JPH01105247A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the generation of a magenta stain by developing the silver halide photographic sensitive material contg. a specified coupler with a color developer contg. an aromatic primary amine color developing main agent and a specified compd. CONSTITUTION:The silver halide color photographic sensitive material contg. a pyrazoloazole type magenta coupler shown by formula I is developed with the color developer contg. the aromatic primary amine color developing main agent and condensed ring amines shown by formula II. In formula I, R1 is hydrogen atom or a substituting group, X is hydrogen atom or a group capable of releasing by allowing a coupling reaction with the oxidant of the aromatic primary amine developing main agent, Za, Zb and Zc are each methine or a substd. methine group, etc., one of bindings of Za-Zb and Zb-Zc is a double bond, another of which is a single bond. In formula II, X is a trivalent atomic group necessary for forming a condensed ring, R<11> and R<12> are each alkylene or arylene group, etc. Thus, the generation of the magenta stain can be prevented.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for processing silver halide color photographic materials with excellent stability, and more specifically, to a method for processing silver halide color photographic materials with excellent color development and fading resistance. The present invention relates to a method for processing a silver halide color photographic material that stably forms a silver halide color photographic material.

(Prior art and its problems) Pyrazoloazole magenta couplers are disclosed in Japanese Patent Application Laid-Open No. 59-1
No. 62548, No. 60-43659.

No. 59-171956, No. 60-172982, No. 60-33552, and U.S. Patent Section 3,061.432
Various studies have been conducted because of its excellent hue. However, according to research conducted by the present inventors, when this pyrazoloazole-based magenta coupler is processed with a conventional color developer, the photographic properties vary significantly, and furthermore, magenta staining is likely to occur over time after processing. It turned out that it had serious drawbacks.

First of all, it has become clear that variations in the concentration of sulfite ions conventionally added to color developers have a significant effect on variations in photographic properties. Therefore, in order to keep the sulfite ion concentration stable, various preservatives and chelating agents have been added, but no effective means have been found. Next, when sulfite ions were removed, the concentration fluctuations of hydroxylamines and color developing agents increased, which also had an adverse effect on photographic properties. Therefore, a preservative that replaces sulfite ions is required, but U.S. Patent Section 4,17
Triethanolamines described in No. 0,478 and No. 4,2
Even when the poly(ethyleneimine)s described in No. 52,892 were added, sufficient effects could not be obtained. Furthermore, when sulfite ions are removed from the color developer, a new problem has been discovered in that staining tends to occur over time after processing.

In particular, the generation of magentastin when using the above-mentioned pyrazoloazole magenta couplers is particularly noticeable in the absence of sulfite ions, and conventional anti-fading and anti-stinting techniques (for example, U.S. Patent Section 2,360)
, No. 290, No. 2.418, 613, No. 2,675,
No. 314, No. 2,701,197, No. 2,704,7
No. 13, No. 2,728,659, No. 21732.30
No. 0, No. 2,735.765, No. 2゜710.801
No. 2,816,028.

British Patent No. 1,363,921, JP 58-241
Hydroquinone derivatives described in US Pat. No. 41, etc., gallic acid derivatives described in US Pat. No. 3,457,079, US Pat.
No. 65, No. 3,698.909, Special Publication No. 49-209
p-alkoxyphenols described in U.S. Patent No. 77, U.S. Patent No. 52-6623, U.S. Pat.
, No. 764,337, JP-A No. 52-35633, No. 5
p-oxyphenol derivatives described in No. 2-147434 and No. 52-152225, U.S. Patent Section 3,70
There are bisphenols described in No. 0,455. As a stain prevention technique, even if techniques such as those disclosed in JP-A-49-11330, JP-A-50-57223, JP-A-56-85747, and JP-B-Sho 56-8346 are used, sufficient effects cannot be obtained.

(Means for Solving the Problems) The present inventors have conducted various studies to overcome the drawbacks of the above-mentioned conventional silver halide color photographic light-sensitive materials using pyrazoloazole-based magenta couplers. formula(
By processing a silver halide color photographic light-sensitive material containing a pyrazoloazole magenta coupler represented by I) with a color developer containing a certain type of condensed amine, it is possible to suppress the occurrence of magentastin, and to improve the photographic quality. It was discovered that the variation in sex can be reduced, and based on this knowledge, the present invention was accomplished.

That is, the present invention provides a silver halide color photographic light-sensitive material containing at least one type of pyrazoloazole magenta coupler represented by the following general formula (I), an aromatic primary amine color developing agent and the following general formula (II). The present invention provides a method for processing a silver halide color photographic light-sensitive material, which is characterized in that it is processed with a color developer containing at least one type of condensed cyclic amine represented by the following formula.

Numerical formula (I) (wherein R1 represents a hydrogen atom or a substituent, X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer, Za, Zb
E and Zc are methine, substituted methine, =N- or -NH
-, one of the Za-zb bond and Zb-Zc bond is a double bond, and the other is a single bond.

In the case of Zb-Zc or a carbon-carbon double bond, this includes the case where it is part of an aromatic ring, and further includes the case where R1 or X forms a dimer or more multimer, Za, Z
When b or Zc is a substituted methine, this also includes the case where the substituted methine forms a dimer or more multimer) General formula (II) (wherein, X is 3 necessary to complete the condensed ring) (R11 and R12 represent an alkylene group, arylene group, alkenylene group, and aralkylene group, where R11 and R12 may be the same or different from each other.) Below, couplers of general formula (I) Explain the details.

In the general formula (I), R1 represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group that is separated by a coupling reaction with an oxidized aromatic primary amine developer.
Za, Zb and Zc represent methine, substituted methine, =N- or -NH-, and one of the Za-Zb bond and Za-Zc bond is a double bond and the other is a single bond.

In the case of zb-Zc or a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. Furthermore, it also includes the case where R1 or X forms a dimer or more multimer, and when Za, Zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or more multimer.

In the general formula (I), those having two or more general formulas (2M represented by Il) in the polymer/molecule are blueish, and bis forms and polymer couplers are also included in this. Here, the polymer coupler may be a homopolymer consisting only of a monomer having a moiety represented by the general formula (I) (preferably one having a vinyl group, hereinafter referred to as vinyl monomer), or an aromatic-class amine. Copolymers may also be made with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of the developer.

The compound represented by the general formula (Il) is a negative fused tj!L complex m-type coupler, and its color-forming nucleus exhibits isoelectronic aromaticity with naphthalene. The general formula (
Among the couplers represented by I), preferred compounds are 1
HF-imidazo (/, co-b) pyrazoles, lH-pyrazolo (t, r-b) pyrazoles, iH-pyrazolo (
, t, 1-c) [1,2,44] triazoles, lH
-pyrazolo CI, r-b) (l, s, II] triazoles, lH-pyrazolo (/, t-d) tetrazoles, and lH-biran o (z, j-a) benzimidazoles, each of which is a general Formula (m), (IV), (V)
, (VI), (■) and (■), particularly preferred compounds are (III), (V) and (■).
A more preferred compound is (VI).

<m) (N) () fVIl General formula (substituents R2, R3 and R up to ml-(~■)
4 is a hydrogen atom, a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group,
Acylamino group, anilino group, ureido group, imide group -
Sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group ,
Al; represents a oxycarbonyl group or an aryloxycarbonyl group; The case where R2, R3, R4 or X, represented by the group t-, is a divalent group and forms a bis body is also included. In addition, the general formula +In1~(■
) when the part represented by 9 is a vinyl monomer,
R2, R3 or R4 represents a simple bond or a linking group, through which the moiety represented by the formula +111~(菰) and the vinyl group are bonded.

More specifically, R2-R3 and R4 are hydrogen atoms, halogen atoms (for example, chlorine atoms, bromine atoms).

etc.), alkyl groups (e.g. methyl group-propyl group, i
-propyl group -t-butyl 44 nee trifluoromethyl group, tridecyl group, j-(,!,≠-di-t-amylphenoxy)propyl group -1-dodecyloxyethyl group,
3-phenoxyprobyl group-"-hexylsulfonyl-
Ethyl group, cyclo is methyl group, benzyl group, etc.), aryl group NFile.

phenyl group, ≠-t-i tylphenyl group, λ, 4t-di-t-amylphenyl group-Hiro-tetradecanamidophenyl group, etc.), heterocyclic group (e.g., J-furyl group-cortienyl group, cobyrimidine/L' nibenzothiazolyl group, etc.), cyano group, alkoxy group (e.g. methoxy group, ethoxy group, comethoxyethoxy group, codedecyloxyethoxy group, cophenoxyethoxy group, λ-methanesulfonylethoxy group, etc.) ), aryloxy Tg (e.g., phenoxy group, dimethylphenoxy group, ≠-1-butylphenoxy group, etc.), heteroOff
loxy groups (e.g., copenzimidazolyloxy groups, etc.), acyloxy groups (e.g., acetoxy groups, hexadecanoyloxy groups, etc.), carbamoyloxy groups (
For example, -N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy group (e.g., trimethylsilyloxy group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.), 1° acylamino group (e.g., Acetamide group, benzamide group, tetradecanamide group, α-(co.

≠-di-t-amylphenoxyl-butyramide group, r-
(3-t-butyl-μm hydroxyphenoxy) phthylamide group, α-(μm (Hiro-hydroxyphenylsulfonyl) phenoxy) f cuff 7 mid group, etc.), anilino group (e.g., phenylamino group, cochloroaniline group, etc.), lino group, cochloro-j-tetradecanamideanilino group, cochloro-y-dodecyloxycarbonylanilino group, N-acetylanilino group, λ-chloro1-(c
t-(j-t-butyl-Fredo-hydroxyphenoxy)dodecanamido)anilino group-, etc.), ureido groups (e.g., phenylureido group, N-butyl-N'-methylureido group, methylureido group, N, N dibutylureido group, etc.), imide group (e.g.

N-succinimide group, 3-penzylhydantoinyl group, Hiro-(coethylhexanoylamine)phthalimide group, etc.), sulfamoylamino group (911eva, N,
N-dipropylsulfamoylamino group, N-methyl-
N-decylsulfamoylamino group 1 etc.), alkylthio group (e.g. methylthio group, octylthio group, tetradecylthio group-cophenoxyethylthio group, J-phenoxypropylthio group, 3-<Hiro-t-7) 'tylphenoxy)propylthio group 1), arylthio group (e.g. -phenylthio group, λ-butoxy, -t-octylphenylthio group, 3-interdecylphenylthio group, cocarboxyphenylthio group, dilutetradecanamidophenylthio group, etc.), heterocyclic thio groups (e.g. -cobenzothiazolylthio group, etc.), alkoxycarbonylamino groups (e.g.

methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (e.g., phenoxycarbonylamino group, co-butylphenoxycarbonylamino group, etc.), sulfonamide group (e.g. Yo-ba, methanesulfonamide group, navel subcanesulfonamide group, benzenesulfonamide hair, p-)luenesulfonamide group, octadecanesulfonamide group, λ-methyloxy-1-1
-phthylbenzenesulfonamide a, etc.1, carbamoyl group (e.g., (ke, N-ethylcarbamoyl group).

N, N-dibutylcarbamoyl group, N-1-dodecyloxyether)carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N-(J-(,!, Hiroji tcr
t-amylphenoxy)propyl)carbamoyl group, etc.), acyl group (e.g., acetyl group, +2.IA-di-tcrt-amylphenoxy)acetyl group, benzoyl group, etc.), sulfamoyl group (e.g., Moyl group, N,N-dipropylsulfamoyl group,
N-(,2-dodecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N,N
-'; ethylsulfamoyl group -, etc.), sulfonyl group (
For example, methanesulfonyl group, -°cutanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, W
+, sulfinyl 1NFlltc.

Octanesulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, @41, alkoxycarbonyl group (e.g., methoxycarbonyl group - butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.) -aryloxycarbonyl group (for example, -phenyloxycarbonyl group, 3- is ntadecyloxycarbonyl group, etc.), -X is a hydrogen atom, 2 halogen atoms (for example, -chlorine atom, bromine atom, iodine atom, etc.).

A carboxyl group, or a group linked by an oxygen atom (e.g., acetoxy group, propanoyloxy group, benzoyloxy group, co,≠-dichlorobenzoyloxy group-ethoxyoxaloyloxy group, pyruvinyloxy group, cinnamoyloxy group, Phenoxy group, ≠-cyanophenoxy group, ≠-methanesulfonamidophenoxy group, dermethanesulfonylphenoxy group, α-naphthoxyg, J-1
7 Tadecylphenoxy group, penzyloxycarbonyloxy group, nidoxy group, l-cyanoethoxy group, benzyloxy group, cophenethylmoxy group, -monophenoxyethoxy group,! -phenyltetrazolyloxy group, -penzothiazolyloxy group, etc.), a group linked through a nitrogen atom (e.g., benzenesulfonamide) group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group ,Ko.

3,≠,! , one interfluorobenzamide group, λ,
3.4! , z, t--<ntafluorobenzamide group, octanesulfonamide group, p-cyanophenylurei)' group, N,N-diethylsulfamoylamino group, /-piperidyl group, ! ,! -dimethyl-S, 4t-
Dioquin-3-oxazolidinyl group, /-benzyl-ethoxy-3-hydantoynyl group, 2N-/, /-dioxo-3(coH)-oxo-1,nibenzisothiazolyl group, -1oxo/, 2- Dihydro/-pyridinyl group, imidazolyl group, pyrazolyl group, 3. ! -Diethy Lou/, Ko, 4! -) lyazol-7-yl group,! - or 6-promobenzotriazo-roof-yl, j-methyl-/, 2. J, ≠-triazol-/-yl group-penzimidazoryl group, 3-benzyl-/-hydantoinyl group, l-benzyl-! -hexadecyloxy-3-hydantoynyl group,! -Methyl-l-tetrazolyl group, Hiro-methoxyphenyl 7:/ group, Hiro-piparoylaminophenylazo group, co-hydroxy≠-propanoylphenylazo group, etc.), groups linked by sulfur atoms (
Example Eva, phenylthio group,! -carboxyphenylthio group, 2-butoxy-1-1-octylphenylthio group,
≠-Methanesulfonamidophenylthio group,! ,! -dibutoxyphenylthio group, ≠-methanesulfonylphenylthio group, Hiro-octanesulfonamidophenylthio group, coptoxyphenylthio group, ≠-dodecyloxyphenylthio group, 2-(neehexanesulfonylethyl)
-! -tert-octylphenylthio group, benzylthio group, λ-cyanoethylthio group, l-ethoxycarbonyltridecylthio group -yo-phenyl-λ.

3.Hiroshi! -tetrazolylthio group, nibenzothiazolylthio group, -1dodecylthio group, 2-dodecylthio-j
-thiophenylthio group, coffinyl-3-dodecyl-
/, X, ≠-triazolyl, monothio group, etc.).

When R2, R3, R4 or X becomes a monovalent group to form a bis body, this monovalent group is described in more detail as follows:
Substituted or unsubstituted alkylene group (e.g., methylene group, ethylene group, /, 10-decylene group --CHzCHz
-OCH2'C112-1, etc.), a substituted or unsubstituted phenylene group (e.g. /, tA-phenylene group, 7.3
-phenylene group.

-N) TCO-R2-CON) (- group + R2 represents a substituted or unsubstituted alkylene group or phenylene group, and those represented by the general formula (I[[) to (■)) are present in the vinyl monomer. In some cases, the linking group represented by R2, R3 or R4 is an alkylene group (the substituted hole is an unsubstituted alkylene group - for example, a methylene group, an ethylene group, /, 10
-decylene group, -CH2CH20CH2CH2-, etc.)
, phenylene group (substituted or #substituted phenylene group,
For example -1, Hiro-) Uniren it, /', ! -huynylene group, CH8α -NHCO-1-CONH-1-〇-1-OCO-1 and aralkylene group (e.g.

α etc.).

The vinyl group in the vinyl monomer has the general formula [[11
~ (■) In addition to what is indicated, a? It also includes cases where it has a group. Preferably, the substituent is a water cloud atom, a chlorine atom, or a lower alkyl group having l-φ carbon atoms.

Acrylic acid, α
- g2 from chloroacrylic acid, α-alacrylic acid (for example, methacrylic acid, etc.) and these acrylic acids
! esters or amides (e.g. acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n
-propyl acrylate, n-butyl acrylate, t
-7” thyl acrylate, 1so-butyl acrylate, λ-ethylhexyl acrylate-n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-methyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide, vinyl ester (e.g., thorn, vinyl acetate, vinyl propionate, and vinyl laurate), acrylonitrile, methacrylate, aromatic vinyl compounds (e.g., styrene and its derivatives,
vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid-vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic anhydride, maleic esters, N-vinyl -[lambda]-pyrrolidone, N-vinylpyridine, overcoat, darvinylpyridine, and the like. It also includes the case where Ua or more of the non-color-forming ethylenically unsaturated monomer used herein is used together.

Compound examples and synthesis methods of the couplers represented by the above general formulas (Il+ to (■)) are described in the documents listed below.

The compound with the general formula 1ml is
The compound of the general formula (171 is JP-A-Sho tO-≠36!
A compound with the general formula (Tl) is as follows.

Tokuko Sho≠7-co7411/, etc., the compound with the general formula +Vll is JP-A-Kojter/7/ri! 6> and “pi” 6゜-/
7co9r-, etc., the compound of general formula (■) is
-jJjt! In addition, the compound of the general formula (泗) is
Also described in US Patent No. 3.04/, ≠32, etc. Zaichi 4120≠! , same j2-co1tLL
rrt, t, same j! 7-/77! ! 3-same j9-/7
7! Hirohiro and the same τ / 77! The highly color-forming ballast group described in jt7 etc. has the above general formula TI[l~(
Specific examples of pyrazoloazole couplers used in the present invention, which are applicable to any of the compounds in (1), are shown below.
It is not limited to these, (M-71 (M-co) 1M-Jl Cλ(-li) IM-jl (λ(-tl fλτ-71 iel) IM-ta1 +M-/ 01 [ M-//I IM-/ Co1 (M-13) (M-14) (M-15) CH3n-C6H13 (M-16) n'6H13 (M-17) -C4H9 (M-18) n- C6H13 ζλ(-/?1 1 M-10) 1M-col ) (λ[-here) (M-coJ1 (M-1hiro) /V H3 (λ(-Jjl IM-j t 1 +M- core 1 humiliation
humiliation
41-4'ri) 1M-zol CH! L, $F117Ltl 1M-! II C) T3\H3 H3 1MA l l (M-t2) C6H13(t) Engineering Qol- These couplers are generally 2XIO' to 5xlO-1 mole per mole of silver in the emulsion layer.

Preferably, 1xlO mol to 5xlO-' mol is added.

Two or more types of the above couplers etc. can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers.
Of course it doesn't matter.

In order to introduce the coupler into the silver halide emulsion layer, known methods such as those described in U.S. Pat. No. 2,322,027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.)
, phosphate esters (diphenyl phosphate, triphenyl) phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkyl Amide (
For example, diethyl laurylamide), fatty acid esters (
(e.g., dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g., tributyl trimesate), or a freezing point of about 30°C to 150°C.
After dissolving in an organic solvent 1, such as lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a wood-philic colloid. Ru. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Next, the condensed cyclic amines represented by the general formula (II) used in the present invention will be explained.

In the general formula (n), the number of carbon atoms in X is preferably 20 or less, more preferably 10 or less, and even more preferably 6 or less. Good too.

In general formula (n), the number of carbon atoms in R11 and R12 is preferably 10 or less, more preferably 6 or less, and even more preferably 3 or less.
is preferably an alkylene group or an arylene group,
More preferably, it is an alkylene group.

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

\ Specific examples of X in general formula (II) include C=N-/ etc. can be mentioned.

Specific examples of R11 and R12 in general formula (II) include methylene group, ethylene group, propylene group, butylene group, bentylene group, 1,2-cyclohexylene group, 1-methylethylene group, 1,2-dimethylethylene group. group, l-carboxyethylene group, l,2-phenylene group, 1,2-vinylene group, 1,3-propenylene group, etc.; It may be further substituted with a group, an alkoxy group, an alkylthio group, an amino group, an amide group, an acyl group, a carbamoyl group, a sulfamoyl group, a heterocyclic group, or the like.

Among general formulas (If), particularly preferred are general formulas (I
These are compounds represented by I-a) and (II-b).

It is preferable that the number is 1, more preferably 3 or less, and most preferable that it is 2.

R11, R12, and R13 are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

In the formula, R11 and R12 have the same meanings as above.

In general formula (n-b), the number of carbon atoms in R11 and R12 is preferably 6 or less. R11 and R12 are preferably an alkylene group or an arylene group, most preferably an alkylene group.

Among the compounds represented by the general formulas (na) and (n-b), the compound represented by the general formula (II-a) is particularly preferred.

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

CH3 There are many compounds of general formula (II) according to the present invention, and commercially available products are easily available.

The amount of the compound represented by the general formula ([r)] is preferably 0.01 g to 100 g per color developer IQ.
g, more preferably 0.1 g to 20 g.

Moreover, the compound of general formula ([1)] of the present invention is.

In a system using an aromatic primary amine color developing agent, it has particularly remarkable storage performance when used in combination with a compound that directly stabilizes the developing agent.

Water-soluble antioxidants are generally known as compounds that directly stabilize the developing agent, such as hydroxylamines, hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α
-aminoketones, and vll.

Details of water-soluble antioxidants that are preferably used in combination are explained below.

Hydroxylamines are represented by the following general formula (IX).

General Formula (IX) In the formula, R111 and R112 each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, or an unsubstituted or substituted aryl group.

It is preferable that R111 and R112 are 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 heterocycle.

Alkyl groups and alkenyl groups may be linear, branched, or cyclic, and substituents include halogen atoms (F, CQ
, Br, etc.), aryl groups (phenyl group, ρ-chlorophenyl group, etc.), alkoxy groups (methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (
phenoxy group, etc.), sulfonyl group (methanesulfonyl group, p-toluenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (diethylsulfamoyl group, unsubstituted sulfamoyl group, etc.) ), carbamoyl group (
unsubstituted carbamoyl group, diethylcarbamoyl group, etc.)
, amide group (acetamide group, benzamide group, etc.),
Ureido groups (methylureido groups, phenylureido groups, etc.), alkoxycarbonylamino groups (methoxycarbonylamino groups, etc.), allyloxycarbonylamino groups (
phenoxycarbonylamino group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), cyano group, hydroxy group, carboxy group, sulfo group, nitro group, amino group (unsubstituted amino group) , diethylamino group),
Examples include alkylthio groups (such as methylthio groups), arylthio groups (such as phenylthio groups), and heterocyclic groups (such as morpholyl groups and pyridyl groups).

Here, R111 and RX 1 N may be the same or different.

Furthermore, the substituents of R1''1 and R112 may be the same or different.

Further, the number of carbon atoms in R1''1 and R112 is preferably 1 to 1O.

The nitrogen-containing heterocycle formed by linking II R1' and R'12, which are particularly preferably 1 to 5, includes a piperidyl group, a pyrrolisilyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group, a benztriazyl group, and a benztriazyl group. Examples include zolyl group.

Preferred substituents for R111 and R11Z 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 (X[) used in the present invention are shown below, but the scope of the present invention is not limited to these compounds.

do not have.

fK-(2) NH2゜H nshi, M, -IN-u, M4risi3 IX-(16) 0H CHs-N-C,H,So,C,T(.

IX-(17) ○HC, HsSo
2C, H, -N-C, H45o2C2H.

”9) HO-N So.

＼－－／ “-(20)HO-NO ＼－－／ ”-(22)HO-N'X)-QC,H.

IX-(27) OH HOCH,CH,NCH,CH,○H H” (33)CzH5-N-C2H@OCH3H DC(34) 1soc3H7N-C2H11OCH3
The synthesis of the compound represented by the general formula (IK) is disclosed in U.S. Patent No. 3,661,996, U.S. Pat.
, 293.034, Japanese Patent Publication No. 42-2794, US Pat. No. 3,491,151, US Pat.
It can be synthesized by the known methods described in No. 3,467.711, No. 3,455,916, No. 3,287,125, and No. 3,287,124.

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

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

General formula (X) A*-1x121 N OylJ1 R port 1 In the formula, A121 is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

Substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group , represents an acyl group, a carboxy group, a hydroxyamino group, or hydroxy-SO□-5 or -SO-, Rol is a hydrogen atom.

Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. A10 and R121 may be linked to form a ring structure. Y″z1 is a hydrogen atom or a hydrogen atom formed by a hydrolysis reaction. Represents a possible group.

When A 12 N and R121 are groups having substituents, these substituents include halogen atoms, aryl groups, alkyl groups, alkoxy groups, aryloxy groups, hydroxy groups, sulfonyl groups, sulfonamide groups, sulfamoyl groups, and sulfonamide groups. group, amide group, ureido group, cyano group, hydroxyaminocarbonyl group, carboxy group, nitro group, amino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group,
Examples include heterocyclic groups (pyridyl group, morpholino group, etc.).

Specific examples of Y121 representing a group that becomes a hydrogen atom through a hydrolysis reaction include the following.

l) A substituted or unsubstituted alkyl group as R10 protected by an ester bond or urethane bond.

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

2) The method of protection with an imidomethyl capping group described in JP-A-57-158638, that is, Y1'1 represents, and Z represents a complete heterocycle having at least one 5- or 6-membered ring. represents the multiple atoms required for

In general formula (X!i), A181 is preferably a substituted or unsubstituted alkyl group, aryl group, amino group, alkoxy group or aryloxy group. Particularly preferred are substituted or unsubstituted amino groups, alkoxy groups, or aryloxy groups.

The number of carbon atoms is preferably 1 to 10.

R121 is preferably a hydrogen atom.

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

X-3C4H,○-C-N)T-OH Specific examples other than the above include compound examples I-(1) to I described on pages 12 to 23 of Japanese Patent Application No. 186559/1982.
-(37) etc. can be mentioned.

The compound of the above general formula (X) is disclosed in Japanese Patent Application No. 61-186559.
It can be obtained based on the method described in No.

Hydrazines and hydrazides have the following general formula (X[)
It is a compound represented by

In the general formula (XI), R131, R13'' and R133 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group or heterocyclic group.

R134 is a hydroxy group, a hydroxyamino group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group,
ax'', which represents an alkoxy group, an aryloxy group, a carbamoyl group, or an amino group, represents a divalent group selected from NH, -CO-1-SO,- and -C-; n is 0 or 1; However, when n=O,
R134 represents a substituted or unsubstituted group selected from an alkyl group, an aryl group, and a heterocyclic group.
3 and R134 may jointly form a heterocycle.

To describe the general formula (X[) in more detail, R131,
R132 and R1″3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group (preferably a carbon number 1
~201 such as methyl group, ethyl group, sulfopropyl group, carboxybutyl group, hydroxyethyl group, etc.), aryl group (preferably 6 to 20 carbon atoms, such as phenyl group, 2,5-dimethoxyphenyl group, 4-hydroxyphenyl group) group, 2-carboxyphenyl group, etc.) or a heterocyclic group (preferably a carbon number of 1 to 201, e.g. pyridine-
4-yl group, etc.).

R134 is a hydroxy group, a hydroxyamino group, a substituted or p-substituted alkyl group (preferably a carbon number of 1 to
20, such as methyl group, ethyl group, sulfopropyl group,
carboxybutyl group, hydroxyethyl group, cyclohexyl group, benzyl group, etc.), aryl group (preferably 6 to 20 carbon atoms, such as phenyl group, 2,5-dimethoxyphenyl group, 4-hydroxyphenyl group, 2-carboxyphenyl group) etc.), heterocyclic group (preferably 1 carbon number)
~20, such as a pyridin-4-yl group), an alkoxy group (preferably having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, a methoxyethoxy group, a benzyloxy group,
cyclohexyloxy group, etc.), aryloxy group (preferably 6 to 20 carbon atoms, e.g. phenoxy group, P-methoxyphenoxy group, etc.), carbamoyl group (preferably 1 to 20 carbon atoms, e.g. carbamoyl group, N,N-diethyl Nl+ X131 is -CO-1 Represents a divalent group selected from -SO□- and 10-, where n is O or 1. However, n
When =0, R134 represents a substituted or unsubstituted group selected from an alkyl group, an aryl group, and a heterocyclic group.@R133 and R1''4 may jointly form a heterocycle.

In the general formula (XIJ, R131, R132 and R''
It is preferable that C is a hydrogen atom or an alkyl group, and most preferably R131 and R132 are hydrogen atoms.

In general formula (XI), R134 is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, or an amino group.
is preferable, and -CO- is most preferable.

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

C2H.

/XI-2NH,NH-(CH,hso,HXI-3
NH, NH-(CH, Soup OHC, H40H/XI-13NH2NHCOCH.

Xl-7NH2NHCOOC,H.

/ XI-10NH, NHCONH.

X[-12NH,NH303H N.H. XI-13NH2NHCNH.

Xl-14NH, NHCOCONHNH.

Specific examples other than those mentioned above include compound examples (1-1) to (
T-32) and the like.

The compound of the above general formula (X[) is disclosed in Japanese Patent Application No. 61-17075.
It can be obtained based on the method described in No. 6.

Phenols are compounds represented by the following general formula (Xl[).

General formula (Xl [) where R141 is a hydrogen atom, a halogen atom, an alkyl group, an aryl 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, a ureido group, Represents an alkylthio group, arylthio group, nitro group, cyano group, amino group, formyl group, acyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxysulfonyl group, or aryloxysulfonyl group, which further includes a substituent. It may have.

When there are two or more R141s, their types may be the same or different, and when they are adjacent, they may be bonded to each other to form a ring.R14t is a hydrogen atom or a group that can be hydrolyzed. 0m and n are each 1
Represents an integer from 5 to 5.

To explain General Formula 1) in more detail, R141 is a hydrogen atom, a halogen atom (F, CQ, Br, etc.), an alkyl group (methyl group, ethyl group, t-butyl group, etc.), an aryl group (phenyl group, etc.). ), alkoxy groups (methoxy groups, ethoxy groups, etc.), aryloxy groups (phenoxy groups, etc.), carboxyl groups, sulfo groups, carbamoyl groups,
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 group, cyano group, amino group, formyl group, acyl group (acetyl group, etc.)
, sulfonyl group (methanesulfonyl group, benzenesulfonyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), alkoxysulfonyl group (methoxysulfonyl group, etc.) or aryloxysulfonyl group ( phenoxysulfonyl group, etc.).

When R14m 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, and 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,
Examples include an aryloxysulfonyl group and a peterocyclic group (morpholyl group, pyridyl group, etc.). Furthermore, two or more and two or more types of these substituents may be substituted for R141, and when there are two or more R141, the 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, and includes carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms,
In R141 and its substituents, the carboxyl group and the sulfo group are composed of a sulfur atom, etc., and may be saturated or unsaturated.
K, etc.), and the amino group may form a salt with various acids such as hydrochloric acid.

R148 is based on 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 R14f.
fi=-c-R143 (where R143 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted 7-mino group). That is, it is a method of protecting with an ester bond or a urethane bond.

Another example is protection with an imidomethyl blocking group as described in JP-A-57-158638. Namely.

1m and n are each an integer from 1 to 5.

In general formula (X11), 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.

These are a sulfonamide group, a nitro group, and a cyano group.

Among them, an alkoxy group, an alkylthio group, an amino group, and a nitro group are particularly preferable, and it is more preferable that these are in the ortho or para position of the (oR141) group, and
The number of carbon atoms in R141 is preferably 1 to IO, particularly preferably 1 to 6 i. Preferably R14'' is a hydrogen atom or a hydrolyzable group having 1 to 5 carbon atoms.
``) When there are two or more groups, it is more preferable that they are located in the ortho or para position with respect to each other.

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

"2HO-0-3o, -0-OH ”-3HO-0-No.

”-4HO-0-5o, NH.

Specific examples other than the above include Compound Examples 1-(1) to I described on pages 14 to 27 of Japanese Patent Application No. 188742/1982.
-(42); Specification No. 61-203254, page 13~
Compound examples (1) to (41) described on page 25 can be mentioned.

The compound of the above general formula 〇〇I)
No. 2 and No. 61-203254.

α-Hydroxyketones and α-aminoketones are compounds represented by the following general formula.

General formula (■) In the formula, R"" represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group, and R1S2 represents a hydrogen atom, a substituted or unsubstituted, It represents an alkyl group or an aryl group, and RI S 1 and R 1% 2 may jointly form a carbocycle or a heterocycle. X 1 % 1 represents a hydroxyl group or a substituted or unsubstituted amino group.

To describe the general formula (■) in more detail, R151 is a hydrogen atom, a substituted or unsubstituted alkyl group (preferably 1 to 20 carbon atoms, such as a methyl group, an ethyl group, a hydroxymethyl group, a methoxyethyl group, a cyclohexyl group) Such)
, aryl group (preferably 6 to 20 carbon atoms, such as phenyl group, 2-hydroxyphenyl group), alkoxy group (preferably 1 to 20 carbon atoms, such as methoxy group, ethoxy group, methoxyethoxy group), aryloxy group (preferably 1 to 20 carbon atoms, such as methoxy group, ethoxy group, methoxyethoxy group), Preferably 6 to 20 carbon atoms, e.g. phenoxy group, 4
-methoxyphenoxy group, etc.), or an amino group (preferably carbon number O to 20, such as amino group, N, N-diethylamino group, N-phenylamino group, etc.).

R1'2 is a hydrogen atom, a substituted or unsubstituted alkyl group (preferably 1 to 20 carbon atoms, e.g. methyl group, ethyl group, hydroxymethyl group, etc.) or an aryl group (preferably 6 to 20 carbon atoms, e.g. phenyl group) group, 2-hydroxyphenyl group, etc.) e R”1 and R1%
2 may jointly form a carbocycle or a heterocycle.

X151 is a hydroxyl group or a substituted or unsubstituted amino group (preferably 0 to 20 carbon atoms, such as an amino group,
N,N-diethylamino group, morpholino group, etc.).

In general formula (XI), R1% 1 is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or an alkoxy group, and RI S 2 is a hydrogen atom or a substituted or unsubstituted alkyl group. It is preferable if there is.

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

■-10 CH, CCH, OH Xl-40 CH, CCH, NHC, H.

Xl-50 HC-CH,OH\OH Specific examples other than the above include compound examples (1) to (18) described on pages 15 to 18 of Japanese Patent Application No. 184328/1982.
) etc.

The compound of the above general formula (■) is disclosed in Japanese Patent Application No. 61-184328.
It can be obtained based on the method described in No.

Below, the saccharides used in the present invention will be explained in detail.

Sugars (also called carbohydrates) consist of monosaccharides and polysaccharides.
Monosaccharides, which often have the general formula C,,H2,o, generally include aldehydes or ketones of polyhydric alcohols (called aldoses and ketoses, respectively) and their reduced, oxidized, dehydrated derivatives, and amino acids. A general term for a wider range of derivatives such as sugars and thiosaccharides. Moreover, polysaccharide 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 to these. (These optical isomers can also be used in the same manner.) >2i1 -1: D-glucose W-2: D-galactose summer-3: D-mannose summer-4 = glucosamine>ali+-5: D-oxylose M-6: L-arabinose>12i1-7: D-ribose M- 8: D-Deoxyribose - 9: L-Sorbose - 10: D-Sorbitol (Sorbitol) 0-C
-H -C-OH Clear-C-OH CH,OH The above N types can be obtained as commercial products.

The amounts of these compounds of general formulas (IX) to (XI) and saccharides added to the color developer are determined by the color developer IQ.
Preferably 0.01g to 50g, more preferably 0.
．． It is 5g to 20g.

Other sulfite ions known as preservatives are preferably not substantially contained in the color developing solution of the present invention; "substantially" means that they may be added to the extent that they do not affect the photographic properties; 0~0, O05s
ol/l, preferably 0 to 0.002 ol/l.

The color developer of the present invention also includes preservatives such as U.S. Patent No. 3,615,503 and British Patent No. 1,306,
Hydroxyacetones described in No. 176, JP-A-52-1
α-aminocarbonyl compounds described in JP-A-43020 and JP-A-53-89425, various metals described in JP-A-57-44148 and JP-A-57-53749, etc., JP-A-57-52
- Various saccharides described in No. 102727, No. 59-16014
α,α′-dicarbonyl compound described in No. 1, No. 59-1
Salicylic acids described in No. 80588.

The gluconic acid derivatives described in No. 56-75647 may be contained as necessary, and two or more of these preservatives may be used in combination as necessary, especially when an aromatic polyhydroxy compound is added. preferable.

The color developer of the present invention preferably does not substantially contain benzyl alcohol from the viewpoint of fogging and increase in stain after processing.
5.0 mfl or less per color developer IQ, preferably 2
mA or less, more preferably not at all.

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-I N,N-diethyl-p-phenylenediamine D-24-(N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-32-methyl-4-[N-ethyl-N-(β -hydroxyethyl)aminocoaniline D-44-amino-3-methyl-N-ethyl-N-(β
Methanesulfonamidoethyl)-aniline These P-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, sulfite, P-)-luenesulfonate, among which D-4 is The amount of the aromatic-grade amine developing agent used is preferably about 0.1 to 20 g, more preferably about 0.5 to 1 L, per 11 of the developing solution.
og concentration.

The color developer used in the present invention preferably has a pH of 9
~12. More preferably, it is 9 to 11.0, and the color developer may contain other known developer component compounds. In order to maintain pH, it is preferable to use various buffers.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate)
, potassium 0-hydroxybenzoate, 5-sulfo-2-
Examples include sodium hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds, and the amount added is preferably 0.1 mol/kg or more, particularly 0.1 mol/kg to 0.1 mol/kg.
Particularly preferred is 4 mol/cross.

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer. As the chelating agent, organic acid compounds are preferable, such as aminopolycarboxylic acids described in Japanese Patent Publication No. 48-30496 and Japanese Patent Publication No. 44-30232, Japanese Patent Publication No. 56-97347,
Organic phosphonic acids described in Japanese Patent Publication No. 56-39359 and West German Patent No. 2,227゜639, JP-A-52-102
No. 726, No. 53-42730, No. 54-12112
No. 7, No. 55-126241 and No. 55-65950
Phosphonocarboxylic acids described in No. 6, etc., and other JP-A No. 1973
Examples thereof include compounds described in Japanese Patent Publication No. 8-195845, No. 58-203440, and Japanese Patent Publication No. 53740900.

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

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N.

N,N',N'-tetramethylenephosphonic acid, transcyclohexanethiatetraacetic acid, l,2-diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2° 4-tricarboxylic acid, l-hydroxyethylidene-1,1-diphosphonic acid, N,N''-bis(2-hydroxybenzyl)ethylenediamine-N.

N'-diacetate The amount of these chelating agents added is sufficient to sequester metal ions in the color developer, for example, about 1 to 10 g of O per batch.

Any development accelerator can be added to the color developer if necessary. However, the color developer of the present invention preferably does not substantially contain benzyl alcohol from the viewpoint of pollution, formulation properties, and fog prevention. Here, "substantially" means 2 ml per developer. Hereinafter, it means preferably not containing at all.

The color developer used in the present invention has a significant effect on the stability of a color developer that does not substantially contain benzyl alcohol. Other development accelerators include Re5earch Disclosure Item
No, 17643 XXI, B~D (197
(December 1999, pages 29-30) can be used.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, and 5-chlorobenzotriazole.

Typical examples include nitrogen-containing heterocyclic compounds such as 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention preferably contains a fluorescent brightener.
Diamino-2,2'-disulfostilbene compounds are preferred, and the amount added is preferably 0 to 5 g/Ig to 4
g/sentence.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. Although it is preferable that the amount of replenishment is small, it is 20 to 600 ml and preferably 50 to 300 ml per rn' of light-sensitive material. More preferably 100 m [
It is 1 to 200 m1.

Next, the bleaching solution, bleach-fixing solution, and fixing solution used in the present invention will be explained.

As the bleaching agent used in the bleach solution or bleach-fix solution used in the present invention, any bleaching agent can be used, but in particular, an organic complex of iron (m) ti! (for example, complex salts with aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or 4!1 acids such as citric acid, tartaric acid, malic acid; Persulfates; hydrogen peroxide and the like are preferred.

Among these, organic complex salts of iron (m) are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution, and aminopolycarboxylic acids, aminopolyphosphonic acids, or organic Phosphonic acids or their salts are listed as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid,
Examples include propylene diaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, and the like.

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

These ferric ion complex salts may be used in the form of complex salts, and ferric salts 1 such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid to form a ferric ion complex salt in a solution.The chelating agent may be used to form a ferric ion complex salt. It may be used in excess.

Among the iron chains, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/fL, preferably 0.05 to 0.50 mol/fL.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. Specification No. 812, JP-A-53-956
Publication No. 30, Research Disclosure No. 1712
No. 9 (July 1978 issue), compounds having a mercapto group or disulfide bond, and Japanese Patent Publication No. 45-85
No. 06, JP-A-52-20832, JP-A No. 53-3273
Thiourea compounds described in No. 5, US Pat. No. 3,706,561, and halides such as iodine and bromide ions are preferred because they have excellent bleaching properties.

Other 1 The bleach or bleach-fix solution used in the present invention contains bromide (e.g., potassium bromide, sodium bromide, ammonium bromide), chloride (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodide. (
For example, a rehalogenating agent such as ammonium iodide) may be included. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, as required
One or more types of inorganic acids and organic acids having a pH buffering capacity such as sodium citrate and alcoholic acid, and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; a thiocyanate such as sodium thiocyanate or ammonium thiocyanate; Ethylene bisthioglycolic acid, 3,6-cythia 1
．． These are water-soluble silver halide dissolving agents such as thioether compounds such as 8-octanediol and thioureas, and these can be used alone or in combination of two or more.

In the present invention, it is preferred to use thiosulfate, especially ammonium thiosulfate, the amount of fixing agent per 1M is 0.
．． The amount is preferably 3 to 2 moles, more preferably 0.5 to 1.
It is in the range of 0 mol. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 9.

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

The bleach-fixing solution and fixing solution in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, bisulfite, etc.) as preservatives. potassium, etc.), metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.).

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

The silver halide color photographic light-sensitive material used in the present invention is generally subjected to desilvering treatment such as fixing or bleach-fixing, followed by washing with water and/or stabilizing treatment.

The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the temperature of the washing water, the number of washing tanks (stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is Jour
nal of the 5ociety of Moti
on Picture and Television
Engineers Vol. 64, p. 24B-253 (
The number of stages in the normal multi-stage countercurrent system is preferably 2-6, particularly preferably 2-4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, from 0.5 to 141 cm per 1 m of photosensitive material, but the increased residence time of water in the tank can lead to bacterial growth. However, as a solution to such problems in the processing of the color photosensitive material of the present invention, problems such as the generated floating substances adhering to the photosensitive material occur.
The method of reducing calcium and magnesium described in No. 1632 can be used very effectively. Also,
Isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate described in JP-A No. 61-120145, benzene as described in Japanese Patent Application No. 105-487-1987 Triazole, copper ion, etc. "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi
It is also possible to use the disinfectants described in "Microbial Sterilization, Disinfection, and Anti-Mildew Technology" by Kinshi, Sanitary Technology, and "Encyclopedia of Antibacterial and Antifungal Agents" by Kinshi, Japan Antibacterial and Antifungal Science. Further, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 2
A temperature range of 30 seconds to 5 minutes is selected at 5 to 40°C.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without the water washing step. A compound having an image stabilizing function is added to the stabilizing solution, such as an aldehyde compound represented by formalin or Mp suitable for stabilizing the dye.
Examples include buffering agents and ammonium compounds for adjusting to H.

Furthermore, in order to prevent the proliferation of bacteria in the solution and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, surfactants, optical brighteners, and hardeners may also be added. In the processing of the photosensitive material of the present invention, if stabilization is achieved directly without going through a water washing process, JP-A-57-
No. 8543, No. 5B-14834, 60-220345
All known methods described in No. 1 and the like can be used.

In addition, it is also a preferred embodiment to use chelating agents such as l-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to flow the overflow of washing water, which has been reduced by a multi-stage countercurrent system, into a bleach-fixing bath, which is a pre-bath, and replenishing the bleach-fixing bath with concentrated liquid to reduce the amount of waste liquid.

If the method of the present invention uses a color developer,
Can be applied to any processing process, such as color vapor, color reversal vapor, color direct positive photosensitive materials, color positive film, color negative film, color reversal film, etc., but especially to color vapor and color reversal paper. It is preferable to apply

Silver halide emulsions in light-sensitive materials used for light and brightness are
Any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide, silver chloride can be used.For example, when performing quick processing such as color vapor or low replenishment processing, silver chloride can be used.
A silver chlorobromide emulsion or a silver chloride emulsion containing mol% or more is preferable, and a silver chloride content of 80 to 100 mol% is particularly preferable, and also requires high sensitivity and is easy to store during production. When it is necessary to particularly suppress fog during processing and/or processing, use a silver chlorobromide emulsion containing 50 mol% or more of silver bromide (which may contain 3 mol% or less of silver iodide). ), more preferably 70 mol % or more. Silver iodobromide and silver chloroiodobromide are preferable for color photographic materials, and the silver iodide content is preferably 3 to 15 mol %.

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

The average grain size distribution of the silver halide grains used in the present invention may be narrow or wide, but the value obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size ratio) within 20%, particularly preferably 1
It is preferable to use a so-called monodispersed silver halide emulsion of 5% or less in the present invention, and in order to satisfy the target gradation of the light-sensitive material, grains in the emulsion layer having substantially the same color sensitivity are preferably used. 28 different sizes! The above monodisperse silver halide emulsions (preferably those having the above-mentioned fluctuation rate as monodispersity) can be mixed in the same layer or coated in separate layers. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or in a layered manner.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, rhombidodecahedral, dodecahedral, etc.).
r) crystals or coexistence of these crystals, or irregular (irregular) crystals such as spherical
ular) crystal form, or a composite form of these crystal forms, and may be tabular grains, especially tabular grains with a length/thickness ratio of 5 to 8 or 8 or more. An emulsion in which the grains occupy 50% or more of the total projected area of the grains may be used, or an emulsion consisting of a mixture of these various crystal forms may be used.

These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is Re5earchDi
sclosure vol, 170 1te■No,
1 7643 (I, ■, ■) (1978, 12).

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are described in Research Disclosure Vol. 176, No. 17643 (December 1978) and Research Disclosure Vol. 187, No. 18716 (1979).
, November), and the relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the above two Research Disclosures, and the locations are shown in the table below.

l Chemical sensitizer page 23 page 648 right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizers, pages 23-24 Page 648 right column - Super sensitizers
Page 649, right column 4 Brightener
Page 24 5 Antifogging agent Page 24-25 Page 549 Right column and stabilizer 6 Coupler Page 25 7 Organic solvent Page 25 8 Light absorber, Phi Page 25-26 Page 649 Right column ~ Luther dye, Page 650 Left column Ultraviolet rays Absorbent 9 Anti-stain agent Page 25, right column Page 650, left to right column l
O dye image stabilizer page 25 11 Hardener page 26 page 651 left column 12 Binder page 26 Same as above 13
Plasticizer, lubricant Page 27 Page 650 Right column 14
Coating aid, pages 26-27 Same as above Surfactant 15 Static inhibitor page 27 Same Water Various color couplers can be used in the invention.

Here, the term "color coupler" refers to a compound that can produce a dye through a capping reaction with an oxidized product of an aromatic primary amine developer. Typical examples of useful color couplers include naphthol or phenolic compounds, Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention include pyrazolone or pyrazoloazole compounds and open chain or spring ring ketomethylene compounds.Research Disclosure (RD) 17643
(December 1978) ■-D Section and 18717 (December 1978)
(November 1979).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized, and the coupling active position is substituted with a leaving group rather than a four-equivalent color coupler with a hydrogen atom. Two-equivalent color couplers are preferable, such as couplers in which the amount of silver coated can be reduced.0 Couplers in which color-forming dyes have appropriate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor upon coupling reaction, or DIR couplers that promote development. Couplers that release agents can also be used.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof include U.S. Pat. Same 2nd and 3rd
No. 43,703, No. 2,600,788, No. 2,
No. 908,573, No. 3,062.653, No. 3
, No. 152,896 and No. 3,936,015.

As the leaving group for the two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or the arylthio group described in U.S. Pat. No. 4,351.897 is preferred. Also European Patent Section 73,6
The 5-pyrazolone coupler having a ballast group described in No. 36 provides high color density.

As pyrazoloazole couplers, U.S. Pat.
369,879, preferably pyrazolo(5,1-c)(1,2,4) triazoles described in U.S. Patent No. 3,725.067, Research Disclosure 24220 (
Pyrazolotetrazoles and Research Disclosure 24230 (June 1984) and Research Disclosure 24230 (June 1984)
In view of the low yellow side absorption and light fastness of color-forming dyes, imidazo (1) described in European Patent No. 119,741,
, 2-b) pyrazoles are preferred, according to European Patent Section 119
, pyrazolo (1,5-b) (1,2,
4) Triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, such as the naphthol-based couplers described in U.S. Pat.
, No. 212, No. 4.146,396, No. 4,22
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 8,233 and No. 4,296,200. Specific examples of phenolic couplers include U.S. Patent Nos. 2,369,929 and 2,8
No. 01,171, No. 2,772.162, No. 2,
No. 895,826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, exemplified by U.S. Patent No. 3,772.
, U.S. Pat.
No. 8,308, No. 4,126.396, No. 4,3
No. 34,011, No. 4.327,173, West German Patent Publication No. 3,329.729, and Patent Application No. 1983-426
2,5-diacylamino-substituted phenolic couplers described in No. 71, etc. and U.S. Patent No. 3,446°62
No. 2, No. 4,333,999, No. 4゜451.5
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in No. 59 and No. 4,427,767.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusive couplers are magenta couplers in U.S. Pat. .234.533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and special couplers described above may form dual or more polymeric polymers; typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3,451,82.
No. 0 and No. 4,080.211. Specific examples of polymerized magenta couplers include British Patent Section 2,102% 173 and U.S. Patent No. 4,367.2.
It is described in No. 82.

The various couplers used in the present invention can be used in combination in two or more layers in the same photosensitive layer, or in two or more different layers using the same compound, in order to satisfy the characteristics required for the photosensitive material. It can also be introduced into

Typical usage amounts for color couplers range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.1 mole for yellow couplers.
5 mole, 0.003 to 0.3 for magenta coupler
moles, and for cyan couplers 0.002 to 0.3
It is a mole.

The couplers used in the present invention can be incorporated into the light-sensitive material by one of a variety of known dispersion methods. An example of a high boiling point organic solvent used in the oil-in-water dispersion method is U.S. Pat. No. 2,322,02.
It is stated in issue 7 etc. Further, the process of latex dispersion method, effects, and specific examples of latex for impregnation are described in U.S. Pat.
No. 541, '274 and No. 2,541,230.

The photographic material used in the present invention is coated on a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper, or a rigid support such as glass. . For details on the support and coating method, please refer to Re5e.
arch Disclosure Volume 176 Item
17643 Section X7 (Page 27) Double ■ Section (Page 28) (December 1978 issue).

In the present invention, a reflective support is preferably used.

A "reflective support" is a material that increases the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin containing dispersed light-reflecting substances such as calcium carbonate and calcium sulfate, and those using a hydrophobic resin containing dispersed light-reflecting substances as a support.

(Effects of the Invention) According to the present invention, the generation of magenta tin can be prevented, and the coloring property can be improved by using a birazoroasole magenta coupler.
Color photographic images with excellent fading resistance can be formed. Furthermore, according to the method of the present invention, the sulfite ion component in the color developer is not necessarily necessary, and it has the excellent effect of preventing fluctuations in photographic properties due to the processing solution, and this effect is due to the presence of benzyl alcohol in the developer. Especially if you don't.

(Examples) Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in further detail. However, the present invention is as follows: 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.

1st layer coating solution preparation 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 emulsion dispersion and emulsion EMI and E
A first layer coating solution was prepared by mixing and dissolving M2 and adjusting the gelatin concentration 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. l-oxy-3,5-dichloro-5-triazine sodium salt was used as the gelatin hardening agent for each layer.

Moreover, (Cpd-2) was used as a thickener.

(Layer structure) The composition of each layer is shown below, and the numbers indicate the coating amount (g/ml). Silver halide emulsions represent coating values in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Ti02) and a bluish dye. ] Layer (blue-sensitive layer) Monodisperse silver chlorobromide emulsion (EMI) spectrally sensitized with a sensitizing dye (ExS-1)... Spectral sensitization with a 0.13 sensitizing dye (ExS-1) Sensitized monodisperse silver chlorobromide emulsion (Em2) -0,13 Gelatin °°°1.86 Yellow coupler (ExY-1) -0,44 Yellow coupler (ExY-2) -0,39 Dye stabilizer (C
pd-1) ・-0,19 Solvent (Solv
-1) ・-0, 35 second layer (mixing prevention layer) Gelatin °-0・99 color mixing prevention agent (Cpd-3) -0, 08 third layer (green-sensitive layer) Sensitizing dye (ExS-2, 3) Monodisperse silver chlorobromide emulsion spectrally sensitized (Em, )) -0,05 sensitizing dye (ExS
-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 color image stabilizer (Cpd-5) ・-
0.02 color image stabilizer (Cpd-6)...
・0.03 solvent (Solv-2)
-0,12 solvent (Solv-3)
...0, 25 fourth layer (ultraviolet absorption layer) Gelatin -1,60 ultraviolet absorber (Cpd-7/Cpd-8/Cpd-9-3/2/
6: weight ratio)・-0,70 Color mixture prevention agent (Cpd-10) -0,05
Solvent (Solv-4) −=0,
27 Fifth layer (red sensitive layer) Monodisperse silver chlorobromide emulsion (EMS) spectrally sensitized with a sensitizing dye (ExS-4,5) -0,07 sensitizing dye (ExS-
Monodisperse silver chlorobromide emulsion (EMS
)-0, 16 gelatin - Axis 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)...0.28 Solvent (Solv-2)...-0,2
0 6th layer (ultraviolet absorbing layer) Gelatin -0,54 ultraviolet absorber ((:pd-7/(:pd-9/Cpd-12-1
15/3: weight ratio)...0.21 solvent (Solv-2
) -0,08 Seventh layer (protective layer) Gelatin...1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%)...0.17 Liquid paraffin...0.03 Also, this The anti-irradiation dye is (Cpd-1
3, Cpd-14) was used.

In addition, each layer contains Alkanol
ax F-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 1.0 80 0.08EM
2 G, 75 80 0.07EM3 0
．． 5 B3 0.09EM4 0.
4 83 0.1 OEM5
0.5 73 0.09EM6 0.4
73 0.10EXY-1 C flood xY-2 Cρ E x M-1 See Table 1 xC-1 I xS-1 xS-2 xS-4 xS-5 pd-1 pd-2 O3K pd-3 H H pd -4 pd-5 2H5 u5killtl Cpd-7 Cpd-8 Cpd-9 Cpd-10 H Cpd-11 Cpd-12 Solv-1 dibutyl phthalate 5olv -2 tricresyl phosphate 501v-3
Trioctyl phosphate 5olv -4) Linonyl phosphate pd-13 Cpd-14 Cpd-15 Cpd-16 As shown in Table 1, color photographic papers with different magenta couplers were prepared. The resulting photographic paper was exposed through an optical wedge and then processed in the following steps.

Processing process [J Time color development 38℃ 1 minute 40 seconds Bleach fixing 30
～34℃ 1 minute 00 seconds■ 30～34℃ Rinse for 20 seconds■ 30～34℃ Rinse for 20 seconds■ 30～34℃ Dry for 20 seconds 70～80"C50 seconds (3 tanks countercurrent from rinse ■→■ The composition of each treatment liquid is as follows.

Color developer water 800m
Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,t-di*xx*nic acid (60%) 2.0g Nitrilotriacetic acid 2.0g Benzyl alcohol See Table 1 Diethylene glycol See Table 1 Sodium sulfite
See Table 1 Compounds of the invention A f
See Table 51 Compound B of the invention See Table 1 Potassium bromide 0.5 g Potassium carbonate 30 g N-ethyl-N
-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.5g optical brightener (
Add 1.5 g of UVITEX-CX (manufactured by Ciba Geigi) and water to 1000 mS pH (25
℃) 10.25 bleach-fix solution water 400
ml ammonium thiosulfate (70%) 200
Sodium sulfate 20g Iron ethylenediaminetetraacetate (m) Ammonium Bog Disodium ethylenediaminetetraacetate 10g Add water 1000m pH (258C)
7.00 Rinse solution Ion-exchanged water (calcium and magnesium are each 3 ppm or less) Meanwhile, take a portion of the above color developer and leave it in an open system at 30°C for 30 days, then remove this aged solution. was used and processed in the above treatment steps.

Processing using the color developer solution (aged solution) left for 30 hours was defined as an aged solution test, and processing using the color developer solution (fresh solution) before being allowed to stand was defined as a fresh solution test.

Table 1 shows the photographic properties obtained in the fresh liquid test and aged liquid test.

Photographic properties were expressed in terms of Dmin (magenta density) and gradation.

DIIlin represents the minimum density, and the gradation is expressed as a C degree change from a point representing density 0.5 to a density point on the high exposure side of logE 0.3.

t2) Comparative magenta coupler M-I Comparative magenta coupler opening Comparative magenta coupler M-I From Table 1, in the comparative example, Dmi
Large increase in n and change in gradation (No, 1 to 12)
. In addition, if a color developer other than the one according to the present invention is used,
Even when the color developer of the present invention is used, the change in Dmin is large (No. 4 to 8).

According to the present invention, the fluctuations in the above-mentioned photographic properties are reduced, and the effect is more pronounced especially in the absence of pencil alcohol and in the absence of sulfites (
Comparison of No. 13 and No. 17, and comparison of No. 15 and No. 17).

Example 2 Under the conditions of No. 20 in Example 1, Magenta Cobrado 37 was applied to M-9, M-44, M-45, 1
When the same experiment was carried out by changing the angle to -47° to 52 and 58, favorable results similar to those in Example 1 were obtained.

Example 3 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 coating solution for the first layer) To 19.1 g of yellow coupler (ExY-1) and 4.4 g of color image stabilizer (Cpd-1), 27.2 cc of ethyl acetate and 7.7 g of high boiling point solvent (Solv-1) were added.
, 7 cc (8.0 g) was added and dissolved, and this 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 have the following composition.
A layer coating solution was prepared. The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer.

l-oxy-3°5-dichloro-S-triazine sodium salt was used as the gelatin hardening agent for each layer.

Moreover, (Cpd-1) was used as a thickener.

(Constituent layer) The composition of each layer is shown below. The number is the coating amount (g/rn')
The silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiOz) and a bluish dye. ] Layer (blue-sensitive layer) Monodisperse silver chlorobromide emulsion (EM7) spectrally sensitized with a sensitizing dye (ExS-1)...Spectrally sensitized with a 0.15 sensitizing dye (ExS-1) Sensitized monodisperse silver chlorobromide emulsion (EMS)...0.15 Gelatin -1,86 Yellow coupler (ExY-1) -0,82 Dye stabilizer (Cpd-2)...0. 19 Solvent (S
olv-1) = 0, 35 Second layer (color mixing prevention layer) Gelatin -0,99 Mixing prevention agent (Cpd-3) -...0.08 Third layer (green sensitive layer) Sensitizing dye (ExS- Monodisperse silver chlorobromide emulsion (EM9) spectrally sensitized with 0.12 sensitizing dye (ExS
-2,3) monodisperse silver chlorobromide emulsion (EM
IO)・-0,24 gelatin・
・・1.24 magenta coupler (ExM-1)
=-0, 39 color image stabilizer (Cpd-4)
-0,25 color image stabilizer (Cpd-5)
・-0,12 solvent (Solv-2)
...0, 25 fourth layer (ultraviolet absorption layer) Gelatin ...1.60 ultraviolet absorber (Cpd-6/Cpd-7/Cpd-8 3/2
/S: weight ratio)・-0,70 Color mixture prevention agent (Cpd-9)・-0,05
Solvent (Solv-:l) -0,4
2 Fifth layer (red sensitive layer) Monodisperse silver chlorobromide emulsion (EMII) spectrally sensitized with a sensitizing dye (ExS-4,5)...0.07 sensitizing dye (ExS-4,5)
Monodisperse silver chlorobromide emulsion (E
M12)-0+ 16 gelatin
-0,92 cyan coupler (ExC-1)
-1, 46 cyan coupler (ExC-2)
-, 1, 84 color image stabilizer (Cpd-7/Cpd-8/C
pd-10=3/4/2: weight ratio) -0,17
Dispersion polymer (cpct-tg-0, 14
Solvent (Solv-1) -0, 20
Sixth layer (ultraviolet absorbing layer) Gelatin...0.54 ultraviolet absorber (Cpd-6/Cpd-8/Cpd-10=1)
5/3: weight ratio) -0,21 Solvent (Solv-4) -0,08
Seventh layer (protective layer) Gelatin...1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%) -0,17 Liquid paraffin -0,03 Also, at this time, for preventing irradiation As dyes, (Cpd-12, C
pd-13) was used.

In addition, each layer contains Alkanol
ax F-120 (manufactured by Dainippon Ink Co., Ltd.) was used. (Cpd-14,15) was used as a silver halide stabilizer.

Details of the emulsion used are as follows.

EM7 1.1 1.0 0.10EM
8 Q, 8 1. Q O, 10E M 9
0.45 1.5 0.09EMIO014
1,50,09 EMII O,451,50,09 EM12 0.34 1.6 0.10 Average size The structural formula of the compound used is as follows.

ExM-1 ExC-1 ExS-1 ExS-2 ExS-3 ExS-4 C2H5IeC2H5 ExS-5 Cpd-1 Cpd-25o3K pd-3 (Jl-1 Cpd-4 cpa-'y Cpd-s Cpd-9 H H Cpd-11 (CH2CH+-(n=100-1000)CONHC
4H9 (tl Cpd-12 Cpd-13 Cpd-14 Cpd-15 H 8olv-1 dibutyl phthalate 5olv-2 trioctyl phosphate 5olv-3)
Linonyl phosphate 5olv-4) Lyclesyl phosphate 7ate As shown in Table 2, color photographic papers with different magenta couplers were prepared. The resulting color photographic paper was passed through an optical wedge and processed in an exposure extraction process.

Shikiuni μ I Kuiho color development 35℃ 45 seconds bleach fix 30-35℃ 45 seconds rinse ■ 30-35℃ 20 seconds rinse ■ 30-35℃ 20 seconds rinse ■ 30-35℃ 20 seconds rinse ■ 30-35℃ Dry for 30 seconds at 70-80°C for 60 seconds (3-tank countercurrent flow method from rinsing ■ to ■). The composition of each treatment solution is as follows.

Color developer water 800
ml ethylenediamine-N,N.

N,N-tetramethylenephosphonic acid 1.5 g Sodium sulfite See Table 2 Compounds of the invention C See Table 2 Compounds of the invention D See Table 2 Sodium chloride 1.4 g Potassium carbonate
25g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g Fluorescent brightener (UVITEX CK Ciba Geigi) 2.0g
Add water to 1000m pH (25
℃) 10.10 bleach fixer water 400m
! ; L ammonium thiosulfate (70X) 100
mJl Sodium sulfite 18g Ethylenediaminetetraacetic acid iron(III) Ammonium 55g Ethylenediaminetetraacetic acid disodium 3g Ammonium bromide 40g Glacial acetic acid
Add 8g water 1
000m pH (25°C) 5.5 Rinse solution Ion-exchanged water (calcium and magnesium are each 3 ppm or less) Changes in photographic properties in the fresh solution and aged solution were determined in the same manner as in Example 1, and the above aged solution was further evaluated. The aperture ratio (contact area of processing liquid with air/volume of processing liquid) is 0 at a bee force of lfL.
．． 125 and left at 35°C for 10 days. After standing, the crude drug residual rate of each treated solution was measured by liquid chromatography, and the crude drug residual rate 81) was calculated.

As is clear from Table 2, according to the treatment liquid composition of the present invention, the residual rate of the active ingredient is high and the stability of the treatment liquid is certainly improved (Experiments No. 007 to 31). As shown in the comparative example, the change in photographic properties due to processing of fresh solution and aged solution may not be improved even if the residual rate of the active ingredient is high (Experiment No. 003.4), and both the stability of the processing solution and the change in photographic properties are satisfactory. This is only in the case of the method of the present invention (Experiment Nos. 7 to 31).

Example 4 In No. 7 in Example 3, magenta cobrado 42 was replaced with M-6, M-16, 1-27, G44, G45.
When the same experiment was conducted except for changing to 58 and 58, the same favorable results as in Example 3 were obtained.

Example 5 The samples prepared in Example 1 were prepared in the same manner except that the compound shown in Table 3 was used as the magenta coupler, and each sample was imagewise exposed and then processed according to Table 3. The treatment was carried out in the following steps in combination with the liquid.

Processing process ■ *rtn WLX** Color development
38℃ 1 minute 40 seconds 290ml bleach fixing 30
to 34℃ 1 minute 40 seconds 150ml Rinse 030-3
4℃ 20 seconds □ Rinse■ 30-34℃ 20 seconds □Rinse■ 30
~346C 20 seconds 364ml drying 70~80℃
50 seconds □ (3-tank countercurrent force type from rinsing ■ to ■) (*per 1 m'' of sensitive material) The composition of each processing solution is as follows.

Color developer tank liquid Toyoju Tomisui
800ml 800ml diethylenetriaminepentaacetic acid 1.0g 1.0g1-hydroxyethyridane-1,1-diphosphonic acid (602) 2.0g 2.0
g Nitrilotriacetic acid 2.0 g 2. Og
Compound of the invention E O, 3 mol O,
04 mol (see Table 3) (see Table 3) Compound of the invention F O,0:l sol O
, 04 mol (see Table 3) (see Table 3) Potassium bromide O, Sg - Potassium carbonate 30 g 30 g N-ethyl-
N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.5 g 7.5 g Fluorescent brightener (UV ITEX-CK Add water and observe for 1000 m 1000 m exchange pH (25°C) 10.25 10.
60 Bleach Fixer Tank Liquid Giketsu Kansui
400 d 4
00 Ammonium thiosulfate (70%) 200 m [
i 300ni sodium sulfite 20 g
40 g Ethylenediaminetetraacetic acid iron (m) 7:zmo-tsu A 60g 12
0g Disodium ethylenediaminetetraacetate 10g Add 20g water 10100O1000m 1pH
(25℃) 7.00 6.70 Rinse liquid ion exchange water (calcium, magnesium 3pp each
m or less) Continuous processing (running test) was performed under each condition until three times the tank capacity of the color developer was replenished. and,
Changes in G (green) density in the stain and gradation areas at the start of the running process and after the running process were measured using a Fuji self-recording densitometer. Furthermore, after the sample at the end of the running process was left at 80° C. (5 to 1 ORH) for one month, the change in G concentration in the stain portion was measured again.

The results of the changes in photographic properties obtained are shown in Table 3.

According to the present invention, changes in photographic properties due to running are small, and increase in magenta tin due to time after processing is also small.

Book 1: Comparative magenta couplers M-i and M-c see Example 1.

Book 2: I) win (stin) at the start of running
The increase in Dmin at the end of the run.

Zero 3: Increase in the G density of the gradation area at the end of running compared to the G density of the gradation area during running.

Zero 4: Increase in Dmin after 80°Cl menstruation with respect to Dmin of the sample at the end of running.

As is clear from Table 3, according to the method of the present invention, the change in photographic properties due to running and the change in Dmin of the sample after 80°C chlorination were both the same as in the comparative example (
It can be seen that this was significantly improved over Experiment Nos. 1 to 6).

Example 6 Ion exchange water (calcium and magnesium ions each 3 ppm or less) instead of the rinse liquid used in Example 5
When a running test was conducted in the same manner as in Experiment No. 8, similar excellent results were obtained.

Procedural proceedings (spontaneous) May 27, 1988 Director General of the Patent Office Kunio Ogawa 1, Indication of the case 1988 Patent Application No. 115947 2, Name of the invention Processing of silver halide color photographic light-sensitive materials Method 3: Relationship with the case of the person making the amendment Patent applicant address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52
0) Fuji Photo Film Co., Ltd. Representative: Minoru Ohnishi 4, Agent Address: 7th Floor 6, Midoriya 2nd Building, 3-7-3 Shinbashi, Minato-ku, Tokyo 105, Subject of Amendment 7, Contents of Amendment (1) Details Book 8th page 2nd line from bottom to 9th page 1st
Delete the first line "Contains general formula (I)...".

(2) Delete "r2,3゜4,...benzamide group" in the same book, page 19, lines 9 to lo (7).

(3) “Biruru” in lines 2 to 1 from the bottom of page 21 of the same book
to "vinyl".

(4) Same book, 50th page, r (M-67)
) Add J.

(M-71) (M-68) (M-69) (M-70) NI(SOzL;tsLi:+:+ (M-72) (M-73) (M-82) CsH17(L) (M -85) NO In the same book, page 70, lines 4 and 12, "-general formula (X [[) J] will be corrected to "general formula (X)," respectively.

(6) Add the following on a new line after rXI-14J on page 76, line 3 of the same book.

rXI-15 (7) Correct "oxylose" in the first line of page 89 of the same book to "xylose".

(8) “However,” on page 96, lines 2-7 of the same book.
··means. ”.

(9) In the 8th line of the same page of the same book, "Used...in the developer" is corrected to "Place".

(10) "It is done," in the third line of page 117 of the same book.
Add the following on a new line after .

``Also, in the present invention, it is preferable to use a water-insoluble but organic solvent-soluble polymer contained in the lipophilic fine particles together with a specific oil-soluble coupler. It is preferable to use a water-insoluble and organic solvent-soluble polymer consisting of at least one type of folded unit, but polymers having 141 bonds as the folded unit are preferred in terms of color development and fading improvement effect. preferred.

Furthermore, the repeating unit having no acid group of the polymer is C-0- having 11 groups in its main chain or side chain, or the repeating unit of the polymer having no acid group G1 and 0-
(2) each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group).'' (11) Ibid., page 124 rEXY-IJ and the same chemical formula are corrected as described below.

Mi y-1 Q (12) Correct the chemical formula of Ibid Bege rExY-2J as shown below.

(13) The chemical formula of rCpd-IJ, page 126 of the same book, will be corrected as described below.

□The seal is ≧ b1). ≦ ≦ τ % OII ro Q ma 閤 かんの = b □ −〇 Figure 7 7 schools ■ agon 目 L (15) Correct the chemical formula of "rCpd-2", No. 146 of the same book, as described below.

B　　−　　　　− One (1')l+.

``[(17) ``Example 6... was obtained.'' in the same book, page 160, line 17 to page 161, line 1, is amended as described below.

Example 6 A photosensitive material similar to Example 3 was prepared except that the magenta coupler in the third green-sensitive layer in Example 3 was changed to the magenta coupler of the present invention in equimolar amounts as shown in Table 4. After exposing these photosensitive materials through an optical wedge,
It was treated in the same manner as in Example 3.

Thereafter, in the same manner as in Example 1, changes in photographic properties were determined for the fresh solution and the aged solution.

As is clear from Table 4, when the present invention is used,
It can be seen that the change in photographic properties between the fresh solution and the aged solution is significantly suppressed.

Example 7 A multilayer color photosensitive material having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.
-A.

(Layer structure) The composition of each layer is shown below. The number is the amount of application in g.
It is expressed as For silver halide emulsions and colloidal silver, the amount of coating in terms of silver is expressed in grams, and for spectral sensitizing dyes, the amount added per mole of silver halide is expressed in moles.

Support polyethylene laminate paper [The polyethylene on the 61st layer side contains a white pigment (TiO□) and a bluish dye (ulmarine blue)] E1 layer Silver halide emulsion 0.26 Spectral sensitizing dye (ExSS-1) 1 , Ox 10-' spectral sensitizing dye (ExSS-2) 6, 1 x 10"
"" Gelatin 1.11 cyan coupler (Ex(:C-1) 0, 21 cyan coupler (Exll:C-2) 0,
26 Ultraviolet absorber (ExlJV-1) 0
, 17 solvent (ExS-1) 0
, 23 development regulator (ExGC-1)
0, 02 stabilizer (ExA-1) 0
, 006 nucleation accelerator (ExZS-1) 3 ,
Ox 10-4 nucleating agent (ExZK-1)
a, ox to -' E2 layer gelatin 1.41 Color mixing inhibitor (ExKB-1) 0, 09 Solvent (Ex
S-1) O+ 10 solvent (Ex
S-2) 0, 10 E3 layer silver halide emulsion 0, 23 Spectral sensitizing dye (ExSS-3) 3, Ox l O"" Gelatin 1.05 Magenta coupler (ExMC-1) 0.16 Color image stability Agent (E
xSA-1) 0, 20 solvent (ExS-
3) 0,25 developer gi agent (E
xGC-1) 0, 02 stabilizer (ExA
-1) 0, OOS nucleation accelerator (
ExZS-1) 2.7x 10' nucleating agent (Ex
ZK-1) 1,4 x l O-5 E4 layer gelatin 0.47 Color mixing inhibitor (ExKB-1) 0,03 Solvent (E
xS-1) 0,03 solvent (E
xS-2) 0, 03 E5 layer colloidal silver 0.09 gelatin
0.49 Color mixing prevention agent (ExK
B-1) 0,03 solvent (ExS-1)
0,03 solvent (ExS-2)
0, 03th E6i E7th layer silver halide emulsion same as E4th layer 0.40 Spectral sensitized color It (ExSS-3) 4,2 x 10-
4 Gelatin 2.1 Yellow coupler (ExYC-1) 0, 51 Solvent (ExS-2) 0, 20 Solvent (5-4 in ε) 0.20 Development m
s agent (ExG(nee 1) 0, 06 stabilizer (ExA-1) O, OOl nucleation accelerator (ExZS-1) 5, Ox 10'
Nucleating agent (ExZK-1) l, 2X
10-6 E8 layer gelatin 0.54 Ultraviolet absorber (ExUV-2) 0, 21 Solvent (
ExS-4) 0, 08th E9
Layer gelatin 1.28 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 Latex particles of polymethyl methacrylate (average particle size 2.8 m) 0.05 B1 layer Gelatin 8.70 In addition to the above composition, gelatin hardener ExGK-1 is added to each layer, which is the same as the 82nd layer and the E9th layer.
and surfactant were added.

Compounds used to prepare the sample (ExCC-1) Cyan coupler C [ (ExCC-2) Cyan coupler % + L (ExMC-1) Magenta coupler (ExYC-1) Yellow coupler C2 (ExSS-1) Spectral sensitizing dye (ExSS-2) Spectral sensitizing dye (ExSS-3) Spectral sensitizing dye (EXSS-4) Spectral sensitizing dye ap (ExS-1) Solvent (ExS-2) Solvent (ExS-3) Solvent 1:1 Mixture (volume ratio) (ExS-4) Solvent o=p-→-OC9HI3(ISO) ) 3(ExU
V-1) Ultraviolet absorber (1)': (2): 5:8:9 mixture (weight ratio) of (3) (Ex UV-2) Ultraviolet absorber (1):
(2): 2:9:8 mixture (weight ratio) of (3) (ExSA-1) Color image stabilizer (ExKB-1) Color mixing inhibitor (ExGC-1) Development control agent (ExZS-1) Nucleation Accelerator 2-(3-dimethylaminopropylthio)-5-mercapto-1,3,4-thiadiazole hydrochloride (ExZK-1) Nucleating agent 6-nitoxythiocarbonylamino-2-methyl-1-
Propargyl quinolinium triple olomethane sulfonate (ExGK-1) Gelatin hardener Preparation of l-oxy-3,5-dichloro-s-triazine sodium salt emulsion C-2 Prepare an aqueous solution of potassium bromide and silver nitrate per mole of Ag. 0
．． 3g of 3,4-dimethyl-1,3-thiazoline-2-
They were simultaneously added to an aqueous gelatin solution to which thione had been added at 75° C. over about 20 minutes with vigorous stirring to obtain a monodisperse silver bromide emulsion with an octahedral grain size of about 0.401 Lm. This emulsion contains 6 mg of sodium thiosulfate per mole of silver and 7 mg of sodium thiosulfate per mole of silver.
Chemical sensitization treatment was performed by adding mg of chloroauric acid (tetrahydrate) and heating at 75°C for 80 minutes. The thus obtained silver bromide grains were cored and further grown in the same precipitation environment as the first time, to finally obtain a monodisperse core/shell silver bromide emulsion with an octahedral average grain size of 0.7 JLm. . The coefficient of variation in particle size was approximately 10%.

To this emulsion were added -91.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mole of silver, and the mixture was heated to 60°C.
A chemical sensitization treatment was carried out by heating for 60 minutes to obtain an internal latent image type halogenated emulsion C-2.

Next, the treatment steps and the composition of the treatment liquid are shown below.

Color development 90 seconds 38°C Bleach fixing 40 seconds 33℃ Washing with water (1) 40 seconds 33℃ Washing with water (2) 40 seconds 33℃ Washing with water (3) 15 seconds 33℃ Drying 30 seconds 80℃ The composition of each treatment liquid was as follows.

Color developer ethylenediaminetetrakismethylenephosphonic acid 0.5g diethylene glycol 10ml benzyl alcohol
12.0d potassium bromide
0.65g Sodium sulfite 2.4
gN,N-diethylhydroxylamine 4.0g triethylenediamine (l,4-diazabicyclo[2,2,2]octane) 4.0gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methylaniline sulfate 5.6g potassium carbonate 27.0g optical brightener (diaminostilbene type) 1.0g Add water 1000dpH (25°C)
10.50 Bleach-fix solution Ethylenediamine tetraacetic acid, disodium, dihydrate 4.0g Ethylenediaminetetraacetic acid, Fe(m), ammonium, dihydrate 46.0g Ammonium thiosulfate (7oOg/i) 155m [ip-
Sodium toluenesulfinate 20.0g Sodium bisulfite 12.0g Ammonium bromide
so, 0g ammonium nitrate
Add 30.0g water and looom
[! pH (25°C) 6.20 Wash water Tap water was 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 is passed through a mixed bed column to reduce the concentration of calcium and magnesium ions to 3 mg/fL or less,
followed by 20 mg sodium incyanurate dichloride
/l and 1.5g/JL of sodium sulfate were added.

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

After the color developing solution was aged in the same manner as in Example 1, the color photographic paper was exposed through an optical wedge and then processed in the above processing steps, and the magenta Din was evaluated in the same manner as in Example 1. As a result, as in Example 1, good results were obtained if the structure of the present invention was followed. ” (18) In the same book, page 91, line 15, after “liquid,” add “pollution, liquid preparation properties,”

(that's all)

Claims (1)

[Claims] (1) A silver halide color photographic light-sensitive material containing at least one pyrazoloazole magenta coupler represented by the following general formula (I) is combined with an aromatic primary amine color developing agent and the following general formula (II). 1. A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a color developer containing at least one of the fused cyclic amines shown below. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a coupling reaction with an oxidized aromatic primary amine developer. Represents a group that can leave.Za, Z
b and Zc are methine, substituted methine, =N- or -N
It represents H-, and one of the Za-Zb bond and Zb-Zc bond is a double bond, and the other is a single bond. The case where Zb-Zc is a carbon-carbon double bond includes the case where it is part of an aromatic ring. Furthermore, it also includes the case where R or X forms a dimer or more multimer, and Za, Zb
Or, when Zc is a substituted methine, this also includes the case where the substituted methine forms a dimer or more multimer.) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X is Represents a trivalent atomic group necessary to complete the condensed ring, R^1^1 and R^1^2 are alkylene groups,
It represents an arylene group, an alkenylene group, or an aralkylene group, where R^1^1 and R^1^2 may be the same or different from each other. )