JPH02148035A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve fastness by incorporating a specified compound into a cyan dye image forming layer and at least one of its adjacent layers. CONSTITUTION:The fastness can be improved by incorporating at least one of the compounds represented by formula I in the cyan dye image forming layer and at least one of its adjacent layers. In formula I, each of R1 and R2 is H, alkyl, cycloalkyl, aryl, or the like; Y is a nonmetallic atomic group necessary to form a 5- or 8-membered heterocyclic ring together with the two N atoms except that a heterocyclic ring is formed by linking each of the two N atoms to a hetero atom each by the medium of alkylene groups, further that the hetero ring containing Y forms perhydro-1,2,4,5-tetrazine, and also that 1-phenyl-3-pyrazolidone is formed by substituting the 2-position by an acyl group substituted by H, acetyl, and carboxyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide color photographic light-sensitive material in which fading of a cyan image is prevented.

[Prior art] When silver halide color photographic materials are imagewise exposed and developed, the oxidized aromatic primary amine color developing agent reacts with the coupler to form indophenol, indoaniline, and indamine. , azomethine, phenoxazine, phenazine, and similar pigments are produced,
It is well known that dye images can be formed.

Generally, the quality of these photographic images is not permanent;
Deterioration occurs over time during storage. Especially azomethine dye,
Or, if a color photograph with an image made of indoaniline dye is exposed to light for a long period of time or stored under high temperature and high humidity, the dye image may fade or discolor, and even the white background may become discolored (yellow stain). This usually causes image deterioration.

Such deterioration in image quality is a fatal drawback for recording materials, and improvements are desired.

- Generally, color photographs use cyan, magenta, and yellow dye images, and research is being conducted to improve the solidity of each dye image. Although much research has been conducted on the fastness of magenta dye images, not much research has been conducted on the fastness of cyan dye images17 because magenta dye images do not have low fastness. However, magenta dye images have become more durable as a result of many researches to improve their fastness, and fading and discoloration of cyan images have become more noticeable, so it has been desired to make cyan dye images more solid.

Further, as a method of using an anti-fading agent to improve the light and wet heat fastness of cyan dye images, for example, hindered amine derivatives and phenol derivatives are disclosed in US Patent No. 4.452.884.
4.465.765, JP-A-5JL-48535, JP-A-59-3433, JP-A-59-5246, JP-A-59-
No. 87456, No. 61-2151, No. 61-8675
No. 0, spirochroman derivatives were published in the Special Publication No. 59-5282.
No. 5, amine compounds other than hydrazine were disclosed in JP-A No. 6.
No. 3-149642, No. 6:3-149643, No. 6
It is suggested in No. 3-149645 and No. 63-163347.

Although these compounds have the effect of improving the light and heat fastness of cyan dyes to some extent, the effect is sometimes small or the photographic properties deteriorate.

Further, hydrazine derivatives have been proposed in European Patent Nos. 255 and 722 and Japanese Patent Application Laid-open Nos. 63-220142 and 5850533. However, European Patent 255,7
The compound described in No. 22 has a very small effect of preventing color fading on dyes, and eliminates the developing agent that worsens fading by reacting with the developing agent remaining in the color photographic light-sensitive material after development processing. It is. For this reason, the method described in European Patent No. 255,722 has a limited ability to fade, and its anti-fading effect is very small. Also, JP-A-63
The compound described in No. 220142 lowers the color development of the coupler and causes fog in unexposed areas, thereby adversely affecting photographic properties.

On the other hand, various anti-fading agents have been proposed to improve the fastness of magenta images, but these compounds are certainly effective in solidifying magenta images, but they are not effective against cyan images. Many of them showed little effect and on the contrary accelerated fading.

[Problem 1 to be Solved by the Invention Accordingly, a first object of the present invention is to provide a silver halide color photographic light-sensitive material in which the fastness of a cyan dye image is improved.

A second object of the present invention is to include in the photographic layer a stabilizer that is sufficiently effective in improving the fastness of cyan dye images without causing any change in hue or formation of fog, as well as poor dispersion or crystallization. The object of the present invention is to provide a silver halide color photographic material in which a cyan image is stabilized.

A third object of the present invention is to provide a silver halide color photographic material that improves the color balance of the three fading colors by improving the fastness of cyan images to light and heat.

[Means for Solving the Problems] As a result of various studies, the present inventors have determined that at least one of the cyan dye image forming layer and its adjacent layer has the following general formula [I
The present invention was completed based on the discovery that the object of the present invention can be achieved by containing at least -. species of the compound represented by the following.

General formula [I] [wherein R1 and R2 are a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group,
Represents an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a phosphonyl group, a sulfinyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group. , Y represents a group of nonmetallic atoms necessary to form a 5- to 8-membered heterocycle together with two nitrogen atoms. However, except when the two nitrogen atoms are both linked to a heteroatom via an alkylene group to form a heterocycle, and the heterocycle formed by Y is perhydro-1,2,4,5- Excluding compounds that form tetrazine, and excluding compounds that form 1-phenyl-3-pyrazolidone and the substituent at the 2-position is a hydrogen atom, an acetyl group, or an acyl group substituted with a carboxyl group. . ] ]] Among the compounds represented by the following general formula], compounds in which each of R and R2 has 40 or less carbon atoms, and the total number of carbon atoms is 6 to 50, are preferable.

Margin below Next, the present invention will be explained in detail.

Cyan couplers contained in the cyan dye image forming layer are represented by the following general formulas [C-I], [C-ml, [C-ml and [C-IVI].

General formula [C-ll General formula [C II General formula [C-llll -・Math formula [C ■] -Q40 In the formula, Z represents a hydrogen atom or a group that can be separated during the coupling reaction with the oxidized form of the developing agent. represent.

) [10 is -NHCR13, -NHSO2-R14CR
15, or -302-R16. Here l(+
3, R14, R15 and R16 represent an aliphatic group, an aromatic group, a heterocyclic group, or an amine group which may have a substituent. 1 (13 and R15 further represent an aliphatic oxy group, an aromatic oxy group, or a heterocyclic oxy group.

R's represents a hydrogen atom, an aliphatic group, or a group defined by RIG. R12 is a hydrogen atom, a halogen atom, an aliphatic group,
Represents an aromatic group, a heterocyclic group, an aliphatic oxy group, or a group defined in RIO. XIG represents =CH- or -N-, and the R eyes and R12 may be bonded to each other to form a 5- to 7-membered ring. 1 (21 and R22 may be the same or different, and both represent an aromatic group, a heterocyclic group, or a substituent in which at least one is an electron-withdrawing group. Q10 forms a nitrogen-containing heterocycle) R31, l' (32 and 1733 may be the same or different and each represents a hydrogen atom or a substituent)
R32 and R33 further include at least - of R32 and R33.
represents the group defined by Z. n represents 1 or 2. When n is 2, two R32s may be the same or different.

However, at least -. of R31, R32 and R33 is an electron-withdrawing group. QLO is) = (X
``-Y'') s''<Along with the residue, the heterocycle is also 1.
〈 represents a nonmetallic atom -f group necessary to form an aromatic group. 7X40 and Y2O are nitrogen atoms or W! The 1st substituent is ``a'', which represents a good methine group, m represents 1 or 2, and R40 and R41 are w! I! represents a group. However, R
At least one of 40 and R41 does not represent an electron-withdrawing group. When m is 2, two X40s and two yao may be the same or different.

The aliphatic group referred to in the present invention may be a linear or branched chain or cyclic, saturated or unsaturated, and an argyl group which may be further substituted with a substituent;
They are alkenyl and alkynyl groups. The aromatic group referred to in the present invention is a carbocyclic aromatic group, to which an aromatic ring, a heterocycle, an alicyclic ring, etc. may be condensed, and the group may be further substituted with a substituent. Unexploded IJ-7! A heterocyclic group referred to as ``heterocyclic group'' is a group in which the ring constituent T- has at least one atom selected from oxygen, nitrogen, and sulfur atoms in addition to carbon atoms.
-7 In the negative heterocycle, all of the ring constituent atoms may be heteroatoms. In addition, this hetetff ring group may be a saturated ring or an unsaturated ring, and may be substituted with a substituent. The general formula of the present invention [(, -I
The substituents referred to in TII and [C-IVI are, for example, aliphatic groups, aromatic groups, heterocyclic groups, aliphatic oxy groups, aromatic oxy groups, pederocyclic groups, aliphatic chizai groups, aromatic Group thio group, heterocyclic thio group, halogen atom, 7-syl group, ester group, cal, <moyl group, sulfamoyl group, sulfonyl group, hydroxy group, cyano group, carboxy group, tro group, sulfo group, acyloxy group, silyloxy group, sulfonyloxy group, carbamoyloxy group, amino group which may have a substituent (e.g. amine group, alkyl group),
Amide group, sulfonalamide group, urethane group, ureido group, anilino group.

imide group), etc.

The cyan couplers represented by the general formulas [C-I1 to [C-IVI] will be explained in more detail. Z represents a hydrogen atom or a group that can be separated during the coupling reaction with the oxidized product of the developing agent.
chlorine, bromine, etc.), alkoxy groups (ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, etc.), aryloxy groups (4-chlorophenoxy, l-
methoxyphenoxy group, 4-carboxyphenoxy, etc.), acyloxy group (acetoxy, tetrazocallyoxy, benzoyloxy, etc.), sulfonyloxy group (
(methanesulfonyloxy, toluenesulfonyloxy, etc.), amide groups (dichloroacetylamino, heptafluorobutyrylamino, methanesulfonylamino, toluenesulfonylamino7, etc.), alkoxycarbonyloxy, & (ethoxycarbonyloxy, benzyloxycarbonyloxy, etc.) ), aryloxycarbonyloxy groups (phenoxycarbonyloxy, etc.), aliphatic or aromatic thio groups (ethylthio, phenylthio, tetrazolylthio, etc.), imido groups (succinimide, hydantoinyl, etc.), aromatic azo groups (phenylazo, etc.), etc. . These leaving groups may include photographically useful groups.

The electron-withdrawing group in the general formula [C-ml, [C-IVI] represents a substituent whose value of Hameft's substituent constant σ is larger than 0.

Among the cyan couplers represented by the general formula [(, -Il), preferred ones are the following general formulas [C-Ial, [C-Ib1
．． and [C-Ic1-r.

In the following formulas, 1 (50 represents an aliphatic group, an aromatic group, a heterocyclic group, or an amino group which may have a substituent).

R5+ represents an alkyl group or an acylamino group t2,
R52 represents a hydrogen atom, a halogen radical r-1 aliphatic group, or an alkoxy group. R5+ and R52 combine with η to form 5
~7M ring may be formed, Z represents the same meaning as the general formula [C-I], I7, R53 is -. R of the formula [C-ll]
It has the same meaning as IO, and R54R55,1 (56 and R represent a hydrogen atom or an M substituent.

Among the cyan couplers represented by the general formula [(, ml,
A more preferable one is the following general formula % Formula %] - Formula ITIal - Formula] General formula lIc1 General formula]] - - Formula ITIal General formula % Formula % In the formula, 1 (31, 3 (32 and Z are the general formula [ (,-m
R32' has the same meaning as R32. R60 and R61 represent a hydrogen atom or a substituent. However, at least one of R60 and R61 is an electron-withdrawing group.

Among the cyan couplers represented by the general formula [C-ITIal ~ [C-mel], it is preferable that 31 is an electron-withdrawing group; It is preferable that

- Among the cyan couplers represented by the formula [C-IVI, it is preferable that m is 1 and Q10 is 10-1-8 or more or vinylene.

Among the cyan couplers represented by the general formulas [C-I1 to [C-IVI], particularly preferred are those represented by the general formula [(, -I], among which the general formula [C-Ial
, [(, -Iblffi table is preferred.

Specific examples of particularly preferred cyan couplers include the following compounds.

(C-1) (C (C (C-4) (C-5) (C-1 (C (C-13) (C (t)CsH++ 0 sentence (C (C 0 sentence GsHu(t) (C (C C8H17(t) (C-15) (C-16) (C-17) (C (C (C C!1 (C) 4Hq (C (C CICaH+1 (C (C)) ( C-24) H (C-25) H Hi (CaHq (C (C (C-35)) These cyan couplers are described in U.S. Pat.
No. 9, No. 4, 5 J, 1, No. 647, No. 2゜77
2.162, 4,500,653, 4.564
, No. 586, European Patent Application Publication EPO, 249,453
A2, JP-A-61-390441, JP-A No. 61-153
It can be synthesized by the method described in No. 640, No. 62-257158, etc., or a method analogous thereto.

Cyan couplers of the general formulas [C-ll, [C-III, (c, -ml and [C-TV]) are preferably 2X10-3 moles to 5X10-1 moles per mole of silver in the emulsion layer. I X 10-2 moles - 5 x 0'' moles are added.

Further, these cyan couplers may be used alone or in combination of two or more types.

Next, to describe the compound represented by the general formula [I] in more detail, R and R2 are hydrogen atoms, alkyl groups (e.g., methyl, butyl, tert-butyl, hexadecyl, phenoxyethyl, methoxyethyl), cyclo Alkyl groups (e.g. cyclopentyl, cyclohexyl), alkenyl groups (e.g. 2-propenyl, 13-butadienyl), cycloalkenyl groups (e.g. cyclohexenyl,
cyclooctenyl), aryl groups (e.g. phenyl, naphthyl, methoxyphenyl), heterocyclic groups (e.g. furyl, oxacylyl, thiazolyl), acyl groups (e.g. acetyl, dodecanoyl, benzoyl), sulfonyl groups (e.g.
For example, dodecylsulfonyl, hexadecylsulfonyl,
benzenesulfonyl), phosphonyl groups (e.g. butyloctylphosphonyl, octyloxyphosphonyl, aryloxyphosphonyl), sulfinyl groups (e.g. octylsulfinyl, benzenesulfinyl), alkylcarbamoyl groups (e.g. N-methylcarbamoyl, N-dodecylcarbamoyl, N, N dibutylcarbamoyl),
Arylcarba-thousyl groups (e.g. N-phenylcarbamoyl, N-pmethyphenylcarbamoyl), alkylsulfamoyl groups (e.g. N-methylsulfamoyl, N,N-dibutylcarbamoyl), arylsulfamoyl groups (e.g. N-phenylsulfamoyl, N-p
-methoxyphenylsulfamoyl), alkyloxycarbonyl groups (eg methoxycarbonyl, dodecyloxycarbonyl), and aryloxycarbonyl groups (eg phenyloxycarbonyl, p-methoxyphenoxycarbonyl).

Y represents a group of nonmetallic atoms necessary to form a 5- to 8-membered heterocycle (e.g., pyrazolidine, pyrazoline) together with two nitrogen atoms, and this heterocycle represents a substituent (e.g., alkyl,
alkoxy, alkoxycarbonyl, alkylcarbamoyl, alkylsulfamoylbonylamino, alkylsulfonyl, acyl, halogen, aryl, aryloxy, aryloxycarbonyl, arylcarbamoyl, arylsulfamoyl, arylureido, aryloxycarbonylamino, arylsulfonyl) It may have.

The total number of carbon atoms in R1 and R2 is 6 or more, especially 6 to 5.
Preferably, the number is 0. It is preferable that R1 or R2 each have 40 or less carbon atoms.

Among the compounds represented by the general formula [I], a more preferable compound is a compound in which R and R2 are not hydrogen atoms at the same time.

Among the compounds represented by the general formula [I], a more preferred compound is one in which the nonmetallic atom group forming Y has at least one carbonyl group or sulfonyl group, and these groups are located next to the nitrogen atom. .

Specific examples of the compound of the present invention represented by the general formula [I] are shown below, but the compound is not necessarily limited thereto.

(A l) (A-3) (A (A-4) Below margin (A (A-6) (A OC16H33 (A-9) (A (A (A (A-16) (A l 1) ( A (A-13) H3 (A (A-18) (A (A-20) (A (A-22) (A-23) (A-24) (A (A-29) (A-30) (A (A (A 2 H5 / \ 2 H5 (A-31) (A-32) (A (A -47) The remaining compounds are as follows: JP-A No. 63-95444, No. 63
-115866, He1v, Chew, Acta
,.

Volume 36, page 75 (1953), New Experimental Chemistry Course No. 14
It can be synthesized by the method described in Marukubi et al., Vol., p. 1220 (1977), or by a method analogous thereto.

- Some of the compounds represented by Funato [I] are described in JP-A-6:143145, JP-A No. 63-115866, JP-B No. 60-47573, etc., and are used to prevent fading of magenta couplers. known to be effective. However, a compound that is effective in solidifying magenta images is not necessarily effective in solidifying cyan images.

- When the compound of the present invention represented by Funato [I] was applied to a dye image of a cyan coupler, it showed a remarkable improvement effect on its fastness to heat and light without deteriorating its photographic properties.

The compound represented by the general formula [D] in the present invention varies depending on the type of coupler used in combination, but is suitably used in an amount of 5 to 400 mol%, preferably 10 to 200 mol% based on the coupler. . If the amount is less than this range, the fading prevention effect is extremely small and is not suitable for practical use. Further, if the amount is too large than this range, the progress of development may be inhibited, leading to a decrease in color density.

The compound represented by the general formula [I] used in the present invention has a particularly excellent anti-fading effect when used in a cyan dye image forming layer, and is particularly effective against fading when present in a high boiling point organic solvent together with a cyan coupler. Excellent prevention effect.

The compounds represented by the general formula [I] used in the present invention may be used alone or in combination of two or more.

The color light-sensitive material of the present invention has a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support in this order, or in any arbitrary arrangement thereof. Preferably, it is coated.

Examples of the silver halide used in the present invention include silver chloride, silver bromide, silver chloride (iodo)bromide, and silver iodobromide.
Among these, silver chloride and silver chloride (iodine) bromide are preferred, and furthermore,
The halogen composition of silver halide grains in one emulsion layer is
It is preferable that at least 9.0 mol % of the total silver halide constituting the silver halide grains is silver chloride, and that the silver halide grains are composed of silver chlorobromide containing substantially no silver iodide. Here, "substantially free of silver iodide" means that the silver iodide content is 1.0 mol % or less. A particularly preferred halogen composition of the silver halide grains is silver chlorobromide containing substantially no silver iodide, in which 95 mol % or more of the total silver halide constituting the silver halide grains is silver chloride.

Further, the silver halide grains according to the present invention preferably have a silver bromide localized phase having a silver bromide content of at least more than 10 mol % and less than 70 mol %. The arrangement of such a localized silver bromide phase can be freely determined depending on the purpose, and it may be located inside the silver halide grain, on the surface or subsurface, or divided into the interior and the surface or subsurface. You can leave it there.

Further, the localized phase may have a layered structure surrounding the silver halide grains inside or on the surface, or may have a discontinuously isolated structure. One preferred example of the arrangement of the silver bromide localized phase is a silver bromide content of at least 10 mol %, more preferably more than 20 mol %, on the surface of the silver halide grains (particularly at the corners of the grains). A localized phase is epitaxially grown locally.

It is preferable that the silver bromide content of the localized phase exceeds 20 mol%; however, if the silver bromide content is too high, it may cause desensitization when pressure is applied to the photosensitive material, or the composition of the processing solution may be affected. The silver bromide content of the localized phase may be determined by taking these points into consideration, as fluctuations in the local phase may impart unfavorable characteristics to photographic materials, such as large changes in sensitivity and gradation. , preferably in the range of 20 to 60 mol%, and 3
The most preferable range is 0 to 50 mol%. #The other silver halide constituting the localized phase is preferably silver chloride. #The silver bromide content of the localized phase is determined by X-ray diffraction method (for example, ) or the XPS method (e.g., ``Surface Analysis, - I
MA, Application of Auger Electron/Photoelectron Spectroscopy (published by Kodansha), etc. can be used for analysis.

The localized phase is preferably composed of 0.1 to 20% silver, more preferably 0.5 to 7% silver, based on the amount of gold and silver constituting the silver halide grains of the present invention. preferable.

The interface between the silver bromide localized phase and other phases may have a clear phase boundary, or may have a short transition region where the halogen composition gradually changes. The position of the silver oxide localized phase can be determined by observation using an electron microscope or by the method described in European Patent Application Publication No. 273430A2.

Various methods can be used to form such a localized silver bromide phase. For example, a localized phase can be formed by reacting a soluble silver salt and a soluble halogen salt by a one-sided mixing method or a simultaneous mixing method. Furthermore, the localized phase can also be formed using a so-called conversion method, which involves converting already formed silver halide into silver halide having a smaller solubility product. Alternatively, a localized phase can also be formed by adding silver bromide fine particles and recrystallizing them on the surface of silver chloride particles. These manufacturing methods are described, for example, in the aforementioned European Patent Application No. 273430A2.

In the localized phase of the silver halide grains of the present invention or its substrate,
The effect of the present invention is further improved by containing metal ions different from silver ions (e.g., metal ions of group II of the periodic table, transition metal ions of group II, lead ions, thallium ions) or complex ions thereof. It is preferable.

Localized phases mainly include iridium ions, rhodium ions, iron ions, etc., and substrates mainly include osmium, iridium, rhodium, platinum, ruthenium, palladium,
Metal ions selected from cobalt, nickel, iron, etc. or complex ions thereof can be used in combination.

Furthermore, the type and concentration of metal ions can be changed between the localized phase and the substrate.

In order to incorporate metal ions into the localized phase and/or other grain parts (substrate) of silver halide grains, the metal ions are added to the preparation solution before grain formation, during grain formation, or during physical ripening. For example, metal ions in an aqueous gelatin solution, a halide aqueous solution, a silver salt aqueous solution,
Alternatively, it can be added to other aqueous solutions to form silver halide grains.

Alternatively, metal ions are contained in silver halide fine grains in advance, and this is added to a desired silver halide emulsion, and further,
Metal ions can also be introduced by dissolving the fine grain silver halide. This method is particularly effective for introducing metal ions into the localized silver bromide phase on the surface of silver halide grains. The addition method can be changed as appropriate depending on where in the silver halide grains the metal ions are to be present.

In particular, it is preferred that the localized phase is deposited with at least 50% of the total iridium added during the preparation of the silver halide grains.

Here, depositing the localized phase together with iridium ions means supplying an iridium compound simultaneously with, immediately before, or immediately after supplying silver and/or halogen to form the localized phase. say.

The silver halide grains according to the present invention have (100
) surface, (111) surface, or both surfaces, and even those containing higher-order surfaces are preferably used. It will be done.

The shape of the silver halide grains used in the present invention is cubic,
Those with regular crystal shapes such as tetradecahedrons and octahedrons, those with irregular crystal shapes such as spherical and plate shapes, or composites of these crystal shapes. There are things that have a shape. A mixture of particles with various crystal forms can also be used, but in particular, particles with the above-mentioned regular crystal forms account for 50% or more4-1, preferably 70% or more, and more preferably 70% or more. The silver halide emulsion used in the present invention should preferably contain 90% or more of mole grains having an average aspect ratio (length/thickness ratio) of 5 or more, particularly preferably 8 or more. It may be an emulsion that occupies 50% or more of the projected area.

The size of the silver halide grains according to the present invention may be within the range commonly used, but the average grain size is 0, Igm-1
, 5 gm.

The particle size distribution may be polydisperse or monodisperse, but
It is preferable that the particle size distribution is monodisperse.The particle size distribution, which indicates the degree of monodispersity, is determined by the coefficient of variation in statistics 2 (the value S/d obtained by dividing the standard deviation S by the diameter d when the projected area is approximated as a circle).
is preferably 20% or less, more preferably 15% or less.

Further, two or more kinds of such tabular grain emulsions and monodispersed emulsions may be mixed. When emulsions are mixed, it is preferable that at least one of them has the above-mentioned variation coefficient, and it is more preferable that the variation coefficient of the mixed emulsion satisfies the above-mentioned range of values.

The so-called matrix portion, which is outside the local similarity of the silver halide grains used in the present invention, may have different phases in the interior and the surface layer, or may consist of a uniform phase.

The silver halide emulsion used in the present invention is usually one that has been physically ripened, chemically ripened, and spectrally sensitized.

Chemical sensitizers used for chemical ripening are described in JP-A-62-215272, page 18, lower right column to 2nd column.
Those described in the upper right column of page 2 are preferably used, and as for the spectral sensitizers, those described in the right column L to page 38 of No. 22 of the same publication are preferably used.

Furthermore, during the production of the silver halide emulsion used in the present invention,
As antifoggants or stabilizers used during storage, those described in the "-" column on pages 39 to 72 of the same publication are preferably used.

In color light-sensitive materials, yellow couplers, magenta couplers, and cyan couplers, which develop yellow-magenta and cyan colors, respectively, by coupling with the oxidized product of an aromatic amine color developer are commonly used.

Among the yellow couplers that can be used in the present invention, acylacetamide derivatives such as benzoylacetanilide and pivaloylacetanilide are preferred.

Among them, the following general formula [Y-
1] and [Y-2] are preferred.

[Y-1] [Y-21 In the formula, X represents a hydrogen atom or a coupling-off group.

1li21 represents a diffusion-resistant group having a total carbon number of 8 to 32,
1li22 represents a hydrogen atom, a halogen atom of 1 or more, a lower alkyl group, a lower alkoxy group, or a diffusion-resistant group having a total of 8 to 32 carbon atoms.

1 (23 represents a hydrogen atom or a substituent. When there are two R23s, they may be the same or different.

For more information on pivaloylacetanilide type yellow couplers, see U.S. Pat.
It is described in column 15, line 15 to column 8, line 39, and in column 14, line 50 to column 19, line 41 of the specification of 4°623.616.

For details on benzoylacetanilide type yellow couplers, see U.S. Pat.
No. 3,501, No. 4, 046, No. 575, No. 4,1
It is described in No. 33,958, No. 4,401.752, etc.

Specific examples of pivaloylaceto 7nylide type yellow couplers include compound examples (Y-1) to (Y
~39), among which (y-i), (
Y-4), (Y-6), (Y-7), (Y-15),
(Y-21), (Y-22), (Y-23), (Y-
26), (Y-35), (Y-36), (Y-37),
(Y-38), (Y-39), etc. are preferred.

Also, No. 1 of the above-mentioned U.S. Pat. No. 4,623,616
Compound examples (Y-1) to (Y-33) in columns 9 to 24 can be listed, among which (Y2), (Y-7), (Y-
8), (Y-12), (Y-20), (Y-21), (
Y-23), (Y-29), etc. are preferred.

Other preferred examples include US Pat. No. 3,408.
Typical specific example (34) described in column 6 of specification No. 194
, Compound examples (16) and (19) described in column 8 of the same specification No. 3,933,501, and compound examples (9) described in columns 7 to 8 of the same specification No. 4.046.575. , 4,133
Compound example (1) described in columns 5 and 6 of the specification of No. 958
, Compound Example 1 described in Column 5 of 4,401,752, and the following compounds (a) to (h).

(e) (a) (g) (c) 4H9 Same as above C00cHcOOcI2H25 (h) Among the couplers described in 1- above, those having a nitrogen atom as a leaving atom are particularly preferred.

Examples of the magenta coupler used in the present invention include oil-protected indacilone-based or cyanoacedel-based couplers, preferably 5-pyrozolone-based couplers and birasoloazole-based couplers such as pyrazolotetrazoles. 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.
No. 343.703, No. 2, 600.

No. 788, No. 2,908,573, No. 3゜062
．． No. 653, No. 3,152,896 and No. 3,
No. 936,015, etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, U.S. Pat.
Preferred are the nitrogen leaving groups described in US Pat. No. 10,619 or the arylthio groups described in US Pat. No. 4,351,897. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73.636 provides a high color density.

As a pyrazoloazole coupler, American Poetry No. 2,
369,879, preferably pyrazolo[5,1-C][1,2,4]) as described in U.S. Pat. No. 3,725.067.
Riazoles, Research Disclosure 2422
0 (June 1984) and Lysati Disclosure 24230 (1
Examples include pyrazolopyrazoles described in June 1984). Any of the couplers mentioned above may be polymeric couplers.

Specifically, these compounds have the following general formula (M-1)
, (M-2) or (M-3).

Kai, lower margin green\Z Here, R3+ represents a diffusion-resistant group having a total number of carbon atoms of 8 to 32, and R32 represents a phenyl group or a substituted fer group. R33 represents a hydrogen atom or a substituent. 2 is
Represents a group of nonmetallic atoms necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring is substituted)
& (including a fused ring) may be present.

x2 represents a hydrogen atom or a leaving group.

For details of the substituents of R33 and the substituents of the azole ring, see, for example, US Pat. No. 4,540,654, No. 2.
It is described in the 41st line of the column to the 27th line of the 8th column.

Among the pyrazoloazole couplers, US Pat.
The imidazo[1,2-bl pyrazoles described in U.S. Patent No. 5oo, 63o are preferred;
Biranguchi [1,5-bl [1,2,4] described in No.
Triatool is particularly preferred.

In addition, pyrazolotriazole couplers in which a branched alkyl group is directly connected to the 2, 3 or 6 position of the pyrazolotriazole ring as described in JP-A-61-65245, and as described in JP-A-61-65246 pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide parast group as described in JP-A-61-147254, and European Patent (Publication) No. 226°849. It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No.

Specific examples of these couplers are listed below.

The following margin CH・嬬- times, ]-0, C, 8,, H 1''℃ -CHCH?Nl5O ?HCHrNHs07℃ Same [2CH(JI2NH5O2℃ T can be contained in the dispersed emulsion layer in coexistence with at least one type of boiling point organic solvent.Preferably, a high boiling point organic solvent represented by the following formula (A) to E) is used.

Formula (A) Formula (B) Oo / Formula (C) ON \ Formula (D) WI W2 \ / (Wherein, Wl, W2, and W3 are each a substituted or unsubstituted alkyl group, cycloalkyl group, or alkenyl group , represents an aryl group or a heterocyclic group, W4 represents wz, ow+ or 5-vtz, n is a number from 1 to 5, and when n is 2 or more, W4 may be the same or different from each other. Well, in -Sailor (E), wl and W
2 may form a fused ring) These couplers can also be used in the rhodapuru latex polymer (
For example, the woody colloid can be emulsified and dispersed in an aqueous solution of a woody colloid by impregnating it with a polymer (for example, US Pat. No. 4,203,716) or by dissolving it in a water-insoluble but organic solvent-soluble polymer.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 38100723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxykumaras, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminephenols, hindered amines, and these Typical examples include silylated or alkylated ether or ester derivatives of the phenolic hydroxyl group of each compound.

Also, (biszaritylaldoximato)nickel complex and (bis-N).

Metal complexes typified by N-dialkyldithiocarbamado) nickel complexes can also be used.

Specific examples of organic antifade agents are described in the patent specifications of the following patents.

Hydroquinones are disclosed in U.S. Patent No. 2,360,290;
No. 2,418,613, No. 2,700.453, No. 2,701,197, No. 2,728,659
No. 2,732,300, No. 2,735,76
No. 5, No. 3,982.944, No. 4.430.4
25, British Patent No. 1,363,921, U.S. Patent No. 2,710.801, U.S. Patent No. 2,816,028, etc., 6-hydroxycoumaras, 5-hydroxycoumarans, and spirochromans are U.S. Patent No. 3°432.300
No. 3.573.050, No. 3.574.62
No. 7, No. 3,698,909, No. 3,764,3
No. 37, JP-A-52-152225 Gin, etc., and spiroindanes are described in U.S. Patent No. V 4.360.589, P.
-Flufoxiphenols are U.S. Patent No. 2,735,7
No. 65, British Patent No. 2,066.975, Japanese Unexamined Patent Publication No. 1983
-10539, Japanese Patent Publication No. 57-19765, etc., hindered phenols are disclosed in U.S. Pat.
No. 52-72224, U.S. Patent No. 4,228,
No. 235 and Japanese Patent Publication No. 52-6623, gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Pat.
, 332.886, and Japanese Patent Publication No. 56-21144, hindered amines are disclosed in U.S. Patent No. 3,336.135.
No. 4.268,593, British Patent No. 1,326
, No. 889, No. 1,354゜313, No. 1,41
No. 0,846, JP 51-1420, JP 58-
No. 114036, No. 59-53846, No. 59-78
No. 344, etc., and metal complexes are disclosed in U.S. Pat. No. 4,245,0.
No. 18, No. 4,684,603, No. 4. o50.
No. 938, No. 4,241,155, British Patent No. 2,0
27,731 (A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with the couplers and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the respective color couplers. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the layers on both sides adjacent to the cyan coloring layer.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the wood-philic colloid layer. For example, benzotriazole compounds substituted with aryl groups (e.g., those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (e.g., those described in U.S. Pat. No. 3,314,794,
3,352, 681%), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in U.S. Patent No. 3,352, 681%),
No. 705,805, U.S. Pat. No. 3,707,375), butadiene compounds (e.g., U.S. Pat. No. 4,04
5,229) or benzoxidole compounds (eg, those described in US Pat. No. 3,700,455). An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

The photosensitive material produced according to the present invention may contain a water-soluble dye in the wood-philic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other woody colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in Arthur Vuis, The Macromolecular Chemistry Controversy of Gelatin, published by Academic Press, 1964.

As the support used in the present invention, transparent films such as cellulose nitrace film and polyethylene terephthalate, which are usually used in photographic materials, and reflective supports can be used. For purposes of the present invention, the use of reflective supports is more preferred.

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

As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (%) of white pigment fine particles per specified unit area is most typically calculated by dividing the observed area into adjacent unit areas of 6 μm x 6 g m and projecting onto that unit area. Occupied area ratio (%) of fine particles (Ri
) can be determined by measuring. Occupied area ratio (%)
The coefficient of variation can be determined by the ratio S/H of the standard deviation S of R1 to the average value (R) of R4. The number of target unit areas (n) is preferably 6 or more. Therefore, the coefficient of variation s/R can be determined by s/R.

In the present invention, the coefficient of variation of the occupied area ratio (%) of the pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. If it is 0.08 or less, the dispersibility of the particles can be said to be "substantially uniform."

The following margin The color photographic light-sensitive material of the present invention has a color development phenomenon, bleach-fixing,
It is preferable to perform a water washing treatment (or a stabilization treatment). Bleaching and fixing may be carried out separately instead of in one bath as described above.

In the case of continuous processing, it is desirable that the amount of replenishment of the developer is small from the viewpoint of resource saving and low pollution.

The preferred replenishment amount of color developer is 2 ml per liter of light-sensitive material.
00ml or less. More preferably 120m,
It is below Q. More preferably, it is 100 m1 or less. However, the term "replenishing acid" as used herein refers to the amount of so-called color developer replenisher to be replenished, and the amount of additives, etc. for correcting aging deterioration and concentration is not included in the replenishment amount. The additives mentioned here include, for example, wood for diluting the concentrate, preservatives that tend to deteriorate over time, and alkaline agents that increase the pH.

The color developing solution applied to the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, and a typical example is 3-phenylene diamine compounds.
Methyl-4-amino-N,N-diethylaniline, 3-
Methyl 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-
Examples include toluene sulfonate. Two or more of these compounds can also be used in combination depending on the purpose.

Color developer is an alkali metal carbonate, borate or phosphate pH! It is common to include buffering agents, development inhibitors or antifoggants such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semi-hydrazine, triethanolamine, catechol sulfonic acids, triethylenediamine (l,4-diazabicyclo[2°2,2]octane) various preservatives such as ethylene glycol,
solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, fogging agents such as competition cabranium boron hydride, l-phenyl-3-pyrazolidone. Auxiliary developing agents such as viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, Diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethylimidinoacetic acid, ■-hydroxyethylidene 1.
1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine N, N, N', N
'-tetramethylenephosphonic acid, ethylene glycol (
(0-hydroxyphenylacetic acid) and salts thereof are representative examples.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains dihydroxybenzenes such as hydroquinone, ■-phenyl-3-
Known black and white developing agents such as 3-pyrazolidones such as pyrazolidone or amine phenols such as N-methyl-p-aminephenol can be used alone or in combination.

The pH of these color developing solutions and black and white developing solutions is 9 to 12.
It is common that Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally less than 3 meters per photosensitive material, and by reducing the bromide ion concentration in the replenisher. 500
It can also be less than ml. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the treatment layer with the air.

Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Further T, treatment in a series of bleach-fixing baths;
A fixing treatment may be performed before a bleach-fixing treatment, or a bleaching treatment may be performed after a bleach-fixing treatment depending on the purpose. Examples of bleaching agents include iron (■), cobalt (■),
Compounds of polyvalent metals such as chromium (■) and copper (■), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include ferricyanide: dichromate;
m) or organic complex salts of cobalt (■), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, l.

Aminopolycarboxylic acids such as 3-diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.: persulfates; bromates; permanganates-nitrobenzenes, etc. Can be used. Among these, aminopolycarboxylic acid iron(II) including ethylenediaminetetraacetic acid iron(m) complex salt
I) Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. In addition, iron aminopolycarboxylate (II
I) Complex salts are particularly useful in both bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (m)
The pH of bleach or bleach-fix solutions using complex salts is usually 5.
5-8, but for faster processing, lower p
It can also be treated with H.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Patent No. 1,290,8.
No. 12, No. 2,059.988, JP-A-53-377
No. 36, No. 53-57831, No. 53-37418, No. 1ka 53-72623, No. 5:3-95630,
No. 51-95631, No. 53-104732, No. 5
No. 3-124424, No. 53-141623, No. 53
-28426, Research Disclosure No.
Compounds having a mercapto group or a disulfide group described in No. 17.129 (July 1978) etc.: JP-A-5
Thiazolidine derivatives described in No. 0-140129: Japanese Patent Publication No. 458506, Japanese Patent Publication Nos. 20832-1983, 53
-32735, thiourea derivatives described in U.S. Patent No. 3,706,561: Iodides described in West German Patent No. 1,127.715 and JP-A-58-16235: West German Patent No. 996,410 , 2゜748.430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and other JP-A No. 49-4243.
No. 4, No. 49-59644, No. 53-94927,
No. 54-35727, No. 55-26506, No. 58
Compounds described in No.-163940: Bromide ions, etc. can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a strong promoting effect, and in particular, US Pat. No. 3,893.858 and West German Patent No. 1,29
Preferred are the compounds described in No. 0,812, JP-A-53-95630. Further preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, and ammonium thiosulfates are the most commonly used. Can be used widely. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite additives are preferred.

The silver halide color photographic photosensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment. Water washing at the second stage of water washing depends on the characteristics of the photosensitive material (for example, depending on the materials used, such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent, forward flow, etc.
It can be set in a wide range depending on various other conditions. Among these, the relationship between the number of water washing tanks and Jupiter in the multistage countercurrent method is described in the Journal of the 5ociety
f Notion Picture and Te1ev
ision Engineers Volume 64, P, 2
48-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, it is possible to significantly reduce water washing, but due to the increase in water residence time in the tank, bacteria breed and the generated suspended matter adheres to the photosensitive material. Problems such as this arise. In the processing of the color light-sensitive material of the present invention, as a solution to such problems, the method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61131632J4 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazoles, and chlorinated sodium isocyanurate described in JP-A No. 57-8542, and other chlorinated disinfectants such as hensitriazoles, "Chemistry of Disinfectant and Antifungal Agents" by Hiroshi Horiguchi, It is also possible to use the disinfectants described in "Sterilization, sterilization, and anti-mildew technology of microorganisms" edited by Sanitation Technology Society, and "Encyclopedia of antibacterial and anti-mildew agents" edited by Meki Antibacterial Prevention Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-9. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
- In general, a range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 5J3-148
All known methods described in No. 34 and No. 60-220345 can be used.

Further, following the water washing treatment, there are cases where further stabilization treatment is performed. An example of this is a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photographic materials. Various types of anti-mildew agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in other L processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing.

In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3.342.5
Indoaniline compounds described in No. 97, No. 3,342
, No. 599, Research Fist Disclosure 14, 85
Schiff base-type compounds described in No. 0 and No. 15,159, aldol compounds described in No. 13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, and JP-A No. 53
Examples include urethane compounds described in No.-135628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, a temperature of 33°C to 38°C is standard, but higher temperatures may be used to accelerate processing and shorten processing time, or conversely, lower temperatures may be used to improve image quality or improve the stability of the processing solution. can be achieved. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 2.226.770 or US Pat. No. 3,674.499 may be carried out.

In order to fully exhibit the excellent characteristics of the silver halide photographic light-sensitive material of the present invention, it must be substantially free of benzyl alcohol and contain 0.002 mol/9. It is preferable to process with a color developer containing the following bromide ions for a developing time of 2 minutes and 30 seconds or less.

- “Contains substantially benzyl alcohol” as stated in L.
What is Color Developer L!? ; means 7 ml or less per liter, preferably 0.5 m9. Hereinafter, it most preferably means not included at all.

[Example] The present invention will be described below based on body examples, but is not limited thereto.

[Example 1] A silver halide emulsion (1) of a blue-sensitive silver halide emulsion layer was prepared as follows.

(1 liquid) H2O 1000cc NaC 5.8 g gelatin
25g (2 liquids) Sulfuric acid (IN) 20cc (3 liquids) The following compound (1%) 3cc H3 H3 (4 liquids) KBr aCI Add H2O (5 liquids) AHNO3 Add H2O 0.18g 8.51g 30cc 5g 30cC (6 liquids) KBr O, 70g NaC
l 34.05gK2 I
rC! 16 (0,001 K) 2 c H20 was added to make 285 cc (7 liquids). 100 g of AgNO3 was added to H2O. 285 cc (1 liquid) was heated to 60°C, and (2 liquids) and (3 liquids) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously over a period of 60 minutes. Rxo minutes after the completion of addition of (liquid 4) and (liquid 5), liquid (6) and (liquid 7) were added simultaneously over a period of 25 minutes. After 5 minutes of addition, the temperature was lowered and desalted. Add water and dispersed gelatin, adjust the pH to 6.0, average particle size 1.0 gm, coefficient of variation (standard deviation divided by average particle size; s/d) 0.11, silver bromide 1. A monodisperse cubic silver chlorobromide emulsion of mol % was obtained. Triethylthiourea was added to this emulsion to perform optimal chemical sensitization. Furthermore, the following spectral sensitizing dye (Sen-1) was added to silver halide emulsion 1.
7 x 10-4 moles were added per mole.

Silver halide emulsion (2) in the green-sensitive silver halide emulsion layer and silver halide emulsion (3) in the red-sensitive silver halide emulsion layer.
) by the same method.

They were prepared by varying the chemistry, temperature and addition time.

A spectral sensitizing dye (Sen) was added to silver halide emulsion (2).
-2) was added at 5X10-4 mol per mol of the emulsion, and for silver halide emulsion (3), a spectral sensitizing dye (Sen
-3) was added at 0.9×10 −4 mol per mol of emulsion.

The shapes, average grain sizes, halogen compositions and coefficients of variation of the silver halide emulsions (1) to (3) are as shown below.

(Sen (Sen (river m) (Br mole2) (1) Cube 1.00 1.0 0.11 (2) Cube 0.45 1.0 0.09 (3) Cube 0
．． 34 1.8 0.10 Using the prepared silver halide emulsions (1) to (3), a multilayer color photographic material having the layer structure shown below was prepared. The coating solution was prepared as follows.

19.1 g of 19.1 g of yellow coupler (ExY) and 2 2 of ethyl acetate.
7.2 cc and 3.8 cc of solvent (Solv-1) were added and dissolved, and this solution was mixed with 185 ml of a 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate.
It was emulsified and dispersed in cc. On the other hand, a blue-sensitive sensitizing dye (Sen-1) was added to the silver halide emulsion (1) at a concentration of 5 mol/llz of silver.
．． A 0x10-4 mole addition was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below.

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-oxy3.5-dichloro-5-triazine sodium salt was used as the gelatin hardening agent for each layer.

For the red-sensitive emulsion layer, the following compounds were added at 19X10-3 moles per mole of silver halide, and kaimethyl-1,3,3a,7-chitrazaindene was added at 1.0XIO-2 moles per mole of silver halide. Added.

Furthermore, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 1-(5
-methylureidophenyl)-5-mercaptotetrazole was added at 1.0×10 −3 mol and 1.5×10 −3 mol per mol of silver halide.

In addition, for the red-sensitive emulsion layer, 2-amino-5-mercap)
-1,3,4-thiadiazole was added at 2.5XIO=mole per mole of silver halide.

The composition of each layer is shown below. The abbreviations and structural formulas of each compound are the same as in Example 1.

(Layer structure) Paper support laminated on both sides with polyethylene support [white face M (Ti02) (2, 7
g/rn') and a bluish dye (ulmarine blue)] Layer (blue-sensitive layer) Silver halide emulsion (1) 0.26 gelatin 1.13 yellow coupler (ExY) 0.66 solvent (Solv-4
) 0.28 Second layer (color mixing prevention 1F layer) Gelatin 0.89 Color mixing prevention agent (Cpd-3) o, oa Solvent (Solv
-4) 0.20 solvent (Solv-3
) 0.200.005 Dye (T-1) Third layer (green M) Silver halide emulsion (2) Gelatin, 15. 51 Magenta coupler (ExM) Color image stabilizer (CPD-5) Color image stabilizer (CPD-8) Color image stabilizer (CPD-9) Solvent (Solv-3) Solvent (Solv-5) Fourth layer (ultraviolet light Absorption layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-3) Solvent (Solv-2) Dye (T-2) Fifth layer (red-sensitive layer) Silver halide emulsion (3) Gelatin cyan coupler ((, -1) Color image stabilizer (Cpd-1) Color image stabilizer (Cpd-6) Solvent (Solv-2) Solvent (Solv-7) Solvent (Solv-6) Sixth R (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-1) Solvent (Solv-2) Dye (T-2) Seventh layer (protective layer) Acrylic modified copolymer of gelatin polyvinyl alcohol (degree of modification 17%) Liquid paraffin coating 0, 48 0 , 18 0 , 08 0 , 005 .33 , 05 .03 (Solv 6) Solution (Solv 7) Solvent〇〇〇CH2 CHC4H9 C7,H5 (T l) (ExY) Yellow coupler below margin ('r The above light-sensitive material It was processed using an optical process.

Processing plate, color development, internal fixing, washing with water ■ Washing with water ■ Washing with water ■ Dry color developing solution Water 35°C 35°C 35°C 35°C 35°C 75°C After exposure through rust, next 45 seconds 45 seconds 30 seconds 30 seconds 30 seconds 60 800 m/s and ethylenedi7mine 4N, 11. ) l', N' ~ Tetramethyl acid triethanolamine sodium chloride Potassium carbonate N- ■ Thirut (β-methane sulfone 7 midoethyl) 3-methyl-4-7 mino 7 diline sulfate N, N-bis (HBOXIMETHI S) HYDRAJISHI OPTICAL BRIGHTENER (WHIT
EX4, made by Juju Chemical) Add water 10
0 pH (25℃) l Bleach-fix solution water ammonium thiosulfate solution (700g/l)
eAmmonium ethylenediaminetetraacetic acid ferric ammonium 2wood salt ethylenediaminetetra1f12 sodium ammonium chlorbromide glacial acetic acid 3.0 g 8. Og 1.4 g 5g 700m 5g g 0 g g 8g 100 m 0g g g were used after being treated to 3 ppm or less (electrical conductivity at 25°C was 5 ILs/cm).

Remaining 11 The sample thus obtained was designated as Sample IA, except that the cyan coupler in the fifth layer and the additive [color image stabilizer] (100 mol % based on the coupler) were combined as shown in Table 1. Other samples were prepared in the same manner as sample IA.

After each sample on which a dye image was formed in this manner was exposed to xenon tester (illuminance: 200,000 lux) for 12 days, the residual density at an initial cyan density of 1.0 was expressed as a percentage.

In addition, in order to examine the heat and humidity resistance, 60°C and 70% R-H
The dye residual rate at an initial cyan density of 2.0 when stored for a week is shown as a percentage.

The results obtained are shown in Table 1.

Table 1 Comparative Compound (a) Test Coupler Color Imager Species Stabilizer Dye Remaining Ratio 60℃70$l1l-)1
Consideration 12 days 6 weeks Initial concentration 1.0 Dynamicity 2.0 Compound A-3 Compound A-4 Compound A-7 Compound A-12 Compound A-17 Compound ^-20 Compound ^-29 Compound A-31 Compound A -38 Compounds A to 41 Comparative compound (a) Comparative compound (b) Comparative compound (c) Comparative compound (e) Comparative compound C0 Compound A-6 Compound A-25 Compound A-28 Comparative compound (e) Comparative compound (f ) 70% 85% 851 90% 82% 92$ 83$ 94$ 86$ 93% 82z 91$ 86% 92$ 85% 92% 80 94% 882 90$ 83$ 93$ 71% 852 75% 8f4 72$ 84 $ 73 $ 86 $ 74 $ 85 $ 55% 89% 79% 94% 80 $ 95% 80 $ 94% 65 $ 90 $ 62 $ 8H Comparative example This invention This invention This invention This invention This invention This invention This invention This invention The present inventionComparative examples of the present inventionComparative examplesComparative examplesComparative examplesComparative examplesThe present inventionThe present inventionComparative examplesComparative examplesCompounds described in Japanese Patent Publication No. 61 20856Comparative compound (b) Compounds described in European Patent No. 255.722U.S. Patent No. 4
．． Comparative compound (e) Comparative compound described in European Patent No. 749.645 Comparative compound (e) Comparative compound described in European Patent No. 114,029 (
f) Compound described in Japanese Patent Publication No. 59-52825 These results show that the compound of the present invention is extremely effective in preventing photofading of color images compared to comparative compounds. In addition to this, it can be seen that it also exhibits an excellent effect on preventing fading under wet heat.

[Example 2] IA, IC, ID, lG, lJ, lR, IU of Example 1
, 1■ cyan couplers of each sample are C-2, C-5, (
,-7,C-8,C-22,(,-25,(,-26,
C-32 and C-34 were replaced with the same treatment as in Example 1,
When a fading test was conducted, the compound of the present invention showed an extremely excellent 1F anti-fading effect.

[Effects of the Invention] The silver halide color photographic light-sensitive material of the present invention is a combination of a cyan coupler and the compound of the general formula [I], and has extremely excellent quality storage stability of photographic images.

The silver halide color photographic light-sensitive material of the present invention does not impair color development, and the resulting dye image exhibits extremely high fastness to light, heat, or moist heat.

Patent applicant Fuji Photo Film Co., Ltd. Representative
Person Patent Attorney Yasushi Yanagawa Procedural Amendment 1989 67127 1988 Patent Application No. 302588 2 Name of the invention Silver halide color photographic light-sensitive material 3 Relationship with Nagisa 11 ¥ subject to amendment Name of patent applicant Name (5
20) Fuji Photo Film Co., Ltd. 4, Agent address: Mitsuya Yotsuya Building 8, 2-14 Yotsuya, Shinjuku-ku, Tokyo
Floor 6: The "Detailed Description of the Invention" column of the specification P without the number of claims increased by amendment is amended as follows -4-8 6M- (1) Page 5, line 6 of the specification 11 No. 150533-”
To the wheat (No. 63-229455, No. 6325695)
Insert No. 1, Special Publick No. 60-47578 Katsura 1.

(2) Line 14 of No. 5 of the specification
No. 0142” followed by “, No. 61-229455, No. 6
3-256951, Japanese Patent Publication No. 60-47578, etc. Insert J.

(3) J is deleted from fR32 and R″″ in the 3rd line of the 11th line of the specification.

(4) rl-11- of specification 11, page 13, line 12, 11
The xyphenoxy group J is supplemented with "4-methquinphenoxy".

(5) The structural formula of (C-19) in No. 23r(2) of the specification is corrected as follows.

(8) The structural formula on page 38 (A-17) of the specification is amended as follows.

(6) (A) on page 33 of the specification Correct as follows.

"The structural formula of 02)" (7) The structural formula of A-3) on page 34 of the specification is amended as follows.

(9) In the structural formula of M-8 on page 70 of the specification, 112 CH2O-J is replaced with r in the R33 column f CH, C) I20
−, corrected as g.

(10) "Hydroxyethyliminodiacid j" on page 85, lines 14-15 of the specification is corrected to "hydroxyethyliminodiacetic acid j.

(11) The structural formula of (Sen-3) on page 98 of the specification is amended as follows.

"(12) On page 100 of the Detailed Horoscope, from line 62 to the last line, ``More than that...they are the same.'', delete the word "Agriculture".

(13) Insert the following structural formula next to the last line of 103rd (1) of specification it).

r(ExM) macenta coupler (Cpd (cpci 6) Color image stabilizer (cpci (Cpd 1) Color image stabilizer -(-CH2-CH→n C0NHC4H9(t) ゛Y-average weighting: 60,00 0) Color mixing assistant IF cutting 4: 5 mixture (weight ratio) (Cpd 8) Stin inhibitor J1- agent 12:1 (Solv-2) Solvent 0=P-(-0-C.

(Sol, v = 3) solvent 1 (1゜ 3 mixture (weight ratio) I S O), 3 (Cpd 9) Anti-stain agent (Sol 4) Solvent (UV 1) Ultraviolet absorber (Solv-5') Solvent C2H,.

o=p-←OCH2CHC4H9) 3 (14) Specification pJ (7) xo page 8 line 3 IMl'100 mol%J
Insert r addition 1 after.

(15) Member 112, line 9 of Meishin 1 book [Insert the following sentence before “[effects of the invention]” in 4. 3, lI’ [Example 3] Paper laminated on both sides with polyethylene A multilayer color photographic paper having the layer structure shown in 1 below was prepared on support 1-1.

The coating solution was prepared as described above, and contained 19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1), and 1.8 g of color image stabilizer (Cpd-7) in the first layer.
27.2 cc of ethyl acetate and solvent (Solv-3
) and (Solv-6) were added and dissolved, and this solution was mixed with 8 c of 10% sodium dodecylhensensulfonate.
The mixture was emulsified and dispersed in 185 cc of a 10% geladine aqueous solution containing c. On the other hand, silver chlorobromide emulsion (silver bromide 80.0 mol%, Asahi "111 bodies, ゛r uniform powder grain size - 0.85μ coefficient of variation 0.08 (7) b (7), silver bromide 80 .0%,) f is a body, an average particle size of 0.62μ, and a coefficient of variation of 0.07 are mixed in a ratio of 1:3 (Ag molar ratio)) to a sulfur-sensitized product, and the following blue A sensitizing dye was prepared by adding s, oxxo-' moles of sensitizing dye per mole of silver.The emulsified dispersion described above and this emulsion were mixed and dissolved, and a coating solution for the first layer was prepared so as to have the composition shown in F below. was prepared.

Coating solutions for the knee to seventh shoe layers were also prepared in the same manner as the coating solution for the first layer.

1-oxy3,5-cycloS-triazine sodium salt was used as the ceratino curing agent for each layer.

As the spectral sensitizing dye for each layer, the one described above was used.

Blue-sensitive emulsion layer: (5.0xlO-' mol per mol of silver halide) Green-sensitive emulsion layer: 503-5(13H-N (fshi2+1
5>3 (4.0 x 10-' mol per mol of silver halide) and 503-503H-N(c2us)a (7.0 x 10-' mol per mol of silver halide) Redness + 1 emulsion layer: (halogenated For the red-sensitive emulsion layer (0.9 x 10"" moles per mole of silver), the following compounds were added to
2.6xlO-' mole added per layer, 1
-(5-methylureidophenyl)5-mercaptotetrazole 4.0X per mole of silver halide
10-6 mol, 3.0X IO-5 mol, 1.0
2×10 −2 mol, 2×10 −2 mol were added.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,33a,7-titrasaindene was added at 1.2 x 10-2 mol per mol of silver halide, 1.1xlO- 2 moles were added.

In addition, the above-mentioned dyes were added to the emulsion layer to prevent irradiation.

STI, J SO, K Also, +'i sensitivity +'1 emulsion layer, green sensitivity +I [emulsion layer, red sensitivity 113 agent and (layer structure)] The composition of each layer is shown below. Numbers are painted Ii] Hani (g/r
n') represents 1-. Silver halide emulsion is silver equivalent coating II
Table 1-5゜Support polyethylene laminate paper [Z-F? f ([(11 polyethylene contains white pigment (Ti02) and western flavor dye (IT i!t)]
-th layer (l? sensitive layer) The above-mentioned silver chlorobromide emulsion (AgBr: 80%) 0.26 Ceratin 1.83 Yellow coupler (ExY) 0.83 Color image stabilizer (Cp
d-1) 0.19// (Cpc17
) 0.08 Solvent (Solv-3)
0.18 solvent C3olv-6)
0.18th layer (color mixing prevention 11 layer) Ceratin 099 color mixing prevention 1
F agent (Cpd-6) 0.08 solvent (Sol
v-1) 0.16 solvent (Solv-4
) 0.08 Second layer (green-sensitive layer) Silver chlorobromide emulsion (A g B r 90 mol%, q-parallel,
・P.

One with an average particle size of 0.47μ and a coefficient of variation of 0.12,
AgBr90 mol%, cubic, ゛P-uniform r-size 0
36μ with a coefficient of variation of 0.09 in a 1:1 ratio (A
g molar ratio)) 016 gelatin
1.797 center coupler (,'ExM
) 0.32 color image stabilizer (Cpd-3)
0.20// (Cpd-8)
0゜03ノ/ (Cpd-4)
0. Ol// (
Cpd-9) 0.04 Solvent (Solv-
2) 0.65 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing prevention agent (
Cpd-5) 0.05 Solvent (Solv-5
) 0.24 First 11th layer (red-sensitive layer) Salt (Silver oxide emulsion (AgBr70 mol%, 1'10,000 bodies, ・V
One with an average particle size of 0.49μ and a coefficient of variation of 0.08,
AgBr 70 mol%, ), force, V, average particle size 0.34 μ, coefficient of variation 0.10 mixed at a ratio of 1 = 2 (Ag molar ratio) 0.23 Yaradin
1.34 Cyan coupler (1) (C-
5) 0.13 cyan coupler (2) (C-4)
0.16 color image stabilizer (Cpd-6) o
, 17 color image stabilizer (Cpd-7) 0.40
Solvent (Solv-6) 0.20 6th layer (ultraviolet absorption layer) Ceratin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing prevention agent 11 (Cpd-5) Solvent (Solv-5) 7th layer (Protective layer) Ceratin polyhinyl alcohol acrylic modification degree 17%) Liquid paraffin (CPCI-T) Color image stabilizer 0, 08 1, 33 0, 17 (Cpd 3) Color image stabilizer (Cpd 4) Color image stabilizer (cpci Color image stabilizer -(-CH2 to CH)-.

0NHC4 Average molecular weight: 80゜(Cpd 5〉Color mixing prevention 11-1 (Cpd 8) Color image stabilizer (CPCI 6) Color image stabilizer (Cpd 9) Color image stabilizer (UV-1 Ultraviolet absorber 2:4 :4 mixture (weight ratio) (Sol 4) Solvent (Sol 5) Solvent COOCa I7 (c 4:2:4 mixture of H2 (@weight ratio) 0OC8 (Sol Solvent (Solv 6) Solvent COOC4 (ExY) Yellow coupler ( Solv-2) Solvent 2 H5 0=P+0CH2CHC4 of 2: ■Mixture (weight ratio) (Sol 3) Solvent o = P +O-C9 Hl, -SO)3 Which 1:1 mixture (molar ratio) (ExM) Magenta coupler The sample thus obtained was designated as 3A, and the cyan couplers (1) and (2) of the fifth layer and the added additive [color image stabilizer] (100 mol % based on the coupler) were added as shown in Table 2. Other samples were prepared in the same manner as sample 3A except that they were combined with 3A.These samples were exposed through an optical wedge and then processed in the following steps.

Mixed with Sa-Kaichi Ranbai Hitomi color development 37℃ 3 minutes 30 seconds white mark fixation
33℃ 1 minute 30 seconds washing 24-34℃
Dry for 3 minutes at 70-80°C 1. Composition of the aromatic treatment liquid is as described in F.

Nagataka Shusui on L 800
Diethylenetriaminepentaacetic acid 1゜Ditrilodiacetic acid 2゜Pencil alcohol
E5 Diethylene glycol 10! II'I Sodium sulfate Potassium dibromide 1゜Potassium carbonate 113O N-ethyl-N-(β-methanesulneamidoethyl) 3-methyl-4-aminoaniline mm %m
4-5 g hydroxylamine sulfate
3.0g fluorescent whitening agent (W old 'rEX4B, made by Sumitomo Chemical) 1.0gm υ 0g 0g f1 m! 0g 0g Add water 1000ml pH
(25℃) 10.25 liters of water 4
00m, Q.

Ammonium thiosulfate, (70%) 150m, f
2 Sodium sulfite 18 g Iron Tetraacetate (m) 7 tons (-2 ft1.
5 5 g Ale Nonoa Bunn Shi Vinegar M Sodium Add 5 g water to 10100O.

pH (25°C) 6.70 Each sample with a dye image formed in this way was exposed to light for 4 hours using a fluorescent color fading device (brightness 1.5 cal.nox) and a fading test was performed. As a result, the dye residual rate at the initial tIA level of 1.0 for the color density 1 was reduced.

In addition, in order to check the heat resistance +11, what is the shape of the Σ' starch melon when kept at 100℃ for 400 hours? The dye residual rate at A degree 1.0 was reduced in my room. The obtained results are shown in the second
Shown in the table.

Table 2 4 weeks 400 hours Initial concentration 1.0 C-48-13 C-48-2:I C-4^-32 C-4A-38 C-4A-41 G-4 comparative compound (a) C-4 comparative compound (b) 87'4 811% 90% 91 zero 9t 76 pieces 75 trees C-4 comparative compound (f) (Knee 5 A-15 C-5^-16 C-5A-25 C-5 comparative compound (b) C-12- C-12A-34 C-128-45 (nee 12 comparative compound (e) 3t 5t 0t 88 zero 91% 76 Lord 68* 91 zero 89 zero 2t 89* 87% 93* 90* 5t 85* present invention present invention present invention present invention present invention Comparative example Comparative example 5t 80 trees 89% 88* 90% 82* 81’n.

92* 94* 86 Comparative example Comparative example present invention present invention present invention Comparative example Comparative example present invention present invention Comparative example Table 2 (continued) Comparative compound (h) Trial cyan coupler color image P4 (+) (2) Stabilizer Comparative compound (g Comparative compound (h Comparative compound (i Comparative compound (j Comparative compound (k Comparative compound (g Comparative compound (h Comparative compound (I ^-45 Comparative compound (g) Dye residual rate Fluorescent light 100℃ 4 weeks 400 hours Initial concentration i.

72!1i 88 tree 7H84'4 7:l'4 87 tree 69'J 85! 69 main items 85* 76% 8ji$ 75% 84 bottles 74% 80! ni 91 Lord 88 ne 91! t 89 wood Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Present invention Comparative compound of the present invention (i) Comparative compound (j) Compound described in No. 299455 Compound described in No. 256951 Summer 1 Compound described in No. 50533 Compound described in Japanese Patent Publication No. 60-47578 Comparison compound (k) Compound described in Japanese Patent Publication No. 58-50533 From these results, it can be concluded that the compound of the present invention is extremely effective in preventing photofading of color images compared to the comparative compound. Recognize. It also shows excellent effects not only on stiffness but also on heat fading resistance. J (16) In the structural formula of M-2 on page 68 of the specification, the column R'' is supplemented as follows.

” - Below ”21

Claims (1)

[Claims] A silver halide color photograph characterized in that at least one of the cyan dye image-forming layer and its adjacent layer on a support contains at least one compound represented by the following general formula [I]. photosensitive material. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 and R_2 are hydrogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, aryl groups, heterocyclic groups, acyl groups , represents a sulfonyl group, a phosphonyl group, a sulfinyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkyloxycarbonyl group and an aryloxycarbonyl group,
Y represents a group of nonmetallic atoms necessary to form a 5- to 8-membered heterocycle together with two nitrogen atoms. However, except when the two nitrogen atoms are both linked to a heteroatom via an alkylene group to form a heterocycle, and the heterocycle formed by Y is perhydro-1,2,4,5- Excluding compounds that form tetrazine, and excluding compounds that form 1-phenyl-3-pyrazolidone and the substituent at the 2-position is a hydrogen atom, an acetyl group, or an acyl group substituted with a carboxyl group. . ]