groups, and carboxy groups.

The alkylene group represented by R107 may be linear, branched, or cyclic, and preferably has 1 to 6 carbon atoms, and specifically includes methylene, dimethylene, trimethylene, methyldimethylene, and dimethyl. trimethylene group, hexamethylene group.

−〇−9−■− etc. are mentioned. The arylene group preferably has 6 to 10 carbon atoms, and specific examples include the following. The aralkylene group preferably has 7 to 12 carbon atoms, specifically -C)1□-Ol<Ht->-, -cH,co, -Q-
Examples include. As a method for substituting these alkylene groups, arylene groups, and aralkylene groups, the above-mentioned RL (11,
R1112, 1°3. RLO4, RLOゝ and R10
The same substituents as " can be mentioned. When there are two or more substituents, they may be the same or different.

Especially preferred as RL@1 is an alkylene group.

Specific examples of the compound represented by the general formula (X) are listed below, but the present invention is not limited thereto.

X-6H, NSO, NH30, NH.

Specific examples other than the above include compound example 1-(1
)~! -(27) etc.

The compound represented by the above general formula (X) is
It can be obtained based on the method described in No. 01861.

The amount of the compound represented by the general formula (II)=(X) to be added is preferably 0.01 g to 100 g per color developer IQ.
g, more preferably 0.1 g to 20 g.

In addition, the compounds of general formulas (If) to CX) of the present invention can be used in combination with a compound that directly stabilizes the developing agent in a system using an aromatic primary amine color developing agent.
It has particularly remarkable retention performance. Here, water-soluble antioxidants are generally known as "compounds that directly stabilize developing agents," such as hydroxylamines, hydroxamic acids, hydrazines, hydrazides, phenols, and α-hydroxyketones. , α-aminoketones,
and sugars.

The details of the compounds which are preferably used in combination are explained below. Hydroxylamines are represented by the following general formula (XI).

General formula (XI)
or represents an unsubstituted or substituted aryl group.

Rx11. It is preferable that R112 is an alkyl group or an alkenyl group, and it is more preferable that at least one of them has a substituent. Furthermore, R111 and R112 may be connected together with a nitrogen atom to form a petero ring.

Alkyl groups and alkenyl groups may be linear, monobranched, or cyclic, and substituents include halogen atoms (F, CQ,
Br, etc.), aryl groups (phenyl group, p-chlorophenyl group, etc.), alkoxy groups (methoxy group, ethoxy group, methoxyethoxy group, etc.).

Aryloxy groups (phenoxy groups, etc.), sulfonyl groups (methanesulfonyl groups, P-toluenesulfonyl groups, etc.), sulfonamide groups (methanesulfonamide groups, benzenesulfonamide groups, etc.), sulfamoyl groups (diethylsulfamoyl groups, (substituted sulfamoyl group, etc.)
, carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.), amide group (acetamide group, benzamide group, etc.), ureido group (methylureido group, phenylureido group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, etc.) , an aryloxycarbonylamino group (such as a phenoxycarbonylamino group), an alkoxycarbonyl group (such as a methoxycarbonyl group), an aryloxycarbonyl group (such as a phenoxycarbonyl group), and a cyano group.

Hydroxy group, carboxy group, sulfo group, nitro group, amino group (unsubstituted amino group, diethylamino group, etc.), alkylthio group (methylthio group, etc.).

Examples include arylthio groups (such as phenylthio groups) and heterocyclic groups (such as morpholyl groups and pyridyl groups). Here, R111 and R112 may be the same or different, and the substituents of R111 and H112 may also be the same or different.

Also, Rx11. The number of carbon atoms in H112 is preferably 1 to 10.

Particularly preferred are 1 to 5. Examples of the nitrogen-containing heterocycle formed by linking HAIL and R112 include a piperidyl group, pyrolisilyl group, N-alkylpiperazyl group, morpholyl group, indolinyl group, benztriazolyl group, etc. Can be mentioned.

Preferred substituents for R111 and R112 are a hydroxy group, an alkoxy group, a sulfonyl group, an amide group, a carboxy group, a cyano group, a sulfo group, a nitro group, and an amino group.

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

do not have.

U-1(i)H C,H,-N-C,H,OCH.

X[-2(i)H isoC,H,-N-C,H40CH3X[-3(i)
H CH, -N-C□H, OC, H.

Summer-160H CH3-N-C, H, SO, CtH.

XI-170H ■ C, H, So, C, H4-N-C, H45o, C2H.

Xl-34NH2OH The compound represented by general formula (XI) can be synthesized by the known method shown below.

U.S. Patent Nos. 3,661,996 and 3,362,96
No. 1, No. 3,293, No. 034, Special Publication No. 42-279
No. 4, U.S. Patent No. 3,491,151, U.S. Patent No. 3,655
, No. 764, No. 3,467.711, No. 3,455,
No. 916, No. 3,287,125, No. 3,287,1
No. 24.

These compounds may form salts with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, and acetic acid.

Hydroxamic acids are represented by the following general formula (Xfl).

General formula (Xll) In the formula, A121 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted 7-aryl group, a substituted or unsubstituted 7-mino group, a substituted or unsubstituted heterocyclic group,
Substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group.

Substituted or unsubstituted carbamoyl group, W1-substituted or unsubstituted sulfamoyl group, acyl group, carboxy group,
Examples of the m substituent representing a hydroxyamino group or a hydroxyaminocarbonyl group include a halogen atom, an aryl group, an alkyl group, an alkoxy group, an aryloxy group, a hydroxy group, a sulfonyl group, a sulfonamide group, and a sulfamoyl group.

Sulfo group, amide group, ureido group, cyano group, hydroxyaminocarbonyl group, carboxy group, nitro group, amino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic group (pyridyl group, morpholino group) etc.) etc.

Preferably, AX21 is a substituted or unsubstituted alkyl group, aryl group, amino group, alkoxy group, or aryloxy group. Particularly preferred examples include substituted or unsubstituted amino groups, alkoxy groups, and aryloxy groups.

The number of carbon atoms is preferably 1 to 1O.

Preferably x121 is -C-.

R'21 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted 7-aryl group.

At this time, A121 and HLII may be linked to form a ring structure, and the substituents are the same as those listed for A121. Preferably R1'' is a hydrogen atom.

yllL represents a hydrogen atom or a group that can become a hydrogen atom through a hydrolysis reaction.

Specific examples where yllL represents a group that can become a hydrogen atom through a hydrolysis reaction include the following.

l) A method of protection with an ester bond or a urethane bond, where Y0'' represents -c-n12''.

R″22 is a substituted or unsubstituted alkyl group.

Examples include a substituted or unsubstituted aryl group and a substituted or unsubstituted amino group.

2) The method of protecting with an imidomethyl capping group described in JP-A No. 57-158638, that is, Y121 is represents multiple atoms.

Specific compounds are shown below, but are not limited thereto.

Compound example X1l-2CH3-C-NH-○H ■ xn-3C, Hs○-C-NH-○H
2N-C-NH-OH (2) The above compound can be obtained based on the description in Japanese Patent Application No. 186559/1982.

Hydrazines and hydrazides are represented by the following general formula (XIII
) is a compound represented by

General formula (XIII) In the formula, -R131, R132, and R133 are hydrogen atoms, substituted or unsubstituted alkyl groups (1 to 20 carbon atoms, such as methyl group, ethyl group, sulfopropyl group, carboxybutyl group, hydroxyethyl group) ), aryl groups (having 6 to 20 carbon atoms, e.g. phenyl group, 2,5-dimethoxyphenyl group, 4-hydroxyphenyl group, 2-carboxyphenyl group, etc.) or heterocyclic groups (having 1 to 20 carbon atoms, e.g. pyridine) R134 represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted alkyl group (having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, or a sulfopropyl group).

carboxybutyl group, hydroxyethyl group, cyclohexyl group, benzyl group, etc.), aryl group (carbon number 6-2
01 For example, phenyl group, 2,5-dimethoxyphenyl group, 4-hydroxyphenyl group, 2-carboxyphenyl group, etc.), heterocyclic group (1 to 20 carbon atoms, e.g. pyridin-4-yl group, etc.), alkoxy group ( Carbon number 1-20
, such as methoxy group, ethoxy group.

methoxyethoxy group, benzyloxy group, cyclohexyloxy group, etc.), aryloxy group (carbon number 6 to 20, e.g. phenoxy group, p-methoxyphenoxy group, etc.), carbamoyl group (carbon number 1 to 201, e.g. carbamoyl group, N, N -diethylcarbamoyl group, hydrazinocarbonyl group, etc.), amino group (carbon number 0-20, e.g. amino group, N-phenylamino group).

hydrazino group, etc.).

i1゛" X131 represents a divalent group selected from -co-, -so, - or -C-, and n is 0 or 1. In particular,
When 0, 1<L34 represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and H13ff and R134 may jointly form a petero ring.

In general formula (XIII), HL31, RI2, RIJ3
is preferably a hydrogen atom or an alkyl group, and most preferably R131 and Rlxi are hydrogen atoms.

In general formula (XIII), R1ff4 is preferably an alkyl group, aryl group, alkoxy group, carbamoyl group, or amino group. X 13 L is -CO- or -5O
2- is preferred, and -CO- is most preferred).

C,H.

XIII-I NH,N C,H.

Xllll-2NH, NH-fCH, Soup So, HXIII
-3NH,NH-(CH2 juice 0HXIII-4NH,-
N N-CH.

C2H4OH XIII-5NH,N 2H40H XIII-6NH, NHCOCH.

Xllll-7NH,NHCOOC,H.

XIII-1o NH2NHCONH.

Xllll-12NH,NH30,H H XIII-13NH, NHCNH.

Xllll-14NH, NHCOCONHNH.

The above compound can be obtained based on the description in Japanese Patent Application No. 170756/1983.

Phenols are represented by the following general formula (Xm).

General formula (Xm In the formula, RL41 is a hydrogen atom, a halogen atom (F, C
Q, Br, etc.), alkyl groups (methyl, ethyl, butyl, etc.), aryl groups (phenyl, etc.), alkoxy groups (methoxy, ethoxy, etc.), aryloxy groups (phenoxy, etc.), carboxyl Base.

Sulfo group, carbamoyl group, sulfamoyl group, amide group (acetamide group, benzamide group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), ureido group, alkylthio group (methylthio group, etc.), arylthio group ( phenylthio group, etc.), nitro group, cyan group, amino group, formyl group, acyl group (acetyl group, etc.), sulfonyl group (methanesulfonyl group, benzenesulfonyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxy Represents a carbonyl group (such as a phenoxycarbonyl group), an alkoxysulfonyl group (such as a methoxysulfonyl group), and an aryloxysulfonyl group (such as a phenoxysulfonyl group).

When R141 is further substituted, examples of the substituent include a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, an amide group, a sulfonamido group, Ureido group, alkylthio group, arylthio group, nitro group, cyano group, amino group, formyl group, acyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group, and heterocyclic group ( morpholyl group, pyridyl group, etc.),
Furthermore, two or more and two or more kinds of these substituents may be substituted on RL41. Also, if there are two or more R141s, their types may be the same or different,
Furthermore, when they are adjacent to each other, they may be bonded to each other to form a ring.

The ring structure is a 5- to 6-membered ring, composed of carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, etc., and may be saturated or unsaturated.
1 and its substituents, the carboxyl group and the sulfo group are alkali divalent (Na, etc.) and also,
The amino group may form a salt with various acids such as hydrochloric acid.

R142 represents a hydrogen atom or a hydrolyzable group. A hydrolyzable group is a group that can become a hydrogen atom by hydrolysis, and a specific example thereof is R""=
-C-R14'' (where R143 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted amino group). In other words, protected with an ester bond or a urethane bond. This is the way to do it.

Another example is protection with an imidomethyl blocking group as described in JP-A-57-158638. That is, υ represents a plurality of atoms necessary to complete a 6-membered heterocycle), and m and n are each an integer from 1 to 5.

In general formula (XIV), R141 is preferably an alkyl group, a halogen atom, an alkoxy group, an alkylthio group, a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, an amino group, or an amide group.

They are a sulfonamide group, a nitro group and a cyano group. Among these, an alkoxy group, an alkylthio group, an amino group, and a nitro group are particularly preferable, and these are more preferably located at the ortho position or the rose position of the oo14 group, and 11
The number of carbon atoms in 41 is preferably 1 to 10, particularly preferably 1 to 6.

Preferred R142 is a hydrogen atom or a hydrolyzable group having 1 to 5 carbon atoms. Also, <oRL
42) When there are two or more groups, it is more preferable that they are located at the ortho position or the rose position with respect to each other.

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

OOH The above compound is Japanese Patent Application No. 61-188742 and No. 61-188742.
No. 203253.

α-hydroxyketones and a-aminoketones are represented by the following general formula (XV).

General formula (XV) In the formula, R15'' is a hydrogen atom, a W-substituted or unsubstituted alkyl group (C1-201, e.g. methyl group, ethyl group, hydroxymethyl group, methoxyethyl group, cyclohexyl group, etc.), aryl group (6 to 20 carbon atoms, e.g. phenyl group, 2-hydroxyphenyl group, etc.), alkoxy group (
C1-201, e.g. methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (C6-2
01 represents a phenoxy group, 4-methoxyphenoxy group, etc.) or an amino group (carbon number 0-201, e.g. amino group, N,N-diethylamino group, N-phenylamino group, etc.), R1!2 is a hydrogen atom, Represents a substituted or unsubstituted alkyl group (1 to 201 carbon atoms, e.g. methyl group, ethyl group, hydroxymethyl group, etc.) or aryl group (6 to 201 carbon atoms, e.g. phenyl group, 2-hydroxyphenyl group, etc.). RL m 2 may jointly form a carbocycle or a heterocycle.

XXfL represents a hydroxyl group, a substituted or unsubstituted 7-mino group (having 0 to 20 carbon atoms, such as an amino group, an N,N-diethylamino group, a morpholino group, etc.).

In general formula (XV), R15l is a hydrogen atom, an alkyl group,
An aryl group or an alkoxy group is preferred.

Further, RIS2 is preferably a hydrogen atom or an alkyl group.

(XV-1) ○ CH, CCH, CH (XV-4) ○ CH, CCH, NHC2H.

(XV-5) ○ HC-CH,OH CH The above compound can be obtained based on Japanese Patent Application No. 188741/1982.

The "saccharide" used in the present invention will be explained in detail.

Sugars (also called carbohydrates) are composed of fountain sugars and polysaccharides.
Monosaccharides, which often have the general formula CnH2,O, generally include aldehydes or ketones of polyhydric alcohols (called aldoses and ketoses, respectively) and their reduced, oxidized, and dehydrated derivatives, as well as amino sugars, thiosaccharides, etc. A general term for a wider range of derivatives such as sugars. Also, many M
The group refers to a product obtained by dehydration condensation of two or more of the above-mentioned monosaccharides.

More preferred among these saccharides are aldoses having a reducing aldehyde group and derivatives thereof, and particularly preferred among these are those corresponding to monosaccharides.

Specific examples of saccharides that can be used in the present invention are listed below, but the present invention is not limited thereto. (These optical isomers can also be used in the same way.)XV
I- to D-oxylose XVI-2: L-arabinose XVI-3: D-ribose XVI-4: D-deoxyribose XVI-5: D-glucose XVI-6: D-galactose XVI-7: D- Mannose XVI-8: Glucosamine XVI-9: L-Sorbose XVI-10: D-')Ruhitu)-C'))IiHuman-Az)CH,○H -C-○H The above compound is easily available as a commercial product.

The amount of the compounds represented by these general formulas (XI) to (XVI) to be added is Q, 01g to 50g per color developer IQ.
, preferably o, s g to 20 g.

In the present invention, the compound of formula (A), (B) or (C) having a low molecular weight or easily soluble in water may be added to the processing solution and incorporated into the sensitive material during the development process. A preferred method is to add it to the wood-philic colloid layer of the photosensitive material at the stage of producing the photosensitive material. The latter method is usually performed by dissolving gelatin in a high-temperature solvent (oil) Qi at a temperature of 170°C or higher at atmospheric pressure, a low-temperature solvent alone, or a mixed solvent of the above-mentioned oil and a low-boiling point solvent. It is prepared by emulsifying and dispersing it in an aqueous solution of woody colloids such as.

In unreleased I51, the compound of formula (A), (B) or (no) is preferably dissolved in a high-temperature organic solvent, and there is no particular restriction on the particle size of the emulsified dispersion particles, o, 05% to 0.
5 is preferable, and o, tJL to 0.3p is particularly preferable. In particular, from the viewpoint of the effect of the present invention, it is preferable that the compound of formula (A), (B) or (of) is co-emulsified with the coupler. In this case, oil /Coupler ratio is 0.00 to 2 in terms of weight ratio.
．． Preferably, it is 0.

Further, in the present invention, the proportion of the compound of formula (A), (B) or (C) is 1Xl0-2 per mole of coupler.
If the amount of the compound of formula (A), (B) or (C) (7), which is from 1 to 10 moles, preferably from 3XIO-2 to 5 moles, is less than 1XIO-2 moles, the effects of the present invention tend to be difficult to achieve. If the amount exceeds 10 moles, the coloring reaction tends to be inhibited or the compound of formula (A), (B) or (C) decomposes and the color image tends to be impaired. In particular, the amount of compound (B) added is 2xlO' to 2xlO' per mole of coupler.
A range of XIO-1 mole is preferred.

Specific examples of the oil include phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, dimethoxyethyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl). -p-t-butylphenyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide, dibutyl lauryl amide), fatty acid esters (e.g. dibutyl laurylamide), butoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), compounds containing epoxy rings (e.g. U.S. Pat. No. 4,540,657
(compounds described in the above), phenols (e.g. C5H11
(t) Ethers (eg phenoxyethanol, diethylene glycol monophenyl ether) may be mentioned. Examples of the low-temperature solvent used as a replenishing solvent include organic solvents with a boiling point of 30°C to 150°C at atmospheric pressure, such as lower alkyl acetates such as ethyl acetate, isopropyl acetate, butyl acetate, ethyl propionate,
methanol.

Ethanol, secondary butyl alcohol, cyclohexanol, fluorinated alcohol, methyl isobutyl ketone, β-
Ethoxyethyl acetate, methyl cellosolve acetate acetone, methyl acetone, acetonitrile, dioxane, dimethyl formamide, dimethyl sulfoxide,
Examples include chloroform and cyclohexane.

In addition, instead of high-temperature organic solvents, not only oil-based solvents (including those that are solid at room temperature such as wax) for additives such as couplers, but also latex polymers can be used, or couplers, color mixing inhibitors, etc. The additive itself, such as an ultraviolet absorber, may also serve as an oily solvent.

Latex polymers include acrylic acid methacrylic acid and its esters (e.g. methyl acrylate, ethyl acrylate, butyl methacrylate, etc.), acrylamide, t-butylacrylamide, methacrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate, etc.) , acrylonitrile, styrene, divinylbenzene, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid esters (e.g. maleic acid methyl ester), N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and 4-vinylpyridine, etc. A latex polymer produced using one or more of these seven polymers is used.

Examples of surfactants used in the present invention when dispersing a solution of the compound of formula (A>, (B) or (C)) alone or together with a coupler in an aqueous protective colloid solution include saponin, alkyl Examples include sodium sulfosuccinate and sodium alkylbenzenesulfonate.

It is preferred to use anionic surfactants having sulfonic acid groups, such as the compounds listed below, alone or in combination.

In addition, in unreleased 11, compound (A) or (B) may be added to any of the color developing solution, bleaching, fixing solution, washing solution, and rinsing solution, and in this case, the formula in these processing solutions (
The concentration of the compound A), (B) or (C) is between 10-5 mol/liter and 10-1 mol/liter.

Furthermore, the compound of the present invention can be used in combination with the antioxidants or antifading agents shown below.

Incidentally, representative patents that describe agents or antioxidants as anti-fading agents include the following IJ patents.

U.S. Patent No. 3,935.016, U.S. Patent No. 3.982.9
No. 44, No. 3,700,455, No. f53,764
, No. 337, No. 3,432,300, No. 3,57
No. 4,627, No. 3,573.050, No. 4,2
54,216 specification, JP 55-21004, JP 54-145530, JP 52-152225, JP 5
No. 3-20327, No. 53-17729, JP-A-61
-72246, 61-73152, 61-90
No. 155, No. 61-90156, No. 61-14555
No. 4, specification No. 55-6321.

Japanese Patent Publication No. 54-12337, Specification No. 48-31625, British Patent No. 1,347,556, British Patent Publication B1
No. 42,066.975 The ultraviolet absorber that can be used for unreleased IJ+ is available from Research Disclosure (R,
D,) No. 17643 No.
) is a benzotriazole derivative represented by

(In the formula, R51, R52' R5: l, R54, R55
may be the same or different, hydrogen atom, alkoxy group.

Represents an alkyl group, a halogen atom, or an alkoxycarbonyl group.

H3 10"0゛JN しt'i3 In the color photograph manufacturing method of this ff1l!II, except for using the compounds of formulas (A), (B) and (C) in L by the method in U. 1 is the same as a normal color photograph manufacturing method.

The color photographic light-sensitive materials to which the color photographic production method of the present invention can be applied are not particularly limited, and in addition to color paper, color negative films for general use or movies, color reversal films for slides or televisions, Typical examples include color positive film and color reversal vapor. Unreleased IJJ is also research disclosure 17123 (197
It can also be applied to black-and-white light-sensitive materials using a mixture of three color couplers as described in J.

Therefore, the couplers used in this color photographic light-sensitive material are not particularly limited, but examples include the following.

(a) Yellow coupler couplers represented by general formulas (Y-I) and (Y-II).

General formula (Y-I) (wherein = RII represents a 22-substituted or non-21-substituted N-phenylcarbamoyl group, and Zl is a compound that can be separated in the reaction with an oxidized product of an aromatic primary amine color developing agent. General formula (y-n) (wherein, R1□ represents a substituted or unsubstituted N-phenylcarbamoyl group, and Z1□ represents an oxidized product of an aromatic primary amine color developing agent. R1□ represents a hydrogen atom or a substituent; S represents a group capable of leaving in the reaction of
General formula (Y-1), (Y-2) representing an integer of ~5
A typical chemical structure of the yellow coupler represented by is as described in the following American time, n specification table, and the numbers in parentheses represent the Carano number giving a detailed explanation of the chemical structure.

U.S. Patent No. f 53,894,875 (1-2).

No. 3,408,194 (2-3), No. 4.404.2
No. 74 (3-17), No. 4,022,620 (3-7)
), No. 4,057,432 (1-4), etc.

(b) Magenta coupler Couplers represented by the following general formulas (M-I) and (M-n).

General formula (M-I) Ar (wherein R2□ represents an alkyl group, aryl group, acyl group or carbamoyl group, Ar is phenyl group)
Z represents a phenyl group substituted with 21 groups or one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups, or acylamino groups;
2□ represents a hydrogen atom or a group that can be separated in the reaction with the oxidized product of the aromatic primary amine color developing agent) General formula (M-■) (wherein, R22 is a hydrogen atom or a 2t!!78 group , and Z21 represents a hydrogen atom or a group that can be separated in reaction with an oxidized product of an aromatic primary amine color developing agent, or -
Represents NH-, z -z bond and z23-z22
One of the bonds is a dimeric bond and the other is a single bond.

When Z23-Z2□ is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring.) General formula (M-1), (M-2
) The typical chemical structure of magenta coupler is:
The following represents the content described in the U.S. patent of Denshosaku et al.

The numbers in parentheses represent the number of columns or pages in which detailed explanations of chemical structures II are given.

U.S. Patent No. 53,519,429 (2-6), 3,
558,319 (2-3), 3,725.067 (2-8), 3,935,015 (3-7), 4
, 241,168 (2-14), 4,351,89
No. 7 (2-6), No. 4.367.282 (3-1O)
, No. 4,540.654 (2-8), JP-A-61-61
5245 (pp. 378-384), WO-86-191
5 (pages 5-10) etc.

(C) Cyan coupler A coupler represented by the following general formula (C-I).

General formula (C-I) f-1 For.

(In the formula, R31 represents an alkyl group, a cycloalkyl group, an aryl group, an amino group, or a heterocyclic group.

R32 represents an acylamino group or an alkyl group.

R33 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R may be bonded with R32 to form a ring; Z31 is a hydrogen atom.

A typical chemical structure of a cyan coupler represented by the general formula (c-B), which represents a group that can be separated in reaction with a halogen atom or an oxidized product of an aromatic primary amine color developing agent, is shown in the following U.S. patent specification. The numbers in parentheses represent the number of columns in which the chemical structure is explained in detail.

U.S. Patent No. 2,920,961(1), U.S. Patent No. 3.77
No. 2,002 (1-3), No. 3.864.366 (
2-6), No. 4,124,396 (2), t54
, No. 333,996 (2-8), No. 4,565,77
No. 7 (3-5), No. 4,564,586 (2-4)
etc.

Each of the above couplers has a secondary form or a higher multimer form with yf
j may be formed.

Specific examples of these couplers are listed below (this ffi
Of course, IJI is not limited to this.

(y-2) I (Y-3) t (Y-5) α (y-13) C1 (Y-14) α (y-ls) α (Y-20) (Y-21) H3 (Y- 22) IA (Y-23). 2 Shih3 (M-1) OC113 (M-16) (M-17) Shil (M-18) (M-26) (M-29) (M-30) (M-32) (M-33 ) (M-34) CH so(M 3(i) (M-37) 豐(M-38) 6ri(M-39) (M-40) (C-1) (C-2) α (c -3) (C-4) (C-5) H (C-6) H しV (C-9) l4 (C-12) (C-13) (C-14) (C-15) (C -16) 2H5 (C-17) (C-18) (C-19) (C-20) 5ti+1 to ltl (C-24) Oll (C-25) (C-26) (C-28) i11 books In the method for producing a color photograph of the invention, a conventional photographic processing method is applied except that a compound of formula (A), (B) or (() is appropriately contained in the processing solution.

The shapes of the silver halide grains used in the present invention include cubic, octahedral, dodecahedral, and tetradecahedral crystal shapes, and irregular crystal shapes such as spherical shapes. Grains in the form of two flat plates having a thickness ratio of 5 or more may be used, or emulsions having composite forms of these various crystal forms or mixtures thereof may be used.

The composition of silver halide includes silver chloride, silver L, and mixed silver halide.The silver halide preferably used in the present invention does not contain silver iodide, or even if it contains silver iodide, it contains less than 3% mole of salt (iodide). ) silver bromide, (iodine oligochloride or (iodine) silver bromide.

The average grain size of the silver halide grains is 2P or less and 0.
ip- or higher is preferable, but 1.3JL is particularly preferable.
Below 0. Is the particle size distribution greater than or equal to tsp narrow or wide? In order to improve graininess and sharpness, the number of particles or the average particle size is ±40
% or less, preferably within ±30%, more preferably 12
It is preferable to use a so-called "monodispersed" silver halide emulsion in the present invention, which has a narrow grain size distribution in which 95% or more of all grains fall within 0%, and also satisfies the target gradation of the light-sensitive material. In order to increase Can be applied in multiple layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The silver halide emulsion used in the present invention contains sulfur or selenium I inside or on the grains. Chemical sensitization can be carried out by J sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. A detailed example can be found in the patent described in, for example, Research Disclosure Magazine No. 17643-m (published December 1978), page 23.

Furthermore, the silver halide emulsion used in the present invention is as follows.

Using cyanine dyes, merocyanine dyes, etc.

Spectral sensitization can be achieved by conventional methods.

It is preferable that the color developer used in the present invention does not substantially contain benzyl alcohol.When preparing a low replenishment type color developer replenisher, if it contains benzyl alcohol, the dissolution rate is slow and it takes time to dissolve. This may result in the formation of a tar-like substance. On the other hand, a color developing solution that does not contain benzyl alcohol has the advantage that even if it is a low replenishment type, it has a short dissolution time and does not generate tar-like substances, making it easy to prepare a low replenishment type developer replenisher.

In addition, by preventing fluctuations in the solution composition during continuous processing using a color developing solution that does not contain benzyl alcohol, the replenishment amount can be reduced to less than half the standard replenishment amount (165 m
! /rn' or less), there is no generation of tar-like substances,
A consistent finish with no change in stain can be obtained.

As additives used in color developing solutions,
Specification No. 1667, pages 14 to 22, patent application 1982-11
Specification No. 8418, pages 545 to 50, patent application No. 1984-3
Various compounds described in IJ1 specification No. 2462, pages 11 to 22 can be used. Furthermore, the color developer contains tetrazaindenes and benzindazoles as antifoggants.

Benzotriazoles, benzimidazoles.

Particular preference is given to using benzothiazoles, benzoxazoles, heterocyclic thiones, such as 1-phenyl-5-mercaptotetrazole, aromatic and aliphatic mercapto compounds.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be carried out simultaneously with the fixing process as a one-bath bleach-fixing process, or may be carried out separately.In order to further speed up the process, a bleach-fixing process may be performed after the bleaching process. , a method of bleach-fixing after fixing is also possible 0 An aminopolycarboxylic acid iron complex salt is usually used as a bleaching agent in the bleach or bleach-fix solution of the present invention 6 Used in the bleach or bleach-fix solution of the present invention As additives, various compounds described on pages 522 to 30 of Japanese Patent Application No. 61-32462 can be used.

If the color developing solution does not contain benzyl alcohol, the leuco conversion reaction of the cyan dye in the bleach-fix solution is difficult to occur, so the pH of the bleach-fix solution or the amount of oxidizing agent can be lowered.

The replenishment amount of bleach-fix solution is usually about 330 mt/rrl''
If the color developer does not contain benzyl alcohol, it is possible to lower the replenishment amount to 60 d/rn' or less.

After the desilvering process (bleach-fixing or fixing), water washing and/or stabilization is performed.Additives used in the water washing and stabilization process include those from page 30 of Japanese Patent Application No. 32462/1983. A variety of compounds described on page 36 can be used.

The amount of replenisher in each processing step is preferably small. The amount of replenisher is preferably 0.1 to 50 times, more preferably 3 times, the amount of prebath brought in per unit surface area of the photosensitive material.
~30 times.

(Example) Next, the present invention will be explained in more detail based on examples.

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

(Preparation of 1st fi coating solution) Yellow coupler (ExY-1) and (ExY-2)
10.2g, 9.1g and color image stabilizer (Cpd-
1) Add and dissolve 27.2 cc of ethyl acetate and 7.7 cc (8.0 g) of high boiling point solvent (Solv-1) to 4.4 g, and dissolve this solution in a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. 185cc
It was emulsified and dispersed. This emulsified dispersion and emulsions EMI and EM2 were mixed and dissolved, and the gelatin concentration was adjusted to have the following composition to prepare a first layer coating solution. 2nd to 7th layer
The layer coating solution was also prepared in the same manner as the first layer coating solution.

1-oxy-3,5-dichloro-5-)-riazine sodium salt was used as the gelatin hardening agent for each layer.

Moreover, Cpd-2 was used as a thickener.

(Layer composition) The composition of each layer is shown below, the numbers are coating amount (g/rn')
represents. The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminated paper [white pigment (T i O2) on the polyethylene on the first layer side
Contains blue dye. ] 1st layer (blue sensitive layer) Monodisperse silver chlorobromide emulsion (EMI) spectrally sensitized with a sensitizing dye (ExS-1)...0.13 sensitizing dye (ExS-1)
Monodisperse silver chlorobromide emulsion (EM2) spectrally sensitized with S-1)
) ・-0,13 gelatin
...1.86 Yellow Cabler (ExY-1)
-0,44 yellow coupler (E x Y -2)
...0.39 color image stabilizer (Cpd-1) ・
...0.19 solvent (So 1v-1) -
0.35 2nd layer (color mixing prevention layer) Gelatin ・-0.99 Color mixing prevention agent (Cpd-3) ・・・0.08 3rd layer (
Green-sensitive layer) Monodisperse silver chlorobromide emulsion (EM3) spectrally sensitized with sensitizing dyes (ExS-2, 3)...0,05 sensitizing dye (ExS-2, 3)
-2,3) monodisperse silver chlorobromide emulsion (EM
4)...0.11 gelatin
...1.80 magenta coupler (ExM-1) -
0,39 Color image stabilizer (Cpd-4)...0
．． 20 Compound of the present invention See Table 1 Solvent (Solv-2)...0.12 Solvent (Solv-3) -0,25 4th layer (ultraviolet absorbing layer) Gelatin'...1.60 Ultraviolet light Absorbent (Cp d-7/ Cp d-8/Cp d-
9=3/2/6 : Weight ratio)・-0,70 Color mixing prevention agent (
Cpd-10) ...0.05 solvent (So 1
v-4) -0,27 5th layer (red-sensitive layer) Monodisperse silver chlorobromide emulsion (EMS) spectrally sensitized with sensitizing dye (ExS-4,5)...0.07 sensitization Pigment (E
xS-4, 5) Spectrally sensitized monodisperse silver chlorobromide emulsion (
EM6) ...0.16 gelatin
...0.92 cyan coupler (ExC-1)
・=0.32 color image stabilizer (Cpd-8/Cpd-
9/Cpd-12=3/4/2: weight ratio)...0.
17 Polymer for dispersion (Cpd-11) ...0.2
8 solvent (So 1 v-2) -0,20
6th layer (ultraviolet absorbing layer) Gelatin...0.54 ultraviolet absorber (Cpd-7/Cpd-9/Cpd-12-1
15/3: weight ratio)・-0,21 solvent (So 1 v
-2) -0,08 7th layer (protective layer) Gelatin...1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%)...0,17 Liquid paraffin...0.03 . At this time, Cpd-
13, Cpd-14 was used.

Further, in each layer, Alkanol
xF-120 (manufactured by Dainippon Ink Co., Ltd.) was used. Cpd-15,16 was used as a silver halide stabilizer.

Details of the emulsion used are as follows.

EMI Cube 1.0 80 0.08EM2
Cube 0.75 80 0.07EM3
Cube 0.5 83 0.09EM4 Cube 0.4 83 0.1OEM5 Cube 0.
5 73 0.09EM6 Cube 0.4
73 0.10 The structural formula of the compound used is as follows.

ExY-1 I H3 xC-1 xS-I xS-2 xS-3 xS-4 xS-5 pd-1 pd-2 pd-3 H pd-4 pd-7 pd-8 pd-9 Cpd-10 0H 11 Cpd-11 Solv-1 dibutyl phthalate 5 olv-2 tricresyl phosphate 5 olv-3 trioctyl phosphate 5 OIV-4) linonyl phos 7
Ato pd-13 Cpd-14 Cpd-15 H Cpd-16 After exposing the above photosensitive material through an optical wedge, it was processed through the following steps.

Processing process list - Time color development
38℃ 1 minute 40 seconds U white 30-3
4℃ 1 minute 00 seconds rinse ■ 30-34℃
Rinse for 20 seconds ■ Rinse for 20 seconds at 30-34℃ ■ Dry for 20 seconds at 30-34℃
70-80℃ 50 seconds (rinse ■→■
A three-tank countercurrent flow system was adopted. ) The composition of each treatment liquid is as follows.

Color developer water 800
mfL diethylenetriamine pentavinegar @ 1. Og nitrilotriacetic acid 2.0g Benzyl alcohol 16mJ1 Diethylene glycol 10ml Additives A, B
See table PJ1 Potassium bromide
o, 5g potassium carbonate 3
Add 0 g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl 5.5 g methyl-4-aminoaniline sulfate and
5℃) 10.251n main 1st section water 400
rrQ.

Ammonium thiosulfate (70%) 200m4 Sodium sulfite 20g Add water
1000mfLp100℃)
7.00 anal water shame mother liquor,
Both the replenisher and the tap water were mixed with an H-type strongly acidic cation exchange resin (Amberlite IR-12θB manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-4 manufactured by Rohm and Haas).
Water was passed through a mixed bed column packed with 00) to reduce the concentration of calcium and magnesium ions to 3 mg/fL or less, followed by 20 m of sodium isocyanurate dichloride.
g/l and 1.5 g/l of sodium sulfate were added.

The pH of this liquid is in the range of 6.5 to 7.5.

Next, for each of the above-mentioned developed photosensitive materials, the G density of the non-image area was measured one hour after processing, and after being left at 60°C and 70% RH for two months, the non-image area was again measured. The concentration of stain was measured, and the increase in stain (ΔD,) from 1 hour after treatment was measured.

These results are referred to as Experiment No. 1-27.As is clear from Table 1, compared to Experiments Nos. 1 to 4, Experiments Nos. 5 to 27 had a higher staining effect after treatment according to the method of the present invention than Experiments Nos. 1 to 4. It can be seen that -H can be significantly suppressed.

Example 2 Same as Example 1 except that the compound of the present invention was used in the fifth layer instead of the third layer of the photosensitive material, or the dispersing polymer used in the fifth layer was removed and the compound of the present invention was used instead. Similarly, photosensitive materials of Experiment Nos. 1 to 24 shown in Table 2 below were prepared. 0 The photosensitive materials prepared above were subjected to photographic processing under the processing conditions shown below. The stain of an image formed in the same manner was measured. The results are shown in Table 2.

Processing process 1-billion absorption color development
38℃ 1 minute 40 seconds bleach fixing 30~3
4℃ 1 minute OO seconds rinse ■ 30-34℃
Rinse for 20 seconds ■ 20 seconds at 30-34℃ ■ Dry for 20 seconds at 30-34℃
70 to 80'C for 50 seconds (3-tank countercurrent flow method from rinsing ■ to ■). The composition of each treatment solution is as follows.

Color developer water 80
0ml diethylenetriaminepentaacetic acid 1.0g nitrilotriacetic acid 2.0g triethylenediamine (1,4-diazabicyclo[2,2,2cos, 0g octane) Potassium bromide 0.5g potassium carbonate 30g thyl-4-aminoaniline sulfate Add 4.0g of diethylhydroxylamine water to 1000ml pH (25°C)
10.25 type lLL Hinoki 400m
Ammonium thiosulfate (70%) 200ml Sodium sulfite 20g Add water
1000m pH (25℃)
7.00 Rinse liquid ion exchange water (calcium, magnesium 3pp each
m or less) From Table 2, as shown by IJJ et al., it can be seen that the rise in stain after photographic processing is significantly suppressed according to the undeveloped method. Furthermore, this effect was particularly remarkable when a dispersing polymer was used in the method of the present invention.

Example 3 Compound (A-35) or (B-74) or (C-
A photosensitive material was prepared in the same manner as in Example 1 except that 2) was used, and photographic processing and storage tests were conducted in the same manner as in Example 1, and a remarkable stain suppressing effect was obtained.

Example 4 A multilayer photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

(Preparation of first layer coating solution) 27.2 c of ethyl acetate was added to 19.1 g of yellow coupler (ExY-1) and 4.4 g of color image stabilizer (Cpd-1).
c and high boiling point solvent (Solv-1) 7.7cc (8
, 0 g) was added and dissolved, and the Kono solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. This emulsified dispersion and emulsions EM7 and EM8 were mixed and dissolved, and the gelatin concentration was adjusted to tJRm to prepare a first layer coating solution so as to have the following composition. Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. The gelatin hardening agent for each layer is 1
-oxy-3,5-dichloro-5-) riazine sodium salt was used.

Moreover, Cpd-2 was used as a thickener.

(Layer composition) The composition of each layer is shown below, the numbers are coating amount (g/rn')
represents. The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminated paper [white pigment (T i O2) on the polyethylene on the first layer side
] 1st layer (blue-sensitive layer) Monodisperse silver chlorobromide emulsion (EM7) spectrally sensitized with a sensitizing dye (ExS-1) ・・・o, 15 sensitizing dye ( Ex
S-1) Spectrally sensitized monodispersed silver chlorobromide emulsion (EMS
) -0,15 gelatin
・-1,86 yellow coupler (ExY-1) -0
,82 color image stabilizer (Cpd-2) -0,19
Solvent (Solv-1) ・=0.35 second
Layer (color mixing prevention layer) Gelatin...0.99 Color mixing prevention agent (Cp d -3) = 0, 08f
Monodisperse silver chlorobromide emulsion (EM9) spectrally sensitized with 53M (green) sensitizing dye (ExS-2, 3) -0,12 sensitizing dye (ExS-2, 3)
Monodisperse silver chlorobromide emulsion (E
M to) ...0.24 gelatin
-...1.24 Compound of the present invention
m3 table reference magenta coupler (ExM-1)
-0,39 color image stabilizer (Cpd-4) -0
,25 color image stabilizer (Cpd-5) -0,12
Solvent (So] v-2) = -0,25
4th layer (ultraviolet absorbing layer) Gelatin...1.60 ultraviolet absorber (Cp d -6/Cp d -7/Cp
d-8=3/2/6: weight ratio)...0
．． 70 Color mixing prevention agent (Cpd-9)...0,
05 Solvent (Sol v-3) = -0,
42 5th layer (red sensitive layer) Monodisperse silver chlorobromide emulsion (EM 11) spectrally sensitized with sensitizing dye (ExS-4,5)...0.07 sensitizing dye (ExS-4) , 5) Monodisperse silver chlorobromide emulsion (E M 12) spectrally sensitized with 0.16 gelatin
...0.92 cyan coupler (
ExC-1) = 1.46 cyan coupler (ExC
-2) ...1.84 color image stabilizer (Cpd-7/
Cpd-8/Cpd-10=3/4/2: weight ratio)・
・・0,17 dispersion polymer (Cpd-11) ・
-0,14 solvent (So 1 v l)
=・0.20 6th layer (ultraviolet absorbing layer) Gelatin ...0.54 ultraviolet absorber (Cpd-6/Cpd 8/Cpd-10=
115/3: East μ ratio)...0.21 Solvent (So I v-4)...0.08 Seventh layer (protective layer) Gelatin - Acrylic modified copolymer of 1,33 polyvinyl alcohol (modified -0.17 liquid paraffin...0.03 At this time, as an irradiation prevention dye, Cpd-
12, Cpd-13 was used.

Furthermore, each layer contains Alkanol
cx F-120 (manufactured by Dainippon Ink Co., Ltd.) was used. cpa-14,15 was used as a silver halide stabilizer.

Details of the emulsion used are as follows.

Ultraviolet absorber (Cpd-6/Cpd-8/Cpd-10
=115/3: weight ratio)...0.21 solvent (So
l v-4) ...-0,08 7th layer (protective layer) Gelatin - Acrylic modified copolymer of 1,33 polyvinyl alcohol (degree of modification 17%) ...0.17 Liquid paraffin ...0. 03 Also, at this time, as the irradiation prevention dye, Cpd
-12 and Cpd-13 were used.

Furthermore, it is used as an emulsifying dispersant and coating aid in each layer.

Alkanol XC (Dupont), sodium alkylbenzene sulfonate, succinate and Mag
efacx F-120 (manufactured by Dainippon Ink Co., Ltd.) was used. Cpd-14,1 as a stabilizer for silver halide
5 was used.

Details of the emulsion used are as follows.

EM7 Cube 1.1 1.0 0.1OEM8
Cube 0.8 1.0 0. lOEM9 Cube 0.45 1.5 0.09EMIO Cube 0
．． 34 1.5 0.09EMII Cube 0.4
5 1.5 0.09EM12 Cube 0.34
1.6 0.10 The structural formula of the compound used is as follows.

xY-1 0th base xC-1 xS-I xS-2 xS-3 xS-4 xS-5 pd-1 C, pd-2 pd-3 Cpd-4 Cpd-5 Cpd-6 C4Hg (tl Cpd-7 H Cpd-8 Cpd-9 H Cpd-10 Cpd-11 1-1 (CH2CHEtoi "--(n=100--10
”']2C0NHCaHolt+ Cpd-12 Cpd-13 Cpd-14 H Cpd-15 XC-1! Cresyl Phosphate Next, for each of the above-mentioned photosensitive materials that had been developed, the G density of the non-image area was measured one hour after processing, and then the G density was measured at 60°C-7.
After leaving it for 100 F1 under 0% RH, the density of the non-image area was measured again. Table 3 shows the increase in stain over time after treatment.

After exposing the two-leg photosensitive material to light through an optical wedge, it was processed through the following steps.

Processing process Temperature Time Color development 35℃ 45 seconds bleach fixing
30-35℃ 45 seconds rinse ■ 30-35
℃ 20 seconds rinse■ 30-35℃ 20
Second rinse■ 30-35℃ 20 second rinse■
Dry for 30 seconds at 30-35℃ 70
~80''C for 60 seconds (3-tank countercurrent force type from rinsing ■ to ■) The composition of each treatment solution is as follows.

Color developer water 800m
1 Additives A, B Refer to Table 3 Sodium chloride 1.4g Potassium carbonate 25g Add thyl-4-amine aniline sulfate solution.
Ammonium thiosulfate (70%) 100 mJJ Sodium sulfite 18 g Ammonium bromide 40 g Ice vinegar #
Add 8g wood
1000mLp1000℃) 5.5 Rinse solution ion exchange water (3pp each for calcium and magnesium
m or less) As is clear from Table 3, it can be seen that the increase in stain after treatment can be significantly suppressed by the Honsori 1 method compared to the comparative example.

Example 5 A photosensitive material similar to that of Experiment No. 1 or 2 of Example 2 was used, except that the compound of the present invention used in the third layer of Example was used in the first layer or the fifth layer. When the sample was prepared and treated in the same manner as in Example 3, significant suppression of staining was observed.

Example 6 A color photographic material was prepared by coating a paper support laminated on both sides with polyethylene and coating the following 12 layers starting from the first layer. The first layer coating side of the polyethylene contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive Layer Composition) The components and coating amounts in units of g/rn' are shown below. For silver halide, the coating amounts are shown in terms of silver.

1st layer (antihalation layer) Black colloidal silver...-(110 Gelatin...2.00 2nd layer (
Low sensitivity red sensitive layer) 3.5 mol%, average particle size 0.5 JL)...0.15
Gelatin -1,00 Compound A-35 of the present invention (LOmo 1% relative to coupler) Cyan coupler (ExC-1)...0.30 Antifading agent (Cpd-1,2,3)... 0.15 Coupler solvent (Solv-1,2)-0.06 Third layer (low sensitivity red sensitive layer) 8.0 mol%, average particle size 0.7)...0.11 Gelatin... 0.50 cyan coupler (ExC-1)...0.10 anti-fading agent (CpcL-1,2,3)-0,05 coupler melt (Solv-1,2)-0,04 4th layer ( (intermediate layer) Yellow colloidal silver -...0.02 Gelatin...1.00 Shi color development inhibitor (Cpd-4) -0,08 Color mixing inhibitor solvent (So 1 v-3,4)...0 .16 Polymer latex (Cpd-5) -O,IO 5th layer (low sensitivity green sensitive layer) %, average particle size 0.4μ) -0,20 Gelatin -0,70 Magenta coupler (ExM-1) =・0.40 Anti-fading agent (Cpd
-6) -0,05 anti-fading agent (Cpd-7)
-0,05 anti-fading agent (Cpd-8)
+++o, 02 coupler solvent (Solv-3,5)
・=0.15 6th layer (high sensitivity green sensitive layer) Gelatin ...0.70 Magenta coupler (ExM-1) ・-0-40 anti-fading agent (Cp d -6) ・-0,05 anti-fading Agent (Cpd-7) ...0.05 Anti-fading agent (Cpd-8) ...0.02 Coupler solvent (Solv-3,5) -0.15 7M (yellow filter single layer) Yellow colloidal silver・・0.20
Gelatin...1.00 Color mixture prevention agent (Cpd-4) ・-0,06 Color mixture prevention agent solvent (Cpd-3,5)・-o, is Bommer latex (Cp d-5)・-0,10 8th layer (low sensitivity blue sensitive layer) Gelatin -0.50 shots 1
51 Compound C-2... (10 mol to coupler
%) Yellow coupler (ExY-1) -0,20 Stain inhibitor (Cpd-8) -0,001 Power puller soluble g (Solv-2) -0,05 9th layer (High 1ii
L degree blue sensitive layer) Le%, average particle size 1.4IL) -0,20 gelatin -O,SO Compound of the present invention C-2... (10 mo1% based on coupler) Yellow coupler (ExY-1) -0,20 Stain inhibitor (Cpd-8) -0,001 Coupler Solv 11 (Solv-2)...-0,05 1st O layer (
Ultraviolet absorption layer) Gelatin -1,50 Ultraviolet absorption 1 (Cpd-9, l, 3) -1,00 Color mixing inhibitor (C
pd-10) -0,08 UV absorber solvent (S
o l v-2) -0,30 Irradiation prevention dye (Cpd-11) -0,04 11th layer (protective layer) Gelatin...1.00 Gelatin hardening agent (H-1) -...0 .17Ex
S-1 ExS-2 ExS-3 ExS-4 O3H pd-1 pd-2 pd-3 9d-4 H pd-5 Polyethyl acrylate pd-6 pd-8 CH3CH3 pd-9 pd-10 pd-11 pd- 12 SO3K 5ol to Sυ3
v-1 di(2-ethylhexyl) phthalate 5olv-2 trinonyl phosphate 5olv-3)-licresyl phosphate 5olv-4
Dibutyl phthalate 5olv-5 Triobutyl phosphate H-11,2-
Bis(vinylsulfonylacetamido)ethane After exposing the silver halide color photographic material prepared as described above, it was processed according to the following steps.

Processing process Time Temperature 1st development 60 seconds 38°C 1st water washing 5 Q II 33 II color development buoy 5 pieces 90 horns 38 horns t)l White 60 no!
38 ll bleach constant M60 II 38 III
2Washing 60n 33n Drying 451n 75u The composition of each treatment solution was as follows.

U4 mother liquor complement nitro-N,N,N-)-limethylene 1. Og
1.0g Phosphonic acid, pentasodium salt, diethylenetriamine pentaacetic acid, pentasodium 3. Og
3.0 [thorium salt potassium sulfite 30.0g
30.0g potassium thiocyanate
1.2g 1.2g charcoal potassium
35.0g 35.0g Potassium hydroquinone monosulfonate 25.0g 25.
0gum■-Phenyl-3-pyrazolidone 2.0g
2.0g potassium bromide
0.5g ---1--potassium iodide
5.0mg -------
Add water 100100O
looomJlpH9,069,70 pH was adjusted with hydrochloric acid or potassium hydroxide.

First washing liquid mother liquor Fubi ethylenediaminetetramethylenepho 2.0g
Add the same disodium sulfonate phosphate 5.0g water to the mother liquor and adjust the pH to 1000m
7,00 pH was adjusted with hydrochloric acid or potassium hydroxide.

Come on L! Mother liquor 6-way benzyl alcohol 15.0m sentence
18.0rrl diethylene glycol
12. OmfL 14. OmfL3.6-Sythia 1
．． 8-Octane 2.00g 2.50g Nitrilo-N,N,N-)-rimethyle 0.5g
0.5g Phosphonic acid 5sodium salt Diethylenetriaminepentaacetic acid 5s 2. Og
2-Qg thorium salt diethylhydroxylamine 4.2g
4.2g DABCO5.0g 5.0g N-ethyl-N-(β-methanesul 6.0g
9. Qg (honamidoethyl)-3-methyl-aminoaniline sulfate ethylenediamine 10.0m 12.0mm Total optical brightener diaminostilbene type)
1.0g 1.2g Potassium Bromide
0.5g ---- Potassium iodide 1° Omg
−−−−−−Add water
lOolooOloooomuppH10,0611
,00 pH was adjusted with hydrochloric acid or chloride.

Bleach liquid FU solution □ Ethylenecyamine 4-diamine acid, 2-natrium lo, og
Add the same lamb salt ethylenediaminetetraacetic acid, Fe(m), 120g ammonium, dichloroammonium bromide, 100g ammonium nitrate, 10g water to the mother liquor, and make 1000ml of pH 6.
, 30 pH was adjusted with acetic acid or aqueous ammonia.

Bleach-fix solution Mother solution Replenisher Ethylenediamine tetraacetic acid, di-sodium 5. Og
Mother liquor contains the same rum, dihydrate ethylenediaminetetraacetic acid, Fe([II), 80.0
g ammonium l hydrate sodium sulfite is, 0 g ammonium thiosulfate (700 g/Jl) 160 m
fL2-mercapto-1,3,4-triazole 0.5gpH
6,50 pH was adjusted with acetic acid or aqueous ammonia.

2nd washing solution Both the mother solution and the replenisher are a mixture of tap water filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas). Water was passed through a bed column to reduce the concentration of calcium and magnesium ions to 3 mg/l or less, followed by sodium incyanurate dichloride 20 mg/l.
1 and 1.5 g/Jl of sodium sulfate were added. The pH of this liquid is in the range of 6.5 to 7.5.

When the above photosensitive material was processed, B and G were obtained as in Example 1.
The increase in stain after treatment was significantly suppressed in both the R8 and R8 layers.

Example 7 Emulsion A and Emulsion B were produced as follows.

4 seedlings A An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added to an aqueous gelatin solution containing 0.3 g of 3.4-dimethyl-1°3-thiazoline-2-thione per mole of Ag at about 75°C with vigorous stirring. It took 20 minutes to add them at the same time, and the average particle size was o, 4. An octahedral monodispersed silver bromide emulsion of m was obtained. A chemical sensitization treatment was carried out by adding sodium thiosulfate and gold chloride (tetrahydrate) in an amount of 6 mg each per mole of silver to this emulsion and heating the emulsion at 75° C. for 80 minutes. Using the silver bromide particles thus obtained as cores, the particles were further grown by further treatment for 40 minutes in the same precipitation environment as the first time.
Finally, an octahedral monodisperse core/shell silver bromide emulsion with an average grain size of 0.7 μm was obtained. After washing with water and desalting, this emulsion contains 1 silver
Sodium thiosulfate and chloroauric acid (tetrahydrate) were added in an amount of 1.5 mg per mole, and heated at 60° C. for 60 minutes to perform a chemical sensitization treatment, thereby obtaining an internal latent image type silver halide emulsion A.

4 Mouse 1 Gold chloride # (4
Using 20 mg each of sodium thiosulfate (water salt) and sodium thiosulfate, 1 mol each per 81 moles was then subjected to surface chemical sensitization.
．． Internal latent image type silver halide emulsion B was obtained in exactly the same manner as emulsion A except that 5 mg of chloroauric acid (tetrahydrate) and 6.5 mg of sodium thiosulfate were used.

A full multilayer color photographic paper having the layer structure shown in Table 1 was prepared using a core/shell type internal latent image type emulsion on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

First layer coating lacquer tone 11: Add 10 ml of ethyl acetate and 4 ml of solvent (c) to 10 g of magenta coupler (a) and 2-3 g of color image stabilizer (b), dissolve, and dissolve this solution in 5 mfL of 1O% sodium dodecylbenzenesulfonate. lO% including
It was emulsified and dispersed in a 90mM aqueous solution. On the other hand, 90 g of a red-sensitive emulsion was prepared by adding the following red-sensitive dye to the above-mentioned silver halide emulsion (containing 70 g/kg of Ag) per 1 mole of silver halide to make a red-sensitive emulsion. A coating solution for the first layer was prepared by mixing and dissolving the emulsion and a development accelerator and adding gelatin to a concentration of yA so as to have the composition shown in Table 4.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. 1-3 as gelatin hardener for each layer
．． 5-dichloro-5-)-riazine sodium salt was used. The following spectral sensitizers were used in each emulsion.

The structural formulas of the compounds used in this example, such as couplers, are as shown below.

(a) Magenta coupler Green-sensitive pigment; Red-sensitive milk pigment; Blue-sensitive milk pigment; The following dye was used as the irradiation prevention dye.

Anti-irradiation dye for green-sensitive emulsion layer Anti-irradiation dye for red-sensitive emulsion layer (b) 1:1.5 mixture (weight ratio) of color image stabilizer (c) Solvent (d) Development accelerator H H (f) Cyan coupler co Y"-yur'rr□8j Hiro1, □,, ftlf
gl Color image stabilizer (h) solvent fl Ultraviolet absorber C4H, (1) C5:3 mixture (molar ratio) of CH2CH2COOCsl”L7 (j) Color mixing inhibitor H (k) Solvent (iso CgH190 (P-0 ( 4 Yellow Coupler (H) Color Image Stabilizer The color photographic paper thus prepared was subjected to wedge exposure (1/10 second, 10 CMS) and then subjected to the following processing step A, and the color image density was measured.

Processing step A Time Temperature color development 3 minutes 30 seconds 33°C Bleach fixing 1 minute 30 seconds 33 nol Stable ■ 1 minute 3377 Stable ■ l minute 33 /7 Stable ■ 1 minute 33 II The stabilizing bath replenishment method is the stabilizing bath. A so-called self-flow replenishment method was adopted in which the overflow liquid of the stable bath (2) was refilled to the stable bath (2), and the overflow liquid of the stable bath (2) was led to the stable bath (2).

Color developer mother liquor Diethylenetriaminepentaacetic acid 2.0g Benzyl alcohol 12.8g Diethylene glycol 3.4g DABCO 2.0g Sodium bromide 0.26g Diethylhydroxylamine 2.60g Sodium chloride
3.20g3-methyl-4-amino-N-4
, 25g Ethyl-N-(β-methanesulfonamidoethyl)-aniline potassium carbonate 30.0g Optical brightener (stilbene type) 1.0g Add water
1ooo+nJJpH10,20 The pH was adjusted with potassium hydroxide or hydrochloric acid.

Bleach-fix solution mother liquor Ammonium thiosulfate 110g Sodium bisulfite log diethylenetriaminepentaacetic acid 56g Iron (I[[)ammonium, l-hydrate ethylenediaminetetraacetic acid 2s 5g Thorium.
Dihydrate 2-mercapto-1,3,40,5g - Add triazole water and boil for 1000m pH 6,
5 pH was adjusted with ammonia wood or hydrochloric acid.

k Grave mother liquor l-Hydroxyethylidene-1,6mM 1.1'-diphosphonic acid (60%) Bismuth chloride 0.35g Polyvinylpyrrolidone 0.25g Ammonia wood
2.5m nitrilotriacetic acid, 3Na
1.0g 5-Chloro-2-methyl-450mg -inthiazolin-3-one 2-year-old cutyl-4-isothia 50 mg zolin-3-one optical brightener (4,4-diazil, Og nostilbene type) Add water and loooom standing pi-1
7,5 pH is potassium hydroxide or 11! Adjusted with acid.

Next, a photosensitive material was prepared in which undeveloped IJI compound A-35, B-74, or C-2 was added in an amount of 10 mo1% based on the coupler to the 1.3.5 layer of the above photosensitive material, and the above-mentioned treatment was performed. As in Example 1, the occurrence of staining was significantly suppressed in each of the B, G, and R layers.

(Effects of the Invention) According to the present invention, it is possible to expose and develop a silver halide color photographic light-sensitive material to form a color photographic image with excellent image quality that is less likely to cause staining, especially in reflective light-sensitive materials. , the effect is noticeable. Further, according to the method of the present invention, the stability of the color developer itself is excellent, and there is no possibility that the composition of the color developer changes and affects photographic performance.

Claims (1)

[Scope of Claims] After imagewise exposure, a silver halide color photographic light-sensitive material having a layer containing at least one of the compounds represented by the following general formulas (A) to (C) is treated with fused cyclic amines. , monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, ethers,
At least one selected from oximes and amides
1. A method for forming a color image, comprising processing with a color developer containing a seed compound and an aromatic primary amine color developing agent. General formula (A) ▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, A is a substituted or unsubstituted alkyl group, aryl group, heterocyclic group, acyl group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, or amino group, R_1 and R_2
each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, and R_3 and R_4 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, or arylthio group. In the formula, R_5 represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group, and P represents an oxygen atom or a sulfur atom. ) General formula (B) RoSO — 2 A metal atom, an alkaline earth metal atom, a nitrogen-containing organic base, an ammonium group, or the following structural formula (
D). Structural formula (D) ▲There are numerical formulas, chemical formulas, tables, etc.▼ (R_1_1 represents a hydrogen atom, each substituted or unsubstituted alkyl group, aryl group, or heterocyclic group,
R_1_2 represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an aryl group, an acyloxy group, or a sulfonyl group, and R_1_3 represents a hydrogen atom or a group that can be hydrolyzed. )) General formula (C) R-SH (In the formula, R represents an alkyl group, an alkenyl group, or an aryl group.)